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สถาบันค้ นคว้ าและพัฒนาผลิตภัณฑ์อาหาร มหาวิทยาลัยเกษตรศาสตร์ 0-2942-8629 ต่อ 626, 908
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1. CA1251461 - 3/21/1989
PHOSPHOROUS COMPOUNDS FOR PROTECTING CULTIVATED PLANTS
FROMTHE PHYTOTOXIC ACTION OF HERBICIDES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CA1251461
Inventor(s):
DIEL PETER J (--); MAIER LUDWIG (--)
Applicant(s):
CIBA GEIGY AG (--)
IP Class 4 Digits: C07F; A01N
IP Class:C07F9/30; A01N57/18; C07F9/38
E Class: A01N25/32; C07F9/30A1; C07F9/32A1; C07F9/38A1; C07F9/40A1; C07F9/53A1
Application Number:
CA19840467588 (19841113)
Priority Number: CH19840002748 (19840606); CH19830006135 (19831115)
Family: CA1251461
Equivalent:
EP0143078; US4739093; US4734119; ES8601082; BR8405841; HU200084
Abstract:
Abstract of CA1251461
Novel phosphorus compounds for protecting cultivated plants from tile phytotoxic action of herbicides
Novel acylated hydrazinomethylphosphonic acids, hydrazinomethylphosphonates,
hydrazinomethylphosphinic acids, hydrazinomethylphosphinates or hydrazinomethylphosphine oxides
of formula I below are able as "antidotes" or "safeners" to protect cultivated plants from the phytotoxic
action of herbicides. Suitable crops are preferably maize, sorghum, cereals, rice and soybeans and the
herbicides employed are in particular chloroacetanilides. The acylated hydrazinomethylphosphonates,
hydrazinomethylphosphinates or hydrazinomethylphosphine oxides have the formula I >;IMG; (I)
wherein R1 and R2 are each independently hydroxy, alkyl, aryl, phenylalkyl, alkoxy, alkenyloxy,
alkynyloxy, aryl or phenylalkoxy, the radicals of which may be substituted, R3 is a halogenated
alkanoyl or alkenoyl radical R4 is hydrogen, a halogenated alkanoyl or alkenoyl radical or an alkyl,
alkenyl or phenylalkyl radical, or an alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl or
phenylcarbonyl radical which may be unsubstituted or substituted or is an alkoxycarbonyl or
phenylalkoxycarbonyl radical which may also be unsubstituted or substituted or is an alkoxycarbonyl
or phenylalkoxycarbonyl radical which may also be substituted,Description:
Description of corresponding document: US4734119
The present invention relates to novel acylated hydrazinomethylphosphonates,
hydrazinomethylphosphinates and hydrazinomethylphosphine oxides which, as herbicide antagonists,
are able to protect cultivated plants from the phytotoxic action of herbicides, in particular of
chloroacetanilide herbicides, to compositions containing an acylated hydrazinomethylphosphonate,
hydrazinomethylphosphinate or hydrazinomethylphosphine oxide, and to compositions which, in
addition to containing such an antagonist (also called antidote or safener), already contain the
herbicide, and to a method of selectively controlling weeds, which comprises the use of a herbicide and
said safener. The invention also relates to the preparation of novel acylated
hydrazinomethylphosphonates, hydrazinomethylphosphinates and hydrazinomethylphosphine oxides.
2/612
It is known that herbicides belonging to a very wide range of compound classes such as triazines, urea
derivatives, carbamates, thiocarbamates, haloacetanilides, halophenoxyacetic acids etc., when
employed in an effective concentration, often also damage cultivated plants to a certain extent in
addition to the weeds which it is desired to control. Too high concentrations are often applied
unintentionally and randomly whenever peripheral zones overlap on zonal spraying, whether as a
consequence of the action of wind or through miscalculating the sweep of the spray device employed.
The climatic conditions or the nature of the soil may be such that the concentration of herbicide
reommended for normal conditions acts as an overdose. The quality of the seeds may also be a factor in
the tolerance of the herbicide. To counteract this problem, different compounds have already been
proposed which are able specifically to antagonise the harmful action of the herbicide on the cultivated
plant, i.e. to protect the cultivated plant without noticeably influencing the herbicidal action on the
weeds to be controlled.
However, it has been found that the proposed antidotes very often have a species-specific activity both
with respect to the cultivated plants and to the herbicide and also, in some cases, contingent on the
mode of application, i.e. a specific antidote is often suitable only for a specific cultivated plant and a
few classes of herbicides.
The direct pre- to postemergence treatment of certain useful plants with antidotes as antagonists of
specific classes of herbicides in a crop area is disclosed in German Offenlegungsschrift specifications
Nos. 2 141 586 and 2 218 097 and in U.S. Pat. No. 3,867,444.
Further, German Offenlegungsschrift No. 2 402 983 discloses that maize plants can be effectively
protected against damage by chloroacetanilides by adding an N-disubstituted dichloroacetamide as
antidote to the soil.
The compounds of the present invention are able to protect cultivated plants such as cereals, maize,
rice, sorghum or soybeans from the phytotoxic action of herbicides belonging to different chemical
classes.
The novel acylated hydrazinomethylphosphonic acids, hydrazinomethylphosphonates,
hydrazinomethylphosphinic acids, hydrazinomethylphosphinates and hydrazinomethylphosphine
oxides have the formula I ##STR2## wherein R1 and R2 are each independently hydroxy, C1 -C4
alkyl, aryl, C1 -C4 alkoxy, C2 -C4 alkenyloxy, C2 -C4 alkynyloxy, C2 -C4 haloalkoxy containing 1 to
5 halogen atoms, C2 -C8 alkoxyalkoxy, C1 -C4 cyanoalkoxy, or are C1 -C4 phenylalkyl or aralkoxy
which is unsubstituted or substituted in the phenyl nucleus by halogen, cyano, nitro or C1 -C4 alkyl,
R3 is a haloalkanoyl radical --COCX1 X2 --R6 or an alkenoyl radical which is is substituted by 1 to 3
halogen atoms and contains 2 to 4 carbon atoms in the alkenyl moiety,
R4 is hydrogen or a substituent as defined for R3, or is a --COOR7 or --COR8 radical or a C1 -C4 alkyl
or C2 -C4 alkenyl radical, or is a C1 -C4 phenylalkyl radical which is unsubstituted or substituted in
the phenyl ring by halogen, cyano, nitro or C1 -C4 alkoxy,
R5 is hydrogen or a C1 -C4 alkyl, C2 -C4 alkenyl or C2 -C4 alkynyl radical,
R6 is hydrogen, halogen or a C1 -C6 alkyl radical,
R7 is a C1 -C4 alkyl radical or a C1 -C4 phenylalkyl radical which is unsubstituted or substituted in the
phenyl ring by halogen, cyano, nitro or C1 -C4 alkoxy,
R8 is a C1 -C4 alkyl, C2 -C4 alkenyl or C2 -C4 alkynyl radical, or is a phenyl or C1 -C4 phenylalkyl
radical which is unsubstituted or substituted by halogen, cyano, nitro or C1 -C4 alkoxy,
R9 is hydrogen, C1 -C4 alkyl, or phenyl which is unsubstituted or substituted by halogen, cyano, nitro
or C1 -C4 alkoxy,
R10 is hydrogen or C1 -C4 alkyl and
X1 and X2 are each halogen or one of X1 and X2 is also hydrogen.
Alkyl by itself or as moiety of another substituent may be methyl, ethyl, n-propyl and isopropyl, and nbutyl, isobutyl, sec-butyl and tert-butyl. Examples of alkenyl radicals are vinyl, allyl, methallyl, butenyl
and butadienyl. Examples of alkynyl radicals are ethynyl, propynyl and butynyl.
Aralkyl radicals comprise phenyl and naphthyl radicals which are linked through C1 -C4 alkyl. Aralkyl
is preferably phenylethyl and, most preferably, benzyl.
3/612
Halogen is fluorine, chlorine, bromine and iodine, with chlorine being preferred.
Effective safeners are such compounds of formula I, wherein
R1 and R2 are each C1 -C4 alkoxy (phosphonates),
R1 is C1 -C4 alkoxy and R2 is C1 -C4 alkyl (phosphinates),
R1 and R2 are each C1 -C4 alkyl (phosphine oxides), and such compounds, wherein each of R1 and R2
is a C1 -C4 alkyl or C1 -C4 alkoxy radical,
R3 is the chloroacetyl, dichloroacetyl or 2,3,3-trichloroacrylic acid radical,
R4 is hydrogen or a substituent as defined for R3, or is a C1 -C4 alkyl, C2 -C4 alkenyl, aralkyl, C1 -C4
alkylcarbonyl, C1 -C4 alkoxycarbonyl, benzoyl or benzyloxycarbonyl radical and
R5 is hydrogen; and the following compounds:
hydrazino-N-benzyloxycarbonyl-N'-chloroacetyl-N'-methyl-O,O-diethylphosphon ate,
hydrazino-N-benzyloxycarbonyl-N'-dichloroacetyl-N'-methyl-O,O-diethylphosph onate,
hydrazino-N-benzyloxycarbonyl-N'-dichloroacetyl-N'-methyl-O,O-di-isopropyl- phosphonate,
hydrazino-N-methoxycarbonyl-N'-chloroacetyl-N'-methyl-O,O-diethylphosphonat e,
hydrazino-N-methoxycarbonyl-N'-dichloroacetyl-N'-methyl-O,O-diethylphosphon ate,
hydrazino-N-t-butyloxycarbonyl-N'-chloroacetyl-N'-methyl-O,O-diethylphospho nate,
hydrazino-N-t-butyloxycarbonyl-N'-dichloroacetyl-N'-methyl-O,O-diethylphosp honate,
hydrazino-N'-chloroacetyl-N'-methyl-O,O-diethyl-phosphonate,
hydrazino-N-benzyloxycarbonyl-N'-dichloroacetyl-N'-methyl-O-isopropyl-methy lphosphinate,
hydrazino-N-benzyloxycarbonyl-N'-dichloroacetyl-N'-methyl-O-ethylmethylphos phinate and
hydrazino-N-benzyloxycarbonyl-N'-dichloroacetyl-N'-methyl-O-ethylethylphosp hinate.
The preparation of the novel acylated hydrazinomethylphosphonates, hydrazinomethylphosphinates
and hydrazinomethylphosphine oxides of formula I is effected in a manner known per se.
The synthesis steps may be illustrated for example by the following equations: ##STR3##
The derivative of the respective phosphorous, phosphonic or phosphinic acid is condensed with an
alkylidenehydrazine which is protected by a carbonic acid radical thus affording an acylated
hydrazinomethylphosphonate, hydrazinomethylphosphinate or hydrazinomethylphosphine oxide.
If R1 and R2 are alkyl radicals, an acylated hydrazinomethylphosphine oxide is also obtained as
follows: ##STR4##
The halomethylphosphine oxide is condensed with a carbazate.
These condensation reactions are carried out in an inert organic solvent.
The protective group --COOR7 can, if desired, be removed ##STR5##
This removal is effected by simple hydrolysis in alkaline or acidic medium or also by hydrogenolysis
in acidic medium with hydrogen and a catalyst such as palladium on activated carbon if R7 is benzyl.
The above mentioned hydrazinomethylphosphonyl, hydrazinomethylphosphinyl and
hydrazinomethyloxophosphino derivatives can be acylated with 1 or 2 molar equivalents of
haloalkanoyl halide or haloalkenoyl halide. ##STR6##
These reactions are carried out at low temperature in the range from -20 DEG C. to +50 DEG C. in an
inert organic solvent in the presence of at least an equimolar amount of an acid acceptor.
If R4 or R5 is an alkyl, alkenyl, alkynyl or aralkyl radical, said radicals may be introduced into a
compound of formula I by alkylating an acylated hydrazinomethylphosphonate,
hydrazinomethylphosphinate or hydrazinomethylphosphine oxide of the formula below with X--R8
##STR7##
These reactions are also carried out in an inert organic solvent in the presence of at least an equimolar
amount of an acid acceptor.
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In the above equations R1, R2, R3, R5, R6, R9 and R10 are as defined for formula I, Hal is halogen,
preferably chlorine or bromine. The process of the present invention for the preparation of a compound
of formula I comprises reacting a hydrazinomethylphosphonate, hydrazinomethylphosphinate or
hydrazinomethylphosphine oxide of formula II ##STR8## wherein R1, R2, R4, R5, R9 and R10 are as
defined for formula I, in an inert organic solvent in the presence of at least an equimolar equivalent of
an acid acceptor with an acyl halide of formula III
R3 --Hal
(III),
wherein R3 is as defined for formula I and Hal is chlorine or bromine.
Suitable inert organic solvents for these reactions are in particular halogenated hydrocarbons such as
chloroform, methylene chloride, ethylene chloride and also aromatic compounds such as benzene,
toluene or xylene. Further suitable inert organic solvents are ethers such as diethyl ether, dioxane or
tetrahydrofuran, higher boiling hydrocarbons such as cyclohexane or dimethylformamide, as well as
mixtures of such solvents.
The reaction is carried out in the temperature range from -20 DEG to the boiling point of the solvent.
When the condensation reactions exotherm, it is convenient to cool the reaction mixture initially, so
long as hydrogen halide evolves, and, at the conclusion of the reactions, after all has been added, to stir
the mixture further with heating.
Depending on the end use, the safener or antidote of the formula I can be used for pretreating seeds of
the cultivated plant (dressing of the seeds or cuttings) or it can be added to the soil before or after
sowing. However, it can also be applied pre- or postemergence by itself alone or together with the
herbicide. The treatment of the plant or seeds with the safener can therefore in principle be carried out
irrespective of the time of application of the phytotoxic chemical. It can, however, also be carried out
by simultaneous application of phytotoxic chemical and safener (tank mixture). The pre-emergence
treatment includes both treatment of the crop area before sowing (ppi=pre-plant incorporation) and
treatment of the crop areas after sowing but before emergence of the plants.
The rates of application of the safener with respect to the herbicide depend largely on the mode of
application. Where a field treatment is carried out, either simultaneously as tank mixture or with
separate application of herbicide and safener, the ratio of safener to herbicide is in the range from 1:100
to 5:1. Full protective action is usually obtained at a ratio of safener to herbicide of 1:5 to 1:50. When
dressing seeds and taking similar specific protective measures, however, much lower amounts of
safener are required compared with e.g. the amounts of herbicide later employed per hectare of crop
area. For seed dressing, 0.1 to 10 g of safener per kg of seeds are normally required. Full protection is
usually obtained with 0.1 to 2 g of safener per kg of seeds. If it is desired to apply the safener shortly
before sowing by seed soaking, antidote solutions which contain the active ingredient in a
concentration of 1 to 10,000 ppm are used. Full protective action will normally be obtained with
safener concentrations of 100 to 1000 ppm.
As a rule there is a substantial interval of time between protective measures such as seed dressing and
treatment of seedlings with a safener of the formula I and the possible later field treatment with
agricultural chemicals. Pretreated seeds and plants can later come in contact with different chemicals in
agriculture, horticulture and forestry. Accordingly, the invention relates to plant protection
compositions which contain a safener of the formula I as active ingredient, together with conventional
carriers. If appropriate, such compositions may be additionally mixed with the chemical from whose
effects it is desired to protect the cultivated plant.
Cultivated plants within the scope of this invention are all plants which, in any form, can be harvested
(seeds, roots, stalks, tubers, leaves, blossoms) and from which extracts can be obtained (oils, sugar,
starch, protein) and which are cultivated for this purpose. These plants comprise e.g. all species of
cereals such as wheat, rye, barley, oats and, in particular, rice, sorghum, maize, and also cotton, sugar
beet, sugar cane, soybeans, beans, and peas.
The safener can be employed wherever it is desired to protect a cultivated plant of the kind indicated
above from the harmful effects of an agricultural chemical. As already mentioned, possible agricultural
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chemicals are primarily herbicides of the most widely varying compound classes, in particular
haloacetanilides and thiocarbamates.
Numerous haloacetanilides whose harmful effects on cultivated plants can be antagonised with the
novel hydrazinomethylphosphonates, hydrazinomethylphosphinates and hydrazinomethylphosphine
oxides of the formula I are known in the art (q.v. German patent applications Nos. 2 305 495, 2 328
340, 2 212 268, 2 726 252 and 2 805 757, and U.S. Pat. Nos. 3,946,044, 4,022,608 and 4,039,314).
Such haloacetanilides may be illustrated by the general formula VII ##STR9## wherein Hal is halogen,
preferably chlorine or bromine, each of R4 and R5 independently of the other is hydrogen, halogen,
lower alkyl, alkoxy, alkylthio, haloalkyl, alkoxyalkyl or alkylthioalkyl, Z is hydrogen, halogen, lower
alkyl, alkoxy, alkylthio, haloalkyl, alkoxyalkyl or alkylthioalkyl, which radicals Z are preferably in the
3-position with respect to the nitrogen atom, n is 0 to 3, A is alkylene, preferably methylene, 1,1ethylene, and 1,2-ethylene which may be substituted by 1 or 2 lower alkyl groups, and R6 is lower
alkoxy, hydroxycarbonyl, alkoxycarbonyl, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl,
cyano, an unsubstituted or substituted nitrogen-containing heterocyclic radical, alkanoyl, unsubstituted
or substituted benzoyl, unsubstituted or substituted 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4triazol-3-yl or 1,3,4-triazol-1-yl.
Typical examples of such haloacetanilides are:
N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline
N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline
N-chloroacetyl-N-(2-methoxyethyl)-2,6-dimethylaniline
N-(2-allyloxyethyl)-N-chloroacetyl-2,6-dimethylaniline
N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(2-isopropoxyethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(2-methoxyethyl)-2-ethyl-6-methylaniline
N-chloroacetyl-N-(methoxyethyl)-2,6-diethylaniline
N-(2-ethoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline
N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-methylaniline
N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline
N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline
N-(2-ethoxyethyl)-N-chloroacetyl-2,6-diethylaniline
N-chloroacetyl-N-(2-n-propoxyethyl)-2-ethyl-6-methylaniline
N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline
N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methylaniline
N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline
N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline
N-chloroacetyl-N-methoxycarbonylmethyl-2,6-dimethylaniline
N-chloroacetyl-N-(2,2-diethoxyethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,3-dimethylaniline
N-(2-ethoxyethyl)-N-chloroacetyl-2-methylaniline
N-chloroacetyl-N-(2-methoxyethyl)-2-methylaniline
N-chloroacetyl-N-(2-methoxy-2-methylethyl)-2,6-dimethylaniline
N-(2-ethoxy-2-methylethyl)-N-chloroacetyl-2-ethyl-6-methylaniline
N-chloroacetyl-N-(1-ethyl-2-methoxyethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(2-methoxyethyl)-2-methoxy-6-methylaniline
N-n-butoxymethyl-N-chloroacetyl-2-tert-butylaniline
N-(2-ethoxyethyl-1-methylethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(2-methoxyethyl)-2-chloro-6-methylaniline
N-(2-ethoxyethyl)-N-chloroacetyl-2-chloro-6-methylaniline
N-(2-ethoxyethyl)-N-chloroacetyl-2,3,6-trimethylaniline
N-chloroacetyl-1-(2-methoxyethyl)-2,3,6-trimethylaniline
N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline
N-but-3-yn-1-yl-N-chloroacetylaniline
N-chloroacetyl-N-propargyl-2-ethyl-6-methylaniline
N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methylaniline
N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methylaniline
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N-chloroacetyl-N-(2-furanylmethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(2-furanylmethyl)-2-ethyl-6-methylaniline
N-chloroacetyl-N-(2-tetrahydrofuranylmethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(N-propargylcarbamoylmethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(N,N-dimethylcarbamoylmethyl)-2,6-dimethylaniline
N-(n-butoxymethyl)-N-chloroacetyl-2,6-diethylaniline
N-(2-n-butoxyethyl)-N-chloroacetyl-2,6-diethylaniline
N-chloroacetyl-N-(2-methoxy-1,2-dimethylethyl)-2,6-dimethylaniline
N-chloroacetyl-N-isopropyl-2,3-dimethylaniline
N-chloroacetyl-N-isopropyl-2-chloroaniline
N-chloroacetyl-N-(1H-pyrazol-1-ylmethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(1H-pyrazol-1-ylmethyl)-2-ethyl-6-methylaniline
N-chloroacetyl-N-(1H-1,2,4-triazol-1-ylmethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(1H-1,2,4-triazol-1-ylmethyl)-2,6-diethylaniline
N-benzoylmethyl-N-chloroacetyl-2,6-dimethylaniline
N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline
N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2,6-diethylaniline
N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-ethyl-6-methylaniline
N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-tert-butylaniline
N-chloroacetyl-N-(4-chlorobenzoylmethyl)-2,6-dimethylaniline
N-chloroacetyl-N-(1-methyl-5-methylthio-1,3,4-triazol-2-ylmethyl)-2,6-dieth ylaniline.
In addition to chloroacetanilides, other classes of herbicides are also suitable, for example
thiocarbamates:
S-ethyl-N,N-dipropylthiocarbamate
S-ethyl-N,N-diisopropylthiocarbamate
S-2,3-dichloroallyl-N,N-diisopropylthiocarbamate
S-propyl-N-butyl-N-ethylthiocarbamate
S-2,3,3-trichloroallyl-N,N-diisopropylthiocarbamate
S-propyl-N,N-dipropylthiocarbamate
S-ethyl-N-ethyl-N-cyclohexylthiocarbamate
S-ethyl-N-hexahydro-1H-azepine-1-carbothioate
S-isopropyl-N,N-hexamethylene-thiocarbamate
S-(p-chlorobenzyl)-N,N-diethylthiocarbamate
N-ethylthiocarbonyl-cis-decahydroquinoline
N-propylthiocarbonyl-decahydroquinaldine
S-ethyl-N,N-bis(n-butyl)-thiocarbamate
S-tert-butyl-N,N-bis(n-propyl)-thiocarbamate.
In addition to the chloroacetanilides and thiocarbamates, other classes of herbicides are also suitable,
for example:
Triazines and triazinones: 2,4-bis(aminopropylamino)-6-methylthio-1,3,5-triazine ("prometryn"), 2,4bis(ethylamino)-6-methylthio-1,3,5-triazine ("symetrin"), 2-(1',2'-dimethylpropylamino)-4-ethylamino6-methylthio-1,3,5-triazine ("dimethametryn"), 4-amino-6-tertbutyl-4,5-dihydro-3-methylthio-1,2,4triazin-5-one ("metribuzin"), 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine ("atrazin"), 2chloro-4,6-bis(ethylamino)-1,3,5-triazine ("simazin"), 2-tertbutylamino-4-chloro-6-ethylamino-1,3,5triazine ("terbuthylazin"), 2-tert-butylamino-4-ethylamino-6-methoxy-1,3,5-triazine ("terbumeton"), 2tert-butylamino-4-ethylamino-6-methylthio-1,3,5-triazine ("terbutryn"), 2-ethylamino-4isopropylamino-6-methylthio-1,3,5-triazine ("ametryn"),
Ureas: 1-(benzothiazol-2-yl)-1,3-dimethylurea; phenylureas such as 3-(3-chloro-p-tolyl)-1,1dimethylurea ("chlortoluron"), 1,1-dimethyl-3-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)urea
("fluormeturon"), 3-(4-bromo-3-chlorophenyl)-1-methoxy-1-methylurea ("chlorbromuron"), 3-(4bromophenyl)-1-methoxy-1-methylurea ("metobromuron"), 3-(3,4-dichlorophenyl)-1-methoxy-1methylurea ("linuron"), 3-(4-chlorophenyl)-1-methoxy-1-methylurea ("monolinuron"), 3-(3,4dichlorophenyl)-1,1-dimethylurea ("diuron"), 3-(4-chlorophenyl)-1,1-dimethylurea ("monouron"), 3(3-chloro-4-methoxyphenyl)-1,1-dimethylurea ("metoxuron"); sulfonylureas, e.g. N-(2chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, N-(2-
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methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethylpyridin-2-yl)urea, N-(2,5-dichlorophenylsulfonyl)N'-(4,6-dimethoxypyrimidin-2-yl)urea, N-[2-(2-butenyloxy)phenylsulfonyl]-N'-(4-methoxy-6-methyl1,3,5-triazin-2- yl)urea, as well as the sulfonylureas listed in European patent publications Nos. 44808
and 44809;
Chloroacetamides: N-[1-isopropyl-2-methylpropen-1-yl(1)]-N-(2'-methoxyethyl)-chloroacetamide .
Diphenyl ethers and nitrodiphenyl ethers: 2,4-dichlorophenyl-4'-nitrophenyl ether ("nitrofen"), 2chloro-1-(3'-ethoxy-4'-nitrophenoxy)-4-trifluoromethylbenzene ("oxyfluorfen"), 2',4'-dichlorophenyl-3methoxy-4-nitrophenyl ether ("chlormethoxynil"), methyl-2-[4'-(2",4"dichlorophenoxy)phenoxy]propionate, N-(2'phenoxyethyl)-2-[5'(2"-chloro4"[trifluoromethylphenoxy)phenoxy]propi onamide, 2-methoxyethyl-2-[2-nitro-5-(2-chloro-4trifluoromethylphenoxy)-phenoxy]pr opionate; 2-chloro-4-trifluoromethylphenyl-3'-oxazolin-2'-yl-4'nitrophenyl ether;
Benzoic acid derivatives: methyl-5-(2'.4'-dichlorophenoxy)-2-nitrobenzoate("bifenox"), 5-(2-chloro-4'trifluoromethylphenoxy)-2-nitrobenzoic acid ("acifluorfen"), 2,6-dichlorobenzonitrile ("dichlobenil").
Nitroanilines: 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline ("trifluralin"), N-(1'-ethylpropyl)-2,6dinitro-3,4-xylidine ("pendimethalin").
Oxadiazolones: 5-tert-butyl-3-(2',4'-dichloro-5'-isopropoxyphenyl)-1,3,4-oxadiazol-2-one
("oxadiazon").
Phosphates: S-2-methylpiperidinocarbonylmethyl-O,O-dipropylphosphorodithioate ("piperophos").
Pyrazoles: 1,3-dimethyl-4-(2',4'-dichlorobenzoyl)-5-(4'-tolysolfonyloxy)pyrazole.
Other suitable herbicides are .alpha.-(phenoxyphenoxy)propionic acid derivatives and .alpha.-(pyridyl2-oxyphenoxy)propionic acid derivatives.
The concentration of safener, provided it is not used for seed dressing, varies from about 0.01 to 5 parts
by weight per part by weight of herbicide. The most suitable ratio for achieving optimum effects in the
particular cultivated plant is determined from case to case, i.e. depending on the type of herbicide
employed.
The compounds of formula I are used in unmodified form or, preferably, as compositions, together
with the adjuvants conventionally employed in formulation technology, and are therefore formulated in
known manner to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions,
wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymeric
substances. As with the nature of the compositions, the methods of application such as spraying,
atomising, dusting, scattering or pouring are chosen in accordance with the intended objectives and the
prevailing circumstances.
The formulations, i.e. the compositions containing the compound of the formula I and, where
appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing
and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where
appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms,
e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl
phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their
ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether,
ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone,
dimethylsulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such as
epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such
as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it
8/612
is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable
granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or
bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In additon, a great
number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite
or pulverised plant residues.
Depending on the nature of the compound of the formula I to be formulated, suitable surface-active
compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and
wetting properties. The term "surfactants" will also be understood as comprising mixtures of
surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active
compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted
ammonium salts of higher fatty acids (C10 -C22), e.g. the sodium or potassium salts of oleic or stearic
acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil.
Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty
sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or
unsubstituted dor substituted ammonium salts and contain a C8 -C22 alkyl radical which also includes
the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of ligonsulfonic acid, of
dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These
compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene
oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and
one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium,
calcium or triethylanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid
or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding
phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of
ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols,
or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether
groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the
alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with
polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to
10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and
10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units
per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil
polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol,
polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and
polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, an N-substituent, at least
one C8 -C22 alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl
or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or
ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium
bromide.
The surfactants customarily employed in the art of formulation are described e.g. in the following
publications:
9/612
"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ridgewood, N.J., 1981; H.
Stache, "Tensid-Taschenbuch", 2nd Edition, C. Hanser Verlag, Munich & Vienna, 1981; M. and J.
Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81.
The herbicidal compositions usually contain 0.1 to 95%, preferably 0.1 to 80%, of a compound of the
formula I, 1 to 99.9%, of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of a
surfactant.
Preferred formulations are composed in particular of the following constituents (%=percentage by
weight):
>;tb;______________________________________
>;tb;Emulsifiable concentrates
>;tb;active ingredient:
>;tb;
1 to 20%, preferably 5 to 10%
>;tb;surfactant: 5 to 30%, preferably 10 to 20%
>;tb;liquid carrier:
>;tb;
50 to 94%, preferably 70 to 85%
>;tb;Dusts
>;tb;active ingredient:
>;tb;
0.1 to 10%, preferably 0.1 to 1%
>;tb;solid carrier: 99.9 to 90%, preferably 99.9 to 99%
>;tb;Suspension concentrates
>;tb;active ingredient:
>;tb;
5 to 75%, preferably 10 to 50%
>;tb;water:
94 to 25%, preferably 90 to 30%
>;tb;surfactant: 1 to 40%, preferably 2 to 30%
>;tb;Wettable powders
>;tb;active ingredient:
>;tb;
0.5 to 90%, preferably 1 to 80%
>;tb;surfactant: 0.5 to 20%, preferably 1 to 15%
>;tb;solid carrier: 5 to 95%, preferably 15 to 90%
>;tb;Granulates
>;tb;active ingredient:
>;tb;
0.5 to 30%, preferably 3 to 15%
>;tb;solid carrier: 99.5 to 70%, preferably 97 to 85%.
>;tb;______________________________________
Whereas commercial products will be preferably formulated as concentrates, the end user will normally
employ dilute formulations. The formulations can be diluted to a concentration as low as 0.001% The
rates of application are normally from 0.01 to 10 kg a.i./ha, preferably from 0.025 to 5 kg a.i./ha.
The compositions may also contain further ingredients such as stabilisers, antifoams, viscosity
regulators, binders, tackifiers, as well as fertilisers and other compounds for obtaining special effects.
The invention is illustrated by the following Examples in which the temperatures are indicated in
degrees Celsius ( DEGC.) and the pressures in millibars (mbar).
EXAMPLE 1
Preparation of hydrazino-N-benzyloxycarbonyl-N'-methyldiethylphosphonate (intermediate)
##STR10##
15 g of N-methylenebenzyl carbazate are mixed with 12.2 ml of diethyl phosphite at room temperature
and heated with stirring to 110 DEG. 1 ml of boron trifluoride etherate is added and stirring is
continued for 11/2 hours at 110 DEG-115 DEG, the mixture is cooled and then taken up in methylene
chloride at room temperature. The solvent is removed by evaporation and the residue dried under high
vacuum affording 23.4 g of an orange-brown oil which crystallises on standing.
10/612
Melting point: 56 DEG-57 DEG.
Analysis calculated: C, 49.37%; H, 6.69%; N, 8.86%; P, 9.79%; found: C, 48.6%, H, 6.6%; N, 9.0%; P,
9.8%.
Instead of boron trifluoride ethereate, gaseous hydrochloride acid, tin chloride or an alkali metal
alcoholate can be used as catalyst. The reaction can also be carried out without a catalyst but in that
case at a higher temperature. Instead of methylene chloride, an aromatic solvent such as benzene,
toluene or xylene can be used.
The N-methylenebenzyl carbazate used as starting material was prepared as follows:
A mixture of 102.3 g of benzyl carbazate and 20.3 g of paraformaldehyde in 800 ml of methanol is
heated to 50 DEG. 11.06 ml of triethylamine are added and the mixture is stirred for 2 hours reflux.
The solvent is removed by rotary evaporation. The viscous residue is dissolved in methanol, treated
with activated carbon and filtered and the filtrate is concentrated. The residue is dried under a vacuum
of 1 mbar and at 50 DEG affording 105 g of the title compound as a white powder with a melting point
of 87 DEG-91 DEG. According to the NMR spectrum the product is obtained as monomer. It contains
0.03% water of crystallisation.
Analysis calculated: C, 60.51%; H, 5.68%; N, 15.68%; found: C, 60.5%; H, 5.8%; N, 15.6%.
20 g of benzyl carbazate hydrochloride are dissolved in 200 ml of water. 15 ml of a 37% formaline
solution are stirred in dropwise at circa 15 DEG. After 2 hours the precipitate is filtered with suction,
stirred in two 300 ml portions of water and each time filtered with suction. The precipitate is then
dissolved in methylene chloride, the solution is dried over sodium sulfate and filtered. The solvent is
distilled off and the residue is dried in vacuo affording 15.9 g of N-methylenebenzyl carbazate which
melts at 125 DEG-127 DEG. According to the NMR spectrum the product is obtained as trimer.
Analysis calculated: C, 60.67%; H, 5.66%; N, 15.72%; found: C, 60.2%; H 5.5%; N, 15.8%. Nmethylenecarbazoyl methylester (CH2 .dbd.N--NHCOOCH3), N-methylenecarbazoyl ethylester (CH2
.dbd.N--NHCOOC2 H5) and N-methylenecarbazoyl t-butylester (CH2 .dbd.N--NHCOO t-C4 H9) can
be obtained in similar manner.
The following N-phosphomethylhydrazino compounds can be obtained in the manner described in
Example 1:
>;tb;__________________________________________________________________________
>;tb; ##STR11##
>;tb;R1
>;tb; R2
>;tb;
R7
>;tb;
R9
>;tb;
R10
>;tb;
Physical data
>;tb;__________________________________________________________________________
>;tb;iC3 H7
>;tb; iC3 H7 O
>;tb;
benzyl H H b.p. 195 DEG/1.1 mbar
>;tb;
Analysis
>;tb;C2 H5
>;tb; CH3
>;tb;
benzyl H H cal. C 49.0% H 6.8% N 9.5% P 10.5%
>;tb;
found C 49.2% H 6.8% N 9.5% P 10.3%
>;tb;C2 H5
>;tb; C2 H5
>;tb;
benzyl H H cal. C 52.0% H 7.05% N 9.33% P 10.32%
>;tb;
found C 51.5% H 7.1% N 9.3% P 10.1%
>;tb;iC3 H7
>;tb; CH3
11/612
>;tb;
benzyl H H cal. C 52.0% H 7.05% N 9.33% P 10.32%
>;tb;
found C 51.1% H 7.0% N 9.3% P 10.0%
>;tb;CH3
>;tb; iC4 H9 O
>;tb;
benzyl H H m.p. 58-60 DEG
>;tb;iC3 H7
>;tb; C3 H7 O
>;tb;
CH3
>;tb;
H H b.p. 138-140 DEG/0.2 mbar
>;tb;C2 H5
>;tb; C2 H5 O
>;tb;
CH3
>;tb;
H H b.p. 160-165 DEG/0.2 mbar
>;tb;iC4 H9
>;tb; CH3
>;tb;
CH3
>;tb;
H H b.p. 170-173 DEG/0.2 mbar
>;tb;CH2
>;tb; iC4 H9 O
>;tb;
C2 H5
>;tb;
H H b.p. 173-175 DEG/0.2 mbar
>;tb;iC3 H7
>;tb; iC3 H7 O
>;tb;
C2 H5
>;tb;
H H b.p. 160 DEG/0.06 mbar
>;tb;C2 H5
>;tb; C2 H5 O
>;tb;
C2 H5
>;tb;
H H b.p. 170 DEG/0.1 mbar
>;tb;
Analysis
>;tb;C2 H5
>;tb; C2 H5 O
>;tb;
t-C4 H9
>;tb;
H H cal. C 42.55% H 8.21% N 9.93% P 10.98%
>;tb;
found C 42.9% H 8.6% N 10.4% P 10.6%
>;tb;CH3
>;tb; iC4 H9 O
>;tb;
t-C4 H9
>;tb;
H H m.p. 75-77 DEG
>;tb;
Analysis
>;tb;C2 H5
>;tb; C2 H5 O
>;tb;
C2 H5
>;tb;
H C2 H5
>;tb;
cal. C 42.55% H 8.2% N 9.93% P 10.9%
>;tb;
found C 42.9% H 7.9% N 9.93% P 10.1%
>;tb;C2 H 5
>;tb; C2 H5 O
>;tb;
C2 H5
>;tb;
CH3
>;tb;
CH3
>;tb;
cal. C 42.55% H 7.9% N 9.93% P 10.9%
>;tb;
found C 42.3% H 8.% N 9.93% P 10.4%
>;tb;C2 H5
>;tb; C2 H5 O
>;tb;
C2 H5
>;tb;
H C6 H5
>;tb;
oil
>;tb;C2 H5
12/612
>;tb; CH3
>;tb;
C2 H5
>;tb;
CH3
>;tb;
CH3
>;tb;
cal. C 42.8% H 8.4% N 11.1% P 12.2%
>;tb;
found C 41.8% H 8.2% N 10.9% P 11.8%
>;tb;C2 H5
>;tb; C2 H5
>;tb;
C2 H5
>;tb;
H C2 H5
>;tb;
oil
>;tb;C2 H5
>;tb; C2 H5
>;tb;
C2 H5
>;tb;
H C6 H5
>;tb;
oil
>;tb;__________________________________________________________________________
>;tb; ##STR12##
>;tb;R1
>;tb; R2
>;tb;
R8
>;tb;
R9
>;tb;
R10
>;tb;
Physical data
>;tb;__________________________________________________________________________
>;tb;C2 H5
>;tb; C2 H5 O
>;tb;
Benzyl H H Analysis
>;tb;
cal. C 52.0% H 7.05% N 9.3% P 10.3%
>;tb;
found C 51.8% H 7.1% N 9.0% P 10.1%
>;tb;isoC3 H7
>;tb; isoC3 H7
>;tb;
Benzyl H H oil
>;tb;C2 H5
>;tb; CH3
>;tb;
Benzyl H H oil
>;tb;C2 H5
>;tb; C2 H5 O
>;tb;
Phenylethyl
>;tb;
H H Analysis
>;tb;
cal. C 53.5% H 7.4% N 8.9% P 9.8%
>;tb;
found C 53.3% H 7.5% N 8.9% P 9.6%
>;tb;isoC3 H7
>;tb; isoC3 H7 O
>;tb;
Phenylethyl
>;tb;
H H
>;tb;C2 H5
>;tb; CH3
>;tb;
Phenylethyl
>;tb;
H H
>;tb;__________________________________________________________________________
EXAMPLE 2
Preparation of hydrazino-N-ethoxycarbonyl-N'-methylphosphonic acid (intermediate)
(HO)2 PO--CH2 --NHNH--COOC2 H5
A sulfurating flask is charged with a solution of 10 g of hydrazino-N-carbethoxy-N-methyldiisopropylphosphonate in 60 ml of chloroform; 38.5 g of trimethyl bromosilane are added dropwise to
13/612
the solution with stirring at room temperature. After the trimethyl bromosilane has been added, the
mixture is stirred further for 24 hours at room temperature. The solvent is removed by rotary
evaporation and the residue is dried under a high vacuum. The semisolid substance is taken up in 20 ml
of ethanol, and propylene oxide is added to the solution. After the addition of 60 ml of ether stirring is
continued for an hour affording the title compound in the form of white crystals which are filtered off
and dried.
Yield: 4.5 g; decomposition point: 204 DEG-206 DEG.
This compound can also be obtained by boiling hydrazino-N-carbethoxy-N'-methyl-diisopropylphosphonate for 3 hours in 48% hydrobromic acid.
EXAMPLE 3
Preparation of hydrazinomethyl-O,O-diethylphosphonate
H2 N--NH--CH2 --PO(OC2 H5)2
168 g of hydrazino-N-benzyloxycarbonyl-N'-methyl-O,O-diethylphosphonate are dissolved in 2 l of
ethanol and the solution is decarboxylated by hydrogenolysis by adding 1.1 molar equivalents of HCl
gas and a small amount of 5% palladium on carbon catalyst. After hydrogen absorption has ceased, the
catalyst is removed, the alcohol is distilled off under reduced pressure and the residue is taken up in
500 ml of ethyl acetate and 250 ml of water. The phases are separated and the organic phase is
extracted again with water. The aqueous phases are combined and concentrated at 50 DEG and 1 mbar.
The residue is dried at 50 DEG and 0.05 mbar affording 104.5 g of hydrazino-N-methyl-O,O-diethylphosphonate hydrochloride as a yellow oil.
Analysis calculated: C, 25.2%; H, 7.4%; N, 11.7%; Cl, 16.4%; P, 13.0%; found: C, 25.5%; H, 7.3%; N
11.6%; Cl, 16.5%; P, 13.0%.
The product contains 1.1 molar equivalents of HCl and 0.8 molar equivalent of water of crystallisation.
53.0 g of this hydrochloride are suspended in 1 l of methylene chloride and the suspension is cooled to
-5 DEG. Then 31.6 g of 30% aqueous NaOH solution are added dropwise with stirring and good
cooling. Subsequently an amount of potassium carbonate necessary to bind all the water is added in
portions. The methylene chloride solution is decanted off and the potassium carbonate is digested twice
with methylene chloride. The organic phases are combined and dried. The solvent is removed by
evaporation affording 38.3 g of the title compound as a pale oil.
Spectral data: @1 H NHR CH3 (t, 6H,) 1.2 ppm), P--CH2 (d, 2H, 3.08 ppm) NHNH2 (s, 3H, 3.65
ppm), OCH2 (q, 4H, 4.02 ppm) (CDCl3, 60 MHz).
Hydrazinomethyl-O-isopropyl-methyl-phosphinate and its hydrochloride salt were prepared in a
manner similar to that described in this Example. ##STR13##
Spectral data: @1 H NMR CH3 (d, 6H, 0.95 ppm), P-CH3, ;CH--(m, 4H, 1.8 ppm) OCH2, P--CH2 (m,
4H, 3.75 ppm), NHNH2 (s, 4.85 ppm) (D2 O, 60 MHz).
EXAMPLE 4
Preparation of hydrazinomethyl-methylphosphinic acid (intermediate) ##STR14##
A mixture of 6.8 g of hydrazinomethyl-O-isopropoxymethylphosphinate hydrochloride and 50 ml of
6N hydrochloric acid is heated under reflux for 5 hours and subsequently concentrated by rotary
evaporation under reduced pressure. The residue is dried under high vacuum at 50 DEG affording 5.6 g
of a viscous semisolid product which is triturated with ethanol, filtered and dried under high vacuum
affording 2.2 g of hydrazinomethyl-methylphosphinic acid as a white powder.
@1 H-NMR (in D2 O) CH3 P 1.37 (d, JPCH 14 Hz, 3H); CH2 P 3.15 (d, JPCH 11 Hz, 2H); NH, OH
4.9 (s) (ppm).
14/612
EXAMPLE 5
Preparation of hydrazinomethanephosphonic acid (intermediate)
(HO)2 PO--CH2 NHNH2
A mixture of 64 g of N-benzoyl-N'-methyl-diethylphosphonylhydrazine and 400 ml of 6N hydrochloric
acid is boiled under reflux with stirring for 20 hours while continuously removing alcohol from the
reaction mixture by means of a distillation bridge. The reaction mixture is cooled in an ice-bath to 5
DEG, the precipitated benzoic acid is filtered off and washed with a small amount of ice-water. The
filtrate and the washings are concentrated by rotary evaporation. The oily residue is dissolved in a
small amount of water and adjusted with propylene oxide to pH 4 with stirring and cooling. The
resultant precipitate is filtered with suction, washed with a small amount of ice-water and recrystallised
from water by adding a small amount of activated carbon affording 12 g (42.6% of theory) of
hydrazinomethanephosphonic acid as white crystals which have a decomposition point of 196 DEG.
EXAMPLE 6
Preparation of hydrazino-N'-chloroacetyl-N'-methyl-O,O-diethylphosphonate ##STR15##
A solution of 20 g of hydrazino-N-benzyloxycarbonyl-N'-chloroacetyl-N'-methyl-O,O-diethylphospho
nate in 200 ml of ethanol is hydrogenated by adding 1.1 molar equivalents of HCl gas and a small
amount of 5% palladium on carbon catalyst. After oxygen absorption has ceased, the catalyst is
removed and the filtrate is concentrated. The residual oil is taken up in ethyl acetate and water and the
phases are separated. The aqueous phase is neutralised with triethylamine and extracted with ether. The
combined ethyl acetate and ether phases are dried and concentrated and the residual oil is
chromatographed through silica gel eluted with a methylene chloride/methanol (95:5) soluton. The
solvent is removed by evaporation affording a wax-like product as residue.
Analysis calculated: C, 32.51%; H, 6.25%; N, 10.83%; Cl, 13.71%; P, 11.97%; found: C, 32.14%; H,
6.13%; N, 10.77%; Cl, 13.48%; P, 11.89%.
EXAMPLE 7
Preparation of N,N'-bis-dichloroacetylhydrazinomethyl-O,O-diethyl-phosphonate ##STR16##
7.0 g (0.0384 mole) of hydrazinomethanephosphonic acid diethylester and 15.3 ml (0.0845 mole) of
diisopropylamine are dissolved at -5 DEG in a sulfurating flask in a mixture of 90 ml of
tetrahydrofuran and 60 ml of cyclohexane. 8.35 ml (0.0845 mole) of dichloroacetyl chloride are added
dropwise to the mixture with cooling and stirring. The mixture is stirred at room temperature for one
hour, the amine hydrochloride is filtered with suction and the solvent is removed under a water jet
vacuum. The residual brown oil (24.3 g) is dissolved in 250 ml of ethyl acetate. The solution is washed
with two 50 ml portions of water, dried and concentrated by rotary evaporation. The residue is dried
under high vacuum affording 16.3 g of beige powder. The powder is chromatographed through a
column of silica gel eluted with methylene chloride/methanol (95:5). The solvent is removed by
evaporation affording 8.1 g of N,N'-dichloroacetylhydrazinomethanephosphonic acid diethylether with
a melting point of 121 DEG-123 DEG.
Analysis calculated: C, 26.76%; H, 3.74%; N, 6.94%; Cl, 35.1%; P, 7.67%; found: C, 27.0%; H, 3.6%;
N, 6.9%; Cl, 34.8%; P, 7.7%.
The following compounds are prepared in a manner similar to those described in the foregoing
Examples:
>;tb;__________________________________________________________________________
>;tb; ##STR17##
>;tb;No. R1
>;tb;
R2
>;tb;
R3 R4 R5
>;tb;
Physical data
15/612
>;tb;__________________________________________________________________________
>;tb;1 C2 H5 O
>;tb;
C2 H5 O
>;tb;
COCH2 Cl
>;tb;
COOCH2 C6 H5
>;tb;
H wax
>;tb;2 C2 H5 O
>;tb;
C2 H5 O
>;tb;
COCHCl2
>;tb;
COOCH2 C6 H5
>;tb;
H wax
>;tb;3 iC3 H7 O
>;tb;
iC3 H7 O
>;tb;
COCH2 Cl
>;tb;
COOCH2 C6 H5
>;tb;
H
>;tb;4 iC3 H7 O
>;tb;
iC3 H7 O
>;tb;
COCHCl2
>;tb;
COOCH2 C6 H5
>;tb;
H oil (yellow)
>;tb;5 C2 H5 O
>;tb;
C2 H5 O
>;tb;
COCH2 Cl
>;tb;
COCH2 Cl
>;tb;
H m.p. 98-101 DEG
>;tb;6 iC3 H7 O
>;tb;
iC3 H7 O
>;tb;
COCCl3
>;tb;
COOC2 H5
>;tb;
H m.p. 75-77 DEG
>;tb;7 C2 H5 O
>;tb;
C2 H5
>;tb;
COCH2 Cl
>;tb;
COOCH2 C6 H5
>;tb;
H
>;tb;8 C2 H5 O
>;tb;
C2 H5
>;tb;
COCHCl2
>;tb;
COOCH2 C6 H5
>;tb;
H m.p. 86-89
>;tb;9 CH3
>;tb;
CH3
>;tb;
COCH2 Cl
>;tb;
COOCH2 C6 H5
>;tb;
H
>;tb;10 CH3
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COOCH2 C6 H5
>;tb;
H
>;tb;11 iC3 H7 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COOCH2 C6 H5
>;tb;
H 87-88 DEG
>;tb;12 C2 H5 O
>;tb;
C2 H5 O
>;tb;
COCH2 Cl
16/612
>;tb;
>;tb;
>;tb;13
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;14
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;15
>;tb;
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>;tb;
>;tb;
>;tb;16
>;tb;
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>;tb;
>;tb;
>;tb;17
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;18
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;19
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;20
>;tb;
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>;tb;
>;tb;
>;tb;21
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;22
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;23
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;24
>;tb;
COOCH3
H oil (yellow)
C2 H5 O
C2 H5 O
COCHCl2
COOCH3
H m.p. 95-98 DEG C.
iC4 H9 O
CH3
COCH2 Cl
COOCH3
H oil
iC4 H9 O
CH3
COCHCl2
COOCH3
H m.p. 83-86 DEG C.
CH3
CH3
COCH2 Cl
COOCH3
H
CH3
CH3
COCHCl2
COOCH3
H
C2 H5 O
C2 H5 O
COCH2 Cl
COOC(CH3)3
H m.p. 74-80 DEG C.
C2 H5 O
C2 H5 O
COCHCl2
COOC(CH3)3
H m.p. 112-114 DEG C.
C2 H5 O
C2 H5 O
COCClCCl2
COOC(CH3)3
H m.p. 69-73 DEG C.
iC4 H9 O
CH3
COCH2 Cl
COOC(CH3)3
H m.p. 93-97 DEG C.
iC4 H9 O
CH3
COCHCl2
COOC(CH3)3
H m.p. 76-78 DEG C.
CH3
CH3
COCH2 Cl
COOC(CH3)3
H
CH3
CH3
17/612
>;tb;
>;tb;
>;tb;
>;tb;25
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;26
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;27
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;28
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;29
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;30
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;31
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;32
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;33
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;34
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;35
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;36
COCHCl2
COOC(CH3)3
H
C2 H5 O
C2 H5 O
COCClCCl2
COOCH2 C6 H5
H m.p. 50-53 DEG
iC3 H7 O
iC3 H7 O
COCClCCl2
COOCH2 C6 H5
H
iC4 H9 O
CH3
COCClCCl2
COOCH2 C6 H5
H m.p. 107-108 DEG
C2 H5
C2 H5
COCClCCl2
COOCH2 C6 H5
H
CH3
CH3
COCClCCl2
COOCH2 C6 H5
H
C2 H5 O
C2 H5 O
COCClCCl2
COOCH3
H m.p. 79-82 DEG
iC4 H9 O
CH3
COCClCCl2
COOCH3
H m.p. 124-128 DEG
C2 H5
C2 H5
COCClCCl2
COOCH3
H
CH3
CH3
COCClCCl2
COOCH3
H
C2 H5 O
C2 H5 O
COCClCCl2
COOC(CH3)3
H
iC4 H9 O
CH3
COCClCCl2
COOC(CH3)3
H m.p. 80-83 DEG
C2 H5
18/612
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;37
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;38
>;tb;
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>;tb;
>;tb;
>;tb;39
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;40
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;41
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;42
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;43
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;44
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;45
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;46
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;47
>;tb;
>;tb;
>;tb;
>;tb;
C2 H5
COCClCCl2
COOC(CH3)3
H
CH3
CH3
COCClCCl2
COOC(CH3)3
H
C2 H5 O
C2 H5 O
COCH2 Cl
COOC2 H5
H oil
C2 H5 O
C2 H5 O
COCHCl2
COOC2 H5
H oil
C2 H5 O
C2 H5 O
COCClCCl2
COOC2 H5
H m.p. 60-62 DEG
iC4 H9 O
CH3
COCH2 Cl
COOC2 H5
H resin
iC4 H9 O
CH3
COCHCl2
COOC2 H5
H m.p. 76-78 DEG
iC4 H9 O
CH3
COCClCCl2
COOC2 H5
H m.p. 94-96 DEG
C2 H5
C2 H5
COCH2 Cl
COOC2 H5
H
C2 H5
C2 H5
COCHCl2
COOC2 H5
H m.p. 117-119 DEG
C2 H5
C2 H5
COCClCCl2
COOC2 H5
H
CH3
CH3
COCH2 Cl
COOC2 H5
H
19/612
>;tb;48
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;49
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;50
>;tb;
>;tb;
>;tb;
>;tb;51
>;tb;
>;tb;
>;tb;
>;tb;52
>;tb;
>;tb;
>;tb;
>;tb;53
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;54
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;55
>;tb;
>;tb;
>;tb;
>;tb;56
>;tb;
>;tb;
>;tb;
>;tb;57
>;tb;
>;tb;
>;tb;
>;tb;58
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;59
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;60
>;tb;
>;tb;
>;tb;
>;tb;
CH3
CH3
COCHCl2
COOC2 H5
H
CH3
CH3
COCClCCl2
COOC2 H5
H
C2 H5 O
C2 H5 O
COCH2 Cl
H
H oil (yellow)
C2 H5 O
C2 H5 O
COCHCl2
H
H
C2 H5 O
C2 H5 O
COCClCCl2
H
H
C 2 H5 O
C2 H5 O
COCHCl2
COCHCl2
H m.p. 121-123 DEG
C2 H5 O
C2 H5 O
COCClCCl2
COCHCl3
H
iC4 H9 O
CH3
COCH2 Cl
H
H
iC4 H9 O
CH3
COCHCl2
H
H
iC4 H9 O
CH3
COCClCCl2
H
H
iC4 H9 O
CH3
COCH2 Cl
COCHCl2
H
iC4 H9 O
CH3
COCHCl2
COCHCl2
H m.p. 125-129 DEG
iC4 H9 O
CH3
COClCCl2
COCHCl2
H
20/612
>;tb;61
>;tb;
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>;tb;
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>;tb;
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>;tb;
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>;tb;
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>;tb;
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>;tb;
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>;tb;
>;tb;69
>;tb;
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>;tb;70
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;71
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;72
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;73
>;tb;
>;tb;
>;tb;
>;tb;
C2 H5
C2 H5
COCH2 Cl
H
H
C2 H5
C2 H5
COCHCl2
H
H
C2 H5
C2 H5
COCClCCl2
H
H
C2 H5
C2 H5
COCH2 Cl
COCHCl2
H
C2 H5
C2 H5
COCHCl2
COCHCl2
H
C2 H5
C2 H5
COCClCCl2
COCHCl2
H
CH3
CH3
COCH2 Cl
H
H
CH3
CH3
COCHCl2
H
H
CH3
CH3
COCClCCl2
H
H
CH3
CH3
COCH2 Cl
COCClCCl2
H
CH3
CH3
COCH2 Cl
COCHCl2
H
CH3
CH3
COCHCl2
COCHCl2
H
C2 H5 O
C2 H5 O
COCH2 Cl
CH2 CHCH2
H
21/612
>;tb;74
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;75
>;tb;
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>;tb;
>;tb;
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>;tb;
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>;tb;
>;tb;
>;tb;77
>;tb;
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>;tb;
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>;tb;78
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;79
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;80
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;81
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;82
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;83
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;84
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;85
>;tb;
>;tb;
>;tb;
C2 H5 O
C2 H5 O
COCHCl2
CH2 CHCH2
H
C2 H5 O
C2 H5 O
COCH2 Cl
CH2 C6 H5
H
C2 H5 O
C2 H5 O
COCHCl2
CH2 C6 H5
H
C2 H5 O
C2 H5 O
COCH2 Cl
COCH3
H
C2 H5 O
C2 H5 O
COCHCl2
COCH3
H
C2 H5 O
C2 H5 O
COCH2 Cl
COC6 H5
H
C2 H5 O
C2 H5 O
COCHCl2
COC6 H5
H
iC4 H9 O
CH3
COCH2 Cl
C2 H5
H
iC4 H9 O
CH3
COCHCl2
C2 H5
H
iC4 H9 O
CH3
COCH2 Cl
CH2 C6 H5
H
iC4 H9 O
CH3
COCHCl2
CH2 C6 H5
H
iC4 H9 O
CH3
COCH2 Cl
COCH3
22/612
>;tb;
>;tb;86
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;87
>;tb;
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>;tb;
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>;tb;
>;tb;
>;tb;89
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;90
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;91
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;92
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;93
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;94
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;95
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;96
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;97
>;tb;
>;tb;
H
iC4 H9 O
CH3
COCH2 Cl2
COCH3
H
iC4 H9 O
CH3
COCH2 Cl
COC6 H5
H
iC4 H9 O
CH3
COCHCl2
COC6 H5
H
CH3
CH3
COCH2 Cl
C2 H5
H
CH3
CH3
COCHCl2
C2 H5
H
CH3
CH3
COCH2 Cl
CH2 C6 H5
H
CH3
CH3
COCHCl2
CH2 C6 H5
H
CH3
CH3
COCH2 Cl
COCH3
H
CH3
CH3
COCHCl2
COCH3
H
CH3
CH3
COCH2 Cl
COC6 H5
H
CH3
CH3
COCHCl2
COC6 H5
H
CH3
CH3
COCH2 Cl
23/612
>;tb;
CH2 CHCH2
>;tb;
H
>;tb;98 CH3
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
CH2 CHCH2
>;tb;
H
>;tb;99 iC3 H7 O
>;tb;
iC3 H7 O
>;tb;
COCH2 Cl
>;tb;
COOC2 H5
>;tb;
H m.p. 62-68 DEG
>;tb;100 iC3 H7 O
>;tb;
iC3 H7 O
>;tb;
COCHCl2
>;tb;
COOC2 H5
>;tb;
H m.p. 69-70
>;tb;101 iC3 H7 O
>;tb;
iC3 H7 O
>;tb;
COCClCCl2
>;tb;
COOC2 H5
>;tb;
H m.p. 108-110 DEG
>;tb;102 iC4 H9 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COOCH2 C6 H5
>;tb;
H m.p. 84-85 DEG
>;tb;103 iC4 H9 O
>;tb;
CH3
>;tb;
COCH2 Cl
>;tb;
COOCH2 C6 H5
>;tb;
H m.p. 82-85 DEG
>;tb;104 HO HO COCHCl2
>;tb;
COOCH3
>;tb;
H m.p. 145-147 DEG*
>;tb;105 HO HO COCHCl2
>;tb;
COOC2 H5
>;tb;
H m.p. 92-94 DEG*
>;tb;106 C2 H5 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COOCH2 C6 H5
>;tb;
H oil
>;tb;107 C2 H5 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COOCH3
>;tb;
H m.p. 130-138 DEG
>;tb;108 C2 H5 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COOC2 H5
>;tb;
H m.p. 110-112 DEG
>;tb;109 C2 H5 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COOC(CH3)3
>;tb;
H m.p. 99-101 DEG
>;tb;110 C2 H5 O
24/612
>;tb;
C2 H5 O
>;tb;
COCHCl2
>;tb;
COCH2 C6 H5
>;tb;
H m.p. 106-108 DEG
>;tb;111 C2 H5 O
>;tb;
C2 H5 O
>;tb;
COCHCl2
>;tb;
COCH2 CH2 C6 H5
>;tb;
H m.p. 87-89 DEG
>;tb;112 C2 H5 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COCH2 C6 H5
>;tb;
H m.p. 88-89 DEG
>;tb;113 C2 H5 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COCH2 CH2 C6 H5
>;tb;
H
>;tb;114 iC3 H7 O
>;tb;
iC3 H7 O
>;tb;
COCHCl2
>;tb;
COCH2 C6 H5
>;tb;
H
>;tb;115 iC3 H7 O
>;tb;
iC3 H7 O
>;tb;
COCHCl2
>;tb;
COCH2 CH2 C6 H5
>;tb;
H
>;tb;116 iC3 H7
>;tb;
iC3 H7
>;tb;
COCl3
>;tb;
COOC2 H5
>;tb;
H m.p. 75-77 DEG
>;tb;117 HO HO COCHCl2
>;tb;
COOCH3
>;tb;
H m.p. 145-147 DEG*
>;tb;118 HO HO COCHCl2
>;tb;
COOC2 H5
>;tb;
H m.p. 92-94 DEG*
>;tb;__________________________________________________________________________
>;tb; *diisopropylamino salt
>;tb;__________________________________________________________________________
>;tb; ##STR18##
>;tb;No.
>;tb; R1
>;tb;
R2
>;tb;
R3
>;tb;
R4
>;tb;
R5
>;tb;
R9
>;tb;
R10
>;tb;
Physical data
>;tb;__________________________________________________________________________
>;tb;119
>;tb; C2 H5 O
>;tb;
C2 H5 O
>;tb;
COCHCl2
>;tb;
COOC2 H5
25/612
>;tb;
H H C2 H5
>;tb;
oil
>;tb;120
>;tb; C2 H5 O
>;tb;
C2 H5 O
>;tb;
COCHCl2
>;tb;
COOC2 H5
>;tb;
H H Phenyl
>;tb;
m.p. 88-90 DEG
>;tb;121
>;tb; C2 H5 O
>;tb;
C2 H5
>;tb;
COCHCl2
>;tb;
COOC2 H5
>;tb;
H H C2 H5
>;tb;
m.p. 85-88 DEG
>;tb;122
>;tb; C2 H5 O
>;tb;
C2 H5
>;tb;
COCHCl2
>;tb;
COOC2 H5
>;tb;
H H Phenyl
>;tb;123
>;tb; C2 H5 O
>;tb;
CH3
>;tb;
COCHCl2
>;tb;
COOC2 H5
>;tb;
H CH3
>;tb;
CH3
>;tb;__________________________________________________________________________
EXAMPLE 8
Formulation Examples for compounds of the formula I or mixtures thereof with herbicides
>;tb;______________________________________
>;tb;(a) Wettable powders
>;tb;
(a) (b) (c)
>;tb;______________________________________
>;tb;Compound of formula I or mixture
>;tb;
20% 60% 0.5%
>;tb;thereof with a herbicide
>;tb;sodium lignosulfonate
>;tb;
5%
5% 5%
>;tb;sodium laurylsulfate
>;tb;
3%
-->;tb;sodium diisobutylnaphthalenesulfonate
>;tb;
-6% 6%
>;tb;octylphenol polyethylene glycol ether
>;tb;
-2% 2%
>;tb;(7-8 moles of ethylene oxide)
>;tb;highly dispersed silicic acid
>;tb;
5%
27% 27%
>;tb;kaolin
67% -->;tb;sodium chloride --59.5%
>;tb;______________________________________
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a
suitable mill, affording wettable powders which can be diluted with water to give suspensions of the
desired concentration.
26/612
>;tb;______________________________________
>;tb;(b) Emulsifiable concentrates
>;tb;
(a) (b)
>;tb;______________________________________
>;tb;Compound of formula I or mixture
>;tb;
10% 1%
>;tb;thereof with a herbicide
>;tb;octylphenol polyethylene glycol ether
>;tb;
3% 3%
>;tb;(4-5 moles of ethylene oxide)
>;tb;calcium dodecylbenzenesulfonate
>;tb;
3% 3%
>;tb;castor oil polyglycol ether
>;tb;
4% 4%
>;tb;(36 moles of ethylene oxide)
>;tb;cyclohexanone
30% 10%
>;tb;xylene mixture
50% 79%
>;tb;______________________________________
Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
>;tb;______________________________________
>;tb;(c) Dusts
(a) (b)
>;tb;______________________________________
>;tb;Compound of formula I or mixture
>;tb;
0.1% 1%
>;tb;thereof with a herbicide
>;tb;talcum
99.9% ->;tb;kaolin
-99%
>;tb;______________________________________
Dusts which are ready for use are obtained by mixing the active ingredient with the carriers, and
grinding the mixture in a suitable mill.
>;tb;______________________________________
>;tb;(d) Extruder granulate (a) (b)
>;tb;______________________________________
>;tb;Compound of formula I or mixture
>;tb;
10% 1%
>;tb;thereof with a herbicide
>;tb;sodium lignosulfonate 2% 2%
>;tb;carboxymethylcellulose 1% 1%
>;tb;kaolin
87% 96%
>;tb;______________________________________
The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently
moistened with water. The mixture is extruded and then dried in a stream of air.
>;tb;______________________________________
>;tb;(e) Coated granulate
>;tb;______________________________________
>;tb;Compound of formula or mixture
>;tb;
3%
>;tb;thereof with a herbicide
>;tb;polyethylene glycol 200
>;tb;
3%
>;tb;kaolin
94%
>;tb;______________________________________
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with
polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
>;tb;______________________________________
27/612
>;tb;(f) Suspension concentrate
>;tb;
(a)
(b)
>;tb;______________________________________
>;tb;Compound of formula I or mixture
>;tb;
40%
5%
>;tb;thereof with a herbicide
>;tb;ethylene glycol
10%
10%
>;tb;nonylphenol polyethylene glycol ether
>;tb;
6%
1%
>;tb;(15 moles of ethylene oxide)
>;tb;sodium lignosulfonate 10%
5%
>;tb;carboxymethylcellulose
>;tb;
1%
1%
>;tb;37% aqueous formaldehyde solution
>;tb;
0.2% 0.02%
>;tb;silicone oil in the form of a 75%
>;tb;
0.8% 0.8%
>;tb;aqueous emulsion
>;tb;water
32%
77%
>;tb;______________________________________
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension
concentrate from which suspensions of any desired concentration can be obtained by dilution with
water.
>;tb;______________________________________
>;tb;(g) Salt solution
>;tb;______________________________________
>;tb;Compound of formula I or mixture
>;tb;
5%
>;tb;thereof with a herbicide
>;tb;isopropylamine
1%
>;tb;octylphenol polyethylene glycol ether
>;tb;
3%
>;tb;(78 moles of ethylene oxide)
>;tb;water
91%
>;tb;______________________________________
BIOLOGICAL EXAMPLES
The ability of the compounds of formula I to protect cultivated plants from the phytotoxic effects of
potent herbicides can be inferred from the following Examples. The compounds of formula I are
referred to as safeners in the test procedures.
EXAMPLE 9
Test with herbicide and safener in maize. Preemergence application of herbicide and safener as tank
mixture
Plastic containers measuring 25 cm.times.17 cm.times.12 cm are filled with sandy loam and LG 5
maize seeds are sown therein. After the seeds have been covered, a dilute solution of the safener to be
tested and the herbicide is sprayed as tank mixture onto the surface of the soil. The protective action of
the safener is evaluated (in %) 21 days after application. Plants treated with herbicide alone (no
protective action) and completely untreated control plants (100% protective action) are used for
reference purposes. The results are reported below.
Herbicide: 2-Chloro-2',6'-dimethyl-N-(ethoxymethyl)acetanilide.
Safener: Hydrazino-N-benzyloxycarbonyl-N'-dichloroacetyl-N'-methyl-O,O-diethylphosp honate
(Compound 1)
28/612
>;tb;______________________________________
>;tb;
Relative protective
>;tb;Herbicide Safener action in %
>;tb;______________________________________
>;tb;2 kg/ha 0.25 kg/ha 25%
>;tb;2 kg/ha 0.125 kg/ha 25%
>;tb;4 kg/ha 0.5 kg/ha 37.5%
>;tb;4 kg/ha 0.25 kg/ha 25%
>;tb;6 kg/ha 0.75 kg/ha 50%
>;tb;6 kg/ha 0.375 kg/ha 37.5%
>;tb;______________________________________
Herbicide: 2-Chloro-2'-ethyl-N-(2"-methoxy-1"-methyl-ethyl)-aceto-o-toluidide.
Safener: Hydrazino-N-benzyloxycarbonyl-N'-dichloroacetyl-N'-methyl-O,O-diethylphosp honate
(Compound 1)
>;tb;______________________________________
>;tb;
Relative protective
>;tb;Herbicide Safener action in %
>;tb;______________________________________
>;tb;2 kg/ha 0.25 kg/ha 37.5%
>;tb;2 kg/ha 0.125 kg/ha 37.5%
>;tb;4 kg/ha 0.5 kg/ha 75%
>;tb;4 kg/ha 0.25 kg/ha 75%
>;tb;6 kg/ha 0.75 kg/ha 37.5%
>;tb;6 kg/ha 0.375 kg/ha 37.5%
>;tb;______________________________________
Herbicide: 2-Chloro-2',6'-dimethyl-N-(2"-methoxy-1"-methylethyl)-acetanilide
>;tb;______________________________________
>;tb;Herbicide Safener
Relative protective
>;tb;Concentration
>;tb;
No.
Concentration
>;tb;
action in %
>;tb;______________________________________
>;tb;4 kg/ha 1
2
kg/ha 63%
>;tb;4 kg/ha 1
1
kg/ha 63%
>;tb;4 kg/ha 1
0.5 kg/ha 63%
>;tb;4 kg/ha 1
0.25 kg/ha 75%
>;tb;6 kg/ha 1
3
kg/ha 75%
>;tb;6 kg/ha 1
1.5 kg/ha 75%
>;tb;6 kg/ha 1
0.75 kg/ha 75%
>;tb;6 kg/ha 1
0.375 kg/ha 75%
>;tb;4 kg/ha 8
2
kg/ha 50%
>;tb;4 kg/ha 8
1
kg/ha 63%
>;tb;4 kg/ha 8
0.5 kg/ha 63%
>;tb;4 kg/ha 8
0.25 kg/ha 63%
>;tb;6 kg/ha 8
3
kg/ha 50%
>;tb;6 kg/ha 8
1.5 kg/ha 63%
>;tb;6 kg/ha 8
0.75 kg/ha 63%
>;tb;6 kg/ha 8
0.375 kg/ha 75%
>;tb;4 kg/ha 11
2
kg/ha 38%
>;tb;4 kg/ha 11
1
kg/ha 38%
>;tb;4 kg/ha 11
0.5 kg/ha 38%
>;tb;4 kg/ha 11
0.25 kg/ha 50%
>;tb;6 kg/ha 11
3
kg/ha 50%
>;tb;6 kg/ha 11
1.5 kg/ha 50%
>;tb;6 kg/ha 11
0.75 kg/ha 50%
>;tb;6 kg/ha 11
0.375 kg/ha 38%
29/612
>;tb;4 kg/ha 13
2
kg/ha 50%
>;tb;4 kg/ha 13
1
kg/ha 50%
>;tb;4 kg/ha 13
0.5 kg/ha 50%
>;tb;4 kg/ha 13
0.25 kg/ha 63%
>;tb;6 kg/ha 13
3
kg/ha 50%
>;tb;6 kg/ha 13
1.5 kg/ha 63%
>;tb;6 kg/ha 13
0.75 kg/ha 50%
>;tb;6 kg/ha 13
0.375 kg/ha 75%
>;tb;4 kg/ha 42
2
kg/ha 63%
>;tb;4 kg/ha 42
1
kg/ha 63%
>;tb;4 kg/ha 42
0.5 kg/ha 75%
>;tb;4 kg/ha 42
0.25 kg/ha 75%
>;tb;6 kg/ha 42
3
kg/ha 63%
>;tb;6 kg/ha 42
1.5 kg/ha 75%
>;tb;6 kg/ha 42
0.75 kg/ha 75%
>;tb;6 kg/ha 42
0.375 kg/ha 75%
>;tb;4 kg/ha 100
2
kg/ha 50%
>;tb;4 kg/ha 100
1
kg/ha 38%
>;tb;4 kg/ha 100
0.5 kg/ha 50%
>;tb;4 kg/ha 100
0.25 kg/ha 38%
>;tb;6 kg/ha 100
3
kg/ha 63%
>;tb;6 kg/ha 100
1.5 kg/ha 63%
>;tb;6 kg/ha 100
0.75 kg/ha 63%
>;tb;6 kg/ha 100
0.375 kg/ha 63%
>;tb;______________________________________Data supplied from the esp@cenet database Worldwide
Claims:
Claims of corresponding document: US4734119
What is claimed is:
1. A composition for protecting a cultivated plant of cereal, maize, rice or sorghum from the phytotoxic
action of a haloacetanilide herbicide, containing an inert carrier and an effective safening amount of a
compound of the formula ##STR19## wherein R1 and R2 are each independently hydroxy, C1 -C4
alkyl, phenyl, naphthyl, C1 -C4 alkoxy, C2 -C4 alkenyloxy, C2 -C4 alkynyloxy, C2 -C4 haloalkoxy
containing 1 to 5 halogen atoms, C2 -C8 alkoxyalkoxy, C1 -C4 cyanoalkoxy, phenyl-C1 -C4 -alkyl,
halophenyl-C1 -C4 -alkyl, cyanophenyl-C1 -C4 -alkyl, nitrophenyl-C1 -C4 -alkyl, C1 -C4 alkylphenyl-C1 -C4 -alkyl, phenyl-C1 -C4 -alkoxy, halophenyl-C1 -C4 -alkoxy, cyanophenyl-C1 -C4 alkoxy, nitrophenyl-C1 -C4 -alkoxy, C1 -C4 -alkylphenyl-C1 -C4 -alkoxy, naphthyl-C1 -C4 -alkoxy,
halonaphthyl-C1 -C4 -alkoxy, cyanonaphthyl-C1 -C4 -alkoxy, nitronaphthyl-C1 -C4 -alkoxy or C1 -C4
-alkylnaphthyl-C1 -C4 -alkoxy, R3 is --COCX1 X2 --R6 or an alkenoyl radical which is substituted by
1 to 3 halogen atoms and contains 2 to 4 carbon atoms in the alkenyl moiety, R4 is hydrogen or a
substituent as defined for R3, or is a --COOR7 or --COR8 radical or a C1 -C4 alkyl or C2 -C4 alkenyl
radical, or is a phenyl-C1 -C4 -alkyl radical which is unsubstituted or substituted in the phenyl ring by
halogen, cyano, nitro or C1 -C4 alkoxy, R5 is hydrogen or a C1 -C4 alkyl, C2 -C4 alkenyl or C2 -C4
alkynyl radical, R6 is hydrogen, halogen or a C1 -C6 alkyl radical, R7 is a C1 -C4 alkyl radical or a
phenyl-C1 -C4 -alkyl radical which is unsubstituted or substituted in the phenyl ring by halogen, cyano,
nitro or C1 -C4 alkoxy, R8 is a C1 -C4 alkyl, C2 -C4 alkenyl, or C2 -C4 alkynyl radical, or is a phenyl
or phenyl-C1 -C4 -alkyl radical which is unsubstituted or substituted by halogen, cyano, nitro or C1 C4 alkoxy, R9 is hydrogen, C1 -C4 alkyl, or phenyl which is unsubstituted or substituted by halogen,
cyano, nitro or C1 -C4 alkoxy, R10 is hydrogen or C1 -C4 alkyl and X1 and X2 are each halogen or
one of X1 and X2 is also hydrogen.
2. A composition of claim 1 which further contains an effective amount of the haloacetanilide
herbicide.
3. A method of selectively controlling weeds in crops of cereal, maize, rice or sorghum, comprising the
step of treating said crop or crop area with an effective amount of a haloacetanilide herbicide and an
effective amount of a safening compound of the formula ##STR20## wherein R1 and R2 are each
30/612
independently hydroxy, C1 -C4 alkyl, phenyl, naphthyl, C1 -C4 alkoxy, C2 -C4 alkenyloxy, C2 -C4
alkynyloxy, C2 -C4 haloalkoxy containing 1 to 5 halogen atoms, C2 -C8 alkoxyalkoxy, C1 -C4
cyanoalkoxy, phenyl-C1 -C4 -alkyl, halophenyl-C1 -C4 -alkyl, cyanophenyl-C1 -C4 -alkyl,
nitrophenyl-C1 -C4 -alkyl, C1 -C4 -alkylphenyl-C1 -C4 -alkyl, phenyl-C1 -C4 -alkoxy, halophenyl-C1
-C4 -alkoxy, cyanophenyl-C1 -C4 -alkoxy, nitrophenyl-C1 -C4 -alkoxy, C1 -C4 -alkylphenyl-C1 -C4 alkoxy, naphthyl-C1 -C4 -alkoxy, halonaphthyl-C1 -C4 -alkoxy, cyanonaphthyl-C1 -C4 -alkoxy,
nitronaphthyl-C1 -C4 -akoxy or C1 -C4 -alkylnaphthyl-C1 -C4 -alkoxy, R3 is --COCX1 X2 --R6 or an
alkenoyl radical which is substituted by 1 to 3 halogen atoms and contains 2 to 4 carbon atoms in the
alkenyl moiety, R4 is hydrogen or a substituent as defined for R3, or is a --COOR7 or --COR8 radical
or a C1 -C4 alkyl or C2 -C4 alkenyl radical, or is a phenyl-C1 -C4 -alkyl radical which is unsubstituted
or substituted in the phenyl ring by halogen, cyano, nitro or C1 -C4 alkoxy, R5 is hydrogen or a C1 -C4
alkyl, C2 -C4 alkenyl or C2 -C4 alkynyl radical, R6 is hydrogen, halogen or a C1 -C6 alkyl radical, R7
is a C1 -C4 alkyl radical or a phenyl-C1 -C4 -alkyl radical which is unsubstituted or substituted in the
phenyl ring by halogen, cyano, nitro or C1 -C4 alkoxy, R8 is a C1 -C4 alkyl, C2 -C4 alkenyl, or C2 C4 alkynyl radical, or is a phenyl or phenyl-C1 -C4 -alkyl radical which is unsubstituted or substituted
by halogen, cyano, nitro or C1 -C4 alkoxy, R9 is hydrogen, C1 -C4 alkyl, or phenyl which is
unsubstituted or substituted by halogen, cyano, nitro or C1 -C4 alkoxy, R10 is hydrogen or C1 -C4
alkyl and X1 and X2 are each halogen or one of X1 and X2 is also hydrogen.
4. The method of claim 3 wherein the safening compound is applied to the crop plant.
5. The method of claim 3 wherein the safening compound is applied to the crop area a before or during
the application of the haloacetanilide herbicide.
6. The method of claim 3 wherein the safening compound is applied to the seed of the crop plant before
it is planted.Data supplied from the esp@cenet database - Worldwide
31/612
2. DE1800709
- 12/11/1969
SUBSTD PYRIMIDINE DERIVS PLANT FUNGICIDES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE1800709
Inventor(s):
CLAIRE SHEPHARD MARGARET (--)
Applicant(s):
ICI LTD (--)
IP Class 4 Digits: A01N
IP Class:A01N9/22
E Class: A01N57/16; C07D239/26B; C07D239/30B; C07D239/36B; C07D239/38; C07D239/40;
C07D239/42C2; C07D239/48C; C07D239/50; C07D239/52; C07D239/54B; C07D239/54C4;
C07D239/56; C07D239/60; C07F9/6512K2
Application Number:
DE19681800709 (19681002)
Priority Number: GB19670044773 (19671002)
Family: DE1800709
Equivalent:
NL6814057; FR1583150; CH509039
Abstract:
Abstract of DE1800709
Compns. (I) containing compounds of (II) or salts or esters of (II): A, B and C = R, OR, SR, Hal, NO2
or opt. substd. NH2, and B and C may be joined to form a second ring; Y = , OR, SR or Hal, but if
B=H, Y may be H, substd. alkyl, aryl, or SR; R = H or a (1-12C) opt. substd. hydrocarbon residue, and
pref. (1-5C) alkyl. - With the proviso that not more than 2 of A, B, C and Y = H. - Fungicides, active
e.g. vs. puccinia recondita (in wheat), Phytophthora inestans (tomatoes), mildew (in melons, wheat,
barley, apples and grapes), Piricularia oryzae (in rice), and scab (in apples).Description:
Description of DE1800709
B e s c h r e i b u n g "Verfahren zur Bekämpfung von Pilzkranzheiten bei Pflanzen" Die Erfindung
bezieht sich auf ein Verfahren zur Bekämpfung von Pilzkrankheiten bei Pflanzen und auf
Zusammensetzungen, die sich fUrdieses Verfahren eignen Gemäss der Erfindung wird ein Verfahren
zur Bekämpfung von Pilz- krankheiten bei PfLanzen vorgeschlagen, welches dadurch ausge-führt
wird, dass man auf die Pflanzen, die mit Pilzkrankheiten befallen sind oder bei denen die Gefahr eines
Befalls durch Pilzkrankheiten besteht, ein disubstituiertes Pyrimidinderivatder Formel
EMI2.1
worin -A, -B und -C, Mir -R, -OR, -SR, Halogen, Nitro oder Amino Gruppen stehen; -Y für eine -R, Or, -SR oder eine Halogen-Gruppe steht, vorausgesetzt dass Y Wasserstoff, substituiertes Alkyl, Aryl
oder BB ist, wenn B Wasserstoff ist; und R für Wasserstoff oder eine Kohlenwasserstoff- oder
substituierte Kohlenwasserstoffgruppeateht; oder ein Salz oder einen Ester eines
solchenpyrimtdinderivats aufbringt.
Mit dem Ausdruck "disubstituiertesPyrimidinderivat1, ist eine Verbindung gemeint, in der mindestens
zwei der vierWasserstoff- atome im Pyrimidinring durch andere Gruppen ersetzt worden sind; d.h.
dass mindestens zwei der vier Gruppen A, B, C und YfUr andere Radikale als Wasserstoff stehen. In
den Ausdruck "Amino" sei auch substituiertes Amino eingeschlossen; es wird auch darauf
hingewiesen, dass dieOruppen B und C unter Bildung eines Rings verknüpft sein können. Wenn R
32/612
eine Kohlenwasserstoffgruppe ist, dann enthält sie in zweckmässiger Weise 1 bis 12 Kohlenstoffatome.
Insbesondere Icann sieetne Alkylgruppe mit 1 bis 5 Kohlenstoffatomen sein.
Durch daserfindung,sgemässe Verfahren knnen unter anderem folgende Pilzerkrankungen bei Pflanzen
behandelt werden
Puccinia recondita (Rost) an Weizen
Phytophthora infestens (späte Trockenfäule) an Tomaten
Sphaerotheca fuliginea (pulvriger Mehltau) am Kürbis
Erysiphe graminis (pulvriger Mehltau) an Weizen und Gerate
Podosphaere leucotricha (pulvriger Mehltau) am Apfel
Uncinula necator (pulvriger Mehltau) am Rebstock
Plasmopara viticola (flaumriger Mehltau) am Rebstock
Piricularia oryzae (Brand) am Reis
Venturia inaequalis (Schorf) am Apfel Im allgemeinen ist diefungizide Aktivität dererfindungsgemäss
verwendeten Verbindungen vorbeugend; d.h., wenn die Verbindungen auf gesunde Pflanzen vor einer
Infektion aufgebracht werden, dann verhindern sie eine nachfolgende Infektion solcher Pflanzen.
In einigen Fällen wird diese vorbeugende Aktivität verlagert, wobei beispielsweise der chemische Stoff
inStaubform oder in flüssiger Form auf dieWurzeln der Pflanze aufgebracht wird und von diesen
aufgenommen wird, so dass das Laubwerk eine vorbeugende Aktivität zeigt. Manchmal teigen die
Verbindungen auch eine heilende Aktivität, wobei sie die Krankheit von infizierten Pflanzen
beseitigen.
Bevorzugte Klassen von Pyrimidinderivaten,die gemäss der Erfindung verwendet werden kannen, sind
die folgenden s Derivate, die in 5-Stellung substituiert sind;und Derivate, tn denen -Y für-5t steht.
Verbindungen, die besondersbeim erftndungsgemässen Verfahrenbrauchbar sind, sind die folgenden:
2,5,6-Trihydroxypyrimidin (besonders aktiv gegen Erysiphe graminis bei Weizen); 2,4,6-Trihydroxy5-nitropyrimidin, 2-Mercapto-4,6-dimethylpyrimi din, 2-Chloro-4-amino-5-nitropyrimidin, 6-Bromo4-hydroxy-chinazolen (alle besonders aktiv gegen Plasmoparavitioola); die Hydrochloride von 2Hydroxy-4,6-dimethylpyrimidin, (2-Methylthio-4-methyl-5-n-propyl-6-pyrimidinyl)-benzoat, Diäthyl(4-methyl5-n-propyl-2-n-propylthio-6-pyrimidinyl)-phosphat, (alle besonders aktiv gegen Venturia
inaequalis); 2-Carbamoylmethyal-4,6-dihydroxypyrimidin (besonders aktiv gegen Uncinula
necator);Diäthyl-(2n-propylthio-4-methyl-5-n-propyl-6-pyrimidinyl)-phosphat und die entsprechende
(2-Benzylthio-) verbindung (beide aktiv gegen Piricularia oryzae); 2-Mercapto-4-benzyl-6hydroxypyrimidin, 2-Methylthio-6-dimethylcarbymoyloxypyrimidin, 2-Methylthio-4,5dimethyl-6dimethylcarbamoyloxypyrimidin, diäthyl-(2-methylthio4-methyl-5-n-propyl-6-pyrimidinyl9-phosphat,
2-Äthylthio-4-methyl6-hydroxypyrimidin und 2,4-Dimethyl-5-n-butyl-6-hydroxypyrimidin (alle
besonders aktiv gegen Podsphaera leucotricha).
Die Erfindung betrifft auch fungizide Zusammensetzungen, die als aktiven Bestandteil
Pyrimidinderivate der oben angegeben Formel oder deren Salze enthalten. Diese Zusammensetzungen
kannen zusätzlich feste Verdünnungsmittel, wiez.B. Kaolin, Bentonit oder Talcum; flüssige
Verdünnungsmittel wie z.B. Wasser oder Erdöle, die vorzugsweise ein Netzmittel oder
Dispergiermittel enthalten, insbesondere der kationischen,anionischen oder nichtionischen Type, wie
quaternäre Ammoniumverbindungen, Alkylphenol/ Xthylenoxyd-Kondensate unddgl.; und andere
biologisch aktive Verbindungen enthalten.Wennsie flüssig sind, dann können die
ZusammensetzungenLdeungen, Suspensionen,Emulsionen oder Disperatomen sein, und sie können
auf die Pflanzen durch Bespritzen des Laubwerks, oder, wennzweckmässig, durch Trinken der
Wurzeln derPflanse aufgebracht werden.Leiste Zusammensetzungen kennen, wenn zweckmässig, auf
dem Boden in der Nähe der Basis der Pflanze zur Aufnahme durch die Wurzelnaufgebracht werden,
oder sie können auf das Laubwerk der Pflanze aufgestäubt werden.
Die Zusammensetzungen, die in Porm von wässrigen Lösungen, Suspensionen, Dispersionen oder
Emulsionen verwendet werden sollen, werden im allgemeinen in form eines Feststoffs oder eines
flüssigenKonzentrats, das einen hohen Anteil des aktiven oder der aktiven Bestandteile enthält,
geliefert, wobei das genannteKonzen- trat vor demGebrauch in Wasser dispergiert wird. Diese
Konzentrate müssen oft längere Zeiten einer lagerung standhalten und nach einer solchen Lagerung mit
Wasser verdUnnt werden können, um wässrige Präparate herzustellen, die eine ausreichende Zeit
33/612
homogen bleiben, so dass sie durch eine herkömmliche Spritzeinrichtung angewendet werden
können.Im allgemeinen enthalten Konzentrate inzweckmässiger Weise 10 bis 85 Gew.-% des aktiven
Bestandteils oder der aktiven Bestandteile und im allgemeinen 25 bis 60Gew.-% des aktiven
Bestandteils oder deraktiv standteile. Wenn sie zur Herstellung wässriger Präparate vei werden, dann
könnensolche Präparate dieverschiedensten Mengen des aktiven Bestandteils oderder aktiven
Bestandteile enthal u was von demZweck abhängt, für den sie verwendet werden sollen, aber
einwässriges Präparat, das zwischenO,OOl und 1,0Gew.- des aktiven Bestandteils oder der aktiven
Bestandteile enthalt,wird gewöhnlich verwendet.
Die erfindungsgemäss au verwendenden Pyrimidine können durch Ln der Technik ansich bekannte
Standardverfahren hergestellt werden.Verbindungen, die Substituenten -SR in der 2-Stellung
enthalten, können durchKondensation von Thioharnstoff oder dessen Derivate mit geeigneten ssKetoestern oder ähnlichen Verbindungen hergestellt werden.Beispielsweise kann 2-Mercapto- 4,6dimethylpyrimidin durch Kondensation von Acetylaceton mitThioharnstoff hergestellt werden. In
ähnlicher Weise können 2-Hydroxyverbindungen durch ähnlicheXondensat ionen hergestellt werden,
wobei Harnstoff anstelle von Thioharnstoff verwendet wird.
Halogenverbindungenkönnen durch Halogenierung der entsprechenden Hydroxyverbindungen
hergestellt werden. Aminoverbindungen können durch Umsetzung derentsprechenden
Halogenverbindungen mit einemtiberschuss des entsprechenden Amins hergestellt werden.Nitroverbindungen kennen durchverschiedene Methoden hergestellt werden, beispielsweise kann 2,4,6Trihydroxy-5-nitropyarimidin durch Behandlung von Barbitsäure mit rauchender Salpetersäure
hergestellt werden.
Salze von Verbindungen kennen dadurchhergettellt werden, dass man die Verbindungen mit
konzentrierten starken Säuren, wiez..B.
HCl, behandelt; Salze von Hydroxy- oder Mercaptoverbindungen können auch durch Behandlung mit
starken Alkalien , wie z.B.
NaOH, hergestellt werden. Ester von Verbindungen, wie z.B.Benzoate, Phosphate und Carbamate,
können durch Standardverfahren aus den entsprechenden -OH oder -SH-Ve:tindungen
hergestelltwerden Die Erfindung wird durch diefolgenden Beispiele näher erläutert, Beispiele 1 - 41
Erfindungsgemässe Zusammensetzungen wurden in der forlgenden Weise hergestellt und gegen
verschiedene Pilzkrankheiten bei Pflanzen getestet. DieZusammensetzungen wurden auf vorbeugende,
heilende und verlagerte Aktivität geprüft, und die Resultate sind in der folgenden Tabelleangegeben.
Bei den Vorbeugungstests wurden Pflanzen mit einer Lösung oder Suspension der aktiven Verbindung
in Wasser mit der angegebenen Konzentration (gewöhnlich 500ppa) derart bespritzt, dass die Blätter
nass waren. Das Wasser enthielt 0,1 Gew.-% eines Netzmittels, wie z.B. Äthylenoxyd/OctylphenolKondensat. 24 Stunden nach dem Bespritzen wurden die Pflanzen mit der Testkrankheit geimpft, und
am Ende des Tests wurde das Ausmass der Krankheitvisuell bestimmt.Die Verlagerungstest wurden
in ähnlicher Weite ausgeführt, mit dem Unterschied, das der Boden, in dem die Pflanzen wuchsen,
entweder durch Durchnässen mit der Lösung des aktiven Bestandteils oder durchEinarbeitung einer
festen Zusammensetzung, die denaktiven Bestandteil enthielt, behandelt wurde. 1Bei heilenden
Testswurden die Pflanzen mit der Krankheit geimpft und dann nacheiner Reihe von Tagen, was von
der Krankheit abhing, mit eine Lösung oder Suspension solcher Art, wie sie beim vorbeugenden Test
verwendet wurde, bespritzt (so dass die Blätter nass waren). Die Resultate sind in der Tabelle in
Einstufungen angegeben,welche dasprozentuale Ausmass der Krankheit wie folgtangeben:
Einstufung Krankheit, %
0 61 - 100
1 26 - 60
2 6 - 25
30-5 Die meisten Resultate in der Tabelle beziehen sich auf den vorbewenden Test 3 die Resultate
derheilenden Tests sinddurch E nach der Einstufungszahl und die Verlagerungstests durch T nach der
Einstufungszahl angegeben.Die lateinischen und deutschen
Nemn der Testkrankheiten sind mit den entsprechenden Wirts pflanzen und der Anzahl der Tage, die
zwischen der Behandlung und der Bestimmung bei den schützenden Tests verstrichen, in der
Folge angegeben.
34/612
EMI9.1
Krankheit
>;tb; >;SEP; Test
>;tb; >;SEP; Lateinischer >;SEP; Name >;SEP; Deutscher >;SEP; Name >;SEP; Wirtspflanze >;SEP;
periode
>;tb; Puccinia >;SEP; recondita >;SEP; Rost >;SEP; Weizen >;SEP; 10 >;SEP; page
>;tb; Phytophthora >;SEP; infestans >;SEP; späte >;SEP; Trocken- >;SEP; Tomate >;SEP; 4 >;SEP; "
>;tb; >;SEP; fäule
>;tb; Sphaerotheca >;SEP; fuliginea >;SEP; pulvriger >;SEP; Mehl- >;SEP; Gurke >;SEP; 10 >;SEP; "
>;tb; >;SEP; tau
>;tb; >;SEP; Erysiphe >;SEP; graminis >;SEP; pulvriger >;SEP; Mehl- >;SEP; Weizen >;SEP; 10
>;SEP; "
>;tb; >;SEP; tau
>;tb; >;SEP; Gerate >;SEP; 10 >;SEP; "
>;tb; Podsphaere >;SEP; leucotrische >;SEP; pulvriger >;SEP; Mehl- >;SEP; Apfel >;SEP; 10-14
>;SEP; "
>;tb; >;SEP; tau
>;tb; Uncinula >;SEP; necator >;SEP; pulvriger >;SEP; Mehl- >;SEP; Rebstock >;SEP; 14 >;SEP; "
>;tb; >;SEP; tau
>;tb; Plasmopara >;SEP; viticola >;SEP; flaumiger >;SEP; Mehl- >;SEP; Rebstock >;SEP; 7 >;SEP; "
>;tb; >;SEP; tau
>;tb; Piricularia >;SEP; oryzae >;SEP; Brand >;SEP; Reis >;SEP; 7 >;SEP; "
>;tb; Venturia >;SEP; inaequalis >;SEP; Schorf >;SEP; Apfel >;SEP; 14 >;SEP; "
>;tb; Tabelle I
EMI10.1
Beispiel >;SEP; A >;SEP; B >;SEP; C >;SEP; Y >;SEP; Krankheit >;SEP; Konzentra- >;SEP;
Einstufung
>;tb; Nr. >;SEP; tion
>;tb; 1 >;SEP; -CH3 >;SEP; -H >;SEP; -CH3 >;SEP; S >;SEP; Venturia
>;tb; >;SEP; # >;SEP; inaequalis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; CH2 >;SEP; Erysiphe
>;tb; >;SEP; C=O >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; # >;SEP; (Gerste)
>;tb; 2 >;SEP; -OH >;SEP; -H >;SEP; -CH2# >;SEP; -SH >;SEP; Plasmopara >;SEP; 500 >;SEP; 3
>;tb; >;SEP; viticola >;SEP; 125 >;SEP; 3
>;tb; >;SEP; Podosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 3
>;tb; 3 >;SEP; -CH3 >;SEP; -N-N-# >;SEP; -OH >;SEP; OH >;SEP; Piricularia >;SEP; 500 >;SEP; 3
>;tb; >;SEP; # >;SEP; oryzae >;SEP; 125 >;SEP; 2
>;tb; >;SEP; COOH
>;tb; 4 >;SEP; NH-CH2 >;SEP; -NH2 >;SEP; -CH3 >;SEP; Cl >;SEP; Plasmopara >;SEP; 500 >;SEP;
3
>;tb; >;SEP; CH >;SEP; viticola >;SEP; 125 >;SEP; 2
>;tb; >;SEP; (OC2H5)2
>;tb; 5 >;SEP; -CH3 >;SEP; -H >;SEP; -CH3 >;SEP; -SH >;SEP; Plasmopara >;SEP; 500 >;SEP; 3
>;tb; >;SEP; viticola >;SEP; 125 >;SEP; 3
>;tb; >;SEP; Piricularia >;SEP; 500 >;SEP; 3
>;tb; >;SEP; oryzae >;SEP; 125 >;SEP; 2
>;tb; Tabelle I (Fortsetzung)
EMI11.1
Beispiel >;SEP; A >;SEP; B >;SEP; C >;SEP; Y >;SEP; Krankheit >;SEP; Konzentra- >;SEP;
Einstufung
>;tb; Nr.>;SEP; tion
>;tb; 6 >;SEP; -OH >;SEP; NO2 >;SEP; -OH2 >;SEP; -OH >;SEP; Plasmopara >;SEP; 500 >;SEP; 3
35/612
>;tb; >;SEP; viticola >;SEP; 125 >;SEP; 3
>;tb; >;SEP; Podosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 3
>;tb; 7 >;SEP; -OH >;SEP; -H >;SEP; -OH >;SEP; CH2CO >;SEP; Incinula >;SEP; 300 >;SEP; 3
>;tb; >;SEP; NH2 >;SEP; necator >;SEP; 23 >;SEP; 3
>;tb; >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 3
>;tb; 8 >;SEP; -CH3 >;SEP; -H >;SEP; -CH3 >;SEP; H >;SEP; Venturia >;SEP; 500 >;SEP; 3
>;tb; >;SEP; inaequalis
>;tb; >;SEP; (Hydrochloridsalz)
>;tb; 9 >;SEP; -OH >;SEP; -H >;SEP; -OH >;SEP; ## >;SEP; Venturia >;SEP; 500 >;SEP; 3
>;tb; >;SEP; inaequalis >;SEP; 125 >;SEP; 2
>;tb; 10 >;SEP; -H >;SEP; NO2 >;SEP; -NH2 >;SEP; -Cl >;SEP; Plasmopara >;SEP; 500 >;SEP; 3
>;tb; >;SEP; viticola >;SEP; 125 >;SEP; 3
>;tb; >;SEP; Venturia >;SEP; 500 >;SEP; 3
>;tb; >;SEP; inaequalis >;SEP; 125 >;SEP; 3
>;tb; 11 >;SEP; kondensierter >;SEP; -NHC2H4OH >;SEP; -CCl3 >;SEP; Venturia >;SEP; 500
>;SEP; 3
>;tb; >;SEP; Benzolring >;SEP; inaequalis >;SEP; 125 >;SEP; 3T
>;tb; >;SEP; O
>;tb; >;SEP; #
>;tb; 12 >;SEP; -Cl >;SEP; CH2-C >;SEP; -H >;SEP; CH2#Cl >;SEP; Plasmopara >;SEP; 125 >;SEP;
2
>;tb; >;SEP; # >;SEP; viticola
>;tb; >;SEP; O
>;tb; >;SEP; C2H5
>;tb; Tabelle I (Fortsetzung)
EMI12.1
Beispiel >;SEP; A >;SEP; B >;SEP; C >;SEP; Y >;SEP; Krankheit >;SEP; Konzentra- >;SEP;
Einstufung
>;tb; Nr.>;SEP; tion
>;tb; 13 >;SEP; -CH-CH-CBr-CH- >;SEP; -OH >;SEP; -HH >;SEP; Plasmopara >;SEP; 500 >;SEP; 3
>;tb; >;SEP; viticola >;SEP; 125 >;SEP; 3
>;tb; 14 >;SEP; -CH3 >;SEP; -H >;SEP; -CH3 >;SEP; -SH >;SEP; Plasmopara >;SEP; 500
>;tb; >;SEP; NH2 >;SEP; viticola
>;tb; >;SEP; (Hydrocloridsalz) >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Gerste)
>;tb; >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 3
>;tb; 15 >;SEP; -O.CO# >;SEP; -C3H7n >;SEP; -CH3 >;SEP; -SCH3 >;SEP; Venturia >;SEP; 500
>;SEP; 3
>;tb; >;SEP; inaequalis
>;tb; >;SEP; Plasmopara >;SEP; 500 >;SEP; 3
>;tb; >;SEP; viticola
>;tb; >;SEP; Piricularis
>;tb; >;SEP; oryzae >;SEP; 500 >;SEP; 3
>;tb; 16 >;SEP; O >;SEP; C3H7n >;SEP; CH3 >;SEP; -SC3H7n >;SEP; Venturia >;SEP; 500 >;SEP; 3
>;tb; >;SEP; inaequalis
>;tb; >;SEP; Piricularia
>;tb; >;SEP; oryzae >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Podosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Weizen)
>;tb; Tabelle I(Fortsetzung)
EMI13.1
36/612
Beispiel >;SEP; A >;SEP; B >;SEP; C >;SEP; Y >;SEP; Krankheit >;SEP; Konzentra- >;SEP;
Einstufung
>;tb; Nr. >;SEP; tion
>;tb; 17 >;SEP; -CCl3 >;SEP; -H >;SEP; -CCl3 >;SEP; -Cl >;SEP; Puccinia
>;tb; >;SEP; recondita >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Piricularia
>;tb; >;SEP; oryzae >;SEP; 500 >;SEP; 3
>;tb; 18 >;SEP; -CH3 >;SEP; -H >;SEP; -CH3 >;SEP; -S-#NO2 >;SEP; Sphaerotheca
>;tb; >;SEP; NH2 >;SEP; fuliginea >;SEP; 500 >;SEP; 3
>;tb; 19 >;SEP; -Cl >;SEP; -H >;SEP; -CCl3 >;SEP; -# >;SEP; Puccinia >;SEP; 500 >;SEP; 2
>;tb; >;SEP; recondita
>;tb; >;SEP; Sphaerotheca
>;tb; >;SEP; fuliginea >;SEP; 500 >;SEP; 3
>;tb; 21 >;SEP; -OH >;SEP; -NO2 >;SEP; -OH >;SEP; -OH >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500
>;tb; >;SEP; Uncinula
>;tb; >;SEP; necator >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Pedosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 3
>;tb; 22 >;SEP; -OH >;SEP; -NHCONH# >;SEP; -NH2 >;SEP; CH3 >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Erysiphe
>;tb; >;SEP; gramminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Gerste)
>;tb; >;SEP; Uncinula
>;tb; >;SEP; nector >;SEP; 500 >;SEP; 2
>;tb; Tabelle I (Fortsetzung)
EMI14.1
Beispiel >;SEP; A >;SEP; B >;SEP; C >;SEP; Y >;SEP; Krankheit >;SEP; Konzentra- >;SEP;
Einstufung
>;tb; Nr.>;SEP; tion
>;tb; 23 >;SEP; -NH2 >;SEP; -NH2 >;SEP; -OH >;SEP; -OH >;SEP; Piricularia
>;tb; >;SEP; oryzae >;SEP; 500 >;SEP; 3
>;tb; 24 >;SEP; -H >;SEP; -H >;SEP; -OH >;SEP; -SH >;SEP; Erysiphe
>;tb; >;SEP; cichoracearum >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 3
>;tb; 25 >;SEP; -CH3 >;SEP; -Br >;SEP; -OH3 >;SEP; -SCH3 >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 3
>;tb; 26 >;SEP; -H >;SEP; -OCOCH3 >;SEP; -OH >;SEP; -COCH3 >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Gerste)
>;tb; 27 >;SEP; -OH >;SEP; -H >;SEP; -OH >;SEP; ## >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Gerste)
>;tb; >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 3
>;tb; 28 >;SEP; -H >;SEP; -OH >;SEP; -OH >;SEP; -OH >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 2
>;tb; >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; Tabelle I (Fortsetzung)>;/RTI;
EMI15.1
Beispiel >;SEP; A >;SEP; B >;SEP; C >;SEP; Y >;SEP; Krankheit >;SEP; Konzentra- >;SEP;
Einstufung
>;tb; Nr. >;SEP; tion
37/612
>;tb; 29 >;SEP; -OH >;SEP; NO2 >;SEP; -NH2 >;SEP; CH3 >;SEP; Uncinula >;SEP; 500 >;SEP; 3
>;tb; >;SEP; necator
>;tb; >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Podoshaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 2
>;tb; >;SEP; Piricularia
>;tb; >;SEP; oryzae >;SEP; 500 >;SEP; 3
>;tb; 30 >;SEP; -OH >;SEP; -H >;SEP; -OH >;SEP; -CH2CONH2 >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Uncinula >;SEP; viticola >;SEP; 500 >;SEP; 3
>;tb; >;SEP; necator >;SEP; 500 >;SEP; 3
>;tb; 31 >;SEP; -NH2 >;SEP; NHCO(CHOCH)4- >;SEP; -NH2 >;SEP; -SCH3 >;SEP; Piricularia
>;tb; >;SEP; oryzae >;SEP; 500 >;SEP; 3
>;tb; 32 >;SEP; -CH3 >;SEP; -H >;SEP; -OCON(CH3)2 >;SEP; -SCH3 >;SEP; Podosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 2
>;tb; >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 2
>;tb; Tabelle I (Fortsetzung)
EMI16.1
Beispiel >;SEP; A >;SEP; B >;SEP; C >;SEP; Y >;SEP; Krankheit >;SEP; Konzentra- >;SEP;
Einstufung
>;tb; Nr. >;SEP; tion
>;tb; 33 >;SEP; -CH3 >;SEP; -CH3 >;SEP; -OCON(CH3)2 >;SEP; -SCH3 >;SEP; Podosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Phytosphthora
>;tb; >;SEP; infestans >;SEP; 500 >;SEP; 2T
>;tb; 34 >;SEP; -CH3 >;SEP; -C2H7n >;SEP; -OP(OC2H5)2 >;SEP; -SCH3 >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Weizen)
>;tb; >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Gerste)
>;tb; >;SEP; Podosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Piricularis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; oryzae >;SEP; 2T
>;tb; 35 >;SEP; -OH >;SEP; -H >;SEP; -CH3 >;SEP; -SC2H5 >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 3
>;tb; 36 >;SEP; -CH3 >;SEP; C4H9n >;SEP; -OH >;SEP; -CH3 >;SEP; Erysiphe
>;tb; >;SEP; cichoracearum >;SEP; 500 >;SEP; 3E
>;tb; >;SEP; Podosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 2
>;tb; Tabelle I (Fortsetzung)
EMI17.1
Beispiel >;SEP; A >;SEP; B >;SEP; C >;SEP; Y >;SEP; Krankheit >;SEP; Konzentra- >;SEP;
Einstufung
>;tb; Nr.>;SEP; tion
>;tb; 37 >;SEP; -OH >;SEP; -H >;SEP; -NH2 >;SEP; -SH >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 2
>;tb; 38 >;SEP; -OH >;SEP; -CH3 >;SEP; -OH >;SEP; -SCH3 >;SEP; Erysiphe
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>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Weizen)
>;tb; >;SEP; Plasmopara
>;tb; >;SEP; viticola >;SEP; 500 >;SEP; 2
>;tb; 39 >;SEP; -OH >;SEP; -NH.CO.CH2Cl >;SEP; -CH3 >;SEP; -OH >;SEP; Piricularia
>;tb; >;SEP; oryzae >;SEP; 500 >;SEP; 3
>;tb; 40 >;SEP; -(CH2)4- >;SEP; -O.CO.N(CH3)2 >;SEP; -SCH3 >;SEP; Piricularia
>;tb; >;SEP; oryzae >;SEP; 500 >;SEP; 2-3
>;tb; >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; (Weizen)
>;tb; >;SEP; (Gerste) >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 3
>;tb; 41 >;SEP; -(CH2)4- >;SEP; -O.CO.N(CH3)2 >;SEP; -SC2H5 >;SEP; Erysiphe
>;tb; >;SEP; graminis >;SEP; 500 >;SEP; 3
>;tb; >;SEP; Podosphaera
>;tb; >;SEP; leucotricha >;SEP; 500 >;SEP; 2
>;tb; >;SEP; Venturia
>;tb; >;SEP; inaequalis >;SEP; 500 >;SEP; 3
>;tb; Die rolgenden Beispiele erläuternerfindungsgemässe Zusammensetzungen.
Beispiel 42 Dieses Beispiel erläutert ein Konzentrat, das einmiseh- bares Ö1 enthält, welches leicht
durch Verdünnung mit Wasser in ein rlUssiges Präparat umgewandelt werden kann, das sichfUr Spritz
zwecke eignet. Das Konzentrat besitzt die folgende Zusammensetzung:
Gew.-% Verbindung von Beispiel Nr. 5 Tabelle I 25,0 'LUBROL'L
(Alkylphenol(Äthylenoxydkondensate; "Lubrol" ist ein Warenzeichen) 2,5
Calciumdodecylbenzolsulfonat 2,5 "AROMASOL" H (Alkylbenzollösungsmittel; "Aromasol" ist ein
Warenzeichen) 70,0
100,00 Beispiel 43 Dieses Beispiel erläutert ein benetzbares Pulver, das die folgende
Zusammensetzung aufweist: :
Gew.-% Verbindungvon Beispiel Nr. 11 Tabelle I 25,0 Natriumsilicat 5,0 Calciumgnosulfonat 5,0
Porzellanerde 65,0
100,0 Beispiel 44 Dieses Beispiel erläutert ein Stäuberpulver, welches direkt auf Pflanzen oder andere
Oberflächen aufgebracht werden.kann und 1 Gew.-%der der und bindung von Beispiel 21 von Tabelle
I/99 Gew.-% Talcum enthält.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of DE1800709
P a t e n t a n s p r ü c h e:
1. Verfahren zur Bekämpfung von Pilzkrankheiten bei Pflanzen dadurch gekennzeichnet, dass man auf
die Pflanzen, die mit Plizkrankheiten befallensind oder bei denen die Gefahr eines Befalls durch
Plizkrankheiten besteht, ein disubstituiertes Pyrimidinderivat der Formel
EMI20.1
worin -A, -B und -C für -R, -OR, -SR, Halogen, NItro oder Amino Gruppen stehen; -Y für eine -R, OR, -SR oder eine Halogen-Gruppe steht, vorausgesetzt, dass Y Wasserstoff, substituiertes Alkyl, Aryl
oder -SR ist, wenn -B Wasserstoff ist; und R für Wasser~ stoff oder eine Kohlenwasserstoff- oder
substituierte Kohlenwasserstoffgruppe steht; oder ein Salz oder einen Ester eines solchen
Pyrimidinderivats aufbringt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Pyrimidinderivat auf gesunde
Pflanzen als ein vorbeugendes Funizid aufgebracht wird.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Pyrimidinderivat in der 5-Stellung
substituiert ist.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass -YfUr zur steht.
39/612
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Pyrimidinderivat 4-Amino-2-chloro5-nitropyrimidin ist.
6. Fungizide Zusammensetzung, dadurch gekennzeichnet, dass sieein Pyrimidinderivat der Formel
EMI21.1
worin -A, -B und -C für -R, -OR, -SR, Halogen, Nitro oder Amino Gruppen stehen; -Y für eine -R, OR, -SR oder eine Halogengruppe steht, vorausgesetzt dass B Wasserstoff, Y substituiertes Alkyl, Aryl
pder -SR ist, wenn -B Wasserstoff ist; und R für Wasserstoff oder eine Kohlenwasserstoff- oder
substituierte Kohlenwasserstoffgruppe steht; oder ein Salz eines solchen Pyrmidinderivats und einem
Träger enthält, der aus einen flüssigen Verdünnungsmittel und einem Netzmittel oderaus eine festen
Verdünnungsmittelbesteht.
7. Zusammensetzung nach Anspruch 6, dadurch gekennzeichnet, dass sie 10 bis 85 Gew.-%
disubstituiertes Pyrimidinderivat enthält.
8. Zusammensetzung nach Anspruch 6, dadurch gekennzeichnet, sie 0,001 bis 1 Gew.-%
disubstituiertes Pyrimidinderivat enthält.
9. Zusammensetzung nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass in dem
genannten Derivat Y für-8R steht.
10. Zusammensetzung nach einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, dass in dem
genannten Derivat A für eine -OGH- Gruppe steht.
11. Zusammensetzungnach einem derAnspruch. 6 bis 9, dadurch gekennzeichnet, dass in dem
genannten Derivat A für eine -NH2 -Gruppe steht.
12. Zusammensetzung nach einem der Ansprüche 6 bis 10, dadurch gekennzeichnet, dass in dem
genannten Derivat A für Chlor steht.
13. Zusammensetzung nach einem der Ansprüche 6 bis 12, dadurch gekennzeichnet, dass in dem
genannten Derivat B für eine Nitrogruppe steht.
14. Zusammensetzung nach einem der Ansprüche 6 bis 13, dadurch gekennzeichnet, dass in dem
genannten Derivat mindestens eine der Gruppen A, B, C und Y für -CCl3 steht.
15. Zusammensetzung nach einem derAnsprUche 6 bis14, dadurchgekennzeichnet, dass in
demgenannten Derivat mindestens eine der Gruppen A, B, C Und Y für -R steht.
16. Zusammensetzung nach einem der Ansprüche 6 bis 9 oder 15,da('urch gekennzeichnet, dass in
dem genannten Derivat -R eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen ist.
17. Zusammensetzung nacheine der AnsprUche 6 bis 8 oder 10 bis 16, dadurch gekennzeichnet, dass
in dem, genannten Derivat -Y eine Arylgruppe ist.Data supplied from the esp@cenet database Worldwide
40/612
3. DE2022207
- 4/13/1972
PHOSPHORIC ACID ESTERS - USEFUL AS FUNGICIDAL AND HERBICIDAL
AGENTS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE2022207
Inventor(s):
AYA MASAHIRO (--); KISHINO SHIGEO (--); YAMADA YASUO (--);
FUKAZAWA NOBUO (--); SHIOKAWA KOZO (--)
Applicant(s):
BAYER AG (--)
E Class: A01N57/14; C07F9/165A1
Application Number:
DE19702022207 (19700506)
Priority Number: JP19690035314 (19690509)
Family: DE2022207
Abstract:
Abstract of DE2022207
Agents contng. cpds. of form (I) (where R1 and R2=alkyl (1-16C); X= -O or -S; Z = H or methyl;
Y=aralkyl or w Wn; W= H, halogen, nitrol or alkyl (1-4C); n = 1 or 2; have fungicidal and herbicidal
activity and may be used against moulds such as Archimycetes, Phycomycetes, Ascomycetes,
Basidiomycetus and Fungi imperfecti in cultures, esp. rice. Agents may also be used as preemergent
herbicides in cultures against Graminae, broad- leaved- and perannual weeds in cultures without
phytotoxicity to culture plants esp. rice, and without leaving residual toxicity or heavy
metals.Description:
Description of DE2022207
Fungizide und herbizide Komposition für Acker- und
Gartenbauzwecke
Die vorliegende Erfindung betrifft eine fungizide und herbizide Komposition für Acker- und
Gartenbauzwecke, die dadurch gekennzeichnet ist, dass sie einen organischen Phosphorsäureester der
allgemeinen Formel
EMI2.1
worin R1 undR2 jeweils einen Alkylrest mit 1 bis 6 C-Atomen oder einenCycloalkylrest mit 1 bis 6
C-Atomen, X ein Sauerstoff- oder Schwefelatom, Z ein Wasserstoffatom oder einen Methylrest und Y
einen Aralkylrest oder einen Rest der allgemeinen Formel
EMI2.2
worin W ein Wasserstoff oder Halogenatom oder einen Nitro- oder Alkylrest mit 1 bis 4
Kohlenstoffatomen und n die Zahlen 1 oder 2 bedeuten, enthält.
Bisher wurden Verbindungen, die Sdwermetalle enthielten, welche jedoch auf Mensch und Haustier
schädigend wirkten, wie z.B.
quecksilberorganische oderarsenorganische Verbindungen, bei der Bekämpfung von
ernstenKrankheiten des Reises wie piricularia oryzae und hypochnus sasakii, wegen ihres
ausgezeichneten fungiziden Effekts und aus ökonomischen Gründen verwendet.
Vor kurzem wurde jedoch die Anwendung von organischen Quecksilberverbindungen
alsAckerbauchemikalien während der Wachstumsperiode der Reispflanzen ausGesundheitsgrnden
verboten, da diese eine direkte,bzw0 indirekte Toxizität gegenüber dem menschlichen Körper
41/612
aufweisen0 Dementsprechend war die Entwicklung von billigen und gegen die oben erwähnten
Reiskrankheiten wirkungsvollen Chemikalien, die trotzdem auf Mensch und Haustier weniger toxisch
wirken, ingrossem Stil erforderlich.
Aus der deutschenpatentschrift Nr.1 039 528 ist es bekannt, dass organische Phosphorsäureester der
folgenden allgemeinene Formel insektizide Wirkungaufweisen:
EMI2.3
Darin bedeuten R3 einen niedrigen Alkylrest und R4 ein Wasserstoffoder Chloratom oder einen
Methylrest.
In dieser Patentschrift wird jedoch nichts davon erwähnt, dass man von diesen Verbindungen
fungizide und herbizide Eigenschaften erwarten kann.
Es wurde nun überraschend gefunden, dass die Verbindungen der allgemeinen Formel I
ausgezeichnete fungizide und herbizide Eigenschaften haben.
Verbindungen gemäss der vorliegenden Erfindung sind bei der Bekämpfung von Pflanzenkrankheiten,
die durch verschiedene Pilzarten, wie Archimyceten, Phycomyceten, Ascomyceten, Basidiomyceten
und Fungi imperfectihervorgerufenuerden, wirksam. Spezielle Verbindungen, die Substituenten wie
Methyl-, Äthyl-, n-Propyl-, i Propyl-, n-Butyl-, i-Butyl-, sec.Butyl- oderGyclohexylreste ie- wels für
R1 und R2, Sauerstoff und Schwefel für X, Wasserstoff oder den Methylrest für Z, den Benzylrest,
Phenylrest, chlor-, dichloroder methylsubstituierten Benzyl- oder Phenylrest für Y in der allgemeinen
Formel I aufweisen, haben hervorragende fungizide Wirkung, speziell bei der Bekämpfung von
schweren Krankheiten der Reispflanze, wiez.B. von piricularia oryzae, cochliobalusmvabeanus und
hypochnus sasakii.
Die Verbindungen gemäss der vorliegenden Erfindung zeigen ihre ausgezeichnete Wirkung auch in
Form herbizider Kompositionen.
Sie zeigen eineselll gute selektive herbizide Wirkung, wenn gewisse Mengen vor dem Keimen des
Unkrautes auf den Boden aufgebracht werden. Diese Verbindungen werden sehr wirkungsvoll bei der
Bekämpfung von Unkraut jeglicher Art in den Reisfeldern, wie von Unkräutern der Familie Graminae
von breitblätterigen und vonmehrjähri gen Unkräuternverwendet, ohne dass sie irgendeine
Phytotoxizität für die Kulturpflanzen, speziell für Reispflanzen, besitzen.
Diese Verbindungen töten alles Unkraut, zeigen dann aber keinen selektiven herbiziden Effekt, wenn
sie in grossen Mengen angewendet werden. Der AusdruckUnkraut" bezieht sich im weitesten Sinne
auf alle Pflanzen, die an Stellen wachsen, wo sie unerwünscht sind..
Die Verbindungengemäss der vorliegenden Erfindung besitzen ein weites Spektrum von guten
biologischen Wirkungen. Sie können zur Bekämpfung von Pflanzenkrankheiten speziell Krankheiten
von Reispflanzen, wie oben erwähnt? eingesetzt werden, wenn sie als Fungizide dienen sollen, aber sie
können ebenso zur Bekämpfung von Unkräutern in Reisfeldern gemäss einer anderen
Anwendungsmethode verwendet werden Diese Verbindungen haben vom Standpunkt der
Wirtschaftlichkeit der im agrarischen Produktionsbereich nötigen Arbeit grossen praktischen Wert, wie
auch infolge ihrer produktionssteigernden Wirkung.Ausserdem haben diese Verbindungen einen
grossen Vorteil alsAckerbauchemikalien, da sie keine Schwierigkeiten bezüglich der Resttoxizität von
Anbauprodukten bereiten, zumal sie keine schädlichen Schwermetalle wie die oben genanntenQuecksilberverbindungen enthalten.
Verbindungen gemäss der Erfindung sind in der folgenden Tabelle 1Zngefühtt:
EMI5.1
>;tb; Verbindung >;SEP; Strukturformel >;SEP; physikalische >;SEP; Konstanten
>;tb; >;SEP; S >;SEP;
>;tb; >;SEP; Nr0l >;SEP; If >;SEP; CEi3O\{1 >;SEP; n20 >;SEP; 1 >;SEP; 5938
>;tb; >;SEP; P-S-CH2CH2-S >;SEP; D
>;tb; >;SEP; CHO
42/612
T a b e l l e 1:
>;tb; >;SEP; 5 >;SEP; S.
>;tb;
>;SEP; C2tiSO >;SEP; t >;SEP; 168176oC/O >;SEP; .1 >;SEP; mmHg
>;tb; >;SEP; Nur.2 >;SEP; 021150 >;SEP; P-S-CH2CH2-S >;SEP; '20 >;SEP; 1.5797
>;tb; >;SEP; 5
>;tb; >;SEP; 02H50 >;SEP; Ii' >;SEP; nzo
>;tb; >;SEP; Nur*3 >;SEP; \ >;SEP; P-S-CH2CH2-S >;SEP; 4 >;SEP; -C1 >;SEP; D >;SEP; 1.5S50
>;tb; >;SEP; C2IS50
>;tb; >;SEP; 5
>;tb; >;SEP; S >;SEP; 1! >;SEP; fl20
>;tb; >;SEP; Nr.4 >;SEP; ,ePSCH2CH2SCH3 >;SEP; D >;SEP; 1.5749
>;tb; >;SEP; C2M50
>;tb; >;SEP; S
>;tb; >;SEP; N-*5 >;SEP; zuI-S-C >;SEP; 1P1-S-Cll2CH2-S-CH2 >;SEP; n20 >;SEP; 1,5737
>;tb; >;SEP; C2H5O
>;tb; >;SEP; 5 >;SEP; CM
>;tb; >;SEP; S >;SEP; II >;SEP; 1 >;SEP; 3 >;SEP; CH3 >;SEP; 1b5725
>;tb; >;SEP; Nr.6 >;SEP; / >;SEP; P-S-CHCH2-S >;SEP; zu >;SEP; D
>;tb; >;SEP; C2H50
>;tb; >;SEP; 0
>;tb; >;SEP; Q
>;tb; >;SEP; 25 >;SEP; \ >;SEP; P-S-CH2CH2-S--C1
>;tb; >;SEP; Nr.7 >;SEP; / >;SEP; nnc2H5O
>;tb; >;SEP; C2H50
>;tb;
EMI6.1
>;tb; Verbindung >;SEP; -erulurfome >;SEP; physikalische.
>;tb;
>;SEP; Konstanten
>;tb; >;SEP; Q
>;tb; >;SEP; C2I5o >;SEP; S-C112ell2 >;SEP; -CH3 >;SEP; 20
>;tb; Nr.8 >;SEP; / >;SEP; I-5-C\)i2CI2-S--CM3 >;SEP; 1.5462
>;tb; >;SEP; C2I?50
>;tb; >;SEP; 0 >;SEP; Ci-I
>;tb; Nr.9 >;SEP; C2N50\I >;SEP; 113 >;SEP; 1.5421
>;tb; >;SEP; C2.I50
>;tb; >;SEP; S
>;tb; >;SEP; flC3H7O\ >;SEP; 20
>;tb; Nr.lO >;SEP; 3 >;SEP; ; -5-CiI2CH >;SEP; n2 >;SEP; 1.5646
>;tb; >;SEP; T,-CS:;70 >;SEP; u
>;tb; >;SEP; 0
>;tb; >;SEP; "-C3H70 >;SEP; II
>;tb; Nr.ll >;SEP; /P >;SEP; P S-CH2CH-S >;SEP; e >;SEP; n20
>;tb; >;SEP; n-03U70
>;tb; >;SEP; S
>;tb; >;SEP; 20
>;tb; Nr.12 >;SEP; i >;SEP; C >;SEP; H >;SEP; 0/ >;SEP; 2 >;SEP; 2 >;SEP; O >;SEP; n20 >;SEP;
1.5627
>;tb; >;SEP; i >;SEP; L
>;tb; >;SEP; S
>;tb; >;SEP; t >;SEP; it >;SEP; 20
>;tb; Nur.13 >;SEP; P-S-CH2CH2-S-C1 >;SEP; 1.5697
>;tb; >;SEP; i >;SEP; C3H70
>;tb; >;SEP; s
>;tb; Nr.14 >;SEP; tO3H7O; >;SEP; P1-5-CH2C2-S;OH3 >;SEP; nD20 >;SEP; 1.5606
43/612
>;tb; >;SEP; i-C3I-I7
>;tb; >;SEP; S
>;tb; >;SEP; n20 >;SEP; 1 >;SEP; 5493'
>;tb; Nr.15 >;SEP; C3.170 >;SEP; P-S-CH2CII2-SC4Hg-tert, >;SEP; n20
>;tb; >;SEP; i-C31370
>;tb; >;SEP; i >;SEP; A >;SEP; 70 >;SEP; ç >;SEP; A >;SEP; S >;SEP; .t >;SEP; n >;SEP; A
>;tb;
EMI7.1
>;tb; yrbipdun9 >;SEP; Xtr,uXturQrmssl >;SEP; physikalische
>;tb; >;SEP; Konstanten
>;tb; >;SEP; s
>;tb; >;SEP; I-ezwJO
>;tb; >;SEP; 20 >;SEP; 1.5580
>;tb; Nur.16 >;SEP; PrS-GIIAC!-Ii-S-CI2'n,,
>;tb; >;SEP; i >;SEP; C3lI70
>;tb; >;SEP; Q
>;tb; Wr,17 >;SEP; \ >;SEP; I-S-CI-I2CH2-S >;SEP; e >;SEP; + >;SEP; .>;SEP; 155-1630C/0.1
>;SEP; rnmVg
>;tb; >;SEP; i >;SEP; C31170 >;SEP; n20 >;SEP; 1,5375
>;tb; >;SEP; Q
>;tb; Nr.18 >;SEP; \ >;SEP; P-S-CtI2CH2-S- >;SEP; F >;SEP; -C1 >;SEP; n2Q >;SEP; 1.5442
>;tb; >;SEP; - >;SEP; 22ä >;SEP; -D
>;tb; >;SEP; t-C3I-I7Q >;SEP; 117Q
>;tb; >;SEP; 0 >;SEP; G1 >;SEP; nD >;SEP; 550
>;tb; - >;SEP; -fl
>;tb; >;SEP; \I-i >;SEP; n0 >;SEP; 555O
>;tb; >;SEP; L-C3tEA7D >;SEP; l
>;tb; >;SEP; 0
>;tb; >;SEP; i-G131-i?0, >;SEP; It
>;tb; >;SEP; --- >;SEP; Cì2CM2 >;SEP; D >;SEP; r*Q >;SEP; 1q538
>;tb; Nr.2g >;SEP; -P-S >;SEP; PtS-C,Cz'SI >;SEP; 4 >;SEP; CH >;SEP; ---3 >;SEP; ;>;SEP; 1 >;SEP;
5338
>;tb; >;SEP; i-C3H7Q
>;tb; >;SEP; 0
>;tb; >;SEP; G337a >;SEP; I3
>;tb; >;SEP; x.21 >;SEP; 2o >;SEP; X >;SEP; und >;SEP; 1,53.84
>;tb; >;SEP; -C3ll?
>;tb; >;SEP; C1S
>;tb; Nr.22 >;SEP; ll-S~CH2CH2~S- >;SEP; D >;SEP; 1.53-73
>;tb; >;SEP; i-ccn7d' >;SEP; >;tb; >;SEP; 9
>;tb; >;SEP; I >;SEP; )f
>;tb; >;SEP; - >;SEP; aa7CsZ,r*t, >;SEP; 2-Q
>;tb; >;SEP; - >;SEP; --f-- >;SEP; 'LLj >;SEP; -- >;SEP; & BR>;
>;tb; >;SEP; i.C71::70 >;SEP; 5
>;tb;
EMI8.1
>;tb; 'UC >;SEP; Strukturformel >;SEP; g >;SEP; physikalische
>;tb; >;SEP; Konstanten
>;tb; >;SEP; 0 >;SEP; CiT
>;tb; i-G,f3702
>;tb; >;SEP; Nr*24 >;SEP; / >;SEP; P-SoCIlCH2S >;SEP; D
>;tb; >;SEP; i-CM7O
>;tb; >;SEP; 0
>;tb; "-CqH90t >;SEP; ] >;SEP; j
44/612
>;tb; \P-SICf-I2CH2-S20 >;SEP; 1.5244
>;tb; n-C4H90
>;tb; >;SEP; 0
>;tb; >;SEP; n-C/H,O >;SEP; \II >;SEP; 20
>;tb; Nr.26 >;SEP; / >;SEP; 2 >;SEP; 2 >;SEP; O >;SEP; n20 >;SEP; 1.5320
>;tb; >;SEP; sec >;SEP; C4M90
>;tb; >;SEP; o
>;tb; Nr >;SEP; .27 >;SEP; C4M90\ >;SEP; P-S-C,CH,-S >;SEP; n20 >;SEP; 1.5308
>;tb; >;SEP; i-C >;SEP; H90/ >;SEP; D
>;tb; >;SEP; o
>;tb; >;SEP; -C3H70 >;SEP; II >;SEP; 20
>;tb; Nr.28 >;SEP; / >;SEP; P-S-CI-I2CH7-S20 >;SEP; 1,54rr2
>;tb; >;SEP; C2Hg' >;SEP; I
>;tb; >;SEP; 0
>;tb; >;SEP; n-O.LKsO >;SEP; It >;SEP; "DO
>;tb; Nr.29 >;SEP; \P-S-CH ; CH2-S >;SEP; 4 >;SEP; nT20 >;SEP; 1.56Q
>;tb; >;SEP; C2H50
>;tb; Nr.30 >;SEP; o/'P-S-CH,Cr-I,-s-(/ >;SEP; O >;SEP; n20 >;SEP;
>;tb;
Die Verbindungen gemäss der Erfindung, die durch die allgemeine Formel I ausgedrückt werden,
werden nach einem der in den folgenden Reaktionsschemata gezeigten Verfahren synthetisiert.
Methode A
EMI9.1
Darin haben R1, R2,X, Y und Z oben genannte Bedeutung, M1 bedeutet ein Wasserstoff- oder
Metallatom oder einen Ammoniumrest und Hal ein Halogenatom.
Bei diesem Verfahren wird die Umsetzung durch eine direkte Reaktion der Verbindungen der
allgemeinen Formeln III und IV miteinander oder unter Verwendungen des inerten
organischenLösungs- oder Verdünnungsmittels durchgeführt. Zu diesem Zweck eignen sich
aliphatische oder aromatische Kohlenwasserstoffe (die auch halogeniert sein können), wie Benzin,
chloriertes Methylen, Chloroform, Kohlenstofftetrachlorid, Benzol, Chlorbenzol, Toluol, Xylol usw.;
Äther, wie Diäthyläther, Dibutyläther, Dioxan, Tetrahydrofuran; aliphatische Alkohole und Ketone mit
niedrigeren Siedepunkten, wie Methanol, Äthanol, Isopropanol, Aceton, Methyläthylketon,
Methylisopropylketon und Methylisobutylketon usw., undni- dere aliphatische Nitrile, wie Acetonitril
und Propionitril usw.
Die Reaktion kann auch in Gegenwart einer säurebindenden Substanz durchgeführt werden. Zu diesem
Zweck eignen sich Alkalimetallcarbonate, -bicarbonate und -alkoholate, wie z.B.
Natriumhydrogencarbonat, Kaliumcarbonat, Natriumcarbonat, Kalium- oder Natriummethylat bzw.äthylat und tert.Amine aliphatischer Kohlenwasserstoffe, aromatischer Kohlenwasserstoffe oder
heterocyclische Kohlenwasserstoffe, wie Triäthylamin, Diäthylanilin, Pyridin usw.
Nach einem analogen Verfahren können diese Verbindungen auch nach der folgenden Methode
hergestellt werden:
EMI10.1
Darin haben R1, R2, X, Y und Zdieselbe Bedeutung wie in der allgemeinen Formel I und M2
bedeutet ein Metallatom.
Bei diesem Verfahren wird die Umsetzung in einem inerten organischen Lösungs- oder
Verdünnungsmittel in der Gegenwart von Alkali durchgeführt.
Methode B
EMI10.2
Darin haben R1, R2, X, Y und Z dieselbe Bedeutung wie in der allgemeinen Formel I und M3
bedeutet ein Metallatom oder einen Alkylrest.
Diese Reaktion wird in einem inerten Lösungsmittel oder Verdünnungsmittel wie in Verfahren A
sowie in Gegenwart einer säurebindenden Substanz durchgeführt.
45/612
Methode C
EMI10.3
Darin habenRl, R2, X, Y undZ die in der allgemeinen Formel I angegebene Bedeutung, Hal die
Bedeutung wie in der allgemeinen Formel IV und0 bedeutet ein Wasserstoff- oder Metallatom.
Die Synthese kann auch durch Umsetzung der Verbindungen der allgemeinen Formeln X und XI
direkt, oder unter Verwendung eines inertenLösungs- oder Verdünnungsmittels wie in Methode A
beschrieben und, wenn erforderlich, in Gegenwart von säurebindenden Mitteln durchgeführt werden
Die Reaktionen der Verfahren A, B und C werden innerhalb eines ziemlich weiten
Temperaturbereiches, allgemein zwischen 0 bis 1100C, vorzugsweise zwischen 30 und 800C,
durchgeführt.
Die folgenden experimentellen Beispiele beschreiben das Verfahren zur Herstellung der Verbindungen
gemäss der vorliegenden Erfindung.
Experimentelles Beispiel 1:
EMI11.1
Eine Mischung aus 24,2 g (0,1 Mol) Kaliumsalz der O,O-Diisopropyldithiophosphorsäure, 21,7 gtO,l
Mol) 2-(Phenylthio)äthylbromid und 100 ml Äthyl alkohol wurde auf 600C drei Stunden lang unter
Rühren erhitzt. Nach Beendigung der Reaktion wurde der Äthylalkohol aus der Reaktionsmischung
durch Destillation entfernt. Zu dem Rückstand wurden 100 ml Benzol zugegeben. Die Benzollösung
wurde hintereinander mit Wasser, einerzeigen wässerigen Natriumcarbonatlösung und Wasser
gewaschen und dann über wasserfreiem Natriumsulfat getrocknet. Nach dem Abdampfen des Benzols
werden 25,5 g farbloses öliges O,O-Diiso-propyl-S-[2-(phenylthio)äthyl]phosphordi thioat erhalten.
nD20=1,5627.
Experimentelles Beispiel 2:
EMI11.2
Eine Mischung aus 20,8 g(O,l Mol) Kaliumsalz der O,O-Diäthylthiolphosphorsäure, 25,2 g(o,i
Mol)2- (p-Chlorphenylthio) äthyl- bromid und 100 ml Äthylalkohol wurde bei 600C unter Rühren
zwei Stunden lang erhitzt. Nach beendeter Reaktion wurden der Äthylalkohoi aus
derReaktionsmisehung abdestilliert und100 ml Benzol zum Rückstand zugegeben. Die benzolische
Lösung wurde dann nacheinander mit Wasser und einer 1%igen wässrigen
Natriumcarbonatlösunggewa- schen und über wasserfreiem Natriumsulfat getrocknet.Nach dem
Abdestillieren des Benzols wurden 27,6gfarblos öliges O,O-Diäthyl S-[2-(pchlorphenylthio)äthyl]phosphorthiolat erhalten. nD20=1,5558
Werden die Verbindungen gemäss dr vorliegenden Erfindung als Agrikulturchemikalien verwendet,
werden sie entweder direkt mit Wasser bzw. in Mischung mit Trägermaterialien verdünnt und in
flüssige- Form übergeführt, oder als benetzbare Pulver, emulgierbare Konzentrate, Stäube, Granulate,
Öle, Tabletten, Pasten usw. nach Verfahren, die bei den herkömmlichen Agrikulturchemikalien üblich
sind, verwendet. Als feste Träger eignen sich inaktive Mineralmaterialien, wie z.B. Talk, Ton, Kaolin,
Montmorillonit, Diatomeenerde, Calciumcarbonat usw., als flüssige Verdünnungsmittel sowohl
Lösungsmittel wie auch Nichtlösungsmittel, in denen die Chemikalien durch Hilfsmittel dispergiert
oder gelöst wurden, z.B.Wasser, All.ohole, Benzol, Xylol, Dimethylnaphthalin, aromatische
Naphthas,.i.methylformamid usw. Sie können, um ihre Wirksamkeit zu sichern, in Mischung mit
Hilfsmitteln der Agrikulturchemie wie Spreitmit- teln, Emulgiermitteln, benetzenden Substanzen,
adhäsiven Substanzen usw. angewendetwerden.Weiters können sie angewendet werden in Mischung
mit Insektiziden, Akariziden, Nematoziden, z.B. organischen Phosphorverbindungen,
Carbamatverbindungen, Organochlorverbindungen, Dinitroverbindungen, weiters mit Fungiziden, wie
Organophosphorverbindungen, Organoschwefelverbindungen, Dithiocarbamatverbindungen,
Dinitroverbindungen; mit Antibiotika oder Herbiziddn, wie.
Phenoxyverbindungen,Carbamatverbindungen, Harn stoffverbindun- gen,
Triazinverbindungen,Chlorphenulverbindungen, substituierten Diphenylätherverbindungen und
Anilidverbindungen; bzw. auch in Mi schung mit Pflanzenwachstumsregulatoren, anderen
Agrikulturchemikalien und Düngemitteln.
46/612
Die Mittel gemäss dieser Erfindung enthalten im allgemeinen: 0,1 bis 95 Gew.-%, vorzugsweise 0,5 90 Gew.-% aktive Substanzen.
Die MitteL gemäss der vorliegenden Erfindung können nach einer der unten beschriebenenMethoden
in Anwendung gebracht werden: staubförmig werden sie direkt auf die Stengel und Blätter der
Pflanzen aufgebracht oder für die Saatgutbehandlung verwendet. In Form des emulgierbaren
Konzentrats werden sie mit Wasser verdünnt, um die gewünschte Konzentration zu erhalten und die
Lösung wird dann auf die Stengel und Blätter der Pflanzen aufgebracht. Das benetzbare Pulver wird in
Wasser zu der gewünschten Konzentration verdünnt und die Suspension auf die Stengel und Blätter der
Pflanzen aufgebracht. In körniger Form wird es so wie es ist, auf den Boden aufgebracht.
Die Menge der aktiven Substanz, die in fungiziden Kompositionen Verwendung findet,beträgsetwa 15
bis 1000g/10 a, vorzugsweise 40 bis 600 g/10 a, jedoch kann diese Menge je nach Bedingungen
gesteigert oder verringert werden.
Wird die Verbindung als Herbizid verwendet, zeigt sie nichtselektiveherbizide Wirkung, wenn sie in
grösseren Mengen (20 bis 40 kg aktive Substanz/ha) aufgebracht wird und gute herbizide selektive
Wirkung wenn sie in geringeren Mengen (2,5 bis 5 kg aktive Substanz/ha) angewendet wird.
Die Menge der aktiven Substanz die angewendet wird, variiert je nach der Art des aktivenNrkstoffes,
der Art der Formulierung, der Verwendungsmethode und dem Verwendungszweck.
Im folgenden wird die vorliegende Erfindung durch die folgenden Arbeitsbeispiele speziell illustriert,
die allerdings keineswegs einschränkende Wirkung besitzen.
Arbeitsbeispiel1: 15 Teile der Verbindung Nr.3 gemäss dieser Erfindung, 80 Teile einer Mischung
von Diatomeenerde und Kaolin und 5 Teile eines Emulgators Runnox (Handelsname eines Produktes
der Toho Kagaku Kogyo K.K.) werden gemischt und zueinem bnetzba- ren Pulver vermahlen bzw.
verarbeitet. Dieses wirdtiann nach Verdünnung mit Wasser angewendet.
Arbeitsbeisiel 2: 30 Teile der VerbindungNrX7 gemäss der Erfindung, 30 Teile Xylol, 30 Teile
Kawakasol (Handelsname eines Produktes der Toho Kagaku Kogyo K.K.) werden miteinander
vermischt und gerührt und ein emulgierbares Konzentrat hergestellt. Dieses wird auch wieder nach
Verdünnung mit Wasser angewendet.
Arbeitsbeisiel 3: Zu einer Mischung, die aus 10Teile der Verbindung Nr.18 gemäss der vorliegenden
& indung, 10 Teilen Bentonit, 78 Teilen Zeeklit und 2 Teilen Ligninsulfat besteht, werden 25 Teile
Wasser zugegeben und die Mischung fest geknetet. Das entstandene Gemisch wird dann mit Hilfe
eines Zerkleinerungsgerätes in Körner von 0,75 bis 0,38 mm Durchmesser feingeschnitten. Diese
Körner werden dann bei 40 bis 500C getrocknet und es wird ein Granulat erhalten.
Arbeitsbeispiel 4: 2 Teile der Verbindung 9 gemäss der vorliegenden Erfindung und 98 Teile einer
Mischung von Talk und Ton, werden gemischt, gemahlen und in Form einer
Verstäubungsformulierung verwendet.
Im folgenden werden die Ergebnisse der Wirksamkeitstests der Verbindungen gemäss dieser
Erfindung als Agrikulturchemikalien gezeigt.
Testbeispiel 1: Test gegen piricularia oryzae von Reispflanzen (Topf-Test). Reispflanzen (JukkokuArt) werden in Töpfen mit 12 cm Durchmesser kultiviert. Eine Verbindung der vorliegenden Erfindung
in Form des entsprechenden emulgierbaren Konzentrats, das nach der in Arbeitsbeispiel 2
beschriebenen Methode hergestellt wurde? wurde zur vorgeschriebenen Konzentration von 500 ppm
verdünnt. Die Lösung wurde auf Reispflanzen im Sprossstadium aufgesprüht. Dieses Aufsprühen
wurde durchgeführt, indem man die Töpfe auf einem drehbaren Tisch montiert hatte, der sich in
Verbindung mit der aus der Düse der Sprühkanone abgegebenen Chemikalienmenge bewegte. Die
Chemikalienlösung wurde in einer Menge von 50 cm3/ 3 Töpfe, bei einem Druck von 1,5 kg/cm2
aufgesprüht, so dass die Blätter tropfnass wurden.Die so besprühten Reispflanzen wurden am
nächsten Tag in eine Kammer gegeben und dort bei einer relativen Feuchtigkeit von 100 % und einer
Temperatur von 250C zwei Tage lang belassen. In dieser Zeit wurde eine wässrige Sporensuspension
47/612
von gezüchteter piricularia oryzae durch zweimaliges Sprühen zur Infektion der Reispflanzen
aufgebracht.
7 Tage nach der Besprühung wurde der Infektionsgrad von piricularia oryzae pro Topf ausgewertet
und nach dem folgenden Standard eine Gradeinteilung getroffen, die von 0 bis 5 reicht. Gleichzeitig
wurde auch die Phytotoxizität für die Reispflanzen ermittelt.
Infektionsqrad Prozentsatz der Krankheitsflecken
Fläche
O0%
0,5 >; 2
13-5
2 6 - 10 %
3 11 - 20 %
4 21 - 40 %
5 ; 41
Testbeispiel 2: Test gegen hypochnus sasakii von Reis (Topf Test). Reispflanzen (Kinmaze-Art)
werden in unglasierten Töpfen mit einem Durchmesser von 12 cm aufgezogen. Auf diese Reispflanzen
wurde bei Beginn des Sprossstadiums eine verdünnte Lösung einer Verbindung gemäss der
vorliegenden Erfindung, die nach dem Testbeispiel 1 hergestellt wurde, aufgesprüht.
Am nächsten Tag wurde das Sclerotium von hypochnus sasakii, welches auf Gerstenkörnern zehn
Tage lang gezüchtet worden war, am Unterteil der Test-Reispflanzen aufgebracht. Die behandelten
Pflanzen wurden in einer Kammer bei einer relativen Feuchtigkeit von 95 % oder mehr und
Temperaturen von 28 bis 300C acht Tage lang stehen gelassen, um die Krankheit sich entwickeln zu
lassen.
Der Grad der Entwicklung dieser Krankheit wurde ausgewertetwird auf Grund des Ausmasses der
Krankheitsflecken vom Fuss der Reispflanzen her, wo die Infektion stattfand, klassifiziert. Die
Schädigungsrate wurde nach der folgenden Formel berechnet: Schädigungsrate = ############## x
100 .
Darin bedeutet N die Gesamtzahl der behandeltenStengel,"0 die Zahl der Stengel, an denen keine
Entwicklung der Krankheit beobachtet werden konnte,nl die Zahl derStengel, auf welchen die
Krankheit bis zur erstenBlattscheide vom Boden her beobachtet wurde, n2 die Zahl der Stengel, auf
denen die Entwicklung der Krankheit vom Boden bis zur zweiten Blattscheide Blattscheide beobachtet
wurde und n3 die Zahl der Stengel, auf denen die Entwicklung der Krankheit vom Bo- den bis zur
dritten Blattscheide beobachtet werden konnte.
T a b e l l e 2: Testergebnisse des Testes gegen piricularia oryzae und hypochnus sasakii von Reis
Verbin- Konzentration Infektionsgrad Schädigungs- Phytodung des aktiven Be- vonpiricuiar a grad
durch toxizi standteilsosyzae hypochnus tät sasakii Nr.1 500 ppm 18,0 Nr.2 500 7,1 Nr.3 500 2,0 12,5
Nr.4 500 12,7 Nr.5 500 18,4Nr6 500 14,1 Nr.7 500 2,0 10,9
500 14,6
500 1,5 11,3 Nr.10 500 16,2 13,0 Nr.12 500 15,5 Nr.13 500 17,3 -Nr.14 500 18,3 Nr.15 50025,0
Nr.16500 21,5 Nr.17 500 17,5 Nr.18 500 11,7 Nr.19 500 10,3 Verbin- Konzentration Infektionsgrad
Schädigungs- Phyto dung des aktiven Be- von piricularia grad durch toxizi standteils oryzae hypochnus
tät sasakii
Nr.20 500 ppm 22,0 Nr.21 500 16,7
Nr.22 500 9,8
Nr.23 500 24,0
Nr.24 500 18,3
Nr.25 500 1,5 21,6
Nr.26500 1,2 18,2
Nr.27 500 1,8 20,3 ~
Nr.28 500 2,0 22,5
Nr.29 500 1,8 16,3
Nr.30 500 2,0 15,0 Ar,merkungen: 1. Die Verbindungsnummern entsprechen denen der
Tabelle 1,
48/612
2. Der Infektionsgrad ist der Mittelwert aus drei ge testeten Töpfen,
3. Phytotoxizität: "~" bedeutet, dass kein Schädli cher Effekt auf das Wachstum der Reispflanzen
beobachtet werden konnte.
Testbeispiel 3: Test bezüglich des funziden Effekts gegen verschiedene phytopathogene Pilze (AgarVerdünnungsmethode).
Eine Verbindung gemäss der vorliegenden Erfindung wurde mit einer Reihe von KartoffelAgarkulturnährböden vermischt, so dass die vorgeschriebene Konzentration der wirksamen
Verbindungen darin enthalten war. Nachdem diese Nährboden in Petrischalen mit einem
Durchmesser von 9 cm übergeführt und darin fest geworden waren, wurden sie mit entsprechenden
phytopathogenen Pilzen infiziert.
Nach 4 Tagen Züchtung bei 270C wurden die Wachstumsbedingungen der pathogenen Pilze
ausgewertet und in einem Gradschema von 0 (kein Wachstum) bis 5 (Wachstum wie bei
nichtbehandelten Töpfen) klassifiziert.
Tblle So Testergebnissebezüglich desfungizl.den Effektes gegenverschiedene phytopathogene Pilze
(Agar-Verdünnungsmethode) Verbin- Konzen- Piricu- Pellicu- Alter- Elsinoe Botrytis dung trationlaria
laria naria fawcetti cinerea d.akti- oryzae sasakii kiku ven Be- chiana stand teils ppm
31,3 0 2,0 3,0 0,5 2,0 Nr.7 125,0 0 0,8 2,0 0 0,8
500,0 0 0,5 1,0 0 0,2
31,3 0 3,0 3,5 0,7 3,5 Nr.9 125,0 0 1,5 2,0 0 1,5
500,0 0 0,8 1,5 0 0,4 keine Behand- - 5,0 5,0 5,0 5,0 5,0lung Anmerkung: Die Verbindungsnummern
entsprechen denen in Tabelle 1
Testbeispiel 4: Test gegen Unkräuter vonReisfelderns Testmethode:Nach Füllung von Töpfen mit
1/5000 a Oberfläche mit Erde von Reisfeldern wurden Reissetzlinge (Kinmaze-Art) im 3. bis
4.Blattstadium in die Töpfe unter Überschwqemmungsbedingungen eingepflanzt. Nachdem die
Keimlinge Wurzeln gefasst hatten, wurden Echinochloa crus galli, Samen von breitblätterigen
Unkräutern und Eleocharis acicularis gepflanzt. Die Verbindungen gemäss der Erfindung, die in eine
emulgierbare konzentrierte Lösung oder ein benetzbares Pulver übergeführt wurden, wurden in
Mengen von 500 und 250 g Gehalt an wirksamer Substanz pro 10 a aufgesprüht. Nach drei Wochen
wurde der herbizide Effekt gegen Echinochloa crus galli, Eleocharis acicularis und breitblätterige
Unkräuter sowie die Phytotoxizität auf den jungen Reispflanzen geprüft.
Auswertung Herbizide Wirksamkeit Phytoxizitat 5 höchste Wirksamkeit 5 höchste Phytotoxizität 4
grosse " " 4 grosse " " 3 mittlere " II 3 mittelgrosse II II 2 kleine " " 2 mittlere " " 1 sehr kleine " 1
kleine " " 0 keine " " 0 keine " "
Tabelle 4: Testergebnisse bezüglich der herbiziden Wirkung gegen Unkräuter von Reisfeldern und der
Phytotoxizität gegenüber Reis Verbin- Menge ak- herbizider Effekt Phytotodung tiver Be- Echinochloa
Eleocharis breitblätt- xizität standtei- crus galli acicularis rige Un- auf Reis le q/10 a krauter Nr.1 500 4
450
250 3 - 4 3 4 0Nr.2 500 4 4 5 0
250 4 3 4 0Nr.3 500 3 - 4 4 5 0
250 3 34 ~ 0 Nr.4 500 3 - 4 4 5 0
250 3 34 - 5 0 Nr.5 500 3 - 4 4 4 0
250 3 3 3 0Nr.7 500 4 4 5 0
250 3 - 4 3 4 - 5 0 Nr.11 500 4 4 5 0
250 4 3 4 - 5 0Nr.12 500 5 5 5 0
250 4 4 5 0Nr.13 500 5 4 - 5 5 0
250 4 4 5 0Nr.14 500 5 5 5 0
250 5 44 - 5 0 Verbin- Menge ak- herbizider Effekt Phytoto- dung tiver Be- Eschiochloa Eleocharis
breitblätt- xizität standtei- crus galli acicularis rige Un- auf Reisle q/10 a ~ . kräuter Nr.17 500 5 5 5 0
250 5 4 - 5 4 - 5 0 Nr.18 500 5 5 5 0
250 5 5 5 0 Nr.19 500 4 4 4 0
250 3 - 4 3 3 0 Nr.20 500 5 5 5 0
250 4 4 4 0 Nr.21 500 4 4 4 0
250 3 - 4 3 4O Nr.22 500 5 5 5 0
250 43 - 4 4 0Nr.23 500 4 3 4 0
49/612
250 3 - 4 3 3 0 Nr.25 500 4 4 4 0
250 3 - 4 3 - 4 4 O Nr.26 500 5 5 5O
250 4 3 - 4 5 C Nr.27 500 5 4 5 0
250 4 - 5 3 4 0 Nr.28 500 5 4 5 0
250 4 3 3 0 Nr.29 500 4 4 5 0
250 3 3 4o Nr.30 500 4 - 5 4 5 0
250 3 3 4 0 PCP 500 5 3 4 0(VerGleich)250 30 2 D NIP 40 5 5 5 3 (Vergleich) 20 3 1 2 1 keine
Behandlung - 0 0 0 0.
Anmerkungen: 1. Die Nummern der Verbindungen in dieser Tabelle ent sprechen denen in Tabelle 1
2. breitblättrige Unkräuter sind Monochoria vaginalis
Presl, Rotala indica Koehne, Lindernia pyxidaria
Lin., Dopatrium junceum Hamilton, usw.
3.PCP: Pentachlorphenol (Handelsprodukt) 4. NIP: 2,4-Dichlorphenyl-4'-nitrophenyl-Äther
(Handelsprodukt).Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of DE2022207
Patentansprüche
1) Fungizides und herbizides Mittel, gekennzeichnet durch einen Gehalt an einemPhosphorsOureester
der Formel
EMI22.1
in welcher R1 und R2 jeweils einen Alkylrest mit 1 bis 6 C-Atomen oder einen Cycloalkylrest mit 1
bis 6 C-Atomen, X ein Sauerstoff- oder Schwefelatom, Z ein Wasserstoffatom oder einen Methylrest
und Y einen Aralkylrest oder einen Rest der allgemeinen
Formel
EMI22.2
in welcher W ein Wasserstoff- oder Halogenatom oder einen Nitro- oder
Alkylrest mit 1 bis 4 Kohlenstoffatomen und n die Zahlen 1 oder bedeuten.
EMI22.3
>;tb;
?ilòn >;SEP; und >;SEP; TTnkrUutrp' >;SEP; dd'irh
>;tb; >;SEP; gekennee...chnat, >;SEP; dass >;SEP; daD~zogEr >;SEP; 1
>;tb; >;SEP; 6,e,s >;SEP; r;r,
>;tb; 3) Verwendung vonPhosphorsäureestegemäss Anepruch 1 zur Bekämpfung von Pilzen und
Unkräutern.
4) Verfahren zur Herstellung von fungiziden und herbiziden Mitteln, dadurch gekennzeichnet, dass
man Phosphorsäureester gemässAnspruah 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln
vermischt.Data supplied from the esp@cenet database - Worldwide
50/612
4. DE2022524
- 11/26/1970
PHOSPHATE ESTER BASED INSECTICIDES AND - FUNGICIDES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE2022524
Inventor(s):
AYA MASAHIRO (--); YAMADA YASUO (--); FUKAZAWA NOBUO (--);
SHIOKAWA KOZO (--); KISHINO SIGEO (--)
Applicant(s):
BAYER AG (--)
E Class: C07F9/165A1
Application Number:
DE19702022524 (19700508)
Priority Number: JP19690036711 (19690514)
Family: DE2022524
Abstract:
Abstract of DE2022524
Title based compositions contain a proportion of compound I, with the general formula (in which R1
and R2 are resp. an alkyl gp with 1-6 C atoms or a cycloalkyl gp with 1-6 C atoms, X = C or S, Z = H
or CH3 gp and Y is an aralkyl gp or a gp of general formula II, in which W = H or halogen or a nitro or
an alkyl gp with 1 - 4 C atoms. These Compounds are active general herbicides, especially for rice
cultivation at concns. of 20-40 Kg/ha but show more selective behaviour at 2.5-kg/ha. As fungicides a
concn. of 40-600 g/10a is preferred.Description:
Description of DE2022524
Fungizides und herbizides Mittel für Acker- und Gartenbauzwecke
Die Erfindung bezieht sich auf fungizide und herbizide Mittel für Acker- und Gartenbauzwecke, die
dadurch gekennzeichnet sind, dass sie organische Phosphorsäureester der allgemeinen Formel
EMI2.1
worin R1 und R2 je einen Alkylrest mit 1 bis 6 Kohlenstoffatomen 6der einen Cycloalkylrest mit 1 bis
6 Kohlenstoffatomen, X ein Sauerstoff- oder Schwefelatom, Z ein Wasserstoffatom oder einen
Methylrest und Y-einen Aralkylrest oder einen Rest der allgemeinen Formel
EMI2.2
worin W ein Wasserstoff- oder Halogenatom oder einen Nitro- oder einen Alkylrest mit 1 bis 4 CAtomen bedeutet, als wirksamen Bestandteil enthalten.
Bisher wurden Verbindungen mit einem Gehalt an Schwermetallen, diefür Menschen und Haustiere
schädlich sind, wie z.B. organische Quecksilberverbindungen und organische Arsenverbindungen, auf
breiter Basis angewendet, vor allem zur Bekämpfung ernster Reiskrankheiten, wie hypochnus sasakii
und piricularia oryzae, sowohl wegen ihrer ausgezeichneten fungiziden Wirkung als auch aus
ökonomischen Gründen.
Vor kurzem jedoch wurde die Verwendung von organischen Quecksilberverbindungen als
Ackerbauchemikalien während der Wachstumsperiode der Reispflanzen aus Gründen der öffentlichen
Gesundheit verboten, da diese eine direkte bzw. indirekte Toxizität gegenüber dem menschlichen
Körper aufweisen. Dementsprechend war die Entwicklung von billigen Chemikalien, die sowohl
wirkungsvoll auf die oben erwähten Reiskrankheiten sind als auch weniger toxisch auf Mensch und
Haustier wirken, dringend erforderlich.
Es wurde gefunden, dass organische Phosphorsäureester der alLgemeinen Formel
EMI2.3
51/612
worin R1 und R2 jeweils einen Alkylrest mit 1 bis 6 C-Atomen oder einen Cycloalkylrest mit 1 bis 6
C-Atomen, X ein Sauerstoff- oder Schwefelatom, Z ein Wasserstoffatom oder einen Methylrest und Y
einen Aralkylrest oder einen Rest der allgemeinen Formel
EMI3.1
worin W ein Wasserstoff- oder Halogenatom, einen Nitro- oder einen Alkylrest mit 1 bis 4 C-Atomen
und n die Zahlen 1 oder 2 darstellt, bedeuten, fungizide und herbizide Wirkungen aufweisen.
Als Ergebnis weiterer Studien wurde überraschend gefunden, dass Verbindungen der allgemeinen
Formel1, welche Derivate der Verbindungen der allgemeinen Formel II sind, also Verbindungen, die
man durch Transformation des Thioäthers der Verbindung II in den Sulfoxid-Typ der Verbindung I
erhält, stärkere fungizide und herbizide Wirkungen besitzen.
Die vorliegende Erfindung betrifft Verbindungen der allgemeinen Formel1 mit fungiziden und
herbiziden Eigenschaften, Kompositionen, die diese Verbindungen als wirksamen Bestandteil enthalten
sowie die Verfahren zum Schutz von Kulturpflanzen gegen Krankheiten und Unkräuter unter
Verwendung dieser Kompositionen.
Verbindungen gemäss der vorliegenden Erfindung sind bei der Bekämpfung von Pflanzenkrankheiten,
die durch verschiedene Pilzarten, wie Archymyceten,Phycomyceten, Ascomyceten, Basidiomyceten
und Fungi imperfecti hervorgerufen werden, wirksam. Insbesondere Verbindungen, die Substituenten
wie Methyl, äthyl, n-Propyl,i-Propyl, n-Butyl, i-Butyl,sec.-Butyloder Cyclohexylreste für R1 bzw.R2,
Sauerstoff und Schwefel für X, Wasserstoff oder den Methylrest für Z, den Benzylrest, Phenylrest,
chlor-, methyl-, äthyl-, n-propyl-, i-propyl-, n-butyl-,i-butyl-, sec.butyl- oder nitro-substituierten
Benzyl- oder Phenylrest für Y in der allgemeinen Formel I aufweisen, haben hervorragende fungizide
Wirkung, speziell bei der Bekämpfung von schweren Krankheiten der Reispflanze, wie z.B. piricularia
oryzae,cocbliobolus mVabeanus und hypochnus sasakii,
Die Verbindungen gemäss der vorliegenden Erfindung zeigen ihre ausgezeichnete Wirkung auch in
Form herbizider Kompositionen. Sie zeigen sehr gute selektive herbizide Wirkung, wenn gewisse
Mengen vor dem Keimen des Unkrautes auf den Boden aufgebracht werden.Diese Verbindungen
werden sehr wirkungsvoll bei der Bekämpfung von Unkraut jeglicher Art in den Reisfeldern, wie von
Unkräutern der Familie Graminae, von breitblättrigen und von mehrjährigen Unkräutern verwendet,
ohne dass sie irgendeine Phytotoxizität für die Kulturpflanzen, speziell die Reispflanzen, zeigen.
Diese Verbindungen töten alles Unkraut, zeigen dann aber keinen selektiven herbiziden Effekt, wenn
sie in grossen Mengen angewendet werden. Der Ausdruck "Unkraut" bezieht sich im weitesten Sinne
auf alle Pflanzen, die an Stellen wachsen, wo sie unerwünscht sind.
Die Verbindungen gemäss der vorliegenden Erfindung besitzen ein weites Spektrum von guten
biologischen Wirkungen. Sie können bei der Bekämpfung von Pflanzenkrankheiten, speziell
Krankheiten von Reispflanzen, wie oben erwähnt, eingesetzt werden, wenn sie als Fungizide dienen
sollen, aber sie können ebenso'zur Bekämpfung von Unkraut in Reisfeldern verwendet werden, wenn
sie gemäss einer anderen Anwendungsmethode verwendet werden. Diese Verbindungen haben vom
Standpunkt der Wirtschaftlichkeit der im agrarischen Produktionsbereich nötigen Arbeit grossen
praktischen Wert, wie auch infolge ihrer produktionssteigernden Wirkung. Ausserdem haben diese
Verbindungen den grossen Vorteil als Ackerbauchemikalien, da sie keine Schwierigkeiten bezüglich
der Resttoxizität von Anbauprodukten bereiten, zumal sie keine schädlichen Schwermetalle wie die
oben genannten Quecksilberverbindungen enthalten.
Beispiel für Verbindungen gemäss der Erfindung sind in der folgenden Tabelle 1 angeführt: T a b e l
le1:
EMI5.1
>;tb; Verbindung >;SEP; Strukturformel >;SEP; hvsikalische >;SEP; Konstanten
>;tb; >;SEP; S >;SEP; O
>;tb; >;SEP; Nr.1 >;SEP; / >;SEP; P-S-CH2CH2-Se >;SEP; n20 >;SEP; 1.5812
>;tb; >;SEP; C2H5C/' >;SEP; 4
>;tb; >;SEP; S >;SEP; O
>;tb; >;SEP; C21i50 >;SEP; \
52/612
>;tb; >;SEP; Nr >;SEP; . >;SEP; 2 >;SEP; / >;SEP; P-S-CH2CH2-S42 >;SEP; n20 >;SEP; 1.>;SEP;
5852
>;tb; >;SEP; L >;SEP; L
>;tb; >;SEP; Nur.3 >;SEP; C2HsO;t15c2cn2OI5lc3 >;SEP; O >;SEP; 1.575
>;tb; >;SEP; Nr >;SEP; .3 >;SEP; C2H5 ; t >;SEP; O >;SEP; CH3 >;SEP; nDO >;SEP; 1.5765
>;tb; >;SEP; 5 >;SEP; 0
>;tb; >;SEP; C2I-ISO >;SEP; I >;SEP; o >;SEP; 1.5803
>;tb; >;SEP; Nr.4 >;SEP; / >;SEP; P-S-CH2CH2-S-cH242) >;SEP; n20 >;SEP; 1.5803
>;tb; >;SEP; L- >;SEP; ,
>;tb; >;SEP; S >;SEP; C3 >;SEP; O
>;tb; >;SEP; C2H5OXIt >;SEP; 20 >;SEP; 1l
>;tb; >;SEP; Nr.5 >;SEP; L >;SEP; nt
>;tb; >;SEP; C2H50
>;tb; >;SEP; -S >;SEP; O
>;tb; >;SEP; C2H50\II >;SEP; (I
>;tb; >;SEP; PS >;SEP; Ci >;SEP; 1.5594
>;tb; >;SEP; Nr.6 >;SEP; L >;SEP; n20
>;tb; >;SEP; C2H50
>;tb; >;SEP; S >;SEP; O >;SEP; 22081L >;SEP; n20 >;SEP; 1.5642
>;tb; >;SEP; Nur,7 >;SEP; / >;SEP; 1P1-SCHCH >;SEP; D
>;tb; >;SEP; n-C3H70.>;SEP;
EMI6.1
>;tb; Verbindung >;SEP; Strukturformel >;SEP; physikalische >;SEP; Konstante
>;tb; >;SEP; tE >;SEP; p{J >;SEP; CHCHCSIj/\ >;SEP; 20
>;tb; Nur.8 >;SEP; 22 >;SEP; II >;SEP; O >;SEP; n20 >;SEP; 1.5360
>;tb; >;SEP; n-C3H70
>;tb; >;SEP; 5 >;SEP; 0
>;tb; Nr.9 >;SEP; i-031j70 >;SEP; II >;SEP; O
>;tb; Nr.9 >;SEP; I-S-CH,CH,-S- >;SEP; 1,5622
>;tb; >;SEP; i-C3H70
>;tb; >;SEP; S >;SEP; O
>;tb; Nr.lO >;SEP; / >;SEP; P-S-CH2CH2-S- >;SEP; S >;SEP; -C1 >;SEP; n20 >;SEP; 1.5694
>;tb; >;SEP; i-C3H70
>;tb; >;SEP; S >;SEP; O
>;tb; >;SEP; i-C3H70 >;SEP; II >;SEP; 0HCH511\c >;SEP; 20
>;tb; Nur.11 >;SEP; P-s- >;SEP; 22---H3 >;SEP; rlD >;SEP; 1.5617
>;tb; >;SEP; i >;SEP; C3H70
>;tb; >;SEP; S >;SEP; -O
>;tb; Nr.12 >;SEP; / >;SEP; P-S-CH2CH2-S- >;SEP; O >;SEP; -C4Hg-tert >;SEP; 5 >;SEP; 20 >;SEP;
1,5507
>;tb; >;SEP; i >;SEP; C3H70 >;SEP; - >;SEP; -CH2CH2-S--C4H9-tert >;SEP; fl
>;tb; >;SEP; S >;SEP; OCH3
>;tb; >;SEP; itC3H7O\ >;SEP; II >;SEP; CCHS11 >;SEP; 20
>;tb; Nr.13 >;SEP; / >;SEP; P-S-CH2CH2-S- >;SEP; b >;SEP; n20 >;SEP; 1,5637
>;tb; >;SEP; ICH70 >;SEP; 0
>;tb; >;SEP; S >;SEP; O
>;tb; >;SEP; Nr.14 >;SEP; i-C3H70 >;SEP; / >;SEP; P-S-CH2CH2-S >;SEP; 4 >;SEP; N02 >;SEP;
n20 >;SEP; ..?0 >;SEP; 1,5916
>;tb; >;SEP; i-C3H70
>;tb; >;SEP; t.
>;tb;
>;SEP; 5 >;SEP; cm3 >;SEP; t
>;tb; >;SEP; t >;SEP; i-C3H70 >;SEP; \t >;SEP; 20
>;tb; >;SEP; Nr.15 >;SEP; / >;SEP; P*S"CHCH2-S >;SEP; lt;- >;SEP; und >;SEP; 1,5589
>;tb; >;SEP; idC3Hi >;SEP; n,
>;tb; >;SEP; t >;SEP; h >;SEP; I >;SEP; 1 >;SEP; 1 >;SEP; 0 >;SEP; n >;SEP; t
53/612
>;tb;
EMI7.1
>;tb; Verbindung >;SEP; Strukturformel >;SEP; phy >;SEP; sikal >;SEP; ische >;SEP; Konstanten
>;tb; >;SEP; O
>;tb; Nr >;SEP; . >;SEP; lb >;SEP; -S-CH2CH2-Se >;SEP; n >;SEP; >;SEP; 1 >;SEP; 342
>;tb; >;SEP; '-C?H,O"13
>;tb; >;SEP; O >;SEP; 0
>;tb; >;SEP; C3H7O\tt >;SEP; ii >;SEP; n20
>;tb; Nr.17;; >;SEP; ZP-S-CH2CM2-S-O~cl >;SEP; n20 >;SEP; 1. >;SEP; 5440
>;tb; >;SEP; i-C3H70
>;tb; >;SEP; O >;SEP; 0
>;tb; >;SEP; - >;SEP; .ffi >;SEP; n-C4H90\ >;SEP; II >;SEP; 20
>;tb; Nr.18 >;SEP; / >;SEP; P-S-CH2CH2-S >; ) >;SEP; n20 >;SEP; 1.5231
>;tb; >;SEP; n-C4Hi
>;tb; >;SEP; 5 >;SEP; S
>;tb; sec-C4H5o\} >;SEP; y >;SEP; 20 >;SEP; n20 >;SEP; 1.>;SEP; 5548
>;tb; >;SEP; sec-C4fl90
>;tb; >;SEP; S >;SEP; O
>;tb; >;SEP; F-C,1i,0 >;SEP; I >;SEP; II >;SEP; n20
>;tb; Nr.20 >;SEP; P-S-CH2CH2-S20 >;SEP; n20 >;SEP; 1.5535
>;tb; >;SEP; i-c
>;tb; >;SEP; O >;SEP; 0
>;tb; >;SEP; i-CB70\I >;SEP; II
>;tb; Nr.21 >;SEP; i-C3;H70\ >;SEP; II >;SEP; 1,5433
>;tb; >;SEP; 'D >;SEP; D
>;tb; >;SEP; C2H50
>;tb; >;SEP; o >;SEP; 0
>;tb; >;SEP; n-CqI-IgQ, >;SEP; 11 >;SEP; n20
>;tb; Nr.2CP >;SEP; H2CH"S) >;SEP; n20 >;SEP; 1. >;SEP; 5397
>;tb; >;SEP; U
>;tb; zu >;SEP; o >;SEP; a
>;tb; >;SEP; cHO'PSCHCll'I/\ >;SEP; n2Q >;SEP; 1.5530
>;tb; >;SEP; 2 >;SEP; 5 >;SEP; f)O984 >;SEP; b >;SEP; O >;SEP; 4
>;tb;
Diese Verbindungenkönnenerfindungsgemäss leicht nach einem Verfahren, das durch das folgende
Reaktionsschema charakterisiert wird, hergestellt werden:
EMI8.1
worinRl, R2, X, Y und Z dieselbe Bedeutung, wie in der allgemeinen Formel I besitzen.
Die Reaktion wird in niedrigen aliphatischen Carbonsäuren z.B.
in Essigsäure, vorzugsweise unter Anwendung eines säurebindenden Mittels, z.B. einer 30 bis 40 eigen
wässrigen Wasserstoffperoxidlösung, durchgeführt. Obwohl diese Reaktion in einem verhältnismässig
weiten Temperaturbereich durchgeführt werden kann, ist es von Vorteil, die Umsetzung zwischen 0
und50 C vorzunehmen.
Als weitere Methoden, die Phosphorsäureester des Sulfoxidtyps herzustellen, seien die folgenden
Verfahren aufgezählt:
1. Sobald die erforderliche Menge eines Halogens zu der wässrigmethanolischen Lösung, die den
Phosphorsäureester enthält, zugegeben wird, bildet sich ein entsprechender Sulfoxidester.
2. Ein Phosphorsäureester, der in Wasser suspendiert ist (ohne Verwendung eines Lösungsmittels)
wird mit der erforderlichen Menge Halogen-Hypochlorit oder -Hypobromit oxidiert.
3. Ein Phosphorsäureester, der in Wasser unlöslich ist, wird in einem geeigneten Lösungsmittel gelöst.
Dazu wird die erforderliche Menge Wasser und säurebindendes Mittel zugegeben und danach die
erforderliche Menge Halogen.
54/612
Als oxidierende Substanzen sind speziell Chlor und Brom wirksam, obwohl auch allgemeine
oxidierende Substanzen, wie Wasserstoffperoxid verwendet werden können. Als säurebindende Mittel
eignen sich Alkalicarbonate, Alkaliacetate und Alkalicyanate. Als Lösungsmittel eignen sich
chloriertes Methylen, Tetrachlorkohlenstoff, chloriertesäthylen und Tetrachloräthylen.
Die so erhaltenen Phosphorsäureester des Sulfoxidtyps sind in Wasser leicht löslich, während die
Thionophosphorsäreester des Sulfoxidtyps in Wasser nur schwer löslich sind.
Im folgenden sind einige experimentelle Beispiele zur Erläuterung des Verfahrens zur Herstellung der
erfindungsgemässen Ver- bindungen angeführt:
Experimentelles Beispiel 1:
EMI9.1
17,5 gO,O-Diisoptopyl-S- (phenylthio)äthyl~/phosphordi- thioat werden in 60 ml Eisessig gelöst.7,5
g 30%iges wässriges Hydrogenperoxid wird dann tropfenweise unter Rühren zugegeben, wobei die
Temperatur der Reaktionsmischung unter 30 C gehalten wird.
Das Rühren wird dann noch 2 Stunden bei Raumtemperatur fortgesetzt, nachdem das
Wasserstoffperoxid zugegeben wurde. 200 ml Wasser wur- den dann zu der Reaktionsmischung
zugegeben und die sich dabeibil- dende ölige Schicht abgetrennt. Das Öl wurde dann inlOO ml
BenzOl gelöst und nacheinander mit Wasser, 1%iger Natriumcarbonatlösung und Wasser gewaschen
und dann über wasserfreiem Natriumsulfat getrocknet. Nach dem Abdampfen des Benzols wurden 14,7
g farbloses O,O-Diisopropyl-S-[-(phenylsulphinyl)äthyl]phosphordithioat erhalten.n2D0= 1,5612.
Wenn diese Verbindungen erfindungsgemäss als Agrikulturchemikalien verwendet werden, werden sie
entweder direkt mit Wasser bzw.
in Mischung mit Trägermaterialien verdünnt, und in flüssige Form übergeführt, oder als benetzbare
Pulver, emulgierbare Konzentrate, Stäube, Granulate, Öle, Tabletten, Pasten usw. nachVerfahren, die
bei den herkömmlichen Agrikulturchemikalien angewendet werden, verwendet. Als feste Träger
eignen sich inaktive Mineralmaterialien, wie z.B. Talk, Ton, Kaolin, Montmorillonit, Diatomeenerde,
Calcium carbonat usw., als flüssige Verdünnungsmittel sowohl Lösungsmittel wie auch
Nichtlösungsmittel, in denen die Chemikalien durch Hilfsmittel dispergiert oder gelöst werden, z.B.
Wasser, Alkohole, Benzol, Xylol, Dimethylnaphthalin, aromatischeNaphtha, Dimethylformamid usw.
Sie können, um ihre Wirksamkeit zu sichern, in Mischung mit solchen Hilfsmitteln der
Agrikulturchemie wie Spreitmitteln, Emulgierern, benetzenden Substanzen, adhäsiven Substanzen usw.
angewendet werden. Weiters können sie angewendet werden in Mischung mit Insektiziden,
Akariziden, Nematoziden, z.B. organischen Phosphorverbindungen, Carbamatverbindungen,
Organochlorverbindungen, Dinitroverbindungen, weiters mit Fungiziden, wie
Organophosphorverbindungen,Organoschwefelverbindungen, Dithiocarbamatverbindungen,
Dinitroverbindungen; mit Antibiotika, Herbiziden, wie Phenoxyverbindungen, Carbamatverbindungen,
Harnstoffverbindungen, Triazinverbindungen, Chlorphenolverbindungen, substituierten
Diphenylätherverbindungen und Anilidverbindungen; bzw. auch in Mischung mit
Pflanzenwachstumsregulatoren, anderen Agrikulturchemikalien und Düngemitteln.
Die Mittel gemäss dieser Erfindung enthalten im allgemeinen:0,1 bis 95 Gew.-%, vorzugsweise 0,5 90 Gew.-% aktive Substanzen.
Die Mittel gemäss der vorliegenden Erfindung können nach einer der unten beschriebenen Methoden
in Anwendung gebracht werden:Staubförmig werden sie direkt auf die Stengel und Blätter der Pflanzen
aufgebracht oder für die Saatgutbehandlung verwendet. In Form des emulgierbaren Konzentrats
werden sie mit Wasser usw. verdünnt, um die gewünschte Konzentration zu erhalten und die Lösung
wird dann auf die Stengel und Blätter der Pflanzen aufgebracht. Dasbenetzba- re Pulver wird in
Wasser zu dergewanschten Konzentration verdünnt und die Suspension auf die Stämme. und Blätter
der Pflanzen aufge-bracht. In körniger Form wird es so wie es ist, auf den Boden aufgebracht.
55/612
Die Menge der aktiven Substanz, die in fungiziden Kompositionen Verwendung findet, beträgt etwa
15 bis 1000 g/lO a, vorzugsweise 40 bis 600 g/lO a, jedoch kann diese Mengeje, nach Bedingungen
gesteigert oder verringert werden.
Wird die Verbindung als Herbizid verwendet, zeigt sie nichtselektive herbizide Wirkung, wenn sie in
grösseren Mengent20 bis 40 kg aktive Substanz/ha) aufgebracht wird und gute herbizide selektive
Wirkung wenn sie in geringeren Mengen (2,5bis 5 kg aktive Substanz/ha) angewendet wird.
Die Menge der aktiven Substanz die angewendet wird, variiert je nach der Art des aktiven Wirkstoffes,
der Art der Formulierung, der Verwendungsmethode und dem Verwendungszweck.
Im folgenden wird die vorliegende Erfindung durch die folgenden Arbeitsbeispiele speziell illustriert,
die allerdings keinesweg einschränkende Wirkung besitzen.
Arbeitsbeispiel 1: 15 Teile der VerbindungNr.ll gemäss dieser Erfindung, 80 Teile einer Mischung
von Diatomeenerde und Kaolin und 5 Teile eines Emulgators Runnox (Handelsname eines Produktes
der Toho Kagaku Kogyo K.K.) werden gemischt und zu einem benetzbaren Pulver vermahlen und
verarbeitet. Dieses wird dann nach Verdünnung mit Wasser angewendet.
Arbeitsbeispiel 2: 30 Teile derVerbindung Nr.5 gemäss der Erfindung, 30 Teile Xylol, 30
TeileKdwakasol (Handelsname eines Produktes der Kawasaki Kasei Kogyo K.K.) und 10 Teile eines
Emulgators Sorpol (Handelsname eines Produktes der Toho Kagaku Kogyo K.K.) werden miteinander
vermischt und gerührt, und ein emulgierbares Konzentrat wirderhalten Dieses wird nach Verdünnung
mit Wasserang- wendet.
Arbeitsbeispiel 3: Zu einer Mischung,db aus 10 Teilen der VerbindungNr.lO gemäss der
vorliegenden Erfindung, 10 Teilen Bentonit, 78 Teilen Zeeklit und 2 TeilenLigninsulfat besteht,
werden 25 Teile Wasser zugegeben und die Mischung fest geknetet. Das entstandene Gemilch wird
dann mit Hilfe eines Zerkleinerungsgerätes in Körner von 0,75 bis 0,38 mm Durchmesser fein
geschnitten. Diese Körner werden dann bei 40 bis 500C getrocknet und ein Granulaterhalten
Arbeitsbeispiel 4: 2 Teile der Verbindung Nr.18 gemäss der vorliegenden Erfindung und 98Teileleiner
Mischung von Talk und Ton, werden gemischt, gemahlen und in Form einer
Verstäubungsformulierung verwendet.
Im folgenden werden die Ergebnisse der Wirksamkeitstests der erfindungsgemässen Verbindungen als
Agrikulturchemikalien gezeigt.
Testbeispiel 1: Test gegen piricularia oryzae der Reispflanzen (Topf-Test). Reispflanzen (JukkokuArt) werden in Töpfen mit 12 cm Durchmesser eingesetzt, Eine Verbindung der vorliegenden
Erfindung in Form des entsprechenden emulgierbaren Konzentrats, das nach der in Arbeitsbeispiel 2
beschriebenen Methode hergestellt wurde, wurde zur vorgeschriebenen Konzentration von 500 ppm
verdünnt. Die Lösung wurde auf die Reispflanzen im Sprossstadium aufgesprüht. Dieses Aufsprühen
wurde durchgeführt, indem man die Töpfe auf einem drehbaren Tisch montierte, der sich in
Verbindung mit der aus der Düse der Sprühpistole abgegebenen Chemikalienmenge bewegte. Die
Chemikalienlösung wurde in einer Menge von 50 cm3pro 3 Töpfe, bei einem Druck von 1,5 kg/cm2
aufgesprüht, so dass die Blätter tropfnass wurden.
Die so besprühten Reispflanzen wurden am nächsten Tag in eine Kammer gegeben und dort bei einer
relativen Feuchtigkeit von 100 % und einer temperatur von 25 C zwei Tage lang belassen. In dieser
Zeit wurde eine wässrige Sporensuspension vongezüchteter piricularia oryzae durch zweimaliges
Sprühen zur Infektion der Reispflanzen aufgebracht.
7 Tage nach der Besprühung wurde der Befallsgrad pro Topf ausgewertet und nach dem folgenden
Standard eineGrakdeinteilung getroffen, die von 0 bis 5 reicht.
Gleichzeitig wurde auch die Phytotoxizität auf den Reispflanzen ermittelt.
Infektionsqrad Prozentsatz der Fläche der Krank heitsflecken O 0
0,5 >; 2 l 3-5
56/612
2 6 - 10
311 - 20 %
4 21 - 40 %
5 ; 41
Testbeispiel 2: Test gegen hypochnus sasakii von Reis (Topf Test)Reispflanzen (Kinmaze-Art) werden
in unglasierten Töpfen mit einem Durchmesser von 12 cm aufgezogen. Auf diese Reispflanzen wurde
bei Beginn des Sprossstadiums eine verdünnte Lösung einer Verbindung gemäss der vorliegenden
Erfindung, die nach dem Testbeispiel 1 hergestellt wurde, aufgesprüht.
Am nächsten Tag wurde das Sclerotium des hypochnus sasakii, welches aufGerstenkörnern zehn Tage
lang gezüchtet wordenwar,'am Unterteil der Test-Reispflanzen aufgebracht. Die behandelten Pflanzen
wurden in einer Kammer bei einer relativen Feuchtigkeit von 95 % oder mehr und Temperaturen von
28 bis 30 C acht Tage lang stehen gelassen, um die Erkrankung zur Wirkung zu bringen.
Der Grad der Entwicklung dieser Krankheit wurde ausgewertet und auf Grund der Entwicklung von
Krankheitsfleckchen vom Fuss der Reispflanzen her, wo die Infektion stattfand, klassifiziert. Die
Schädigungsrate wurde nach der folgenden Formel berechnet
3n3 + 2n2+ n1 +OnO
Schädigungsrate =- x 100
3N Darin bedeutet N die Gesamtzahl der behandelten Stengel,n0 die Zahl der Stengel, an denen keine
Entwicklung der Krankheit beobachtet werden konnte,nl die Zahl der Stengel, auf welchen die
Krankheit bis zur ersten Blattscheide vom Boden her beobachtet wurde, n2 die Zahl der Stengel, auf
denen die Entwicklung der-Krankheit vom Boden bis zur zweiten Blattscheide beobachtet wurde, und
n3 die Zahl der
Stengel, auf denen die Entwicklung der Krankheit vom Boden bis, zur dritten Blattscheide beobachtet
werden konnte.
Tabelle2:
Testergebnis der Untersuchungen gegen piricularia oryzae und hypochnus sasakii von Reis
Verbin- Konzentra- Infektions- Schädigungs- Phytotoxizi dung tionen wirk- grad bei pi- rate bei hy- tät
samen Bestand-ricularia pochnus sasa teil oryzae kii
Nr.1500 ppm 2,0 6,0
Nr.2 500 1,5 12,5
Nr.3 500 1,8 16,4
Nr.4 500 18,6# Nr. 4 500 1,8 5,4
Nr.6 500 2,0 15,1
Nr.7 500 12,0
Nr.8 500 10,8
Nr.9 500 9,0
Nr.10 500 15,1 Nr.ll 500 16,5
Nr.12 500 20,0
Nr.13 500 14,8
Nr.14 500 2,0 12,0
Nr.15 500 17,3
Nr.16 500 16,7
Nr.17 500 1,5 21,5# Nr. 18 500 2,0 13,3
Nr.19 500 1,8 25,5
Nr.20 500 2,0 16,6
Nr.21 500 15 ; 1
Nr.22 500 14,3
Nr.23 500 2,0 8,6 >;RTI (0ommerzielles Pro dukt,Vergleich) 500 1,8 26,6 -nicht behandelt - 5,0 68,9
Anmerkunaen: 1. Die Verbindungsnummern entsprechen denen der
Tabelle 1.
2. IBP: O,O-Diisopropyl-S-benzyl,thiophosphat.
3. Der Infektionsgrad ist der Mittelwert aus drei ge testeten Töpfen.
4. Phytotoxizität:"-" bedeutet, dass kein schädlicher
57/612
Einfluss auf das Wachstum der Reispflanzen beobach tet werden konnte.
Testbeispiel 3: Test bezüglich der fungiziden Wirkung gegen verschiedene phytopathogene
Pilze(Agar-Verdünnungsmethode).
Eine Verbindung gemäss der vorliegenden Erfindung wurde in eine Reihe von KartoffelAgarkulturnährböden eingebracht, -so dass die vorgeschriebenen Konzentrationen der wirksamen
Verbindungen darin enthalten waren. Nachdem diese Nährböden in Petrischalen mit einem
Durchmesser von 9 cm übergeführt und fest geworden waren, wurden sie mit den entsprechenden
phytopathogenen Pilzen infiziert.
Nach 4 Tagen der Kultur bei27 0C wurden die Wachstumsbedingungen der pathogenen Pilze
ausgewertet und in einem Gradschema von O(kein Wachstum) bis 5 (Wachstum wie bei
nichtbehandelten Töpfen) klassifiziert.
Tabelle 3: Testergebnisse bezüglich der fungiziden Wirkung gegen verschiedene phatopathoqene
Pilze(Aqar-Verdünnunqsmethode) Verbin- Wirkstoff- Piricu- Pellicu- Alter- Elsinoe Botrytis dung
konzentra- laria laria naria fawcetti cinerea tion ppm oryzae sasakii kikuchi ana
31,3 0 2,0 3,5 0,7 3,0 Nr.l 125,0 0 0,8 2,0 0 2,0
500,0 0 0,5 1,5-Ö 0,5
31,3q 1,0 3,0 0,5 3,0 Nr.5 125,0 Q 0,8 1,5 0 1,5
500,0 0 0,5 1,0 0 0,5 unbehan delt -5,0 - 5,0 5,05.9 5,0 Anmerkung: Die Verbindungsnummern
entsprechen denen in Tabelle 1.
Testbeispiel 4: Test gegen Unkräuter von Reisfeldern- Testmethode: Nach Füllung von Töpfen mit
1/5000 a Oberfläche mit frischer Reisfelderde, wurden junge Reispflanzen (Kinmaze-Art) im 3. bis
4.Blattstadium in die Töpfe bei Überschwemmungsbedin- gungen eingepflanzt. Nachdem die
Keimlinge Wurzeln gefasst hatten, wurden Echinochloa crus galli - Samen von breitblättrigen
Unkräutern und Eleocharis acicularis gepflanzt. Die Verbindungen gemäss der Erfindung, die in eine
emulgierbare konzentrierte Lösung oder ein benetzbares Pulver übergeführt wurden, wurden in
Mengen von 500, 250 und 125 g Gehalt an wirksamer Substanz pro 10 a aufgesprüht. Nach drei
Wochen wurde der herbizide Effekt gegen Echinochloa crus galli, Eleocharis acicularis und
breitblättrige Unkräuter sowie die Phytotoxizität auf die Reispflanzen geprüft.
Auswertung: Herbizide Wirksamkeit Phytotoxizität 5 höchste Wirksamkeit 5 höchste Phytotoxizität 4
grosse IIlt 4 grosselt lt 3 mittlere " " 3 mittelgrosse "2 kleine " tt 2 mittlere II " 1 sehr kleinelt 1
kleine II II 0 keineII lt 0 keine " " Tabelle 4:: Testergebnis bezüglich der herbiziden Wirkung gegen
Unkräuter von
Reisfeldern und der Phytotoxizität >;RTI gegenüber Reis Verbin- Wirkstoff- Herbizide Wirkung auf
Phytotoxizität dung menge in Ech-ino- Eleocharis breitblättr. auf Reis g/10 a chloa acicularis Unkraut
crusqalli Nr.1 500 5 4 5 0
250 4 3 4 0
125 3 - 4 3 3 0
500 4 - 5 4 5 0 Nr.2 250 4 3 4 - 5 0
125 3 3 4 0 Verbin- Wirkstoff- Herbizide Wirkung auf Phytotoxizität dung menge in EchinoEleocharis breitblättr. auf Reis g/10 a chloa acicularis Unkraut crus galli
500 4 4 5 0 Nr.3 250 3 - 4 3 4 0
125 3 3 3 0
500 4 - 5 4 5 0 Nr. 4 250 4 3 5 0
125 3 3 4 0
500 4 4 5- 0 Nr.5 250 3 - 4 4 4 0
125 3 3 3 0
500 4 - 5 4 4 - 5 0 Nr.6 250 4 3 4 0
125 3 3 3 0
500 5 5 5 0 Nr.7 250 5 5 5 0
125 5 4 - 5 5 0
500 5 5 5. 0 Nr.8 250 4 3 4 0
125 3 3 4 0
500 5 5 5 0 Nr.9 250 5 5 5 0
58/612
125 5 4 - 5 5 0
500 5 5 5 0 Nr. 10 250 5 5 5 0
125 5 5 5 0
500 5 5 5 0Nr.ll 250 5 5 5 0
125 5 5 5 0
500 5 5 5 0 Nr. 12 250 5 5 5 0
125 5 4 4 0
500 5 4 5 0 Nr. 13 250 4 - 5 4 4 0
125 4 3 3 0 Verbin- Wirkstoff- Herbizide Wirkung auf Phytotoxizität dung menge in EchinoEleocharis breitblättr. auf Reis g/10 a chloa acicularis Unkraut crus qualli
500 5 5 5 0 Nr.14 250 5 4 - 5 5 0
125 5 4 5 0
500 5 5 5 0 Nr.15 250 5 4 - 5 5
125 5 4 4 - 5 0
500 5 5 5 0 Nr.16 250 5 5 4 - 5 0
125 5 3 4 0
500 5 5 5 0 Nr.17 250 54-5 4-5 0
125 4 - 5 4 4 0
500 4 3 - 4 5 0 Nr.18 250 4 3 5 0
125 3 3 4 0
500 5 5 5 0 Nr.19 250 5 4- 5 5 0
125 4 - 5 4 5 0
500 5 4 5 0 Nr.20 250 4 3 4 0
125 3 3 3 0
500 4 4 4 - 5 0 Nr.21 -250 4 3 4 0
125 3 3 3 0
500 4 4 5 0 Nr.22 250 3 - 4 3 4 0
125e3 3 3 0
500 4 4 5 0 Nr.23 2503 - 4 4 5 0
125 3 - 4 3 4 0 PCP(kom- 500 5 3 40 merzielles Produkt, 250 3 0 2 0 Vergleich) NIP(kom- 40 5 5 5 3
merziellesProdukt, 20 3 1 2 1Vergleich 1 0 0 0 nmerkungen::>;/RTI; 1. Die Nummern der
Verbindungen in dieser Tabelle ent sprechen denen in Tabelle 1.
2. breitblättrige Pflanzen sind: Monochoria vaginalis,
Rotala indica, Lindernia pyxidaria, Dopatrium junceum usw.
Testbeispiel 5: Test gegen Unkräuter von Trockenfeldern.
Testmethode: Nachdem man Töpfe von 30 x 30 cm mit Erde von diluvialen vulkanischen Aschen
gefüllt hat, werden Saaten der unten angeführten Unkräuter, Trockenreis (Hataminori-Art) und Gemüse
ausgesät. Nach Bedeckung mit Erde wird eine Verbindung gemäss der vorliegenden Erfindung in ihrer
Formulierung des emulgierbaren Konzentrats oder benetzbaren Pulvers auf die Oberfläche des Bodens
in einer Menge von400, 200 und 100 g aktiver Verbindung pro 10 a aufgesprüht.
Nach drei Wochen wird der herbizide Effekt gegen verschiedene Arten von Unkräutern, die
Phytotoxizität gegenüber dem Trockenreis und gegenüber gewissen Gemüsen bestimmt, was aus der
nächsten Tabelle ersichtlich ist.
T a b e l l e 5 : Herbizide Wirkung gegen Unkräuter von Trockenfeldern und Phytotoxizität gegenüber
verschiedenen Feld bauprodukten Verbin- Wirkstoff- Herbizide Wirkung Phytotoxizität dung menge
Echino- Finger- Fuchsschwanz wilder Portu- Trok- Japan. Gurke Toma- Karot g/10 a chloa crus gras
gras Amarat lak ken- Ret- te te galli reis tich
400 5 5 5 5 5 0 0 1 0 0
Nr. 10 200 5 5 5 5 5 0 0 0 0 0
100 5 5 5 5 5 0 0 0 0 0
Nr. 11 400 5 5 5 5 5 0 0 0 0 0
200 5 5 5 5 5 0 0 0 0 0
100 5 5 4-5 5 4-5 0 0 0 0 0
400 5 5 5 5 5 0 0 1 0 0
59/612
Nr. 16 200 5 5 4-5 5 5 0 0 0 0 0
100 5 5 4 4 4-5 0 0 0 0 0 CAT 100 5 5 5 5 5 2 3 2 2 2 (Vergleich) 50 4 4 5 5 5 0 1 1 1 1 NIP 400 5 5 5
5 5 3 1 5 5 5 (Vergleich) 200 5 5 4 5 5 0 0 2 2 3 unbehandelt - 0 0 0 0 0 0 0 0 0 0 Anmerkun-gen: 1.
Die Verbindungsnummern entsprechend denen in Tabelle 1.
2. CAT: 2-Chlor-4,6-bis(äthylam,ino)-1,3,5-triazin (Handelsprodukt)
3. MIP: 2,4-Dichlorphenyl-4'-nitrophenyläther (Handelprodukt)>;/RTI;Data supplied from the
esp@cenet database - Worldwide
Claims:
Claims of DE2022524
Pa tentansprilc he1) Fungizide und herbizide Mittel, gekennzeichnet durch einen Gehalt an einem
Phosphorsäureester der Formel
EMI21.1
in welcher R1 und R2 Je einen Alkylrest mit 1 bis 6Kohlenstoff- atomen oder einen Cycloalkylrest
mit 1bip 6 Kohlen stoffatomen, X ein Sauerstoff- oder Schwefelatom, Z ein Wasserstoffatom oder
einen Methylrest und Y einen Aralkylrest oder einen Rest der allgemeinen
Formel
EMI21.2
inwelcher W ein Wasserstoff- oderilalogenatom oder einen Nitro oder einen Alkylrest mit 1 bis 4 CAtomen bedeutet.
EMI21.3
>;tb;
>;SEP; 4
>;tb; gekennzeichnet! >;SEP; daa >;SEP; hoepherstSesfier >;SEP; gemäss >;SEP; Anspruch >;SEP; 1
>;tb; >;SEP; 6/,
>;tb;
EMI21.4
3) Verwendung vonPhosphorsäureestegemäss Anspruch 1 zur Bekämprung von Pilzen und
Unkräutern.
*) Verfahren zurherstellung von fungiziden und herbiziden Mitteln, dadurch gekennzeichnet, dass
man Phosphorsäureester gemäss Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln
vermischt.Data supplied from the esp@cenet database - Worldwide
60/612
5. EP0190105
- 8/6/1986
HERBICIDAL AGENT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=EP0190105
Inventor(s):
FORY WERNER DR (--); NYFFELER ANDREAS DR (--); GERBER HANSRUDOLF DR (--); MARTIN HENRY DR (--)
Applicant(s):
CIBA GEIGY AG (CH)
IP Class 4 Digits: A01N; C07D
IP Class:A01N57/22; A01N25/32; A01N47/36; C07D407/12; C07D317/58; C07D217/06; A01N43/90;
A01N43/84; A01N43/78; A01N43/76; A01N43/60; A01N43/40; A01N43/36; A01N43/30; A01N37/18
E Class: A01N25/32; C07F9/32A1; C07F9/40A1; A01N47/36; C07D217/06; C07D317/58
Application Number:
EP19860810046 (19860127)
Priority Number: CH19850000418 (19850131)
Family: EP0190105
Equivalent:
JP61176504; EP0190105; BR8600383
Cited Document(s):
US4343649; EP0147365; DE332474; GB747592; DE2218097; US3982923
Abstract:
Abstract of EP0190105
There is described a selective herbicidal agent which contains, besides inert additives, a) the
herbicidally active sulphonylurea N-(2-methoxycarbonyl-1- phenylsulphonyl)-N'-(bisdifluoromethoxypyrimidin-2-yl)-urea of the formula I and b) to increase the tolerance of the crop, a
non-phytotoxic amount of a dichloroacetamide of the formula II where Ra and Rb independently of one
another are in each case hydrogen, an unsubstituted or substituted alicyclic hydrocarbon radical, or one
of the two radicals is an amine, or the two radicals together with the nitrogen atom to which they are
bonded are also a 5-12-membered heterocyclic radical. The composition is suitable for controlling
weeds in crops of useful plants, for example cereals, maize, rice, millet, etc.Description:
Description of EP0190105
Herbizides Mittel Die Erfindung betrifft ein selektiv wirkendes Mittel, welches als herbiziden
Wirkstoff den SulfonylharnstoffN-(2-Methoxycarbonyl)- phenylsulfonyl-N-(4s6-bisdifllJoromethoxy-pyrimidin-2-yl)-harnstoff der Formel I enthält
EMI1.1
zusammen mit einem antagonistisch wirkenden Amid der Dichloressigsäure (Antidote), der Formel II
EMI1.2
worin Ra undRb unabhängig voneinander je Wasserstoff einen unsubstituierten oder substituierten
alicyclischen Kohlenwasserstoffrest oder eines davon einen Aminorest oder beide zusammen mit dem
Stickstoffatom, an das sie gebunden sind auch einen 5-12-gliedrigen heterocyclischen Rest bedeuten,
welche die Toleranz der Kulturpflanzen gegenüber der phytotoxischen Wirkung erhöht, ohne dass
deswegen die Herbizidwirkung gegenüber den Unkräutern merklich abfällt.Die Erfindung betrifft
ebenfalls die Verwendung dieses Mittels zur Unkrautbekämpfung in Nutzpflanzenkulturen.
Der Sulfonylharnstoff als Herbizid ist bekannt, siehe beispielsweise die EP-A 84 020, ZA 127/83, USP
4,478,635.
61/612
N-(2-MethoxyCarbonyl)phenylsulfonyl-N'-(4,6-bis-difluormethoxy-pyri- midin-2-yl)-harnstoff ist ein
Herbizid mit recht starker Wirkung.
Dies bringt die Gefahr schädigender Ueberdosierung mit sich.
Schadwirkungen sind nicht nur auf Ueberdosierung zurückzuführen, sie können auch auftreten wegen
abnormalen klimatischen Verhältnissen oder wegen Vorbehandlung des Bodens.
Es hat sich deshalb als wünschenswert erwiesen, die Resistenz oder Toleranz der Kulturpflanzen
gegenüber der phytotoxischen Wirkung der Sulfonylharnstoff-Herbizide zu erhalten. Im US Patent No.
4 343 649 wird beschrieben, dass die bekanntenHerbizid-Antidoten 1,8-Naphthalinsäureanhydrid,
N,N-Diallyldichloracetamid sowiea-Cyano-methoxi- imino-2-phenylacetonitril diese Aufgabe
erfüllen, wenn man sie in Nutzpflanzenkulturen gleichzeitig mit-dem Sulfonylharnstoff-Herbizid
verwendet. Hingegen ist die Toleranz dieser bekannten Herbizid Safener-Mischungen speziell in
Maiskulturen für einen praktischen Einsatz ungenügend.
Ueberraschenderweise wurde nun gefunden, dass sich die Toleranz von Kulturpflanzen speziell Mais
gegenüber der phytotoxischen Wirkung des obigen Sulfonylharnstoff-Herbizides stark erhöht, ohne
dass dadurch die Herbizidwirkung auf die Grosszahl der Unkräuter und Ungräser beeinträchtigt wird,
wenn man das Sulfonylharnstoff Herbizid zusammen mit einem Amid der Dichloressigsäure verwendet
welches als Herbizid-Antagonist oder Antidot wirkt.
Die Herstellung desN-(2-Methoxyzarbonylphenylsulfonyl)-N'-(4,6-bis- >; difluormethoxy)-pyrimidin2-yl-harnstoffes der Formel I geschieht nach an sich bekannten Methoden und ist z.B. in der
veröffentlichten Europäischen Patentanmeldung EP-A 84 020 beschrieben.
Man setzt beispielsweise in einem inerten organischen Lösungsmittel 2Methoxycarbonylphenylsulfonylamid mit dem 2-Phenoxycarbamat des 4,6-bis(difluoromethoxy)pyrimidins um gemäss dem Reaktionsschema:
EMI3.1
Ferner kann man ebenfalls in einem inerten organischen Lösungsmittel das 2Methoxycarbonylphenylsulfonylisocyanat mit 2-Amino-4,6bis(difluoromethoxy)pyrimidin umsetzen,
gemäss dem Reaktionsschema
EMI3.2
Ebensogut kann man in einem inerten organischen Lösungsmittel2-Methoxycarbonyl-phenylsulfonamid mit 2-Isocyanato-4,6-bis(difluormehoxy)pyrimidin umsetzen gemäss dem
Reaktionsschema
EMI3.3
Schliesslich kann man in einem inerten organischen Lösungsmittel, das Phenoxycarbamat des 2Methoxycarbonylphenylsulfonamides mit dem2-Amino-4, 6-bis(difluoromethoxy)pyrimidin umsetzt,
gemäss dem Reaktionsschema
EMI3.4
Die Umsetzungen werden vorteilhafterweise in aprotischen, inerten, organischen Lösungsmitteln
vorgenommen wie Methylenchlorid, Tetrahydrofuran, Acetonitril, Dioxan, Toluol.
Die Reaktionstemperaturen liegen vorzugsweise zwischen-20' ; und+1200C. Die Umsetzungen
verlaufen im allgemeinen leicht exotherm und können bei Raumtemperatur durchgeführt werden.
Zwecks Abkürzung der Reaktionszeit oder auch zum Einleiten der Umsetzung wird zweckdienlich für
kurze Zeit bis zum Siedepunkt des Reaktionsgemisches aufgewärmt. Die Reaktionszeiten können
ebenfalls durch Zugabe von äquimolaren oder katalytischen Mengen von Basen verkürzt werden.
Als Basen können sowohl organische Basen wie Amine, wieTriathyl- aminsChinunlidin, Pyridin etc.
als auch anorganische Basen wie Hydride wie Natrium- oder Calciumhydrid, Carbonate wie Natriumund Kaliumcarbonat verwendet werden.
Das Endprodukt kann durch Einengen und/oderVerdpfen des Lösungsmittels isoliert und durch
Umkristallisieren oder Zerreiben des festen Rückstandes in Lösungsmitteln in denen es sich nicht gut
62/612
lösten, wie Aether, aromatischen Kohlenwasserstoffen oder chlorierten Kohlenwasserstoffen gereinigt
werden.
Die Wirkstoffe der Formel I sind stabile Verbindungen. Ihre Handhabung bedarf keiner vorsorglichen
Massnahme.
Die Zwischenprodukte zur Herstellung desN-(2-Methoxycarbonyl-phenyl- sulfonyl-N'-[4,6-bis(difluoromethoxy)pyrimidin-2-yl]-harnstoffes sind bekannt oder können nach bekannten Methoden
hergestellt werden.
Als Gegenmittel oder Antidot zum Sulfonylharnstoff der Formel1 werden erfindungsgemäss Amide
der Dichloressigsäure der Formel II verwendet.
Eine grössere Anzahl dieser Verbindungen sind als Safener oder Antidotes für Herbizide mit anderer
als Sulfonylharnstoff-Struktur beschrieben worden. Solche Herbizide müssen in vielen Fällen in
höheren Aufwandmengen angewendet werden. Ueberraschenderweise hat es sich nun gezeigt, dass sie
auch ganz besonders den Sulfonylharnstoff der Formel I, welcher eine sehr starke herbizide Wirkung
aufweist, kulturspezifisch speziell in Maiskulturen zu antagonisieren vermögen.
Die Verbindungen der Formel II bis XVI sind zum Schützen von Kulturpflanzen gegen die
schädigende Wirkung desSulfonylharn- stoffes geeignet und können daher in bezug auf ihre
Anwendung in Kombination mit dem vorgenannten Herbizid als Gegenmittel,1:Antidote11 oder auch
als "Safener" bezeichnet werden.
Ein solches Gegenmittel oder Antidote kann je nach Anwendungszweck zur Vorbehandlung des
Saatgutes der Kulturpflanze (Beizung des Samens oder der Stecklinge) eingesetzt oder vor oder nach
der Saat in den Boden gegeben werden. Es kann aber auch für sich allein oder zusammen mit dem
Herbizid vor oder nach dem Auflaufen der Pflanzen appliziert werden. Die Behandlung der Pflanze
oder des Saatgutes mit dem Antidote kann daher grundsätzlich unabhängig vom Zeitpunkt der
Applikation der phytotoxischen Chemikalien erfolgen. Die Behandlung der Pflanzen kann jedoch
durch gleichzeitige Applikation des Sulfonamides der Formel I und des Gegenmittels (Tankmischung)
erfolgen. Die preemergente Behandlung schliesst sowohl die Behandlung derAnbaufläche vor der
Aussaat (ppi- pre plant incorporation) als auch die Behandlung der angesäten, aber noch nicht
bewachsenen Anbauflächen ein.
Die Aufwandmengen des Gegenmittels im Verhältnis zum Herbizid richten sich weitgehend nach der
Anwendungsart. Bei einer Feldbehandlung, bei der Herbizid und Gegenmittel entweder gleichzeitig
(Tankmischung) oder separat appliziert werden, liegt das Verhältnis der Mengen von Gegenmittel zu
Herbizid im Bereich von 1:100 bis 5:1.
In der Regel wird bei einem Mengenverhältnis von Gegenmittel zu Herbizid von 1:5 bis 1:50 die volle
Schutzwirkung erreicht. Bei der Samenbeizung und ähnlichen gezielten Schutzmassnahmen werden
jedoch weit geringere Mengen Gegenmittel im Vergleich mit den später pro Hektar Anbaufläche
verwendeten Mengen an Herbizid benötigt. Im allgemeinen werden bei der Samenbeizung pro kg
Samen 0,1 - 10 g Gegenmittel benötigt. In der Regel wird mit 0,1 - 5 g Gegenmittel pro kg Samen
bereits die volle Schutzwirkung erreicht. Falls das Gegenmittel kurz vor der Aussaat durch
Samenquellung appliziert werden soll, so werdenzweckmässig Lösungen des Gegenmittels verwendet,
welche den Wirkstoff in einer Konzentration von 1 - 10'000 ppm enthalten. In der Regel wird mit
Konzentrationen des Gegenmittels von 100 - 1'000 ppm die volle Schutzwirkung erreicht.
-In der Regel liegt zwischen protektiven Massnahmen, wie Samenbeizung und Behandlung von
Stecklingen mit einem Gegenmittel der Formel II und der möglichen späteren Feldbehandlung mit
Agrarchemikalien ein längerer Zeitraum. Vorbehandeltes Saat- und Pflanzengut kann später in der
Landwirtschaft, im Gartenbau und in der Forstwirtschaft mit unterschiedlichen Chemikalien in
Berührung kommen.
Erfindungsgemässe Mittelkönnen gegebenenfalls zusätzlich jene Agrarchemikalien enthalten, vor
deren Einfluss die Kulturpflanze geschützt werden soll.
63/612
Als Kulturpflanzen gelten im Rahmen vorliegender Erfindung alle Pflanzen, die in irgendeiner Form
Ertragsstoffe, wie Samen, Wurzeln, Stengel, Knollen, Blätter, Blüten, ferner Inhaltsstoffe, wie Oele,
Zucker, Stärke, Eiweiss usw., produzieren und zu diesem Zweck angebaut werden. Zu diesen Pflanzen
gehören beispielsweise sämtliche Getreidearten, wie Weizen, Roggen, Gerste und Hafer, daneben vor
allem Reis, Kulturhirse, Mais, Baumwolle, Zuckerrüben, Zuckerrohr, Soja, Bohnen und Erbsen.
Das Gegenmittel kann überall dort eingesetzt werden, wo eine Kulturpflanze der vorgenannten Art vor
der phytotoxischen Wirkung desN-(2-Methoxyearbonylphenylsulfonyl)-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl-harnstoffes der Formel I geschützt werden soll.
Als Antogonisten oder Gegenmittel werden erfindungsgemäss Dichloracetamide entsprechend der
Formel II verwendet
EMI7.1
In dieser Formel bedeuten R und a Rb unabhangig voneinander je Wasserstoff, einen Alkyl-, Alkenyl, einen Cycloalkyl-, Cycloalkenyl-Rest welcher unsubstituiert oder durch Halogen, Cyano; Hydroxy;
Alkylcarbonyloxy; Alkenylcarbonyloxy; Alkinylcarbonyloxy; Alkoxyalkylcarbonyloxy;
Alkylcarbonylthio; Alkoxycarbonyloxy; Formyloxy; Benzoyloxy; subst. Benzoyloxy;
Haloalkylcarboxy; Alkyloxy; Alkenyloxy; Alkinyloxy; Phenyloxy; subst. Phenyloxy; Heterocyclyloxyund Heterocyclylthio; subst. Heterocyclyloxy- und Heterocyclylthio; Alkylthio; Alkenylthio;
Phenylthio; subst.Phenylthio; Alkoxyalkoxy; Alkoxyalkoxyalkoxy; Alkenyloxyalkoxy; Tetraalkoxy;
Alkylthioalkoxy; Carbamoyloxy; N-mono- und di-Alkylcarbamoyloxy; N-Cycloalkyl- und N, N,NAlkylencarabamoyloxy; Carbamoylthio; Heterocyclyl- und substituiertes
Heterocyclylaminocarbonyloxy; N-mono- unddi-Alkylcarbamoylthio; Thiocarbamoylthio; N-monounddi-Alkylthiocarbamoylthlo; N-Cycloalkyl- undN, N-Alkylenthiocarba- moylthio; Alkyl- und
Alkenylsulfinyl; Alkyl- und Alkenylsulfonyl; Alkyl- und Alkenylsulfonyloxy; Phenyl- und
substituiertes Phenylsulfonyloxy; Phenylsulfinyl und -sulfonyl; substituiertes Phenylsulfinyl und sulfonyl; Heterocyclyl- und substituiertes Heterocyclylsulfonyl; Sulfamoyl; N-Alkyl-, -N-Cycloalkyl-,
N-Phenyl-, substituiertes N-Phenylsulfamoyl, Heterocyclyl- und substituiertes
Heterocyclylsulfamoyl;N-Alkenyl-, N,N-di-Alkyl-, N,N-di-Alkenyl, N,N-Alkyl, Alkenyl-Sulfamoyl;
Aminooxy; Mono- und di-Alkylaminooxy; Alkylcarbonylaminooxy; Phenyl-und substituiertes
Phenylcarbonylaminooxy; Alkanaliminooxy; Benzaldehyd- und substituiertes Benz aldehydiminooxy;
Dialkylketoniminooxy; Phenylalkylketoniminooxy; Dialkylphosphoryl; Phenyl-, Alkyl-Phosphoryl;
Amino; Anilino; substituiertes Anilino; Heterocyclylamino- und substituiertes Heterocyclylamino;
Mono- und di-Alkylamino; Alkenylamino; Alkinylamino; di-Alkenylamino; di-Alkinylamino; N,NAlkyl, Alkenylamino; N,N,N-trialkylammonium; Alkylamido; Alkenylamido; Alkinylamido; Alkyl-Nalkylamido; Benz- und substituiertes Benzamido; Phenylalkylamido; Phenylalkyl-N-alkylamido; Benzund substituiertes Benz-N-Alkylamido; Heterocyclylamido- und substituiertes Heterocyclylamido;
Haloalkyl und-Alkoxyalkylamido;Haloalkyl und AlkoxyN-alkylamido;
Alkoxycarbonylamino;Alkoxyzarbonyl-N-alkylamino; Alkenyloxycarbonylamino- und N-Alkylamino; Hydroxy- und Alkoxyamino; Hydroxy-undAlkoxy-N-Alkylamino; Alkenyloxyamino; Phenylund Alkylaminocarbonylamino; N-Phenyl-N-Alkylaminocarbonylamino; N,NAlkylenaminocarbonylamino; N-Phenyl-N-Alkylaminocarbonyl-Nalkylamino;NPhenylaminocarbonyl-N"-alkylamino; N,N' -di- und tri-Alkylaminocarbonylamino; Heterocyclyl- und
substituiertes Heterocyclylaminocarbonylamino; N-Heterocyclyl- und substituiertes Heterocylyl-N,N'mono- und di-alkylaminocarbonylamino; Alkyl- undAlkenylsulfonylamino; AlkylundAlkenylsulfonyl-N-alkylamino; Phenyl- und substituiertes Phenylsulfonylamino;Phenyl- und
substituiertesPhenylsulfonyl-N-alkylamino; Heterocyclyl- und substituiertes
Heterocyclylsulfonylamino; Alkanal-imino; Benzaldehyd- und substituiertes Benzaldehydimino;
Phenyl- und substituiertes Phenylalkylketonimino; Dialkylketonimino; Guanidino;N,Nt,N''-mono-ditri-und tetra-Alkylguanidino; Amidino; N,N'-mono-undDialkylamidino, Phenyl- und substituiertes
Phenylamidino; Phenyl- und substituiertes Phenyl-N,N'-mono-und di-alkylamidino; Dialkylphosphonyl; Alkyl-oalkylphosphinyl; Alkyl- und Alkenyloxycarbonyl; Phenylalkyloxycarbonyl;
Alkyl- undAlkenylthiocarbonyl; Alkoxyalkoxycarbonyl; Haloalkyloxycarbonyl; Aminocarbonyl;
mono- und di-Alkylaminocarbonyl; mono und di-Alkenylaminocarbonyl; mono- und diAlkinylaminocarbonyl; Phenyl-und substituiertesPhenylalkylaminocarbonyl; Anilino- und
substituiertes Anilinocarbonyl;N-Phenyl- & alkylamino- carbonyl; N,N-Alkylenaminocarbonyl;
Cycloalkylamino- und cycloalkyl N-alkylaminocarbonyl; Hydroxy- und Alkoxyaminocarbonyl;
Haloalkyl und Alkoxyalkylaminocarbonyl; Formyl; Alkyl- und Alkenyl-und Alkinylcarbonyl; Phenylund substituiertes Phenylalkylcarbonyl; Phenyl- und substituiertes Phenylalkenylcarbonyl; Benzoyl;
64/612
substituiertes Benzoyl; Heterocyclylcarbonyl; substituiertes Heterocyclylcarbonyl; Phenyl; Naphthyl;
substituiertes Phenyl- und Naphthyl; Heterocyclische Reste; substituierte heterocyclische Reste
substituiert sein kann.Weiter bedeuten Ra undRb unabhängig voneinander Alkinyl; durch Phenyl,
substituiertes Phenyl, Halogenalkyl, Alkylthio- und Alkenylthioalkyl, Phenylthio- und substituiertes
Phenylthioalkyl, Alkoxy- und Phenoxyalkyl, Alkoxycarbonyl, Aminocarbonyl, mono- und diAlkylaminocarbonyl, Anilino- und substituiertes Anilinocarbonyl, N-Anilino- und substituiertes
Anilino-N Alkylaminocarbonyl,N,N-Alkylenaminocarbonyl, Heterocyclyl- und substituiertes
Heterocyclylaminocarbonyl, Aminoalkyl, mono- und di-Alkyl- und Alkenylaminoalkyl,N, NAlkylenaminoalkyl, Anilino-und substituiertes Anilinoalkyl, Phenyl- und substituiertes
Phenylalkylaminoalkyl, Heterocyclylamino- und substituiertes Heterocyclylaminoalkyl, Heterocyclylund substituiertes Heterocyclylaminoalkylaminoalkyl, substituierter Alkinylrest.Phenyl- und
Naphthylreste, heterocyclische Reste und benzannellierte Heterocyclen können ihrerseits ein- oder
mehrfach durch Halogen; Nitro; Cyano; Pseudohalogen; Alkyl- und Alkenyloxy; Alkyl-und
Alkenylthio; Alkyl; Alkenyl; Alkinyl; Phenylalkinyl; Alkylsulfinyl und -sulfonyl; Hydroxycarbonyl;
Alkoxy- und Benzyloxycarbonyl; Alkenyloxycarbonyl; Alkylendioxy; Aminocarbonyl; mono-und diAlkylaminocarbonyl; Amino; Ammonio; mono- und di-Alkylamino; Alkan- und Alkencarbonyl;
Phenyloxy; durch Halogen, Halogenalkyl, Nitro, Alkoxy, Alkylthio, Alkyl, substituiertes Phenyloxy;
Sulfo; Di-Alkylphosphoryl- und phosphonyl; Sulfamoyl; mono- und di-Alkyl-sulfamoyl; mono- und
di-und tri-Halogenalkyl; Alkylsulfinyl- und -sulfonyl; substituiert sein.
Einer der Reste Ra undRb kann auch Amino; mono- oder di-Alkyl und Alkenylamino; mono- oder diAlkinylamino; substituiertes oder unsubstituiertes Phenylalkylamino; substituiertes oder
unsubstituiertes N-Phenylalkyl-N-alkylamino; substituiertes oder unsubsti tuiertes Heterocyclylamino;
substituiertes oder unsubstituiertesN-Heterocyclyl-N1-Alkylamino; Alkanalimino, substituiertes oder
unsubstituierteBenzaluehydimino, Dialkylketonimino, substituiertes oder unsubstituiertes
Phenylalkylketonimino; Alkyloxycarbonylaminound N-Alkylamino; substituiertes oder
unsubstituiertes Phenylalkoxycarbonylamino- und N-Alkylamino; durch1-3-Alkyl substituiertes
Ureido; durch 1-2 Alkyl substituiertes Phenylureido; durch 1-2 Alkyl substituiertes
Heterocyclylureido;Alkyl-, Alkenyl- und Alkinylamido und N-Alkylamido; substituiertes und
unsubstituiertes Phenylalkylamido; substituiertes und unsubstituiertes Phenyl- und Heterocyclylamido;
substituiertes und unsubstituiertes Phenyl- und Heterocyclyl-N-Alkylamido; Alkylkoxy- und
Alkylthiothionoamino bedeuten, wobei die Alkylreste wie oben angegeben, substituiert sein können.
Unter Alkylresten werden Reste mit 1 bis 18 Kohlenstoffatomen verstanden. Diese Reste können
geradkettig oder verzweigt sein. Die gebräuchlichsten Reste sind beispielsweise Methyl, Aethyl, nPropyl, Isopropyl, n-Butyl, Isobutyl, sek.Butyl, tert.Butyl, n-Pentyl, Isopentyl, n-Hexyl und n-Octyl.
Die Alkenyl- und Alkinylreste können ebenfalls geradkettig oder verzweigt sein und umfassen 3 bis 18
Kohlenstoffatome. Die am verbreitesten Reste sind beispielsweise Allyl, Methallyl, Buten, Butadien,
Propinyl, Methylpropinyl, 1-Butinyl, 2-Butinyl. Cycloalkyl- oder Cycloalkenylreste haben
vorzugsweise 3 - 12 Kohlenstoffatome, sie können auch benzanneliert sein. Typische Vertreter sind
beispielsweise Cyclopropyl, Cyclopentyl, Cyclohexyl, Cyclohexenyl, Indan, Tetrahydronaphthalin,
Decalin. Unter Halogen wird Fluor, Chlor, Brom, Jod, insbesondere Fluor und Chlor
verstanden.Halogenalkyl- und Halogenalkenyl-Reste können ein- oder mehrfach mit Halogen
substituiert sein.
Die obgenannten alicyclischen und cyclischen Kohlenwasserstoffreste können unsubstituiert oder
substituiert sein. Typische Substituenten dieser Reste sind beispielsweise die Halogenatome, über
Sauerstoff, Schwefel oder eine Iminogruppe gebundene Alkyl-, Alkenyl-, Alkinyl-, oder Cycloalkyl-,
Aryl- oder Aralkylreste die ihrerseits wieder substituiert sein können. Diese Substituenten können aber
auch über eine Sulfinyl-, Sulfonyl-, Carbonyl-, Carbonyloxy, Carbonylthio, Carbamoyl-, Sulfamoyloder eine Amino-oxybrücke an die alicyclischen Kohlenwasserstoffreste gebunden sein.
Die Reste R undR, können zusammen mit dem Stickstoffatom an das a sie gebunden sind auch einen
gesättigten oder gesättigten 5 bis 12-gliedrigen Heterocyclus bilden, der noch ein zwei oder drei
weitere Heteroatome oder eine Sulfinyl- resp. Sulfonylgruppe enthält, durch ein oder zwei
Carbonylgruppen unterbrochen sein kann, und welcher benzannelliert, unsubstituiert oder substituiert
sein kann.
65/612
Als Heteroatome kommen dabei ein zwei oder drei weitere Stickstoffatome, bis zwei Schwefel- oder
Sauerstoffatome in Frage, wobei 2 Sauerstoffatome nicht direkt benachbart sein können Beispiele für
solche Heterocyclen, sind untenstehend aufgeführt: Pyrrolin, Pyrrolidin, Imidazolin, Imidazolidin,
Pyrazolin, Pyrazolidin, Isocazolin, Isocazolidin, Oxazolin, Oxazolidin, Isothiazolidin, Thiazoline,
Thiazolidine, Dithiazolidine, Oxadiazolidine, Piperidin, Piperazin, Tetrahydropyrimidin und -pyrazin,
Morpholin, Thiomorpholin, Thiazine, Hexahydrotriazine, Tetrahydrotriazine, Oxadiazine, Oxatriazine,
Hexahydroazepin, Hexahydrodiazepine, Diazepine, Hexahydrooxazepine, Azacyclooctan, Indolin,
Isoindolin, Benzimidazolin, Benzindazolin, Benzoxazolin, Benzthiazoline, Benzisoxazolin,
Benztriazol, Tetrahydrochinolin, Tetrahydroisochinolin, Tetrahydro-chinolin, -chinazolin, -chinoxalin,
-phtalazin, Benzmorpholin, Benzothiomorpholin, Tetrshydrobenzazepine und -diazepine,
Tetrahydrobenzoxazepine, 1,5-diazabicyclo[4,3,0j-nonane, Dihydrobenzoxazine, 1,6diazabicyclo[5,3,0]decane, 1,4-diazabicyclot3,3,03Octane, 1,5-diazabicyclo[4,4,0]decane.
Oben erwähnte Heterocyclen können auch die Bedeutung von Substituenten haben. Weitere Beispiele
von heterocyclischen Systemen mit Substituentenfunktion sind beispielsweise Pyrrol, Imidazol,
Pyrazol, Isoxazol, Oxazol, Isothiazol, Thiazol, Triazole,Oxadiazole, Thiadiazole, Tetrazole,
Oxatriazole, Thiatriazole, Furan, Tetrahydrofuran, Dioxole, Dioxolane, Oxathiole, Oxathiolane,
Thiophen, Tetrahydrothiophen, Dithiolane, Dithiazole, Pyridin, Pyrane, Thiopyrane, Pyridazin,
Pyrimidin, Pyrazin, Tetrahydropyran, Tetrahydrothiopyran, Dioxine, Dioxane,Dithiine, Dithiane,
Oxazine, Thiazine, Oxathiine, Oxathiane, Triazine, Oxadiazine, Thiadiazine,Oxathiazine, Dioxazine,
Azepine, Oxepine, Thiepine, Diazepine,Oxazepine, Indole, Benzofurane, Benzothiophene, Indazole,
Benzimidazole,Benzdioxole, Benzdithiole, Benzisoxazole, Benzthiazole, Benzoxazole, Benzoxathiole,
Benztriazole, Benzoxadiazole, Benzofurazan, Benzothiadiazole, Chinolin, Isochinolin, Chromene,
Chroman, Isochromen, Isochroman, Thiochromene, Isothiochromene, Thiochroman, Isothiochroman,
Cinnolin, Chinazolin, Chinoxalin, Phtalazin, Benzdioxine, Benzdithiine, Benzoxazine, Benzdioxane,
Benzoxathiane, Benzotriazine, Benzazepine, Benzdilazepine, Benzoxazepine, Purine, Pteridine,
Phenoxazine, Phenothiazine.
Die heterocyclischen Reste können wie oben erwähnt substituiert sein.
Die Verbindungen der Formel II sindgrösstenteils aus der Literatur bekannt oder können nach
bekannten Methoden hergestellt werden.
Die Dichloramide der Formel II werden z.B. hergestellt, indem man ein Dichloressigsäurehalid, z.B.
das Chlorid oder Bromid in einem inerten organischen Lösungsmittel, mit einem Amin der
FormelHNR ,Rb umsetzt entsprechend dem Reaktionsschema
EMI12.1
Ac steht für ein Halogenatom oder einen Rest -OCOCHClz.
Die Reaktion wird zweckmässigerweise in einem reaktionsinerten Lösungsmittel bei Normaldruck
durchgeführt. Als Lösungsmittel eignen sich beispielsweise aliphatische oder aromatische
Kohlenwasserstoffe wie Benzol, Toluol, Xylole, Cyclohexan, Petroläther; halogenierte
Kohlenwasserstoffe wie Chlorbenzol, Methylenchlorid, Aethylenchlorid, Chloroform; Aether
undätherartige Verbindungen wie Diäthyläther, Diisopropyläther, t-Butylmethyläther,Dimethoxyäthan,
Dioxan, Tetrahydrofuran, Anisol; Ketone wie Aceton, Methyläthylketon; Ester wie Aethylacetat,
Butylacetat und Gemische solcher Lösungsmittel untereinander.
Als säurebindende Mittel sind Basen, insbesondere tertiäre Amine wie Trimethylamin, Triäthylamin,
Chinuclidin,1,4-Diazabicyclo-(2,2,2)- octan, 1,5-Diazabicyclo(4,3,0)non-5-en oder 1,5Diazabicyclo(5,4,0)undec-7-en geeignet. Es können aber auch anorganische Basen wie Hydride wie
Natrium- oder Calciumhydrid, Hydroxide wie Natrium- und Kaliumhydroxid, Carbonate wie Natriumund Kaliumcarbonat oder Hydrogencarbonate wie Kalium- oder Natriumhydrogencarbonat verwendet
werden.
Die Dichloracetamide der Formel II sind grösstenteils bekannt und in vielen Publikationen beschrieben.
Sie können nach bekannten Methoden hergestellt und entsprechend ihrer chemischen Struktur
verschiedenen Untergruppen zugeordnet werden: Eine erste Gruppe wird durch die Verbindungen der
Formel II verkörpert,
EMI13.1
66/612
worin R Wasserstoff, C1-C8-Alkyl oder C3-C8-Cycloalkyl, a unsubstituiert oder durch-PO(R1)(R2)
, -NR3R4, (O)mCOOR5i -(X )mCX R6, O(AO)m 1R7, -XR7, Cyano-, X"'-Het, Het, C5-C6Cycloalkyl,CR(OR8)(0Rg) oder Halogen substsituiert, oder R ist ein C3-C8-Alkenyl- oder C3-C8Cycloalkenylrest, der unsubstituiert oder durch Halogen, Phenyl, C5-C6-Cycloalkyl oder C1-C4-Alkyl
substituiert ist, oder R ist ein C3-C8-Alkinylrest, der unsubstituiert oder durch Phenyl substituiert ist,
wobei die Phenylkerne unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4Alkoxy,Cl-C4-Halogenalkoxy, Methylthio, Cyan oder Nitro substituiert sind, oder R ist ein Allkoxyiminoalkylrest -CH(Rr) a C{R8)=NORt, R und R je Wasserstoff oder C1-C4-Alkyl und Rt t r s 14 t
Wasserstoff C1-C6-Alkyl,C3-C-Alkenyl oderC3-C 6-Alkinyl, Rb Wasserstoff, dasselbe wie R oder
einen Rest -NR3R4,
EMI14.1
A eineC 1-C4-Alkylenkette,
A1 eineC 1-C8-Alkylenkette die geradkettig oder verzweigt ist und die unsubstsituiert oder durch
Cyan oderCl-C4-Alkoxy oder einen
Alkylamido- oder Halogenalkylamido-Rest substituiert ist,
Het einen gegebenenfalls durch C1-C4-Alkyl, C1-C4-Alkoxy,C1-C4-Alkoxycarbonyl oder C1-C4Alkylthio optimal substituierten
5-6-gliedrigen Heterocyclus mit 1-3 Heteroatomen resp.S(0)1,
Gruppen, wobei Sauerstoff und Schwefel nie direkt benachbart im Ring vorhanden sein können,
sondern in einer 1.3-Anwendung vorliegen müssen, wie im 1,3-Dioxolan-2-yl-, 1,3-Dioxan-2-yl oder
dem
2,4-Dioxan-1-ylrest und welcher zusätzlich durch R in der n l-Stellung und R' an einem Ring
Kohlenstoffatom substituiert sein n kann, n Null oder eine Zahl von 1 bis 3, m Null oder Zahl 1, m'
Null oder 1-4, n' Null oder 1-2, R, R', R1 und R2 unabhängig voneinander Je C1-C4-Alkyl oderC1C4-Alkoxy, R3 Wasserstoff,C1-C4-Alkyl oder C3-C8-Cycloalkyl, R4 Wasserstoff,C1-C4-Alkyl,
Phenyl, durch Halogen,C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Halogenalkyl oderC 1-C4Alkoxy
substituiertes Phenyl oder einen Rest -COOR'5 odaer-COR' 6' R5 und R'5 unabhängin voneinander je
C1-C4-Alkyl, oder C1-C4-Aralkyl wobei der Phenylkern unsubstituiert oder durch Halogen, C1-C4Alkyl,C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio, Cyan oder Nitro
substituiert ist, R6 und R'6 unabhängig voneinander je Wasserstoff, C1-C4-Alkyl,C1-C4-Halogenalkyl,
C2-C5-Alkoxyalkyl, Phenyl oderC1-C4-Aralkyl, wobei der Phenylkern unsubstituiert oder durch
Halogen, C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio,
Cyan oder Nitro substituiert ist, oder R6 und R'6 bedeuten einen C2-C4-Alkenyl- oder einen RestN(R12)(Rl3), R7 Wasserstoff,C1-C4-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, Phenyl und Phenyl(C1C4)Alkyl, wobei die Phenylkerne durch Halogen,C1-C4Alkyl, C1-C4Alkoxy oder C1-C4
Halogenalkyl substituiert sind, R8 undRg unabhängig voneinander je C1-C6-Alkyl oder C3-C6Alkenyl R10C1-C4-Alkyl, C3-C6-Alkenyl, C2-C6-Alkoxyalkyl,C1-C4-Halogenalkenyl oder in
Zusammenhang mit 2 Sauerstoffatomen auch eine C1-C5-Alkylenbrücke, R11 Wasserstoff oder C1C4-Alkyl und R12 und R13 unabhängig voneinander je Wasserstoff, Cl-C8Alkyl, C3-C8-Cycloalkyl,
C3-C8-Alkenyl, Phenyl oderC1-C4Aralkyl wobei der Phenylkern unsubstituiert oder durch
Halogen,Cl-C4-Alkyl, C1-C4-Halogenalkyl,C1-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio,
Cyano, Nitro und R12 und R13 zusammen eine C1-C7-Alkylenkette, die durch Sauerstoff, Schwefel, ;
NH, oder ; N(C1-C4)-Alkyl unterbrochen sein kann.
Z Wasserstoff, C1-C4-Alkyl, Halogen, C1-C4-Halogenalkyl, Nitro,C1-C4-Alkoxy, C1 -C4Halogenalkoxy, C2-C8-Alkoxyalkoxy, der Dioxymethylenrest, ein 1.3-Dioxolan-2-yl- oder1,3Dioxan-2-ylrest, der über eineC 1-C4-Alkylenbrücke gebunden sein kann bedeuten.
X', X' ; , X", X"' Sauerstoff, Schwefel, X Sauerstoff, Schwefel -S(0)1, Solche Verbindungen sind zum
Teil in den veröffentlichten Patentanmeldungen resp. den Patentschriften BE-A 884,911, DE-A
2,747,814, DE-A 2,855,229, EP-A 31 686, HU-A T-26,239A, USP 3,923,494, 4,021,224, 4,396,419,
4,400,203, 4,443,628 sowie der schweizerischen Patentanmeldung4,202/84-0 beschrieben. Folgende
Dichloracetamide eignen sich erfindungsgemäss als Antidote zum Sulfonylharnstoff der Formel I
besonders gut.
Tabelle 1 Nr. R a 1.1 -CH2CH=Ch2 -CH2CH=CH2 1.2 -CH2CH=CH2 -C2H5 1.3 -CH2CH=CH2 C2H4CN 1.4 -CH2CH=CH2 -H 1.5 -C3H7n -CH(CH3)CN 1.6 -CH2PO(OC2H5)2 H 1.7 -C(CH3)3 H
1.8 Cyclopropyl H 1.9 -CH2CH=CH2 -CH2C(CH3)=CH2 1.10 -CH2CH=CH2 -CH2C=CH 1.11-
67/612
CH2CH-CHz -CH2CC1=CH2 1.12 -C2H5 -CHzCCl=CH2 1.13 -CH2CH(CH2)2 C2H4OCH2CH=CH2 1.14 -Cyclopropyl -CH2-CH=CH2 1.15-CH2CH2CH2 -CH(CH3)CN 1.16CH2CCl=CH2 -CH2CCl=CH2 1.17 -CH2CCl=CH2 H 1.18--CH2CH-CHCl -CH2-CH-CHCl 1.19 CH2CH(C2H5)C4H2n -CH(CH3)CH2OCH3 1.20 -CH2CH=CHCL H 1.21 -C3H7n C(CN)(CH3)2
1.22-CH(CH3)2 -CH2COOC2H5 1.23 -CH2CH=CH2-CH2-C0N(CH2CH=CH2)2 1.24 -C2Hs CH2COOC3H7n 1.25 -CH2N(CH3)COCC12CH3 H Tabelle 1 (Fortsetzung) Nr. Ra 1.26(CH2)3NHCOCHC12 H 1.27 -CH2CH=CH2-CH2PO(OC3H7iso)2 1.28 -NHCOOBenzyl CH2PO(OC2H5)2 1.28 -CH(CH3 -CH(CH3)2 1.30 -C4H9n -C2H4CN 1.31 -CH(CH3)2-CzH4CN
1.32 -CH3-C2H4CN 1.33 -CH2CH=CH2 -CH(CH3)CH2OCH3 1.34 -NHCOO Benzyl CH2PO(CH3=OCH(CH3)2 1.35 -NHCOO Benzyl -CH2PO(C2H5)OCH(CH3)2 1.36 -NHCOOC2H5 CH2PO(OC3H7iso)2 1.37 -CH2CH=CH2 -CH2OC2H4OC2H5 1.38-NHCOOC2H5 CH2PO(CH3)OCH2CH(CH3)2 1.39 -CH2CH=CH2 -CH2CONHCH2CH=CH2 1.40 -NHCOOC2H5 CH2PO(OC2H5)2 1.41 -CH2CH=CH2 -CH2OC2H4OCH3 1.42 -CH2CH=CH2-(C2H40)2- C4H9n
1.43-CH2C=#CH -(C2H4O)3-CH3 1.44 -CH2CH=CH2 -(C2H4O2)2CH2CH=CH2 1.45 CH2CH=CH2 -(C2HO)3CH2CH=CH2 1.46 -NHCOO Benzyl -CH2PO(CH3)OC2H5 1.47 CH2CH=CH2 -CH2CH(COCH2)2 1.48 -CH3 -CHO 1.49-(CH2)8NHC0CHCl2 H 1.50 (CH2)6NHCOCHCL2 H Tabelle 1 (Fortsetzung)
EMI19.1
>;tb; Nr. >;SEP; R
>;tb; >;SEP; a >;SEP; b
>;tb; >;SEP; a >;SEP; D
>;tb; 1.51 >;SEP; H >;SEP; H
>;tb; 1.52 >;SEP; -CH2CH-CHCH2N(C3H7n) >;SEP; -C3H7n
>;tb; >;SEP; CoCHC12
>;tb; 1.53 >;SEP; -CH(OH)C13 >;SEP; H
>;tb; 1.54 >;SEP; -CH(CH3)NHCOCHC12 >;SEP; K
>;tb; 1.55 >;SEP; -CH3 >;SEP; -CH2CN
>;tb; 1.56 >;SEP; -C(CH3)=C(CH3) >;SEP; 2 >;SEP; -CzH4OC2H5
>;tb; 1.57 >;SEP; -C2H40CH3 >;SEP; H
>;tb; 1.58 >;SEP; -C2H40CH(CH3)2 >;SEP; -C2H40CH(CH3)2
>;tb; >;SEP; 0
>;tb; >;SEP; II
>;tb; 1.59 >;SEP; -CH2CH3CH2 >;SEP; -CH2-NH-C-CC13
>;tb; 1.60 >;SEP; -C2Hs >;SEP; -CH(CH3)COOCH3
>;tb; 1.61 >;SEP; -C3H60CH3 >;SEP; -CH2NHCOCH2C1
>;tb; 1.62 >;SEP; -CH3 >;SEP; -CH2NHCOCHC12
>;tb; 1.63 >;SEP; -CH2N >; CH3)COCH2Cl >;SEP; H
>;tb; 1.64 >;SEP; -CH3 >;SEP; -C3H6NHCOCHCl2
>;tb; 1.65 >;SEP; -CHa >;SEP; -CzH4-N(CH3)COCHClz
>;tb; 1.66 >;SEP; -C2H5 >;SEP; -CHzNHCOCHzCl
>;tb; 1.67 >;SEP; -NHCOOC4Hgt. >;SEP; -CH2PO(OC2Hs)2
>;tb; 1.68 >;SEP; -C(COOCH3)=C(CH3)2 >;SEP; H
>;tb; 1.69 >;SEP; -(C2H4O)3CH3 >;SEP; H
>;tb; 1.70 >;SEP; -CH >;SEP; -(C2fl40)3CH3
>;tb; 1.71 >;SEP; -NHCOCHC12 >;SEP; -CH2PO(CH3)0C3H7lso
>;tb; 1.72 >;SEP; 3,5,5-Trimethyl- >;SEP; -CH2CH=CH2
>;tb; >;SEP; cyclohex-l-en-yl
>;tb; 1.73 >;SEP; 1-Cyclohexylvinyl >;SEP; -CH9n
>;tb; Tabelle 1 (Fortsetzung)
EMI20.1
>;tb; Nr.>;SEP; R
>;tb; >;SEP; a
>;tb; 1.74 >;SEP; C2H5 >;SEP; -CH2CN
>;tb; 1.75 >;SEP; C3H7i >;SEP; -NHCOCH2C1
>;tb; 1.76 >;SEP; C3H71 >;SEP; -CHzCH2-NHCOCHC12
68/612
>;tb; 1.77 >;SEP; C2H >;SEP; -CH2CH2-NHCOCHCl2
>;tb; 1.78 >;SEP; CH3-9H-COOC2H5 >;SEP; H
>;tb; 1.79 >;SEP; H >;SEP; -(C2H40)2C4Hg-n
>;tb; 1.80 >;SEP; NHCOOC2H5 >;SEP; -CH2PO(CH3)0CzHs
>;tb; 1.81 >;SEP; NHCOCH2CHz-ev >;SEP; - >;SEP; -CH2-PO(OC2Hs)2
>;tb; 1.82 >;SEP; NHCOOC2H5 >;SEP; -CH2Po(oC2H5)2
>;tb; 1.83 >;SEP; NfCOCHzCH2- >;SEP; H
>;tb; 1.84 >;SEP; NHCOOC2HS >;SEP; -CH(C2H5)PO(CzH5)(0C2H5)
>;tb; 1.85 >;SEP; NHCOOC2H5 >;SEP; -CH( >;SEP; j)PO(OC2H5)2
>;tb; 1.86 >;SEP; NHCOCHzH4~( >;SEP; II
>;tb; >;SEP; =w
>;tb; 1.87 >;SEP; NHCOCHz >;SEP; zu >;SEP; -CHzPO(OC3H7-1)2
>;tb; 1.87 >;SEP; NHCOCHz >;SEP; /
>;tb; 1.88 >;SEP; NH2 >;SEP; -CH2PO(OC2Hs)z
>;tb; 1.89 >;SEP; H >;SEP; -CH2COOC2H5
>;tb; 1.90 >;SEP; H >;SEP; -CH2CONHCH3
>;tb; 1.91 >;SEP; H >;SEP; -CHZCH2-ss-C-CHC12
>;tb; >;SEP; /0
>;tb; >;SEP; CH3
>;tb; 1.92 >;SEP; H >;SEP; -CHz-t
>;tb; 1.93 >;SEP; H >;SEP; -CH2CH2--e~CKC12
>;tb; >;SEP; Hj
>;tb; 1.94 >;SEP; HCwCCH2- >;SEP; HC >;SEP; HCmCCH2 Tabelle 1 (Fortsetzung)
EMI21.1
>;tb; Nr. >;SEP; R >;SEP; Rb
>;tb; >;SEP; a
>;tb; >;SEP; o
>;tb; 1.95 >;SEP; CH3 >;SEP; -C3H6-ss-C-CHC12
>;tb; >;SEP; CHJ
>;tb; >;SEP; CR
>;tb; 1.96 >;SEP; -NHCO-f >;SEP; f >;SEP; -CH2P0(0C2Hs)2
>;tb; >;SEP; =
>;tb; >;SEP; C1/
>;tb; >;SEP; /OCH3
>;tb; 1.97 >;SEP; -NHCOw >;SEP; -OCH3 >;SEP; -CHz-PO(OC2H5)2
>;tb; >;SEP; =
>;tb; >;SEP; OCH3
>;tb; >;SEP; FHJ
>;tb; >;SEP; >;SEP; CH3
>;tb; 1.98 >;SEP; -CzH5 >;SEP; - >; >;SEP; /
>;tb; >;SEP; .~ >;SEP; .
>;tb;
>;SEP; CH3
>;tb; 1.99 >;SEP; -CH2CH=CH2
>;tb; >;SEP; .~ >;SEP; .
>;tb;
>;SEP; cS3
>;tb; >;SEP; H3
>;tb; 1.100 >;SEP; -CH2-CH=CH2
>;tb; >;SEP; iH3
>;tb; >;SEP; CH3
>;tb; >;SEP; CH3
>;tb; >;SEP; / >;SEP; TCHB
>;tb; 1.101 >;SEP; -C3H7-n >;SEP; /
>;tb; >;SEP; CH3
69/612
>;tb; 1.102 >;SEP; -NHCOO-C(CH3CC1 >;SEP; -CHzPO(oc2Hs)z
>;tb; 1.103 >;SEP; -NHCOOCHzCCl3 >;SEP; -CH2PO(OC2H5)2
>;tb; 1.104 >;SEP; -NHCO--/ >;SEP; \- >;SEP; -CH2PO(OC3K7-l)z
>;tb; >;SEP; ~s
>;tb; >;SEP; -.-CH3
>;tb; >;SEP; / >;SEP; CH3
>;tb; 1.105 >;SEP; -CH2-CmCH >;SEP; "
>;tb; >;SEP; 'CH
>;tb; >;SEP; sCH3
>;tb; 1.106 >;SEP; -CH2-CH=CH2 >;SEP; -CH2OCH2CH=CH2
>;tb; Die Fahigkeit der Verbindungen der Formel II, junge Maispflanzen vor der phytotoxischen
Wirkung vonN-( 2-Methoxycarbonylphenylsulfonyl)- N'-(4',6'-bis-difluormethoxypyrimidin-2-yl)harnstoff zu schützen, wurde gemäss Beispiel 1 geprüft. Die Resultate sind in der Tabelle la
zusammengefasst.
Beispiel 1: Tankmischung Vorauflauf in Mais Plastiktöpfe (oberer Durchmesser 11 cm. Inhalt 500
ccm) werden mit sandig toniger Lehmerde gefüllt. Acht Maissamen der Sorte 'LG-11' werdeneingesät
und mit Erde bedeckt und anschliessend angegossen.
Die Testpflanzen werden im Gewächshaus kultiviert und im 2- bis 3-Blattstadium mit den
Prüfsubstanzen behandelt. Die als Safener zu prüfende Substanz wird in Wasser gelöst und zusammen
mit dem Herbizid der Formel I in der gegebenen Aufwandmenge auf die Pflanzen gesprüht. 21 Tage
nach der Applikation wird die Schutzwirkung des Safeners in Prozent bonitiert. Als Referenz dienen
dabei mit Herbizid allein behandelte Pflanzen (keine Schutzwirkung) sowie die vollständig
unbehandelte Kontrolle (100X Wachstum). Die Resultate sind in der Tabelle la zusammengefasst.
Tabelle la Herbizid Antidote relative Aufwandmenge No. Aufwandmenge Schutzwirkung 400 g/ha 1.1
200 g/ha 75 % 400 g/ha 1.1 100 g/ha 60 % 400 g/ha 1.1 50 g/ha 40 % 200 g/ha 1.1 200 g/ha 60 % 200
g/ha 1.1 100gha 60 % 200 g/ha 1.1 50 g/ha 60 % 200 g/ha 1.1 25 g/ha 65 XO 100 g/ha 1.1 100 g/ha
30 % 100 g/ha 1.1 50 g/ha 10 % 100 g/ha 1.1 25 g/ha 30 % 100 g/ha 1.1 12,5 g/ha 35 % 400 g/ha 1.2
400 g/ha 25 % 400 g/ha 1.2 200 g/ha 35 % 200 g/ha 1.2 200 g/ha 10 % 400 g/ha 1.3 400 g/ha 25 %
400 g/ha 1.3 200 g/ha 20 % 200 g/ha 1.3 200 g/ha 25 % 200 g/ha 1.3 100 g/ha 20 % 400 g/ha 1.4
400 g/ha 50 % 400 g/ha 1.4 200 g/ha 45 % 200 g/ha 1.4 200 g/ha 20 % 200 g/ha 1.4 100 g/ha 35 %
400 g/ha 1.5 400 g/ha 35 % 400 g/ha 1.5 200 g/ha 45 % 200 g/ha 1.5 200 g/ha 40 % 200 g/ha 1.5 100
g/ha 25 % 400 g/ha 1.6 400 g/ha 15% 400 g/ha 1.6 200 g/ha 35 % 200 g/ha 1.6 200 g/ha 25 % 200
g/ha 1.6 100 g/ha 20 % 400 g/ha 1.7 400 g/ha 10 % 400 g/ha 1.7 200 g/ha 10 % 200 g/ha 1.7 100 g/ha
25 % 400 g/ha 1.8 400 g/ha 30 % 400 g/ha 1.8 200 g/ha 35 % 200 g/ha 1.8 200 g/ha 25 % 200 g/ha
1.8 100 g/ha 25 % Tabelle la (Fortsetzung) Herbizid Antidote relative Aufwandmenge No.
Aufwandmenge Schutzwirkung 400g/ha 1.9 400 g/ha 35 % 400 g/ha 1.9 200 g/ha 40 % 200 g/ha 1.9
200 g/ha 35 % 200gSha 1.9 100 g/ha 35 % 400 g/ha 1.10 400 g/ha 65 % 400 g/ha 1.10 200 g/ha 50 %
200 g/ha 1.10 200 g/ha 25 % 200 g/ha 1.10 100 g/ha 35 % 400 g/ha 1.11 400 g/ha 45 % 400 g/ha
1.11 200 g/ha 45 % 200 g/ha 1.11 200 g/ha 35 % 200 g/ha 1.11 100 g/ha 35 % 400 g/ha 1.12 400 g/ha
40 % 400 g/ha 1.12 200 g/ha 30 % 200 g/ha 1.12 200 g/ha 35 % 200 g/ha 1.12 100 g/ha 30 % 400
g/ha 1.13 400 g/ha 5 % 400 g/ha 1.13 200 g/ha 10 % 200 g/ha 1.13 200 g/ha 20 % 200 g/ha 1.13 100
g/ha 20 % 400 g/ha 1.14 400 g/ha 30 % 400 g/ha 1.14 200 g/ha 30 % 200 g/ha 1.14 200 g/ha 30 %
200 g/ha 1.14 100 g/ha 25 % 400 g/ha 1.15 400 g/ha 35 % 400 g/ha 1.15 200 g/ha 45 % 200 g/ha 1.15
200 g/ha 40 % 200 g/ha 1.15 100 g/ha 25 7O 400 g/ha 1.17 400 g/ha 35 % 400 g/ha 1.17 200 g/ha 30
% 200 g/ha 1.17 200 g/ha 30 % 200 g/ha 1.17 100 g/ha 25 % 400 g/ha 1.19 400 g/ha 5 % 400 g/ha
1.19 200 g/ha 10 % 200 g/ha 1.19 200 g/ha 25 % 200 g/ha 1.19 100 g/ha 30 >;tb; >;SEP; n >;SEP; a
>;tb; 2.46 >;SEP; - >;SEP; ~ >;SEP; -CH2- >;SEP; C3H6-OC2Hs
>;tb; 2.47 >;SEP; - >;SEP; ~ >;SEP; -CH2- >;SEP; C2H4-0C2H5
>;tb; 2.48 >;SEP; - >;SEP; ~ >;SEP; -C2H4 >;SEP; -CH2-CH(OCH3)2
>;tb; 2.49 >;SEP; 2,5(OCH3)2 >;SEP; -CHz- >;SEP; -CH(CH3)2
>;tb; 2.50 >;SEP; 4-oCH3 >;SEP; - >;SEP; -C(CH3) >;SEP; 2- >;SEP; H
>;tb; 2.51 >;SEP; - >;SEP; ~ >;SEP; -CH2-CH(CH3)- >;SEP; -CH(CH3)z
>;tb; 2.52 >;SEP; 3,4(OCH3)2 >;SEP; - >;SEP; -CH(CH3)- >;SEP; H
>;tb; 2.53 >;SEP; 2,4(OCH3)2 >;SEP; - >;SEP; -CH2- >;SEP; -CH(CH3)2
>;tb; 2.54 >;SEP; 2,3(ocH3)2 >;SEP; - >;SEP; -CH2- >;SEP; -CH(CH3)2
>;tb; 2.55 >;SEP; 3-OCH3 >;SEP; - >;SEP; -CH2- >;SEP; -CH(CH3)2
70/612
>;tb; 2.56 >;SEP; - >;SEP; 4-CH3 >;SEP; -CR2- >;SEP; -GzH4-OCzHs
>;tb; 2.57 >;SEP; - >;SEP; in >;SEP; ~ >;SEP; ~B~ >;SEP; in >;SEP; H
>;tb; >;SEP; Po( >;SEP; ac >;SEP; z >;SEP; fi >;SEP; 5 >;SEP; ) >;SEP; z
>;tb; 2.58 >;SEP; 2,4(0CH3) >;SEP; 2 >;SEP; - >;SEP; -CH2- >;SEP; H
>;tb; 2.59 >;SEP; 2,4(0CH3)2 >;SEP; - >;SEP; -CH2- >;SEP; H
>;tb; 2.60 >;SEP; - >;SEP; -CH(CH3)- >;SEP; H
>;tb; 2.61 >;SEP; - >;SEP; 2-CH3 >;SEP; -CHz- >;SEP; H
>;tb; 2.62 >;SEP; - >;SEP; ~ >;SEP; -CzH4 >;SEP; CH3
>;tb; >;SEP; (CH3)z
>;tb; 2.63 >;SEP; -) >;SEP; - >;SEP; CH2 >;SEP; HN=' >;SEP; \
>;tb; >;SEP; (CH3)2
>;tb; 2.64 >;SEP; 3,4 >; OCH3)2 >;SEP; ~ >;SEP; -CH-H- >;SEP; H
>;tb; >;SEP; COCHC12
>;tb; 2.65 >;SEP; 3-OCHz0-4 >;SEP; - >;SEP; C2H4 >;SEP; CH(CH3)2
>;tb; Tabelle 2 (Fortsetzung) Nr.Z A1 R a 2.66 H sche Basen sind geeignete Grundstoffe zur
Herstellung weiterer sekundärer Amine.So entsteht z.B. aus 3,4-Methylendioxybenzyliden-butylamin
und Isopropylmagnesiumjodid die folgende Gleichung (siehe Naturwissenschaften 48 129 (1961)
EMI41.2
Als weiteres Beispiel für die Herstellung von Aminen der Formel III sei die Anlagerung von
Allylmercaptane an Schiff'sche Basen erwähnt, z.B. von 3,4-Methylendioxybenzoliden-allylamin und
Methylmercaptan gemäss dem Schema:
EMI41.3
(siehe EP 93 610) Ebenso erhält man durch Umsetzung von Schiff'schen Basen mit Trichloressigsäure
nach der folgenden Gleichung z.B.N-(a-Trichlor- methyl-3,4-methylendioxybenzyl)-N-isopropyl-amin
EMI42.1
Durch geeignete Reduktion der entsprechend kernsubstituierten Phenylessigsäurealkylamide,z.B. des
3,4-Methylendioxyphenylessigsäure-N-isopropylamides mit Lithiumaluminumhydrid bzw.Boran
entstehen weitere Phenylalkylamine der Formel III
EMI42.2
(siehe dazu auch DE-OS 1 959 898) Verwendet manN >; 3,4-Methylendioxybenzyl)dichloracetamid
und Allylchlorid als Ausgangsstoff, solässt sich der Verlauf des erfindungsgemässen Verfahrens durch
das folgende Formelschema wiedergeben.
EMI42.3
Verwendet man N-Allyl-N-dichloracetamid und 3,4-Methylendioxybenzylchlorid als
Ausgangsmaterial, so lässt sich der Verlauf der erfindungsgemässen Verfahren durch das folgende
Formelschema wiedergeben:
EMI42.4
Zur Herstellung desanspruchsgemäss substitutierten N-Benzyl-Nalkoxy-iminoäthyldichloracetamide der allgemeinen Formel
EMI43.1
wobei die Substituenten R , R und R der in der Formel III r s t gegebenen Bedeutung entsprechen,
stehen verschiedene Verfahren zur Verfügung (D-OS 3 004 871) a) Durch Umsetzung der
Säurechloride der Formel AccocHcl2 worin Ac ein Halogenatom oder den Rest -O-CO-CHC12
darstellt, mit dem Amin der FormelIIIb'
EMI43.2
wobei R , R vornehmlich Wasserstoff bedeuten und Rt Methyl,
8 Aethyl und Allyl bedeuten b) oder Halogenacylamine der Formel
EMI43.3
worin Rs Wasserstoff oder methyl bedeutet mit HClX 200 g/ha 2.5 100 g/ha 40gZha 2.11 25 g/ha 30
Nr. >;SEP; Het >;SEP; R11 >;SEP; R9
>;tb; >;SEP; -(CHz)
>;tb; >;SEP; n
>;tb; 3.1 >;SEP; 1,3-Dioxolan-2-yl >;SEP; -CHzCHz- >;SEP; -CHzCHICH2
>;tb; 3.2 >;SEP; lH-Indol-3-yl >;SEP; -CH2CH2 >;SEP; H
>;tb; 3.3 >;SEP; 2-Furyl >;SEP; -CH2- >;SEP; -CHzCOOCH3
>;tb; 3.4 >;SEP; 2-Pyridyl >;SEP; -CHz- >;SEP; H
>;tb; 3.5 >;SEP; 4-Pyridyl >;SEP; -CH2- >;SEP; -CH2OH2OH
71/612
>;tb; 3.6 >;SEP; 3-Pyridyl >;SEP; -CH2- >;SEP; -CHzCH2OH
>;tb; 3.7 >;SEP; 3-Pyridyl >;SEP; -CH2- >;SEP; H
>;tb; 3.8 >;SEP; 4-Pyridyl >;SEP; -CHz- >;SEP; H
>;tb; 3.9 >;SEP; 2-Pyridyl >;SEP; -CH2- >;SEP; CH3
>;tb; 3.10 >;SEP; 1,3-Dioxolan-2-yl >;SEP; -CH2- >;SEP; -CH2-CHICH2
>;tb; 3.11 >;SEP; 2-Furyl >;SEP; -CH2- >;SEP; H
>;tb; 3.12 >;SEP; 2-Furyl >;SEP; -CH2- >;SEP; -CH(CH3)z
>;tb; 3.13 >;SEP; 2-Furyl >;SEP; -CH2- >;SEP; -CzH5
>;tb; 3.14 >;SEP; 2-Furyl >;SEP; -CH2- >;SEP; -nO3H7
>;tb; 3.15 >;SEP; 2-Furyl >;SEP; -OH2 >;SEP; -C(CH3)3
>;tb; 3.16 >;SEP; 2-Furyl >;SEP; -CH2- >;SEP; 2-Furyl
>;tb; 3.17 >;SEP; 2-Furyl >;SEP; -CH2- >;SEP; 2-Tetrahydro
>;tb; >;SEP; furfuryl
>;tb; 3.18 >;SEP; 3-Tetrahydro- >;SEP; -CH2- >;SEP; H
>;tb; >;SEP; furfuryl
>;tb; 3.19 >;SEP; 2-Methyl-1,3- >;SEP; -OH2 >;SEP; H
>;tb; >;SEP; dioxolan-2-yl
>;tb; Die Fähigkeit der Verbindungen der Formel III, junge Maispflanzen vor der phytotoxischen
Wirkung von N-(2-Methoxycarbonylphenyl3ulfonyl)-N'-(4',6'-bis-difluormethoxypyrimidin-2-yl)harnstoff zu schützen, wurde gemäss Beispiel 1 geprüft. Die Resultate sind in der Tabelle 3a
zusammengefasst.
Tabelle 3a Herbizid Antidote relative Aufwandmenge No. Aufwandmenge Schutzwirkung 400 g/ha 3.1
400 g/ha 25 % 400 g/ha 3.1 200 g/ha 15 % 200 g/ha 3.1 200 g/ha 20 % 200g/ha 3.1 100 g/ha 30 %
400 g/ha 3.2 200 g/ha 5 % 200 g/ha 3.2 100 g/ha 10 % 400 g/ha 3.3 400 g/ha20 W.
400 g/ha 3.3 200 g/ha 10% 400 g/ha 3.8 400 g/ha 45 % 400 g/ha 3.8 200 g/ha 40 % 200 g/ha 3.8 200
g/ha 15 % 200 g/ha 3.8 100 g/ha 20 % 400gVha 3.9 400 g/ha 45 % 400 g/ha 3.9 200 g/ha 40 % 200
g/ha 3.9 200g/ha 35 % 200 g/ha 3.9 100 g/ha 25 % 400 g/ha 3.10 400 g/ha 55% 400 g/ha 3.10 200
g/ha 65 % 200 g/ha 3.10 200 g/ha 50 % 200 g/ha 3.10 100 g/ha 30 % 400g/ha 3.11 400 g/ha 45 % 400
g/ha 3.11 200 g/ha 35 % 200 g/ha 3.11 200 g/ha 20 % 200 g/ha 3.11 100 g/ha 20 % 400 g/ha 3.12 400
g/ha 35 % 400 g/ha 3.12 200 g/ha 30 % 200 g/ha 3.12 200 g/ha 10 % 400 g/ha 3.13 400 g/ha
unabhängig voneinander je Wasserstoff, C1-C8-Alkyl,
12 13 C2-C8-Alkenyl, Phenyl oderCl-C4-Aralkyl, wobei der Phenylkern unsubstituiert oder durch
Halogen,Cl-C4-Alkyl, C1-C4-Halogenalkyl, Cl-C4-Alkoxy, O1-O4-Halogenalkoxy, Methylthio, Cyan
oder Nitro substituiert ist und X Sauerstoff, Schwefel, SO oder SO2, bedeuten.
Solche Verbindungen sind zum Teil in den US Patentanmeldungen Ser. No. 560 465 und 560 466 vom
12. Dezember 1983 beschrieben oder sie können nach bekannten Methoden hergestellt werden.
Folgende Dichloracetamide eignen sich erfindungsgemäss als Antidote zum Sulfonylharnstoff der
Formel I besonders gut.
Tabelle 4
EMI63.1
>;tb; Nr. >;SEP; R25 >;SEP; x >;SEP; R28 >;SEP; R29
>;tb; 4.1 >;SEP; H >;SEP; O >;SEP; CH3 >;SEP; H
>;tb; 4.2 >;SEP; 6-CH3 >;SEP; O >;SEP; CH3 >;SEP; H
>;tb; 4.3 >;SEP; H >;SEP; O >;SEP; H >;SEP; H
>;tb; 4.4 >;SEP; 6-CH3, >;SEP; 8-CH3 >;SEP; O >;SEP; H >;SEP; H
>;tb; 4.5 >;SEP; 5-CH3 >;SEP; O >;SEP; CH3 >;SEP; H
>;tb; 4.6 >;SEP; H >;SEP; s >;SEP; H >;SEP; H
>;tb; 4.7 >;SEP; C1 >;SEP; O >;SEP; CH3 >;SEP; H
>;tb; 4.8 >;SEP; 7-CH3 >;SEP; O >;SEP; CH3 >;SEP; H
>;tb; 4.9 >;SEP; 6-CH3, >;SEP; 6-CH3 >;SEP; O >;SEP; CH3 >;SEP; H
>;tb; 4.10 >;SEP; 6-C1, >;SEP; 8-C1 >;SEP; O >;SEP; CH3
>;tb; 4.11 >;SEP; H >;SEP; O >;SEP; CH3 >;SEP; CH3
>;tb; 4.12 >;SEP; H >;SEP; >;SEP; H >;SEP; OCzHs
72/612
>;tb; 4.13 >;SEP; H >;SEP; S >;SEP; CH3
>;tb; 4.14 >;SEP; S--+O >;SEP; H
>;tb; 4.15 >;SEP; H >;SEP; S(0)z >;SEP; H >;SEP; H
>;tb; 4.16 >;SEP; 5-CH3 >;SEP; O >;SEP; CH3 >;SEP; CH3
>;tb; 4.17 >;SEP; H >;SEP; S---+O >;SEP; (trans) >;SEP; CH3 >;SEP; H
>;tb; 4.18 >;SEP; H >;SEP; S >;SEP; (cis) >;SEP; CH3 >;SEP; H
>;tb; 4.19 >;SEP; H >;SEP; O >;SEP; H >;SEP; COOCH3
>;tb; 4.20 >;SEP; H >;SEP; O >;SEP; H >;SEP; ON
>;tb; 4.21 >;SEP; 6-CH3 >;SEP; O >;SEP; H >;SEP; CH3
>;tb; rabelle 4a
EMI64.1
Nr.R25 R28 R29 D a b c 4.100 H H HO O 2 1 4.101 H H 2-iC3H7 S O 1 0 4.102 H H H S O 1 0
4.103 H H 2-CH3 S O 1 0 4.104 H H 2-CH3 O 0 1 1 4.105 H H H S 0 3 0 4.106 H CH3 H-C=O NH 0
2 0 4.107 H H=O H-C=CO NM 0 2 0 Die Fähigkeit der Verbindungen der Formel V, junge
Maispflanzen vor der phytotoxischen Wirkung von N-(2-Methoxycarbonylphenylsulfonyl)- N'-(4',6'bis-difluormethoxypyrimidin-2-yl)-harnstoff zu schützen, wurde gemäss Beispiel 1 geprüft. Die
Resultate sind in der Tabelle 4b zusammengefasst.
Tabelle 4b Herbizid Antidote relative Aufwandmenge No. Aufwandmenge Schutzwirkung 400 g/ha 4.1
400 g/ha 55 % 400 g/ha 4.1 200 g/ha 55 % 400 g/ha 4.1 100 g/ha 55 % 400 g/ha 4.1 50 g/ha 40 %
200 g/ha 4.1 200 g/ha 65 % 200 g/ha 4.1 100 g/ha 65 % 200 g/ha 4.1 50 g/ha 60 % 200 g/ha 4.1 25
g/ha 60 % 100 g/ha 4.1 100 g/ha 25 % 100 g/ha 4.1 50 g/ha 30 % 100 g/ha 4.1 25 g/ha 30 % 100 g/ha
4.1 12.5 g/ha 30 % 400g/ha 4.2 400g/ha 60 % 400 g/ha 4.2 200 g/ha 70 % 400g/ha 4.2 100 g/ha 70
% 400g/ha 4.2 50 g/ha 50 % 200 g/ha 4.2 200 g/ha 40 % 200 g/ha 4.2 100 g/ha 50 % 200 g/ha 4.2
50 g/ha 45 % 200 g/ha 4.2 25 g/ha 25% 100 g/ha 4.2 100 g/ha 20 % 100 g/ha 4.2 50 g/ha 25 % 100
g/ha 4.2 25 g/ha 25 % 100g/ha 4.2 12.5 g/ha 20 % 400 g/ha 4.3 400 g/ha 10 % 400g/ha 4.3 200 g/ha
15 % 200 g/ha 4.3 200 g/ha 20 % 400 g/ha 4.4 400 g/ha 50 % 400g/ha 4.4 200 g/ha 25 % 200 g/ha
4.4 200 g/ha 30 % 200 g/ha 4.4 100gha 25 % 400 g/ha 4.6 400 g/ha 70 % 400 g/ha 4.6 200 g/ha 65 %
400 g/ha 4.6 100 g/ha 30 % 400g/ha 4.6 50 g/ha 35 % 200 g/ha 4.6 200g/ha 10 % 200 g/ha 4.6 100
g/ha 15 % 200 g/ha 4.6 50 g/ha 25 % 200g/ha 4.6 25 g/ha 40 % Tabelle 4b (Fortsetzung) Herbizid
Antidote relative Aufwandmenge Nu.Aufwandmenge Schutzwirkung 100 g/ha 4.6 100 g/ha 20 % 100
g/ha 4.6 50 g/ha 10 % 100 g/ha 4.6 2.. g/ha 20 % 100 g/ha 4.6 12.5 g/ha 20 % 400 g/ha 4.7 400
g/ha 45 % 400 g/ha 4.7 200 g/ha 35 % 200 g/ha 4.7 200 g/ha 30 % 200 g/ha 4.7 100 g/ha 30 % 400
g/ha 4.8 400 g/ha 55 % 400 g/ha 4.8 200 g/ha 75 % 200 g/ha 4.8 200 g/ha 60 % 200 g/ha 4.8 100
g/ha 65 % 400 g/ha 4.9 400 g/ha 30 % 400 g/ha 4.9 200 g/ha 45 % 200 g/ha 4.9 200 g/ha 30 % 200
g/ha 4.9 100 g/ha 35 % 400 g/ha 4.10 200 g/ha 40 % 200 g/ha 4.10 100 g/ha 20 % 400 g/ha 4.11 400
g/ha 30 >;tb; 7.1 >;SEP; CH3 >;SEP; H >;SEP; H >;SEP; 2 >;SEP; CH3 >;SEP; 1
>;tb; 7.2 >;SEP; CH3 >;SEP; CH3 >;SEP; H >;SEP; 1 >;SEP; - >;SEP; 0
>;tb; 7.3 >;SEP; H >;SEP; H >;SEP; H >;SEP; 2 >;SEP; H >;SEP; 1
>;tb; 7.4 >;SEP; CH3 >;SEP; H >;SEP; H >;SEP; 1 >;SEP; H >;SEP; 1
>;tb; 7.5 >;SEP; CH3 >;SEP; H >;SEP; H >;SEP; 1 >;SEP; - >;SEP; 0
>;tb; 7.6 >;SEP; CH3 >;SEP; H >;SEP; 6-CH3 >;SEP; 1 >;SEP; H >;SEP; 1
>;tb; 7.7 >;SEP; H >;SEP; H >;SEP; 6-CH2-SOz-* >;SEP; -C1 >;SEP; 1 >;SEP; H >;SEP; O
>;tb; >;SEP; =
>;tb; 7.8 >;SEP; H >;SEP; H >;SEP; 6OH2S02'\ >;SEP; -C1 >;SEP; 1 >;SEP; H >;SEP; 1
>;tb; >;SEP; =v
>;tb; 7.9 >;SEP; H >;SEP; H >;SEP; 5-C1 >;SEP; 1 >;SEP; H >;SEP; O
>;tb; 7.10 >;SEP; H >;SEP; H >;SEP; H >;SEP; 1 >;SEP; H >;SEP; H >;SEP; O
>;tb; Die Fähigkeit der Verbindungen der Formel VIII, junge Maispflanzen vor der phytotoxischen
Wirkung vonN-(2-Methoxycarbonylphenyl- suafonyl)-N'-(4',6'-bis-difluormethoxypyrimidin-2-yl)harnstoff zu schützen, wurde gemäss Beispiel 1 geprüft. Die Resultate sind in der Tabelle 7a
zusammengefasst.
Tabelle 7a Herbizid Antidote relative Aufwandmenge No. Aufwandmenge Schutzwirkung 400 g/ha 7.3
400 g/ha 45 % 400 g/ha 7.3 200 g/ha 45 % 200 g/ha 7.3 200 g/ha 35 % 200 g/ha 7.3 100 g/ha 40 %
400 g/ha 7.4 400 g/ha 35 % 400 g/ha 7.4 200 g/ha 25 % 200 g/ha 7.4 200 g/ha 20 % 200 g/ha 7.4 100
g/ha 25 % 400 g/ha7. 5 400 g/ha 55 % 400 g/ha 7.5 200 g/ha 30 % 200 g/ha 9.5 100 g/ha 5 290 C.
73/612
b) Ein Gemisch aus 31,2 g (0,25 Mol)2-Amino-4,6-dihydroxypyrimidin, 340 g 30 %iger wässeriger
Natriumhydroxidlösung (2,5 Mol) und 600 ml Dioxan wird auf 75 C erhitzt. In diese Emulsion leitet
man für 1,5 Stunde gasförmiges Difluorchlormethan ein. Die organische Phase wird abgetrennt und
eingedampft. Der Rückstand wird mit Eiswasser gewaschen und getrocknet. Man erhält so das
gewünschte2-Amino-4,6-bis-(difluormethoxy)-pyrimidin, Smp.74-750C.
c) Eine Lösung von 3,62 g (0,0158 Mol)2-Methoxycarbonylphenyl- sulfonylisocyanat und 2,63
g(0,0116 Mol? 2-Amino-4,6-bis-(difluormethoxy)pyrimidin in 50 ml Dioxan wird 2 Stunden bei 60700C gerührt. Durch Filtration, Eindampfe und Verreiben des Rückstandes in Aether erhält man 3,9 g
(73,7 % d.Th.) N-(2-Methoxycarbonyl-pheny-sulfony)-N'-[4,6-bis-(difluormethoxy)-pyrimidin-2-yl]harnstoff, Smo. 186-188 C.
Beispiele für die Herstellung von Dicloracetamide der Formel II: Beispiel 3: Herstellung von N-(3,4Dimethoxybenzyl)-N-isopropyldichloracetanilid
EMI108.1
In einem 750 ml Vierhalskolben gibt man 126 gN-(3,4-Dimethoxy- benzyl)-N-isopropyl-amin
(dargestellt durch hydrierende Kondensation von 3,4-Dimethoxy-benzaldehyd mit Isopropylamin, Kp.
77,5 -78,5 /0,03 mbar) und 250 ml Toluol undrührt bis sich das Amin gelöst hat. Dazu gibt man 120 g
20 %ige Natronlauge und rührt unter Kühlen des Kolbens in Alkohol/CO2-Bad bis die Temperatur der
Reaktionslösung-100 bis-150C beträgt. Dann tropft man langsam in die gerührte Aminlösung eine
solche von 89 g Dichloressigsäurechlorid in 100ml Toluol. Dabei fällt sofort ein weisser Niederschlag
aus.
Nachdem alles zugetropft ist, was ca. 1 1/2 Stunden in Anspruch nimmt, wird das Kühlbad
weggenommen und das Reaktionsgemisch weitergerührt, bis es Raumtemperatur erreicht. Dann wird
auf Eis/Wasser gegossen und die organische Phase im Scheidetrichter mit Toluol extrahiert. Die
Toluolphasen werden gesammelt, je zweimal mit 1 N Salzsäure und Wasser gewaschen, getrocknet und
eingedampft. Es verbleiben 176 g(91,7 % der Theorie) Titelprodukt als helles zähes Oel mit
BrechungsindexnD22 1.5495, welches schliesslich erstarrt.
Smp.69-72 .
Beispiel 4: Herstellung von 5-Dichloracetyl-3,3,6-trimethyl-9-oxo1,5-Diazabicyclo[4,3,0].-nonan
EMI109.1
Zu einer Lösung von 18,8 g (0,1 Mol) 3,3,6-Trimethyl-9-oxo-1,5diazabcylo[4.3.0]nonan in 100 ml
Toluol gibt man 10,5 g (0,105 Mol) Triäthylamin. Anschliessend kühlt man auf-100C ab und tropft bei
-10 bis-5 C 14,8 g (0,1 Mol) Dichloracetylchlorid zu. Nach 4-stündige Nachrühren wird das
ausgefallene Hydrochlorid des Tri äthylamins abfiltriert. Aus de Filtrat scheiden sich nach dem
Abdampfen des Toluols Kristalle ab, die aus Toluol/Aceton" 1 : 3 umkristallisiert werden können.
Man erhält 21,1 g 5-Dichloracetyl3,3, 6-trimethyl-9-oxo-1 , 5-diazabicyclo[4. 3.Ojnonan vom
Schmelzpunkt182-185 .
Beispiel 5: Herstellung von N-(3,4-Methylendioxybenzyl)-N-isopropyl-dichloracetanilid
EMI109.2
In einem 350 ml Vierhalskolben gibt man 19,3 gN-(3,4-Methylendi- oxybenzyl)-N-isopropyl-amin
(dargestellt durch hydrierende Kondensation von3,4-Methylendioxybenzaldehyd mit Isopropylamin,
Kp.
60 -64 /0.03 mbar) und 60 ml Toluol und rührt bis sich das Amin gelöst hat. Dazu gibt man 20 g
20%ige Natronlauge und rührt unter Kühlen des Kolbens inAlkoholJCOz-Bad bis die Temperatur der
Reaktionslösung-100 bis-150C beträgt. Dann tropft man langsam in die gerührte Aminlösung eine
solche von 14,8 g Dichloressigsäurechlorid in 10 ml Toluol. Dabei fällt sofort ein weisser Niederschlag
aus.
Nachdem alles zugetropft ist, was ca. 1112 Stunde in Anspruch nimmt, wird das Kühlbad
weggenommen und das Reaktionsgemisch weitergerührt, bis es Raumtemperatur erreicht. Dann wird
aufEis/Wasser gegossen und die organische Phase im Scheidetrichter mit Toluol extrahiert. Die
Toluolphasen werden gesammelt, je zweimal mit 1 N Salzsäure und Wasser gewaschen, getrocknet und
eingedampft. Es verbleiben 20,6 g Titelprodukt als helles zähes Oel.
74/612
Beispiel 6: Herstellung vonN-(3, 4-Dimethoxyphenyläthyl )-N-iso- propyl-dichloracetamid.
EMI110.1
In einem Sulfierkolben wird eine Lösung von 22,3 g N-(3,4-phenyläthyl)-N-isopropyl-amin vorgelegt.
Dazu gibt man unter Rühren 20 ml 20%ige wässrige Natronlauge. Dann wird das Reaktionsgemisch
mit einem Kühlbad auf eine Temperatur von-10 bis-150 gekühlt, zu dem man unter Rühren langsam
eine Lösung der berechneten Menge Dichloracetylchlorid in 10 ml Toluol tropft. Nachdem alles
zugegeben ist, nimmt man das Kühlbad weg und rührt während 2 Stunden bei Raumtemperatur weiter.
Dann wird das Reaktionsgemisch auf EislWasser gegossen, mit Toluol extrahiert und die gesammelten
organischen Phasen je einmal mit verdünnter Natronlauge, verdünnter Salzsäure und zweimal mit
Wasser gewaschen, über Natriumsulfat getrocknet und am Rotationsverdampfer eingedampft. Man
erhält so 28,4 g Titelprodukt als dickes Oel.
In analoger Weise zu diesen Beispielen werden die Verbindungen folgender Formel hergestellt:
EMI110.2
Beispiel 7: Herstellung von N-Dichloracetyl-l-methyl-tetrahydroisochinolin
EMI111.1
In einer Mischung von 14,7 gl-Methyl-tetraisochinolin in 60 ml Toluol und 4 g Natriumhydroxyd in
20 ml Wasser werden bei-10 bis 0 14,7 g Acetylchlorid in 70 ml Toluol zugetropft. Die Reaktion
wird während 30 Minuten weitergerührt und mit 100 ml Wasser verdünnt.
Die organische Phase wird mit wässrigem NaOH, Wasser, HC1 gewaschen, über Natriumsulfat
getrocknet und eingedampft. Man erhält 23,8 g eines Oels, das sichwährend dem Stehen verfestigt.
Smp. 74-77 C % C ber. 55,8 %II ber. 5,08 % N ber. 5,43 %C1 ber. 27,47 % C gef. 55,8% H gef. 5,1
% N gef. 5,3 %C1 gef. 27,5 Beispiel 8 Formulierungsbeispiele für Wirkstoffe der Formel II oder
Mischungen a) Spritzpulver a) b) c)
Wirkstoff der Formeln II-XVI oder
Mischung mitdem Herbizid der
Formel I 20% 60 % 0,5 %
Na-Ligninsulfonat 5 % 5% 5 %
Na-Laurylsulfat 3 % Na-Diisobuthylnaphalinsulfonat - 6% 6 X Octylphenolpoly thylenglykol- äther /7-8 Mol AeO) 2 % 2
%
Hochdisperse Kieselsäure 5X 27 % 27 %
Kaolin 67 %
Natriumchlorid - - 59,5X Der Wirkstoff wird mit den Zusatzstoffen gut vermischt und in einer
geeigneten Mühle gut vermahlen. Man erhält Spritzpulver, die sich mit Wasser zu Suspensionen jeder
gewünschten Konzentration verdünnen lassen.
b) Emulsions-Ronzentrat a) b)
Wirkstoff der Formeln II-XVI oder Mischung mit dem Herbizid der Formel I 10 % 1 %
Octylphenolpolyäthylenglykol äther (4-5 Mol AeO) 3 %3 %
Ca-Dodecylbenzolsufonat 3 % 3 % Ricinusölpolyglykoläther (36 Mol AeO)4 % 4 %
Cyclohexanon 30 % 10 %
Xylolgemisch 50 % 79% Aus diesem Konzentrat können durch Verdünnen mit Wasser Emulsionen
jeder gewünschten Konzentration hergestellt werden.
c) Stäubemittel a) b)
Wirkstoff der Formel II oder Mischung mit dem Herbizid der Formel I 0,1 % 1 %
Talkum 99,9 % Kaolin- 99 % Man erhält anwendungsfertige Stäubemittel, indem der Wirkstoff mit
demTrägervermistht -und auf einer geeigneten Mühle Vermahlen wird.
d) Extruder Granulat a) b)
Wirkstoff der Formel II oder Mischung mit dem Herbizid der Formel I 10 % 1%
Na-Ligninsulfonat2 X 2 %
Carboxymethylcellulose1 X 1 %
75/612
Kaolin 87% 96 % Der Wirkstoff wird mit den Zusatzstoffen vermischt, vermahlen und mit Wasser
angefeuchtet. Dieses Gemisch wird extrudiert und anschliessend im Luftstrom getrocknet.
e) Umhüllungs-Granulat
Wirkstoff der Formel II oder Mischung mit dem Herbizid der Formel I 3 %
Polyäthylenglykol(MG 200) 3 %
Kaolin 94 % Der fein gemahlene Wirkstoff wird in einem Mischer auf das mit Polyäthylenglykol
angefeuchtete Kaolingleichmässig aufgetragen. Auf diese Weise erhält man staubfreieUmhüllungsGranulate.
f) Suspensions-Konzentrat a) b)
Wirkstoff der Formel II oder Mischung mit dem Herbizid der Formel I 40 % 5 %
Aethylenglykol 10% 10 % Nonylphenolpolyäthylenglykoläther (15 MOl AeO) 6% 1 %
Na-Ligninsulfonat 10 % 5 %
Carboxymethylcellulose 1% 1 %
37 %ige wässrige Formaldehyd-Lösung 0,2% 0,2 %
Silikonöl in Form einer 75 %igen wässrigen Emulsion 0,8YO 0,8 %
Wasser 32YO 77 % Der fein gemahlene Wirkstoff wird mit den Zusatzstoffen innig vermischt. Man
erhält so ein Suspensions-Konzentrat, aus welchem durch Verdünnen mit Wasser Suspensionen jeder
gewünschtenKonzentra- tion hergestellt werden können.
g) Salzlösung
Wirkstoff der Formel II oder Mischung mit dem Herbizid der Formel I 5 %
Isopropylamin1 %
Octylphenolpolyäthylenglykoläther (78 Mol AeO) 3 %
Wasser 91 %Data supplied from the esp@cenet database - Worldwide
Claims of EP0190105
Claims:
Patentansprüche 1. Selektives herbizides Mittel, dadurch gekennzeichnet, dass es neben inerten
Zuschlagstoffen eine herbizid wirksame Menge von N-(2-MethoxyCarbonylphenylsulfonyl)-N'-(4,6bis-difluormethOxy- pyrimidin-2-yl)harnstoff der Formel I
EMI115.1
und zur Erhöhung der Toleranz der Kultur eine nicht-phytotoxische Menge eines Dichloracetamides
der Formel II enthält
EMI115.2
worin Ra undRb unabhängig voneinander je Wasserstoff, einen unsubstituierten oder substituierten
alicyclischen Kohlenwasserstoffrest oder eines davon einen Aminrest oder beide zusammen mit dem
Stickstoffatom, an das sie gebunden sind auch einen 5-12 gliedrigen heterocyclischen Rest bedeuten.
2. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel II enthält, worin R und Rb
unabhängig voneinander je Wasserstoff, einen Alkyl-, Alkenyleinen Cycloalkyl-, Cycloalkenyl-Rest
welcher unsubstituiert oder durch Halogen, Cyano; Hydroxy;Alkylcarbonyloxy; Alkenylcarbonyloxy;
Alkinylcarbonyloxy; Alkoxyalkylcarbonyloxy; Alkylcarbonylthio; Alkoxycarbonyloxy; Formyloxy;
Benzoyloxy; subst. Benzoyloxy; Haloalkylcarboxy; Alkyloxy; Alkenyloxy; Alkinyloxy; Phenyloxy;
subst. Phenyloxy; Heterocyclyloxy- und Heterocyclylthio; subst. Heterocyclyloxy- und
Heterocyclylthio; Alkylthio; Alkenylthio; Phenylthio; subst.Phenylthio; Alkoxyalkoxy;
Alkoxyalkoxyalkoxy; Alkenyloxyalkoxy; Tetraalkoxy; Alkylthioalkoxy; Carba moyloxy; N-monound di-Alkylcarbamoyloxy; N-Cycloalkyl- und N,N-Alkylencarabamoyloxy; Carbamoylthio;
Heterocyclyl- und substituiertesHeterocyclylaminocarbonyloxy; N-mono- und di-Alkylcarbamoylthio;
Thiocarbamoylthio; N-mono- und di-Alkylthiocarbamoylthio; N-Cycloalkyl- undN,NAlkylenthiocarbamoylthio; Alkyl- und Alkenylsulfinyl; Alkyl- und Alkenylsulfonyl; Alkyl- und
Alkenylsulfonyloxy; Phenyl- und substituiertes Phenylsulfonyloxy; Phenylsulfinyl und -sulfonyl;
substituiertes Phenylsulfinyl und -sulfonyl; Heterocyclyl- und substituiertes Heterocyclylsulfonyl;
Sulfamoyl;N-A1- kyl-, -N-Cycloalkyl-, N-Phenyl-, substituiertes N-Phenylsulfamoyl, Heterocyclylund substituiertes Heterocyclylsulfamoyl;N-Alkenyl-,N, N-di-Alkyl-, N,N-di-Alkenyl, N,N-Alkyl,
Alkenyl-Sulfamoyl; Aminooxy; Mono- und di-Alkylaminooxy; Alkylcarbonylaminooxy; Phenyl-und
substituiertes Phenylcarbonylaminooxy; Alkanaliminooxy; Benzaldehyd- und substituiertes
76/612
Benzaldehydiminooxy; Dialkylketoniminooxy; Phenylalkylketoniminooxy;Dialkylphosphoryl;
Phenyl-, Alkyl-Phosphoryl; Amino; Anilino; substituiertes Anilino; Heterocyclylamino- und
substituiertes Heterocyclylamino; Mono- unddi-Alkylamino;-Alkenylemino; Alkinylamino; diAlfcenylamino; di Alkinylamino; N,N-Alkyl, Alkenylamino; N,N,N-trialkylammonium; Alkylamido;
Alkenylamido; Alkinylamido; Alkyl-N-alkylamido; Benz-und substituiertesBenzamido;
Phenylalkylamido; Phenylalkyl-N-alkylamido;Benz- und substituiertes Benz-N-Alkylamido;
Heterocyclylamido- und substituiertes Heterocyclylamido; Haloalkyl- und
Alkoxyalkylamido;Haloalkyl und Alkoxy-N-alkylamido; Alkoxycarbonylamino;Alkoxycarbonyl-Nalkylamino; Alkenyloxycarbonylamino-und N-Alkylamino; Hydroxy- und Alkoxyamino; Hydroxyund Alkoxy-N-Alkylamino; Alkenyloxyamino; Phenyl- undAlkylaminocarbonylamino; N-Phenyl-N
Alkylaminocarbonylamino; N,N-Alkylenaminocarbonylamino; N-Phenyl N-Alkylaminocarbonyl-Nalkylamino;N-Phenylaminocarbonyl-N'-alkyl- amino; N,N'-di- und tri-Alkylaminocarbonylamino;
Heterocyclyl- und substituiertes Heterocyclylaminocarbonylamino; N-Heterocyclyl- und
substituiertesHeterocylyl-N, N' -mono- unddi-alkylaminocarbonyl- amino;Alkyl- und
Alkenylsulfonylamino; Alkyl- und Alkenylsulfonyl-N-alkylamino; Phenyl- und substituiertes
Phenylsulfonylamino; Phenyl- und substituiertes Phenylsulfonyl-N-alkylamino; Hetero cyclyl- und
substituiertes Heterocyclylsulfonylamino; Alkanal-imino; Benzaldehyd- und substituiertes
Benzaldehydimino; Phenyl- und substituiertes Phenylalkylketonimino; Dialkylketonimino;
Guanidino;N,N',N'-mono-di-tri- und tetra-Alkylguanidino; Amidino; N,N'mono-und Dialkylamidino,
Phenyl- und substituiertes Phenylamidino; Phenyl- und substituiertesPhenyl-N,N1-mono-und dialkylamidino; Di-alkylphosphonyl; Alkyl-o-alkylphosphinyl; Alkyl- und
Alkenyloxycarbonyl;Phenylalkyloxycarbonyl; Alkyl- undAlkenylthiocarbonyl;
Alkoxyalkoxycarbonyl; Haloalkyloxycarbonyl;Aminocarbonyl; mono- und di-Alkylaminocarbonyl;
mono und di-Alkenylaminocarbonyl; mono- und di-Alkinylaminocarbonyl; Phenyl-und substituiertes
Phenylalkylaminocarbonyl; Anilino- und substituiertes Anilinocarbonyl; N Phenyl-Nalkylaminocarbonyl; N,N-Alkylenaminocarbonyl; Cycloalkylamino-und cycloalkyl-Nalkylaminocarbonyl; Hydroxy- und Alkoxyaminocarbonyl; Haloalkyl-und Alkoxyalkylaminocarbonyl;
Formyl; Alkyl- und Alkenyl-und Alkinylcarbonyl; Phenyl- und substituiertesPhenylalkylcarbonyl;
Phenyl- und substituiertes Phenylalkenylarbonyl; Benzoyl; substituiertes Benzoyl;
Heterocyclylcarbonyl; substituiertes Heterocyclylcarbonyl; Phenyl; Naphthyl; substituiertes Phenylund Naphthyl;Heterocyclische Reste; substituierte heterocyclische Reste; substituiert sein können,
weiter bedeuten R a undRb unabhängig voneinander Alkinyl; durch Phenyl, substituiertes Phenyl,
Halogenalkyl, Alkylthio- und Alkenylthioalkyl, Phenylthiound substituiertes Phenylthioalkyl, Alkoxyund Phenoxyalkyl, Alkoxycarbonyl, Aminocarbonyl, mono- und di-Alkylaminocarbonyl, Anilino- und
substituiertes Anilinocarbonyl, N-Anilino- und substituiertes Anilino-N-Alkylaminocarbonyl, N,NAlkylenaminocarbonyl, Heterocyclyl- und substituiertes Heterocyclylaminocarbonyl, Aminoalkyl,
mono- und di-Alkyl- und Alkenylaminoalkyl, N,N-Alkylenaminoalkyl, Anilino-und substituiertes
Anilinoalkyl, Phenyl- und substituiertes Phenylalkylaminoalkyl, Heterocyclylamino- und substituiertes
Heterocyclylaminoalkyl, Heterocyclyl- und substituiertes Heterocyclylaminoalkylaminoalkyl,
substituierter Alkinylrest; Phenyl- und Naphthylreste, heterocyclische Reste und benzannellierte
Heterocyclen können ihrerseits ein- oder mehrfach durch Halogen; Nitro; Cyano; Pseudohalogen;
Alkyl- und Alkenyloxy; Alkyl-und Alkenylthio; Alkyl; Alkenyl; Alkinyl; Phenylalkinyl;
Alkylsulfinyl und -sulfonyl;Hydroxycarbonyl; Alkoxy- und Benzyloxycarbonyl; Alkenyloxycarbonyl;
Alkylendioxy; Aminocarbonyl; mono- und di-Alkylaminocarbonyl; Amino; Ammonio; mono- und diAlkylamino; Alkan- und Alkencarbonyl; Phenyloxy; durch Halogen, Halogenalkyl, Nitro, Alkoxy,
Alkylthio, Alkyl, substituiertes Phenyloxy; Sulfo; Di-Alkylphosphoryl-und phosphonyl;Sulfamoyl;
mono- und di-Alkylsulfamoyl; mono- und di-undtri-Halogenalkyl; Alkylsulfinyl- und -sulfonyl;
substituiert sein, einer der Reste Ra und Rb kann auch Amino; mono- oder di-Alkyl und Alkenylamino;
mono- oder di-Alkinylamino; substituiertes oder unsubstituiertes Phenylalkylamino; substituiertes oder
unsubstituiertes N-Phenylalkyl-N-alkylamino; substituiertes oder unsubstituiertes Heterocyclylamino;
substituiertes oder unsubstituiertes N-Heterocyclyl-N'-Alkylamino;Alkanalimino, substituiertes oder
unsubstituierte Benzaldehydimino, Dialkylketonimino, substituiertes oder unsubstituiertes
Phenylalkylketonimino; Alkyloxycarbonylamino-und N-Alkylamino; substituiertes oder
unsubstituiertes Phenylalkoxycarbonylamino- und N-Alkylamino; durch 1-3-Alkyl substituiertes
Ureido; durch 1-2 Alkyl substituiertes Phenylureido; durch 1-2 Alkyl substituiertes Heterocyclylureido;
Alkyl, Alkenyl- und Alkinylamido und N-Alkylamido; substituiertes und unsubstituiertes
Phenylalkylamido; substituiertes und unsubstituiertes Phenyl- und Heterocyclylamido; substituiertes
und unsubstituiertes Phenyl- und Heterocyclyl-N-Alkylamido; Alkyloxy- und Alkylthiothionoamino
bedeuten, wobei die Alkylreste wie oben angegeben, substituiert sein können; ferner können die Reste
77/612
R und a d Rb können zusammen mit dem Stickstoffatom an das sie gebunden sind auch einen
gesättigten oder gesättigten 5 bis 12-gliedrigen Heterocyclus bilden, der noch ein zwei oder drei
weitere Heteroatome oder eine Sulfinylresp. Sulfinylgruppe enthält durch ein oder zwei
Carbonylgruppen unterbrochen sein kann, und welcher benzannelliert, unsubstituiert oder substituiert
sein kann.
3. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel II enthält, worin Ra Wasserstoff
Cl-C8-Alkyl oder C3-C8-Cycloalkyl, unsubstituiert oder durch -POR1,R2, -NR3R4,-(O) COOR5, (X)mCX"R6, -O(AO)m,-R7, -XR7,Cyan, X11,Het, Het, -SR7, C5-C6-Cycloalkyl, CR(OR9 oder
Halogen substsituiert, oder R ist ein C3-C8-Alkenyl- oder C3-C8-Cycloalkenylrest, der unsubstituiert
oder durch Halogen, Phenyl, C5-C6-Cycloalkyl oderC1-C4-Alkyl substituiert ist, oder R ist ein C3C8-Alkinylrest, der unsubsti a 38 tuiert oder durch Phenyl substituiert >;RTI ist,- wobei die
Phenylkerne unsubstituiert oder durch Halogen,C1-C4-A1kyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy,
C1-C4-Halogenalkoxy, Methylthio, Cyan oder Nitro substi tuiert sind, oder R ist ein Alkoxyiminoalkylrest a -CH(Rr)-C(Rs)=N-ORt, R und R je Wasserstoff oderCl-C4-Alkyl und Rt
Wasserstoff, C1-C4-alkyl, C3-C6-Alkenyl oder C3-C6-alkinyl, Rb Wasserstoff, dasselbe wie R oder
einen Rest -NR3R4,
EMI119.1
A eine C1-C4-Alkylenkette, A1 eineC1-C8-Alkylenkette die geradkettig oder verzweigt ist und die
unsubstituiert oder durch Cyan oderCl-C4-Alkoxy oder einen Alkylamido- oder HalogenalkylamidoRest substituiert ist, Het einen gegebenenfalls durchCl-C4-Alkyl, Cl-C4-Alkoxy, C1-C4Alkoxycarbonyl oderC1-C4-Alkylthio optimal substituierten5-6-gliedrigen Heterocyclus mit 1-3
Heteroatomen resp.S(O)n, Gruppen, wobei Sauerstoff und Schwefel nie direkt benachbart im Ring
vorhanden sein können, sondern in einer 1.3-Anwendung vorliegen müssen, wie im 1,3-Dioxolan-2-yl, 1,3-Dioxan-2-yl oder dem 2,4-Dioxan-1-ylrest und welcher zusätzlich durch R in der n l-Stellung und
R' an einem Ring Kohlenstoffatom substituiert sein n kann, n Null oder eine Zahl von 1 bis 3, m Null
oder die Zahl 1, m' Null oder eine Zahl von 1 bis 4, n' Null oder eine Zahl von 1 bis 2, R, R', R1 und
R2 unabhängig voneinander jeCl-C4-Alkyl oder C1-C4-alkoxy, R3 Wasserstoff, C1-C4-Alkyl oder
C3-C8-Cycloalkyl, R4 Wasserstoff,Cl-C4-Alkyl, Phenyl, durch Halogen, C1-C4-Alkyl, C1-C4Alkoxy,C1-C4-Halogenalkyl oderC1-C4Alkoxy substituiertes Phenyl oder einen Rest -COOR'5 oder COR'6, R5 und R'5 unabhängig voneinander je C1-C4-alkyl,oder C1-C4-Aralkyl wobei der Phenylkern
unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4-Halogenlkyl, C1-C4-Alkoxy, C1-C4Halogenalkoxy, Methylthio, Cyan oder Nitro substituiert ist, R6 und R' unabhängig voneinander je
Wasserstoff, Cl-C4-Alkyl,
6 -Halogenalkyl, C2-C5-alkoxyalkyl, Phenyl oder C1-C4-Aralkyl, wobei der Phenylkern unsubstituiert
oder durch Halogen, C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkyoxy, C1-C4-Halogenalkoxy,
Methylthio, Cyan oder Nitro substituiert ist, oder R6 und R'6 bedeuten einen C2-C4-Alkenyl- oder
einen Rest-N(R12)(Rl3), R7 Wasserstoff,Cl-C4-Alkyl, C3-Cs-Alkenyl, C3-C6-Alkinyl, Phenyl und
Phenyl(C1-C4)Alkyl, wobei die Phenylkerne durch Halogen, C1-C4alkyl, C1-C4Alkoxy oder C1C4Halogenalkyl substituiert sind, R8 und R9 unabhängig voneinander je C1-C6-Alkyl oder C3-C6Alkenyl R10 C1-C4-Alkyl, C3-C6-alkenyl, C2-C6-Alkoxyalkyl, C1-C4-Halogenalkenyl oder in
Zusammenhand mit 2 Sauerstoffatomen auch eine C1-C5-Alkylenbrücke, R11 Wasserstoff oder C1C4-Alkyl und R12 und R13 unabhängig voneinander je Wasserstoff,C1-C8Alkyl, C3-C8-Cycloalkyl,
C3-C8-Alkenyl, Phenyl oderCl-C4Aralkyl wobei der Phenylkern unsubstituieret oder durch
Halogen,Cl -C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio,
Cyano, Nitro und R12 und R13 zusammen eineC1-C7-Alkylenkette, die durch Sauerstoff, C1-C4Alkyl, C1-C4-Halogenalkoxy, C2-C8-Alkoxyalkoxy, der Dioxy Z Wasserstoff, C1-C4-Alkyl, Halogen,
C1-C4-Halogenalkyl, Nitro, Schwefel, ; NH, oder ; N(C1-C4)-Alkyl unterbrochen sein kann.
methylenrest, ein 1.3-Dioxolan-2-yl- oder1,3-Dioxan-2-ylrest, der über eine C1-C4-Alkylenbrücke
gebunden sein kann, X', X", X"' Sauerstoff, Schwefel, X Sauerstoff, Schwefel 4. Mittel gemäss
Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur eine nicht
phytotoxische Menge eines Dichloracetamides der Formel III enthält,
EMI121.1
worin A1 eine C1-C8-Alkylenbrücke, die geradkettig oder verzweigt sein kann und die unsubstituiert
oder durch Cyan, C1-C4-Alkoxy oder einen Alkylamido- oder Halogenalkenylamido-Rest substituiert
sein kann, n Null oder eine Zahl von 1 bis 3, a Wasserstoff 1 8 Alkyl oder C3-C8-Cycloalkyl,
unsubstituiert R Wasserstoff 0 -O - 3 8 oder substituiert durch -PO(R1)(R2), -NR3R4), -(O)mCOOR5,
78/612
-(X')m-CX"R6, Cyano, Het, -X"'-Het, -O-(A-O)m,-R7, -XR7, C5-C6-Cycloalkyl, -CR(OR8)(OR9)
oder Halogen oder Ra ist ein C3-C8-Alkenyloder C3-C8-Cycloalkylrest, der unsubstituiert oder durch
Halogen, Phenyl, C5-C6-Cycloalkyl oder C1-C4-Alkyl substituiert oder Ra ist ein C3-C8-alkinylrest,
der unsubstituiert oder durch Phenyl substituiert ist, wobei die Phenylkerne unsubstituiert oder durch
Halogen,Cl-C4-Alkyl, C1-C4-Halohenalkyl,Cl-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio, Cyan
oder Nitro substituiert sind, oder Ra ist ein Alkoxy-iminoalkylrest
EMI121.2
Rr und R je Wasserstoff oderC1-C4-Alkyl und Rt Wasserstoff, C1-C6-Alkyl, C3-C6-alkenyl oder C3C6-Alkinyl bedeuten, Z Wasserstoff,Cl-C4-Alkyl, Halogen,Cl-C4-Halogenalkyl, Nitro,Cl-C4Alkoxy, C2-C8-Halogenalkoxy, der Dioxymethylenrest, ein 1,3-Dioxolan-2-yl- oder 1,3-Dioxan-2ylrest, der über eineCl-C4-Alkylen- brücke gebunden sein kann, A eineC1-C4-Alkylenkette Het
einen gegebenenfalls durch C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkoxycarbonyl oderCl-C4Alkylthio optimal substituierten 5-6-gliedrigen Heterocyclus mit 1-3 Heteroatomen resp.S(O)n,
Gruppen, wobei Sauerstoff und Schwefel nie direkt benachbart im Ring vorhanden sein können,sondern in einer 1.3-Anwendung vorliegen müssen, wie im 1,3-Dioxolan-2-yl-, 1,3-Dioxan-2-yl oder
dem 2,4-Dioxan-1-ylrest und welcher zusätzlich durch Rn in derl-Stellung undR' n an einem Ring
Kohlenstoffatom substituiert sein kann, m' Null oder eine Zahl von 1 bis 4, m Null oder 1, n Null bis 3,
n' Null bis 3 R, R', R1 und R2 unabhängig voneinander je C1-C4-Alkyl oder c1-C4-alkoxy, R3
Wasserstoff oder Cl-C4-Alkyl, R4 einen Rest -COOR'5 oder -COR'6, R5 und R'5 unabhängig
voneinander jeC-C4-Alkyl, oderCl-C4-Aralkyl wobei der Phenylkern unsubstituiert oder durch
Halogen,Cl-C4-Alkyl, C1-C4-Halogenalkyl,Cl-C4-Alkoxy, 01-04-Halogenalkoxy, Methylthio, Cyan
oder Nitro substituiert ist, R6 Wasserstoff, C1-C4-Alkyl, C1-C4-Halogenalkyl, C2-C5-Alkoxyalkyl,
Phenyl oder C1-C4-Aralkyl, wobei der Phenylkern unsubstituiert oder durch Halogen, C1-C4-Alkyl,
C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio, Cyan oder Nitro substituiert
ist, oder R6 bedeutet einenC2-C4-Alkenyl- oder einen Rest -NR12, R13, R7 Wasserstoff,Cl-C4Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl oder Benzyl, R8 und R9 unabhängig voneinander jeCl-C6Alkyl oder C3-C6-Alkenyl R10 C1-C4-Alkyl, C3-C6-alkenyl, C2-C6-alkoxyalkyl, C1-C4Halogenalkenyl oder in Zusammenhang mit 2 Sauerstoffatomen auch eine c1-C5-Alkylenbrücke, R12
und R13 unabhängig voneinander Je Wasserstoff, C1-C8-Alkyl,C3-C8-Alkenyl, Phenyl oder C1-C4Aralkyl wobei der Phenylkern unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4Halogenalkyl,Cl-C4-Alkoxy, Cl -04-Halogenalkoxy, Methylthio, Cyan oder Nitro substituiert ist und
X', X" und X"' Sauerstoff, Schwefel, X Sauerstoff, Schwefel oder S(O) , bedeuten.
5. Neue Dichloracetamide der Formel III' worin
EMI123.1
A1, einen geradkettigen, verzweigten oder cyclischen C1-C8-Kohlenwasserstoffrest, welcher
unsubstituiert oder durch Alkoxy, Alkylthio, Fluor, Cyan oder Halogenalkyl substituiert sein kann, R ,
einen geradkettigen oder verzweigten, gesättigten oder ungesättigtenCl-C5-Kohlenwasserstoffrest der
unsubstituiert oder durch Alkoxy, poly-Alkoxy, Halogen, Cyan oder Trifluormethyl, substituiert sein
kann, oder Cycloalkyl, Alkylcycloalkyl, Dialkoxyalkyl, 1,3-Dioxolan-2-ylalkyl, 1,3-Dioxolan-4ylalkyl,1 , 3-Dioxan-2-yl-alkyl, Furylalkyl, Tetrahydrofurfurylalkyl oder einen Rest -NH-COORu,
~CH2-COORu, -CH(CH3)COORu oder einen Alkoxyimino-alkylrest -CH(Rr)-C(Rs)=N-ORt, wobei R
Methyl, Aethyl, Propyl oder Allyl, u R und R je Wasserstoff oder C1-C4-Alkyl und Rt Wasserstoff,
>;RTI Cl-C-Alkyl, C3-C6-Alkenyl oder C3-C6-Alkinyl bedeuten.
6. Acylamide gemäss Anspruch 5, dadurch gekennzeichnet, dass A1, fürC1-C6-Alkylen steht.
7. Acylamide gemäss Anspruch 5, dadurch gekennzeichnet, dass A1, fürCl-C3-Alkylen steht.
8. N-(3,4-Methylendioxybenzyl)-N-isopropyl-dichloracetamid gemäss Anspruch 5.
9. Verfahren zur Herstellung der Acylamide der Formel III', Anspruch 5, dadurch gekennzeichnet, dass
man ein Acylhalid der Formel II'
EMI124.1
worin Ac Chlor, Brom, oder den Rest-O-CO-CHC12 bedeutet in ein einem inerten organischen
Lösungsmittel, in Gegenwart der mindestens äquimolaren Menge eines säurebindenden Mittels mit
einem Amin der FormelIIIa' umsetzt
EMI124.2
wobei A1, undRa, die unter Formel III', Anspruch 5 gegebene Bedeutung haben.
79/612
10. Verfahren zur Herstellung der Acylamine der FormelIII', Anspruch 5, dadurch gekennzeichnet,
dass man ein Amin der FormelIIIa'
EMI124.3
worin A1, und R , die unter FormelIII', Anspruch 5 gegebene Bedeutung haben, mit Chloral
odereinem durch Addition an dessen Oxogruppe gebildetenOhloralderivat in einem wassrigen Medium
undloder einen polaren organischen Lösungsmittel, in Gegenwart säurebindender Mittel und der
katalytischen Menge eines anorganischen oder organischen Cyanides umsetzt.
11. Verfahren zur Herstellung von Acylamin der Formel III' gemäss Anspruch 5, dadurch
gekennzeichnet, dass man in einem inerten organischen Lösungsmittel, äquimole Mengen von
Methylendioxybenzol mit N-Methylol-dichloracetamid umsetzt.
12. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel IV enthält,
EMI125.1
worin Het einen gegebenenfalls durch C1-C4-Alkyl,Cl-C4-Alkoxy, C1-C4~Alkoxycarvbonyl oderClC4-Alkylthio optimal substituierten 5-6 gliedrigen Heterocyclus, mit 1-3 Heteroatomen resp.S(O)
Gruppen, wobei Sauerstoff und Schwefel nie direkt benachbart im Ring vorhanden sein können,
sondern in einer 1,3-Anordnung vorliegen müssen, wie im 1,3-Dioxoian-2-yl, 1,3-Dioxan-2-yl oder
dem 2,4 Dioxan-l-ylrest und welcher zusätzlich durch R in der l-Stellung n und R'n an einem Ring
Kohlenstoff substituiert sein kann, Ra Wasserstoff C1-C8-alkyl oder C3-C8-Cycloalkyl unsubstituiert
oder subdtituiert durch -PO(R1)(R2), -NR3,R4, -(O)mCOOR5, -(X)mCXR"6,-O-(A-O-) ,-R7, -XR7,
Cyano, -X"'-Het, Het,-C5-C-Cycloalkyl, -CR(OR8)(OR9) oder Halogen; oder Ra ist ein C3-C8Alkenyl-oder C3-C8-Cycloalkenylrest, der unsubstituiert oder substituiert durch Halogen, Phenyl,C5C6-Cycloal-kyl oder C1-C4-alkyl ist oder R ist ein C3-C8-Alkinylrest der unsubstituiert oder durch
Phenyl substituiert ist, wobei die Phenylkerne unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4Halogenalkyl, C1-C4-alkoxy, C1-C4-Halogenalkoxy, Methylthio, Cyan oder Nitro substituiert sind,
oder R ist ein Alkoxyiminoalkylrest -CH(R )-CH(R )-NORt, R und R je a r 5 Wasserstoff oderCl-C4Alkyl, Rt Wasserstoff,C1-C6-Alkyl, C3-C6-Alkenyl oder C3-C6-Alkinyl, A eineC1-C4-Alkylenkette,
m Null oder eins m' Null oder eine Zahl von 1 bis 4, n' Null bis 2, n Null bis 3, R1 und R2 unabhängig
voneinander je C1-C4-Alkyl oder C1-C4-Alkoxy, R3 Wasserstoff-Alkyl oderCl-C8-Cycloalkyl R4
Wasserstoff,C-C4-Alkyl, Phenyl, durch Halogen,C1-C4-Alkyl7 C1-C4-Alkoxy,Cl-C4-Halogenalkyl
oder C1-C$-Halogenalkoxy substituiertes Phenyl oder einen Rest-COOR'5 oder -COR'6 R5 und R'5
unabhängig voneinander je C1-C4-Alkyl oder C1-C4-Aralkyl wobei der Phenylkern unsubstituiert oder
durch Halogen C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy,
Methylthio, Cyan oder Nitro substituiert ist.
R6 und R' unabhängig voneinander jeWasserstoff,Cl-C4-Alkyl, C1-C4-Halogenalkyl, C2-8Alkoxyalkyl, Phenyl oder C1-C4-Aralkyl wobeider --Phenylkern unsubstituiert oder durch Halogen,
C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio, Cyan oder
Nitro substituiert ist; oder R6 und R'6 bedeuten einen -Alkenyl- oder einen Rest N(R12)(R13)Wasserstoff, Cl-C4-Alkyl, C3-C6-Alkenyl,C3-06-Alkinyl oder Phenyl(C1-C4)Alkyl,
wobei die Phenylkerne durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy oder C1-C4-Halogenalkoxy
substituiert sind R8 undRg unabhängig voneinander jeCl-C6-Alkyl oder C3-C6-Alkenyl,R11
Wasserstoff oder C1-C4-Alkyl, R12 und R13 unabhängig voneinander je Wasserstoff, C1-C8-Alkyl,
C3-C6-Alkenyl, Phenyl oder C1-C4-Aralkyl bedeuten, wobei der Phenylkern unsubstituiert oder durch
Halogen, C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkkoxy, Methylthio,
Cyan oder Nitro substituiert, R12 und R13 zusammen eine C1-C4-Alkylenkette, die durch Sauerstoff,
Schwefel-NH- oder -N(C1-C4)alkyl-unterbrochen sein kann, R Wasserstoff, C1-C4-Alkyl oder Phenyl
welches unsubstituiert oder durch Halogen,Cl-C4-Alkyl, C1-C4-Halogenalkyl,Cl-C4-Alkoxy, C1-C4Halogenalkoxy, Methylthio, Cyan oder Nitro substituiert ist, und X', X", X"' Sauerstoff, Schwefel und
X Sauerstoff, Schwefel oder -S(O) bedeuten.
13. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel V enthält,
EMI127.1
worin R25 Wasserstoff, C1-C4-Alkyl, unsubstituiert oder substituiert durch Hydroxy,Cl-C4-Alkoxy
oder Halogen, R28 Wasserstoff, C1-C4-Alkyl unsubstituiert oder substituiert durch Halogen, Cyan
80/612
oder einen Rest ~COA3;C2-C4-Alkenyl, C2-C4-Alkinyl, C2-C4-Alkoxyalkyl, Cyano oder einen Rest COA;R29 Wasserstoff, C1-C4-Alkyl,01-04-Halogenalkyl, C2-C4-Alkenyl, C2-C4-Alkinyl oder C2C4-Alkxyalkyl,A Cl-C4-Alkyl A3 Cl-C4-Alkyl, C2-C4-Alkenyl oder einen Rest -OR"'5 oder N(R"'12)(R"'13), R"'5Cl-C4-Alkyl, Cl-C4-Aralkyl, wobei der Phenylkern unsubstituiert oder durch
Halogen, C1-C4-Alkyl, C1-C4-Halogenalkoxy,Cl-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio,
Cyano oder Nitro substituiert ist, R"'12 undR"'13 unabhängig voneinander je Wasserstoff,C1-C8Alkyl, C2-C8-Alkenyl, Phenyl oder C1-C4-Aralkyl, wobei der Phenylkern unsubstituiert oder durch
Halogen, C1-C4-Alkyl,O1-O4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio,
Cyan oder Nitro substituiert ist und X Sauerstoff, Schwefel, SO, SOz, bedeuten.
14. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel VI enthält,
EMI128.1
worin m Null oder Zahl 1, R25 Wasserstoff,Cl-C4-Alkyl, unsubstituiert oder substituiert durch
Hydroxy, C1-C4-Alkoxy oder Halogen, R28 und R"'29 Wasserstoff, C1-C$-Alkyl unsubstituiert oder
substituiert durch Halogen, Cyan oder einen Rest -COA3;C2-C4-Alkenyl, C2-C4-Alkinyl, Cyano oder
einen Rest -COA2;R29, R"29 undR1128 sind unabhängig voneinander je Wasserstoff, C1-C4-Alkyl,
C1-C4-Halogenalkyl, C2-C4-Alkenyl, C2-C4-Alkinyl oder C2-C4-Alkoxyalkyl, R28 und R"28 oder
R29 und R"'29 zusammen mit dem Kohlenstoffatom auch die Oxogruppe
EMI128.2
A2 Cl-C4-Alkyl, C2-C4-Alkenyl,-N(R"'12)(R"'l3), A3 C1-C4-Alkyl, C2-C4-Alkenyl oder Einen Rest
-COR"5 oder -N(R"112) (R"13), R"5 C1-C4-Alkyl, 0 C1-C4-Aralkyl, wobei der Phenylkern
unsubstituiert oder durch Halogen,Cl-C4-Alkyl, C1-C4Halogenalkyl,Cl-C4-Alkoxy, C1-C4Halogenalkoxy, Methylthio, Cyano oder Nitro substituiert ist, R"'12 und R"'13 unabhängig
voneinander je Wassrstoff, C1-C8-Alkyl, C3-C8-Alkenyl, Phenyl oderCl-C4-Aralkyl bedeuten, wobei
der Phenylkern unsubstituiert oder durch Halogen,Cl-C4-Alkyl, C1-CC4-Halogenalkyl, C1-C4Alkoxy-Halogenalkoxy, Methylthio, Cyan oder Nitro substituiert ist bedeuten.
15. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel VII enthält,
EMI129.1
worin n Null bis 2, n' Null, 1, 2 oder 3, R25 Wasserstoff, C1-C4-Alkyl, unsubstituiert oder substituiert
durch Hydroxy,Cl-C4-Alkoxy oder Halogen, C1-C4-Alkyl-S(O)n-, Phenyl-S(O) - durch Halogen,
Methyl, Methoxy substituiertes Phenyl-S(O) R26 Wasserstoff,Cl-C6-Alkyl, C3-C6-AlkenylC3-C6Cyclo lkyl, Phenyl oderCl-C4-Aralkyl bedeutet wobei der Phenylkern unsubstituiert oder durch
Halogen,Cl-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy,Methylthio, Cyan
oder Nitro substituiert ist, R'28 Wasserstoff,Cl-C6-Alkyl unsubstituiert oder substituiert durch
Halogen, Cyan oder einen Rest -COA3; C3-C6-Alkenyl, C3-C6-Alkinyl, C2-C6-Alkoxyalkyl, Cyano
oder -COA2, R'29 Wasserstoff, C1-C6-Alkyl, C1-C6-Halogenalkyl, C3-C6-Alkenyl, C3-C6-Alkinyl
oder C2-C6-Alkoxyalkyl, A2 C1-C4-alkyl, C2-C4-Alkenyl, -NR"12R"13A3 C1-C4-Alkyl, C2-C4Alkenyl oder einen Rest -OR"5 oder-NR"13R"14, R"501-04-Alkyl, Cl-C4-Aralkyl, wobei der
Phenylkern unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy,
C1-C4-Halogenalkoxy, Methylthio, Cyano oder Nitro, substituiert ist, R"13 und R"14 unabhängig
voneinander je Wasserstoff,
14 14 C3-C8-Alkenyl, Phenyl oderCl-C4-Aralkyl bedeuten, wobei der Phenylkern unsubstituiert oder
durch Halogen,Cl-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4Halogenalkoxy,Methylthio, Cyan oder Nitro substituiert sein kann, bedeuten.
16. Neue N-Dichloracetyl-tetrahydroisochinoline der Formel VII'
EMI130.1
worin n' Null bis 3 Rw Wasserstoff, Halogen C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio,01-04Halogenalkyl, C3-C6-Halogenalkoxyalkyl, Nitro, der Dioxymethylenrest,R , Rx,R , Rz
Wasserstoff,C1-C -Alkyl, C3-C6-Alkenyl mit der Massgabe, dass einen der Rest Rw, Rx, Ry, Rz
verschieden von Wassserstoff sein muss.
17. Verfahren zur Herstellung der N-Dichloracetyl-tetrahydroisochinoline der Formel VII', Anspruch
16, dadurch gekennzeichnet, dass man ein Acylhalid der Formel II'
EMI130.2
worin Ac Chlor, Brom oder den Rest
81/612
EMI130.3
bedeutet, in einem inerten organischen Lösungsmittel in Gegenwart der mindestens äquimolaren
Menge eines säurebindenden Mittels mit einem Amin der Formel VIIa' umsetzt,
EMI130.4
wobei n',Rw, R , R , R die unter Formel VII', Anspruch 16, gegebene Bedeutung haben.
18. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines-Dichloracetamides der Formel VIII enthält,
EMI131.1
worin n' Null oder eins oder zwei n Null oder eine Zahl von 1 bis 3
R25 Wasserstoff, C1-C4-Alkyl, unsubstituiert oder substituiert durch
Hydroxy,Cl-C4-Alkyl oder Halogen,
R28 Wasserstoff, C1-C4-Alkyl, unsubstituiert oder substituiert durch Halogen, Cyan oder einen Rest COA3;C2-C4-Alkenyl oder
C2-C4-Alkinyl;
R29 Wasserstoff, C1-C4-Halogenalkyl, C2-C4-Alkenyl,
C2-C4-Alkinyl oder C2-C4-Alkoxyalkyl;
R30 dasselbe wie R28 aber unabhängig davon,A3 Cl-C4-Alkyl, C2-C4-Alkenyl, einen Rest -OR"5
oder-NR"12, R"13,
R"'5 C1-C4-Alkyl, C1-C4-aralkyl, wobei der Phenylkern unsubstituiert durch C1-C4-Alkyl, C1-c4Alkoxy,Halogen, C1-C4-Halogenalkyl
Cyan oder Nitro substituiert sein kann; wenn n Null ist kann R5 auch Wasserstoff bedeuten,
R"12 und R"13 unabhängig voneinander je Wasserstoff, C1-C8-akal,
C3-C6-Alkenyl, Phenal oder C1-C4-Aralkyl bedeuren, wobei der
Phenalkern unsubstituiert oder durch Halogen, C1-C4-Alkyl,
C1-C4-Halogenalkyl, C1-C4-alkoxy,C1-C4-Halogenalkoxy, Methylthio
Cyan oder Nitro substituiert sein kann, bedeuten.
19. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel IX enthält,
EMI132.1
worin n Null eins, zwei, oder drei R28 Wasserstoff,Cl-C4-Alkyl unsubstituiert oder substituiert durch
Halogen, Cyan oder einen Rest-CO-A3 C2-C4-Alkenyl oder C2-C4-Alkinyl, C2-C4-Alkoxyalkyl oder
Cyan; R29 Wasserstoff, C1-C4-Alkyl, C1-C4-Halogenalkyl, C2-C4-Alkenyl,C-C4-Alkinyl oderC2C4-AlEoxyalkyl;; A3 C1-C4-Alkyl, C2-C4-alkenyl, einen Rest -OR"5 oder -NR"12, R"13, R5" >;RTI
Cl-C4-Alkyl, C1-C4-Aralkyl wobei der Phenylkern unsubstituiert oder durchCl-C4-Alkyl, Cl-C4Alkoxy, Halogen, C1-C4-Halogenalkyl, Cyan oder Nitro substituiert sein kann; wenn m Null ist, kann
R5 auch Wasserstoff sein; R"12 und R"13 unabhängig voneinander je Wasserstoff, C1-C8-Alkyl, C3C6-Alkenyl, Phenyl oder C1-C4-Aralkyl bedeuten, wobei der Phenylkern unsubstituiert oder durch
Halogen, C1-C4-Alkyl,Cl-C4-Halogenalkyl, C-C4-Alkoxy, C1-C4-Halogenalkoxy, Methylthio, Cyan
oder Nitro substituiert sein kann, bedeuten.
20. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel X enthält,
EMI132.2
n Null eins, zwei, oder drei R"20 einen Rest -COOr'5, COR'6 der auch über eine C1-C4Alkylenbrücke gebunden sein kann, R21, R22 und R23 unabhängig voneinander je Wasserstoff oderC C4-Alkyl R' einenCl-C4-Alkylrest; einen C1-C4-Aralkylrest der im Phenylkern unsubstituiert oder
durch Halogen,C1-C4-hlkyl, Cl-C4-Alkoxy, C1-C4-Halogenalkyl, Cyan oder Nitro substituiert ist;
wenn m Null ist, kann R'5 auch Wasserstoff sein, R'6 Wasserstoff, einenCl-C4-Alkyl, C1-C4Halogenalkyl- oderC2-C8-Alkoxyalkylrest; Phenyl oder C1-C4-Aralkyl wobei der Phenylrest
unsubstituiert oder durch Halogen, Cyan,Cl-C4-Alkyl, Cl -04-Halogenalkyl substituiert sein kann;
einen C2-C4-Alkenylrest oder ein Aminorest-NR12R13, wobei R12 und R13 unabhängig voneinander
je Wasserstoff,C1-C8-Alkyl, C3-C6-Alkenyl, Phenyl oder C1-C4-Aralkyl bedeuten, wobei der
Phenylkern unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy,
C1-C4-Halogenalkoxy, Methylthio, Cyan oder Nitro substituiert sein kann, bedeuten.
21. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel XI enthält,
82/612
EMI133.1
worin R20 Wasserstoff oderCl-C4-Alkyl R"'20 Phenyl, durch Halogen,Cl-C4-Alkyl, Cl-C4-Alkoxy,
C1-C4-Alkylthio substituierts Phenyl, R21 Wasserstoff oderCl-C4-Alkyl R22 Wasserstoff oderClC4-Alkyl R Wasserstoff oderC@-C@-Alkyl R23 @@@@@ V Sauerstoff,
EMI134.1
oder S(O)n, n' Null 1, oder 2 R"25 eine04-C6-Alkylenbrücke, die geradkettig oder verzweigt sein
kann R"26 dasselbe wie R25 bedeuten.
22. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel XII enthält,
EMI134.2
worin m Null oder 1 n Null, 1, 2 oder 3 R"6 Wasserstoff, C1-C4-Alkyl, durch Halogen, C1-C4-Alkoxy
substituiert C1-C4-Alkyl,NR12R13, C2-C4-Alkenyl, Phenyl, C1-C4-Aralkyl wobei der Phenylkern
durch Halogen, C1-C4-Alkyl,Cl-C4-Alkoxy, C1-C4-Alkylthio substituiert sein kam;C1-C8-Alkoxy
R12 Wasserstoff, C1-C8-Alkyl, C3-C6-Alkenyl, R13 Wasserstoff, C1-C8-alkyl, C3-C6-Alkenyl,
Phenyl, C1-C4-Aralkyl wobei Phenyl durch Halogen, C1-C4-Alkyl,Cl-C4-Alkoxy und Alkylthio
substituiert sein kann, R'14 Wasserstoff oderCl-C4-Alkyl, Phenyl, C1-C4-aralkyl wobei der
Phenylkern durch Halogen,C1-O4-Alkyl, C1-C4-Alkoxy und Alkylthio substituiert sein kann; -COR"6 R'15 Wasserstoff oderCl-C4-Alkyl 16 Wasserstoff oder C1-C4-Alkyl R17 Wasserstoff oder C1C4-A1kyl R18 Wasserstoff oderC1-C4-Alkyl R17 und R18 zusammen eine C3-C5-alkylenkette W
einen Rest
EMI135.1
R24 C1-C4-Alkyl, R25 Wasserstoff, C1-C4-Alkyl unsubstituiert oder substituiert durch Hydroxy, C1C4-Alkoxy oder Halogen, R26 Wasserstoff,Cl-C4-Alkyl, C5-C8-Cycloalkyl, Phenyl oder C1-C4Aralkyl wobei der Phenylkern unsubstituiert oder substituiert ist durch Halogen Nitro, Cyan, C1-C4Alkyl,Cl -04-Alkoxy, Methylthio, C1-C4-Halogenalkoxy, Carboxy, C1-C4-Alkylcarbonyl, C1-C4Alkoxycarbonyl, Carbamoyl, C1-C4-alkylcarbamoyl, Di-C1-C4-Alkylcarbamoyl, C1-C4Alkylsulfonyl,Cl-C4-Alkylsulfuryl, Sulfamoyl oder Di-C1-C4-Alkylsulfamoyl bedeuten.
23. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel XIII enthält,
EMI135.2
worin R"20 einen Rest-000R'5, -COR'6 oder einenCl-C4-Alkylrest, der durch COOR'5 oder -COR'6
substituiert ist, R21 Wasserstoff oder C1-C4-Alkyl, R22 Wasserstoff oderCl-C4-Alkyl, R23
Wasserstoff oderC1-C4-Alkyl, R'5Cl-C4-Alkyl, unsubstituiert oder einCl-C4-Aralkylrest dessen
Phenylkern unsubstituiert oder substituiert durch Halogen, Nitro, Cyan, C1-C4-Alkyl,Cl-C4-Alkoxy,
Methylthio, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Carboxy, C1-C4-alkylcarbonyl, C1-C4Alkoxy carbonyl, Carbamoyl, C1-C4-Alkylcarbamoyl, Di-C1-C4-alkylcarbamoyl, C1-C4alkylsulfamoyl, C1-C4-Alkylsulfuryl, Sulfamyl oder Di-C1-C4-alkylsulfamoyl, R'6 Wasserstoff, C C1C4-Alkyl, unsubstituiert oder substituiert durch Halogen oderCl-C4-Alkoxy; Phenyl oderC1-C4Aralkyl, wobei der Phenylkern unsubstituiert oder durch Halogen, Nitro, Cyan, C1-C4-Alkyl,Cl-C4Alkoxy, Methylthio, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Carboxyl, C1-C4Alkylcarbonyl,Cl-C4-Alkoxy- carbonyl, Carbamoyl, C1-C4-Alkylcarbamoyl, Di-C1-C4Alkoxycarbamoyl, C1-C4-Alkylsulfonyl, C1-C4-alkylsulfuryl, Sulfamoyl oder Di-C1-C4alkylsulfamoyl einen Rest -NR12R13, C2-C4-Alkenyl R12 Wasserstoff,Cl-C8-Alkyl, C3-C-Alkenyl,
Phenyl oder C1-C4-Aralkyl wobei der Phenylkern unsubstituiert oder wie oben angegeben substituiert
sein kann, R13 dasselbe wie R12 bedeuten.
24. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel XIV enthält,
EMI136.1
worin R'25 Wasserstoff,Cl-C4-Alkyl, unsubstituiert oder substituiert durch Hydroxy,Cl-C4-Alkoxy,
Halogen, C1-C4-Alkyl-S(O)n,-, Phenyl-S(O)n, R"25 dasselbe wie R'
25 R'26 Wasserstoff, C1-C4-alkyl unsubstituiert oder substituiert durch Rest -S(O)'nR27, -OR'27, C5C8-Cycloalkyl oder durch Phenyl, welches unsubstituiert oder substituiert ist durch Halogen, Nitro,
cyan,Cl-C4-Alkyl, Cl-C4-Alkoxy, Methylthio, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy,
Carboxyl, C1-C4-alkylcarbonyl, C1-C4-Alkoxy carbonyl, Carbamoyl, C1-C4-alkylcarbamoyl, Di-c1C4-alkylcarbamoyl, C1-C4-alkylsulfonyl, C1-C4-alkylsulfuryl, Sulfamoyl oder Di-C1-C4Alkylsulfamoyl, R"26 dasselbe Wie R'26 oder Phenyl, C1-C4-Aralkyl wobei die Phenylkerne durch
83/612
Halogen,Cl-C4-Alkyl, C1-C4-Alkoxy, Cl-C4-Alkylthio, Cl-C4-Halogenalkyl substituiert sein können
R27Cl-C4-Alkyl, unsubstituiert oder substituiert durch Halogen, Nitro, Cyan, C1-C4-Alkyl,C1-C4Alkoxy, Methylthio,Cl -04-Halogenalkyl, C1-C4-Halogenalkoxy, Carboxyl, n' null, eins oder zwei X
Sauerstoff, Schwefel oder S(O)n'Cl-C4-Alkylcarbonyl, Cl-C4-Alkoxycarbonyl, Carbamoyl, C1-C4Alkylcarbamoyl, Di-C1-C4-alkylcarbamoyl, C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyl, Sulfamoyl
oder Di-C1-C4-alkylsulfamoyl, R'27 Wasserstoff oder dasselbe wie R27 bedeuten.
25. Mittel gemäss Anspruch 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel XV enthält,
EMI137.1
worin G Kohlenstoff, Sauerstoff, Schwefel, n" 4 bis 7R'25 Wasserstoff,C1-C4-Alkyl, unsubstituiert
oder substituiert durch Hydroxy, C1-C4-Alkoxy oder Halogen, R"25 Wasserstoff, C1-C4-Alkyl,
unsubstituiert oder substituiert durch Hydroxy,Cl-C4-hlkyl oder Halogen, R26 und R"26 Wasserstoff,
C1-C4-Alkyl unsubstituiert oder substituiert durch Reste-S(O)n,R27, -OR'27 oder durch Phenyl,
welches unsubstituiert oder substituiert ist durch Halogen, Nitro, Cyan, C1-C4-Alkyl, C1-C4-Alkoxy,
Methylthio, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Carboxyl, C1-C4-Alkylcarbonyl, C1-C4Alkoxycarbonyl, Carbamoyl, C1-C4-Alkylcarbamoyl, Di-C1-C4-alkylcarbamoyl,Cl-C4-Alkylsulfonyl,
C1-C4-Alkylsulfuryl, Sulfamoyl oderDi-C1-C4-al- kylsulfamoyl, X Sauerstoff, oder ein RestSO) , n'
Null, 1, oder 2n" 4, 5, 6 oder 7 R27Cl-C4-Alkyl, unsubstituiert oder substituiert durch Phenyl,
welches seinerseits unsubstituiert oder substituiert ist durch Halogen, Nitro, Cyan, C1-C4-Alkyl,Cl-C4Alkoxy, Methylthio, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Carboxyl, C1-C4-alkylcarbonyl,
C1-C4-Alkoxycarbonyl, C1-C4-Alkylsulfonyl, C1-C4-akylsulfuryl, Sulfamoyl oder C1-C4Dialkylsulfamoyl, R'27 Wasserstoff oder dasselbe wie R27 bedeuten.
26. Mittel gemäss Anspruoh 1, dadurch gekennzeichnet dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge eines Dichloracetamides der Formel XVI enthält,
EMI138.1
worin n Null, 1, 2 oder 3, Q einen Rest -(CH2)p Q1 einen Rest -(CHR19)o Q2 einen Rest (CHR'@@)@ Q2 einen R14 Wasserstoff oder C1-C4-Alkyl R"14 Wasserstoff,Cl-C4-Alkyl einen
Rest -COR" oder Phenyl, welches unsubstituiert oder substituiert ist durch Halogen, Nitro, Cyan,C1C4-Alkyl, Cl-C4-Alkoxy, Methylthio,Cl-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Carboxyl,Cl-C4Alkylcarbonyl, Cl-C4-Alkoxy- carbonyl, C1-C4-Halogenalkoxycarbonyl, Carbamoyl, C1-C4Alkylcarbamoyl, Di-C1-C4-Alkylcarbamoyl, C1-C4-Alkylsulfonyl,Cl -C 4-Alkylsulfuryl,
Sulfamoyl,Cl-C4-Alkylsulfamoyl oder Di-C1-C4-alkylsulfamoyl, R17 Wasserstoff oder C1-C4-Alkyl
R18 Wasserstoff oderC1-C4-Alkyl R19 Wasserstoff oderCl-C4-Alkyl R' Wasserstoff oderCl-C4Alkyl
119 1 4 lkyI o Null oder 1,
2 Null oder 1 und o Null oder 1 und p Null oder 1 R"6 Wasserstoff,Cl-C4-Alkyl, unsubstituiert oder
durch Halogen oderCl-C4-Alkoxy substituiert, bedeuten.
27. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nicht-phytotoxische Menge von N,N-Diallyl-dicloracetamid enthält.
28. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge von N-Allyl-N-(2-methoxy-1-methyl-äthyl)-dichloracetamid enthält.
29. Mittel gemäss Anspruch 1, dadurch gekenzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge von N-Benzyloxycarbonal-N'-dichloracetyl-hydrazinomethyläthylphosphinsäure-isopropylester der Formel
EMI139.1
enthält.
30. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge von N-Aethoxycarbonyl-N' -dichloracetyl-hydrazinomethylphosphonsäure-di- isopropylester der Formel
EMI140.1
enthält.
84/612
31. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge vonN-Allyl-N-n-butoxy-äthoxy-äthyl-dichloracetamld enthält.
32. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge von N-(3,4-Dimethoxybenzyl)-N-isopropyl-dichloracetamid enthält.
33. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge von4-DichloracetS1-2,3-dihdro-3-methyl-1,4-benzoxazin enthält.
34. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge von4-Dichloracetyl-2,3-dihydro-3,6-dimethyl-1,4-benzoxazin enthält.
35. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nicht phytotoxische Menge von 4-Dichloracetyl-2,3-dihydro-3-methyl-1,4-benzthiazin enthält.
36. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge vonN-Dichloracetyl-1,2,3,4-tetrahydro-isochinolin enthält.
37. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge von 5-Dichlorscetyl-3,3,6-trimethyl-9-oxo-1,5-diazabicyclof4,3,0]nonan der Formel
EMI141.1
enthält.
38. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge von2,2-Dimethyl-N-Oxazolidinyl-dichloracetamid enthält.
39. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es zur Erhöhung der Toleranz der Kultur
eine nichtphytotoxische Menge von N,N-bis-Dichloracetylpiperazin enthält.
40. Verfahren zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch
gekennzeichnet, dass man das herbizide Mittel nach Anspruch 1 vor, bei oder nach Aussaat der
Kulturpflanzen, vor oder während des Auflaufens der Kulturpflanzen ausbringt.
41. Verfahren zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch
gekennzeichnet, dass man N-(2-Methoxycarbonylphenylsulfonyl)-N'-(4, 6-bisdifluoromethoxypyrimidin-2-yl)-harnstoff der Formel I und Dichloracetamide der Formel II vor, bei
oder nach der Aussaat der Kulturpflanzen, vor oder während des Auflaufens der Kulturpflanzen
gleichzeitig oder nacheinander in beliebiger Reihenfolge ausbringt.
42. Verfahren zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch
gekennzeichnet, dass man das Saatgut der Kulturpflanzen mit einem Dichloracetamid der Formel II
behandelt.
43. Verfahren nach Anspruch 40, dadurch gekennzeichnet, das die Kulturpflanzen Mais, Reis, Hirse
oder Getreidearten sind.
44. Verfahren nach Anspruch 40, dadurch gekennzeichnet, das die Kulturpflanze Mais ist.
45. Verfahren gemäss Anspruch 40, dadurch gekennzeichnet, dass der Sulfonylharnstoff und das
Antidot in einer Aufwandmenge von jeweils 0,005 bis 10 kg pro ha Kulturboden verwendet werden.
46. Verfahren gemäss Anspruch 40, dadurch gekennzeicnet, dass der Sulfonylharnstoff und das Antidot
in einer Aufwandmenge von jeweils 0,05 bis 1 kg pro ha Kulturboden verwendet werden.Data supplied
from the esp@cenet database - Worldwide
85/612
6. EP1241159
- 9/18/2002
AROMATIC DIAMIDE DERIVATIVES, CHEMICALS FOR AGRICULTURAL
OR HORTICULTURAL USE AND USAGE THEREOF
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=EP1241159
Inventor(s):
TOHNISHI MASANORI (JP); KOHNO EIJI (JP); NAKAO HAYAMI (JP);
NISHIDA TATEKI (JP); FURUYA TAKASHI (JP); SHIMIZU TOSHIAKI (JP); SEO AKIRA (JP);
SAKATA KAZUYUKI (JP); FUJIOKA SHINSUKE (JP)
Applicant(s):
NIHON NOHYAKU CO LTD (JP)
IP Class 4 Digits: C07C
IP Class:C07C233/69
E Class: A01N57/14; A01N37/30; A01N41/06; A01N43/16; A01N43/28; A01N43/40; A01N47/12;
A01N47/28; C07C233/66; C07C233/69; C07C233/75; C07C233/78; C07C239/16; C07C271/12;
C07C271/20; C07C271/28; C07C275/14; C07C307/06; C07C311/05; C07C311/18; C07C323/12;
C07C323/43; C07C335/08; C07D295/20B5; C07F9/24C1
Application Number:
EP20000985836 (20001222)
Priority Number: WO2000JP09146 (20001222); JP19990365408 (19991222)
Family: EP1241159
Equivalent:
WO0146124; US2004009982
Abstract:
Abstract of EP1241159
The present invention relates to an aromatic diamide derivative represented by the general formula (I) :
>;CHEM; ÄA>;1; is optionally substituted (C1-C8)alkylene group, (C3-C8)alkenylene group or the
like, B is -O- or -N(R>;4;)- (wherein R>;4; is H, (C1-C6)alkyl, halo(C1-C6)alkyl or the like), R>;1; is
H, (C1-C6)alkyl, optionally substituted phenyl, optionally substituted heterocyclic group, or the like,
R>;2; and R>;3; are each H, (C3-C6)cyclo-alkyl or -A>;2;-R>;8; (A>;2; is -C(=O)-, -C(=S)- or C(=NR>;9;)-, R>;8; and R>;9; are each H, (C1-C6)alkyl or the like), Q>;1; to Q>;5; are each carbon or
nitrogen, X and Y are each halogen, cyano, nitro, (C3-C6)cycloalkyl, optionally substituted phenyl,
optionally substituted heterocyclic group, or the like, n is 0 to 4, m is 1 to 5, and Z>;1; and Z>;2; are
each O or SÜ or a salt thereof, an agricultural and horticultural chemical, and a usage of the chemical.
The agricultural and horticultural chemicals of the present invention exhibit remarkable controlling
effects against various insect pests such as agricultural, forest and horticultural insect pests, and stored
grain insect pests, etc., which injure paddy rice, fruit trees, vegetables, other crop plants, flowers and
ornamental plants, and the like.Description:
Description of EP1241159
TECHNICAL FIELD
[0001] The present invention relates to aromatic diamide derivatives or salts thereof; an agricultural
and horticultural chemical, in particular, an agricultural and horticultural insecticide, which contains
said compound as an active ingredient; and a usage of the chemical.
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BACKGROUND ART
[0002] JP-A-11-240857 discloses a compound analogous to the aromatic diamide derivative of the
present invention but does not describes working examples, physical properties and the like with
respect to the compound of the present invention.
DISCLOSURE OF THE INVENTION
[0003] The production of agricultural and horticultural crops and the like is still badly damaged by
insect pests and the like, and the development of a novel agricultural and horticultural chemical, in
particular, agricultural and horticultural insecticide is desired because of, for example, the appearance
of insect pests resistant to existing chemicals. In addition, because of the increased population of aged
farmers, and the like, various labor-saving application methods are desired and the development of an
agricultural and horticultural chemical having properties suitable for the application methods is desired.
[0004] The present inventors earnestly investigated in order to develop a novel agricultural and
horticultural chemical, and consequently found that the aromatic diamide derivative represented by the
general formula (I) of the present invention is a novel compound not known in any literature, and the
present inventors found a novel use of said derivative as an agricultural and horticultural chemical, in
particular, an agricultural and horticultural insecticide and their effective usage, whereby the present
invention has been accomplished.
[0005] That is, the present invention relates to an aromatic diamide derivative represented by the
general formula (I):
EMI2.1
{wherein A>;1; is a (C1-C8)alkylene group; a substituted (C1-C8)alkylene group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, halo(C1-C6)alkyl groups, (C1-C6) alkoxy groups, halo(C1-C6)alkoxy groups, (C1C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, (C1C6)alkylthio(C1-C6)alkyl groups, (C1-C6) alkoxycarbonyl groups and phenyl group; a (C3C8)alkenylene group; a substituted (C3-C8)alkenylene group having one or more substituents which
may be the same or different and are selected from halogen atoms, cyano group, nitro group, halo(C1C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo
(C1-C6) alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, (C1-C6) alkylthio (C1-C6)alkyl groups,
(C1-C6)alkoxycarbonyl groups and phenyl group; a (C3-C8)alkynylene group; or a substituted (C3C8)alkynylene group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, (C1-C6)alkylthio(C1-C6)alkyl groups, (C1-C6)alkoxycarbonyl groups and
phenyl group,
any of the saturated carbon atoms in the above-mentioned (C1-C6)alkylene group, substituted (C1C8)alkylene group, (C3-C8)alkenylene group, substituted (C3-C8)alkenylene group, (C3C8)alkynylene group or substituted (C3-C8)alkynylene group being able to have a (C2-C5)alkylene
group bonded thereto as a substituent, to form a (C3-C6)cycloalkane ring, and any two of the carbon
atoms in the above-mentioned (C1-C8)alkylene group, substituted (C1-C8)alkylene group, (C3C8)alkenylene group and substituted (C3-C8)alkenylene group being able to form a (C3C6)cycloalkane ring or a (C3-C6)cycloalkene ring together with an alkylene group or an alkenylene
group,
B is -O- or -N(R>;4;)- (wherein R>;4; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl
group; a (C3-C6)alkenyl group; a halo (C3-C6)alkenyl group; a (C3-C6)alkynyl group; a (C3-
87/612
C6)cycloalkyl group; a (C1-C6)alkylcarbonyl group; a halo(C1-C6)alkylcarbonyl group; a (C1C6)alkoxycarbonyl group; a phenylcarbonyl group; a substituted phenylcarbonyl group having on the
ring one or more substituents which may be the same or different and are selected from halogen atoms,
cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo
(C1-C6)alkoxy groups, (C1-C6)alkyl-thio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, and di (C1-C6)alkylamino groups whose (C1-C6)alkyl
groups may be the same or different; a phenyl(C1-C4)alkoxycarbonyl group; a substituted phenyl(C1C4)alkoxycarbonyl group having on the ring one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, and
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different; a phenyl(C1C4)alkyl group; or a substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups,
(C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6)alkoxycarbonyl groups),
R>;1; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy(C1C4)alkyl group; a (C1-C4)alkylthio(C1-C4)alkyl group; a (C2-C6)alkenyl group; a halo(C2-C6)alkenyl
group; a (C3-C6)alkynyl group; a halo(C3-C6)alkynyl group; a (C3-C6)cycloalkyl group; a halo(C3C6)cycloalkyl group; a phenyl group; a substituted phenyl group having one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6) alkoxy groups,
(C1-C6) alkylthio groups, halo (C1-C6) alkylthio groups, (C1-C6) alkylsulfinyl groups, halo(C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1C6) alkylamino groups, di (C1-C6) alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6) alkoxycarbonyl groups; a phenyl (C1-C4) alkyl group; a substituted phenyl(C1C4)alkyl group having on the ring one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a
heterocyclic group; a substituted heterocyclic group having one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; -P(=W>;1;) (-OR>;5;) (-OR>;6;) (wherein W>;1; is an oxygen atom or a
sulfur atom, and each of R>;5; and R>;6;, which may be the same or different, is a hydrogen atom; a
(C1-C6)alkyl group; a halo (C1-C6)alkyl group; a (C1-C4)alkoxy(C1-C4)alkyl group; a (C1C4)alkylthio (C1-C4)alkyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6) alkoxycarbonyl groups; a phenyl (C1-C4) alkyl group; a
substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1-
88/612
C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups,
further, R>;5; being able to bind to R>;6; to form a 5- to 8-membered ring that may contain one or
two atoms which may be the same or different and are selected from oxygen atom, sulfur atom and
nitrogen atom, between adjacent carbon atoms constituting the ring); -C(=W>;1;)-N(R>;5;) (R>;6;)
(wherein W>;1;, R>;5; and R>;6; are as defined above, R>;5; being able to bind to R>;6; to form a 5to 8-membered ring that may contain one or two atoms which may be the same or different and are
selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting
the ring, and R>;5; being able to bind to R>;4; to form a 5- to 8-membered ring that may contain two or
three atoms which may be the same or different and are selected from oxygen atom, sulfur atom and
nitrogen atom, between adjacent carbon atoms constituting the ring); -C(=W>;1;)-R>;5; (wherein
W>;1; and R>;5; are as defined above); -C(=W>;1;)-W>;1;-R>;7; (wherein W>;1;s, which may be the
same or different, are as defined above, and R>;7; is a (C1-C6)alkyl group; a halo (C1-C6)alkyl group;
a (C1-C4)alkoxy(C1-C4)alkyl group; a (C1-C4)alkylthio(C1-C4)alkyl group; a phenyl group; a
substituted phenyl group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a phenyl (C1-C4)alkyl group; a substituted phenyl(C1-C4)alkyl group
having on the ring one or more substituents which may be the same or different and are selected from
halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups,
(C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; or a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo
(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups); -SO2-R>;7; (wherein R>;7; is as defined above); -SO2-N(R>;5;)(R>;6;)
(wherein R>;5; and R>;6; are as defined above, R>;5; being able to bind to R>;6; to form a 5- to 8membered ring that may contain one or two atoms which may be the same or different and are selected
from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the
ring, and R>;5; being able to bind to R>;4; to form a 5- to 8-membered ring that may contain three or
four atoms which may be the same or different and are selected from oxygen atom, sulfur atom and
nitrogen atom, between adjacent carbon atoms constituting the ring); -N(R>;5;) (R>;6;) (wherein R>;5;
and R>;6; are as defined above, R>;5; being able to bind to R>;6; to form a 5- to 8-membered ring that
may contain one or two atoms which may be the same or different and are selected from oxygen atom,
sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the ring, and R>;5; being
able to bind to R>;4; to form a 5- to 8-membered ring that may contain two or three atoms which may
be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom, between
adjacent carbon atoms constituting the ring); or N=C(R>;5;)R>;6; (wherein R>;5; and R>;6; are as
defined above, R>;5; being able to bind to R>;6; to form a 5- to 8-membered ring that may contain one
or two atoms which may be the same or different and are selected from oxygen atom, sulfur atom and
nitrogen atom, between adjacent carbon atoms constituting the ring); in the case of B being -N(R>;4;)-,
R>;1; being able to be -OR>;5; (wherein R>;5; is as defined above), -C(W>;2;)-N(R>;5;)R>;6;
(wherein W>;2; is =CH-NO2, =N-NO2 or =N-CN, and R>;5; and R>;6; are as defined above, R>;5; or
R>;6; being able to bind to R>;4; to form a 5- to 8-membered ring that may contain two or three atoms
which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom,
between adjacent carbon atoms constituting the ring) or -C(W>;2;)-W>;1;-R>;7; (wherein W>;1;,
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W>;2; and R>;7; are as defined above, R>;7; being able to bind to R>;4; to form a 5-to 8-membered
ring that may contain two or three atoms which may be the same or different and are selected from
oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the ring), and
R>;1; being able to bind to A>;1; to form a 5- to 8-membered ring that may contain one or two atoms
which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom,
between adjacent carbon atoms constituting the ring,
each of R>;2; and R>;3;, which may be the same or different, is a hydrogen atom, a (C3C6)cycloalkyl group or -A>;2;-R>;8; (wherein A>;2; is -C(=O)-, -C(=S)-, -C(=NR>;9;)-(wherein R>;9;
is a hydrogen atom, a (C1-C6)alkyl group, a (C1-C6)alkoxy group, a mono(C1-C6)alkylamino group, a
di(C1-C6)alkylamino group whose (C1-C6)alkyl groups may be the same or different, a (C1C6)alkoxycarbonyl group, a phenyl group, or a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups), a (C1-C8)alkylene group, a
halo(C1-C8)alkylene group, a (C3-C6)alkenylene group, a halo (C3-C6)alkenylene group, a (C3C6)alkynylene group or a halo(C3-C6)alkynylene group,
(1) in the case of A>;2; being -C(=O)-, -C(=S)-or -C(=NR>;9;)- (wherein R>;9; is as defined above),
R>;8; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C3-C6)cycloalkyl
group; a halo(C3-C6)cycloalkyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic group; a substituted
heterocyclic group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; or A>;3;-R>;10; (wherein A>;3; is -O-, -S- or -N(R>;11;)- (wherein R>;11; is a hydrogen atom; a (C1C6)alkylcarbonyl group; a halo(C1-C6)alkylcarbonyl group; a (C1-C6)alkoxycarbonyl group; a
phenylcarbonyl group; a substituted phenylcarbonyl group having one or more substituents which may
be the same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl
groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6)alkoxycarbonyl groups; a phenyl(C1-C4)alkoxycarbonyl group; or a substituted
phenyl(C1-C4)alkoxycarbonyl group having on the ring one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups,
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups), and R>;10; is a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C3C6)alkenyl group; a halo(C3-C6)alkenyl group; a (C3-C6)alkynyl group; a halo (C3-C6)alkynyl group;
a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkylcarbonyl group; a halo (C1C6)alkylcarbonyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-
90/612
C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1C4)alkyl group; a substituted phenyl(C1-C4)alkyl group having one or more substituents which may be
the same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl
groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups),
(2) in the case of A>;2; being a (C1-C8)alkylene group, a halo(C1-C8)alkylene group, a (C3C6)alkenylene group, a halo(C3-C6)alkenylene group, a (C3-C6)alkynylene group or a halo(C3C6)alkynylene group, R>;8; is a hydrogen atom; a halogen atom; a cyano group; a nitro group; a (C3C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group;
a substituted phenyl group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; a substituted heterocyclic group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; or -A>;4;-R>;12; (wherein A>;4; is O-, -S-, -SO-, -SO2-, -N(R>;11;)- (wherein R>;11; is as defined above), -C(=O)-, or -C(=N-OR>;13;)
(wherein R>;13; is a hydrogen atom, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a (C3C6)alkenyl group, a halo(C3-C6)alkenyl group, a (C3-C6)alkynyl group, a halo(C3-C6)alkynyl group,
a (C3-C6)cycloalkyl group, a phenyl(C1-C4)alkyl group, or a substituted phenyl(C1-C4)alkyl group
having on the ring one or more substituents which may be the same or different and are selected from
halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups),
(i) in the case of A>;4; being -O-, -S-, -SO-, -SO2- or -N(R>;11;)- (wherein R>;11; is as defined
above), R>;12; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C3-C6)alkenyl
group; a halo(C3-C6)alkenyl group; a (C3-C6)alkynyl group; a halo (C3-C6)alkynyl group; a (C3C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkylcarbonyl group; a halo(C1C6)alkylcarbonyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1C4)alkyl group; a substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups,
(C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
91/612
different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups,
(ii) in the case of A>;4; being -C(=O)- or -C(=NOR>;13;) (wherein R>;13; is as defined above),
R>;12; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C2-C6)alkenyl group;
a halo (C2-C6)alkenyl group; a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1C6)alkoxy group; a halo(C1-C6)alkoxy group; a (C1-C6)alkylthio group; a halo(C1-C6)alkylthio
group; a mono (C1-C6)alkylamino group; a di (C1-C6)alkylamino group whose (C1-C6)alkyl groups
may be the same or different; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenylamino group; a substituted
phenylamino group having on the ring one or more substituents which may be the same or different and
are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a phenyloxy group; a substituted phenyloxy group having on the ring one
or more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6) alkoxy groups, (C1-C6) alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenylthio group; a substituted
phenylthio group having on the ring one or more substituents which may be the same or different and
are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6) alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6) alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups)),
further, R2 being able to bind to A>;1; or R>;1; to form a 5- to 8-membered ring that may contain
one to three atoms which may be the same or different and are selected from oxygen atom, sulfur atom
and nitrogen atom, between adjacent carbon atoms constituting the ring, each of Q>;1; through Q>;5; is
a carbon atom or a nitrogen atom,
each of Xs, which may be the same or different, is a halogen atom; a cyano group; a nitro group; a
(C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxycarbonyl group; a phenyl
group; a substituted phenyl group having one or more substituents which may be the same or different
and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1-
92/612
C6)alkoxycarbonyl groups; a heterocyclic group; a substituted heterocyclic group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; or -A>;5;-R>;14; (wherein A>;5; is O-, -S-, -SO-, -SO2-, -C(=O)-, -C(=NOR>;13;) (wherein R>;13; is as defined above), a (C1C6)alkylene group, a halo (C1-C6)alkylene group, a (C2-C6)alkenylene group, a halo(C2C6)alkenylene group, a (C2-C6)alkynylene group or a halo(C3-C6)alkynylene group,
(1) in the case of A>;5; being -O-, -S-, -SO- or -SO2-, R>;14; is a halo(C3-C6)cycloalkyl group; a
halo(C3-C6)cycloalkenyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic group; a substituted
heterocyclic group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;6;-R>;15; (wherein A>;6; is a (C1-C6)alkylene group, a halo(C1C6)alkylene group, a (C3-C6)alkenylene group, a halo(C3-C6)alkenylene group, a (C3-C6)alkynylene
group or a halo(C3-C6)alkynylene group, and R>;15; is a hydrogen atom; a halogen atom; a (C3C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group;
a substituted phenyl group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;7;-R>;16; (wherein A>;7; is -O-, -S-, -SO- or -SO2-, and R>;16; is
a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C3-C6)alkenyl group; a halo (C3-C6)alkenyl
group; a (C3-C6)alkynyl group; a halo(C3-C6)alkynyl group; a (C3-C6)cycloalkyl group; a halo(C3C6)cycloalkyl group; a phenyl group; a substituted phenyl group having one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups,
(C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6) alkoxycarbonyl groups),
(2) in the case of A>;5; being -C(=O)- or -C(=NOR>;13;)- (wherein R>;13; is as defined above),
R>;14; is a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C2-C6)alkenyl group; a halo(C2C6)alkenyl group; a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxy group;
a (C1-C6)alkylthio group; a mono(C1-C6)alkylamino group; a di(C1-C6)alkylamino group whose (C1C6)alkyl groups may be the same or different; a phenyl group; a substituted phenyl group having one
or more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
93/612
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenylamino group; a substituted
phenylamino group having on the ring one or more substituents which may be the same or different and
are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups,
(3) in the case of A>;5; being a (C1-C6)alkylene group, a halo(C1-C6)alkylene group, a (C2C6)alkenylene group, a halo(C2-C6)alkenylene group, a (C2-C6)alkynylene group or a halo(C3C6)alkynylene group, R>;14; is a hydrogen atom; a halogen atom; a (C3-C6)cycloalkyl group; a halo
(C3-C6)cycloalkyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6) alkoxy groups, (C1-C6) alkylthio groups, halo (C1-C6) alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6) alkylsulfinyl groups, (C1-C6) alkylsulfonyl groups, halo (C1C6) alkylsulfonyl groups, mono (C1-C6) alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;8;-R>;17; (wherein A>;8; is -O-, -S-, -SO- or -SO2-, and R>;17; is
a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;9;-R>;18; (wherein A>;9; is a (C1-C6)alkylene group, a halo(C1C6)alkylene group, a (C2-C6)alkenylene group, a halo(C2-C6)alkenylene group, a (C2-C6)alkynylene
group or a halo(C3-C6)alkynylene group, and R>;18; is a hydrogen atom; a halogen atom; a (C3C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxy group; a halo (C1-C6) alkoxy
group; a (C1-C6)alkylthio group; a halo(C1-C6)alkylthio group; a (C1-C6)alkylsulfinyl group; a
halo(C1-C6)alkylsulfinyl group; a (C1-C6)alkylsulfonyl group; a halo(C1-C6)alkylsulfonyl group; a
phenyl group; a substituted phenyl group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a phenyloxy group; a substituted phenyloxy group having one or more
94/612
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenylthio group; a substituted
phenylthio group having one or more substituents which may be the same or different and are selected
from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups,
(C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo
(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose
(C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; or a heterocyclic group having one or more substituents which may be the same or different and
are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups)), n is an integer of 0 to 4,
further, two adjacent Xs on the aromatic ring being able to be taken together to represent a fused ring
that may have one or more substituents which may be the same or different and are selected from
halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups,
(C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo
(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose
(C1-C6)alkyl groups may be the same or different, and (C1-C6) alkoxycarbonyl groups,
each of Ys, which may be the same or different, is a halogen atom; a cyano group; a nitro group; a
(C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups,
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;5;-R>;14; (wherein A>;5; and R>;14; are as defined above),
further, two adjacent Ys on the aromatic ring being able to be taken together to represent a fused ring
that may have one or more substituents which may be the same or different and are selected from
halogen atoms; (C1-C6)alkyl groups; halo(C1-C6)alkyl groups; (C1-C6)alkoxy groups; halo(C1C6)alkoxy groups; (C1-C6)alkylthio groups; halo(C1-C6)alkylthio groups; (C1-C6)alkylsulfinyl
groups; halo(C1-C6)alkylsulfinyl groups; (C1-C6)alkylsulfonyl groups; halo(C1-C6)alkylsulfonyl
groups; phenyl group; substituted phenyl groups having one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; heterocyclic groups; and substituted heterocyclic groups having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
95/612
groups, mono (C1-C6) alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups,
m is an integer of 1 to 5, and each of Z>;1; and Z>;2; is an oxygen atom or a sulfur atom} or a salt
thereof, an agricultural and horticultural chemical containing aromatic diamide derivative as an active
ingredient, and a usage of the same.
MODE FOR CARRYING OUT THE INVENTION
[0006] In the definition of the general formula (I) shown for the aromatic diamide derivative or salt
thereof of the present invention, the term "halogen atom" means a chlorine atom, a bromine atom, an
iodine atom or a fluorine atom. The term "(C1-C6)alkyl" means a linear or branched alkyl group of 1 to
6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, nhexyl or the like. The term "halo(C1-C6)alkyl" means a substituted and linear or branched alkyl group
of 1 to 6 carbon atoms having as the substituent(s) one or more halogen atoms which may be the same
or different. The term "(C1-C8)alkylene" means a linear or branched alkylene group of 1 to 8 carbon
atoms, such as methylene, ethylene, propylene, trimethylene, dimethylmethylene, tetramethylene,
isobutylene, dimethylethylene, octamethylene or the like. As "the 5- to 8-membered ring which R>;5;
and R>;6; (or R>;2; and A>;1; or R>;1;) form by their binding to each other, i.e., the 5- to 8-membered
ring that may contain one or two (or one to three) atoms which may be the same or different and are
selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting
the ring" or "the 5- to 8-membered ring which R>;5; (or R>;6; or R>;7;) and R>;4; form by their
binding to each other, i.e., the 5- to 8-membered ring that may contain two or three, or three or four
atoms which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen
atom, between adjacent carbon atoms constituting the ring", there can be exemplified azetidine ring,
pyrrolidine ring, pyrroline ring, piperidine ring, imidazolidine ring, imidazoline ring, oxazolidine ring,
thiazolidine ring, isoxazolidine ring, isothiazolidine ring, tetrahydropyridine ring, piperazine ring,
morpholine ring, thiomorpholine ring, dioxazine ring, dithiazine ring, etc.
[0007] The "heterocyclic group" includes, for example, pyridyl group, pyridine-N-oxide group,
pyrimidinyl group, furyl group, tetrahydrofuryl group, thienyl group, tetrahydrothienyl group,
tetrahydropyranyl group, tetrahydrothiopyranyl group, oxazolyl group, isoxazolyl group, oxadiazolyl
group, thiazolyl group, isothiazolyl group, thiadiazolyl group, imidazolyl group, triazolyl group and
pyrazolyl group. The "fused ring" includes, for example, naphthalene, tetrahydronaphthalene, indene,
indane, quinoline, quinazoline, indole, indoline, chroman, isochroman, benzodioxane, benzodioxole,
benzofuran, dihydrobenzofuran, benzothiophene, dihydrobenzothiophene, benzoxazole, benzothiazole,
benzimidazole and indazole.
[0008] The salt of the aromatic diamide derivative of the general formula (I) of the present invention
includes, for example, inorganic acid salts such as hydrochloride, sulfate, nitrate, phosphate and the
like; organic acid salts such as acetate, fumarate, maleate, oxalate, methanesulfonate, benzenesulfonate,
p-toluenesulfonate and the like; salts with a sodium ion, potassium ion, calcium ion or the like.
[0009] The aromatic diamide derivative of the general formula (I) or salt thereof of the present
invention contains one or more asymmetric carbon atoms or asymmetric centers in its structural
formula in some cases and has two or more optical isomers and diastereomers in some cases. The
present invention also includes all of the individual optical isomers and mixtures consisting of these
isomers in any ratio. The aromatic diamide derivative of the general formula (I) or salt thereof of the
present invention has two geometrical isomers due to a carbon-carbon double bond or a carbonnitrogen double bond in its structural formula in some cases. The present invention also includes all of
the individual geometrical isomers and mixtures consisting of these isomers in any ratio. The present
invention also includes hydrates of said compound, depending on the kind of the compound.
[0010] Preferable examples of the aromatic diamide derivative of the general formula (I) or salt
thereof of the present invention are aromatic diamide derivatives in which A>;1; is a (C1-C4)alkylene
group, B is -O- or -N(R>;4;)- (wherein R>;4; is a hydrogen atom or a (C1-C3)alkyl group), R>;1; is a
hydrogen atom, a (C1-C3)alkyl group, a phenyl(C1-C3)alkyl group, a substituted phenyl(C1-C3)alkyl
96/612
group, a (C1-C3)alkylcarbonyl group, a halo(C1-C3)alkylcarbonyl group, a (C1-C3)alkoxycarbonyl
group, a mono (C1-C3)alkylaminocarbonyl group, a di (C1-C3)alkyl-aminocarbonyl group whose (C1C3)alkyl groups may be the same or different, a (C1-C3)alkylsulfonyl group, a mono (C1C3)alkylaminosulfonyl group, a di (C1-C3)alkyl-aminosulfonyl group whose (C1-C3)alkyl groups may
be the same or different, a di(C1-C3)alkoxyphosphono group whose (C1-C3)alkyl groups may be the
same or different, or a di(C1-C3)alkoxythiophosphono group whose (C1-C3)alkyl groups may be the
same or different, each of R>;2; and R>;3; is a hydrogen atom or a (C1-C3)alkyl group, each of Q>;1;
through Q>;4; is a carbon atom, X is a halogen atom, a nitro group, a halo(C1-C6)alkyl group, a
halo(C1-C6)alkoxy group or a halo(C1-C6)alkylthio group, n is an integer of 0 to 2, Q>;5; is a carbon
atom or a nitrogen atom, each of Ys, which may be the same or different, is a halogen atom, a (C1C3)alkyl group, a halo(C1-C3) alkyl group, a (C1-C3)alkoxy group, a halo(C1-C3)alkoxy group, a
halo(C1-C3)alkylthio group or a halo (C1-C3)alkoxyhalo (C1-C3) alkoxy group, m is an integer of 1 to
3, each of Z>;1; and Z>;2; is an oxygen atom; or salts thereof.
[0011] The aromatic diamide derivative of the general formula (I) or salt thereof of the present
invention can be produced, for example, by the production process illustrated below. In the present
invention, the production can be carried out also by, for example, the process disclosed in JP-A-11240857. A process for the production, however, is not limited to these production processes.
Production process 1.
EMI38.1
EMI38.2
EMI38.3
wherein R>;1;, R>;2;, R>;3;, A>;1;, B, Q>;1; through Q>;5;, X, n, Y, m, Z>;1; and Z>;2; are as
defined above.
[0013] An aromatic diamide derivative of the general formula (I-1) can be obtained by allowing an
aromatic carboxylic acid anhydride derivative of the general formula (II) to react with an aromatic
amine of the general formula (III) in the presence of an inert solvent to obtain an aromatic imide
derivative of the general formula (IV), and allowing said aromatic imide derivative (IV) to react with
an amine of the general formula (V) after or without isolation of the aromatic imide derivative (IV).
(1). General formula (II) -; general formula (IV)
[0014] As the inert solvent usable in this reaction, any inert solvent may be used so long as it does
not markedly inhibit the progress of the reaction. There can be exemplified inert solvents including
aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as
methylene chloride, chloroform, carbon tetrachloride, etc.; chlorinated aromatic hydrocarbons such as
chlorobenzene, dichlorobenzene, etc.; acyclic or cyclic ethers such as diethyl ether, dioxane,
tetrahydrofuran, etc.; esters such as ethyl acetate, etc.; amides such as dimethylformamide,
dimethylacetamide, etc.; acids such as acetic acid, etc.; dimethyl sulfoxide; 1,3-dimethyl-2imdazolidinone; and the like. These inert solvents may be used singly or as a mixture thereof.
[0015] Since the reaction is an equimolar reaction, it is sufficient that the reactants are used in
equimolar amounts, though either of them may be used in excess. If necessary, the reaction may be
carried out under dehydrating conditions.
[0016] As to the reaction temperature, the reaction can be carried out at room temperature to the
reflux temperature of the inert solvent used. Although the reaction time is varied depending on the
scale of reaction, the reaction temperature, etc., it may be properly chosen in the range of several
minutes to 48 hours.
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[0017] After completion of the reaction, the desired compound is isolated from the reaction system
containing the desired compound by a conventional method, and if necessary, purified by
recrystallization, column chromatography, etc., whereby the desired compound can be produced. The
desired compound can be subjected to the subsequent reaction step without isolation from the reaction
system.
[0018] The aromatic carboxylic acid anhydride derivative of the general formula (II) can be produced
by any of the processes described in J. Org. Chem., 52, 129 (1987), J. Am. Chem. Soc., 51, 1865 (1 to
29), ditto 63, 1542 (1941), etc. The aromatic amine of the general formula (III) can be produced by any
of the processes described in J. Org. Chem., 29, 1 (1964), Angew. Chem. Int. Ed. Engl., 24, 871
(1985), Synthesis, 1984, 667, Journal of Chemical Society of Japan, 1973, 2351, German Patent LaidOpen DE-2606982, JP-A-1-90163, etc.
(2). General formula (IV) -; general formula (I-1)
[0019] As an inert solvent usable in this reaction, those exemplified as the inert solvent usable in (1)
can be exemplified.
[0020] Since the reaction is an equimolar reaction, it is sufficient that the reactants are used in
equimolar amounts, though the amine of the general formula (V) may be used in excess.
[0021] As to the reaction temperature, the reaction can be carried out at room temperature to the
reflux temperature of the inert solvent used. Although the reaction time is varied depending on the
scale of reaction, the reaction temperature, etc., it may be properly chosen in the range of several
minutes to 48 hours.
[0022] After completion of the reaction, the desired compound is isolated from the reaction system
containing the desired compound by a conventional method, and if necessary, purified by
recrystallization, column chromatography, etc., whereby the desired compound can be produced.
Production process 2.
EMI42.1
wherein R>;1;, R>;2;, R>;3;, A>;1;, B, Q>;1; through Q>;5;, X, n, Y, m, Z>;1; and Z>;2; are as
defined above.
[0024] An aromatic diamide derivative of the general formula (I) can be produced by allowing an
aromatic carboxylic acid anhydride derivative of the general formula (II-1) to react with an amine of
the general formula (V) in the presence of an inert solvent to obtain a phthalamide of the general
formula (VI-2), and treating this aromatic amide (VI-2) as follows after or without isolation. When
R>;2; of the aromatic amide (VI-2) is a hydrogen atom, the aromatic amide (VI-2) is subjected to
condensation reaction in the presence of a condensing agent to obtain a compound of the general
formula (VII-2), which is allowed to react with an aromatic amine of the general formula (III-1) in the
presence of an inert solvent after or without isolation of the compound (VII-2). When R>;2; of the
aromatic amide (VI-2) is other than a hydrogen atom, the aromatic amide (VI-2) is condensed with an
aromatic amine of the general formula (III-1) in the presence of a condensing agent.
[0025] Alternatively, an aromatic diamide derivative of the general formula (I) can be produced by
allowing an aromatic carboxylic acid anhydride derivative of the general formula (II-1) to react with an
aromatic amine of the general formula (III-1) in the presence of an inert solvent to obtain an aromatic
amide of the general formula (VI-1), and treating the aromatic amide (VI-1) as follows after or without
isolation. When R>;3; of the aromatic amide (VI-1) is a hydrogen atom, the aromatic amide (VI-1) is
subjected to condensation reaction in the presence of a condensing agent to obtain a compound of the
98/612
general formula (VII-1), which is allowed to react with an amine of the general formula (V) in the
presence of an inert solvent after or without isolation of the compound (VII-1). When R>;3; of the
aromatic amide (VI-1) is other than a hydrogen atom, the aromatic amide (VI-1) is condensed with an
amine of the general formula (V) in the presence of a condensing agent.
(1). General formula (II-1) -; general formula (VI-1), or general formula (II-1) -; general formula (VI2)
[0026] In the case of either of these reactions, the desired compound can be produced in a manner
similar to that described in production process 1-(2).
(2). General formula (VII-1) or general formula (VII-2) -; general formula (I)
[0027] In the case of this reaction, the desired compound can be produced in a manner similar to that
described in production process 1-(2).
(3). General formula (VI-1) -; general formula (VII-1), or general formula (VI-2) -; general formula
(VII-2)
[0028] In the case of either of these reactions, the desired compound can be produced according to
the process described in J. Med. Chem., 10, 982 (1967).
(4). General formula (VI-1) or general formula (VI-2) -; general formula (I)
[0029] The desired compound can be produced by allowing an aromatic amide derivative of the
general formula (VI-1) or the general formula (VI-2) to react with an amine of the general formula (V)
or the general formula (III-1), respectively, in the presence of a condensing agent and an inert solvent.
If necessary, the reaction can be carried out in the presence of a base.
[0030] The inert solvent used in the reaction includes, for example, tetrahydrofuran, diethyl ether,
dioxane, methylene chloride and chloroform.
[0031] As the condensing agent used in the reaction, any condensing agent used in conventional
amide production may be used. There can be exemplified Mukaiyama reagent (2-chloro-Nmethylpyridinium iodide), DCC (1,3-dicyclohexylcarbodiimide), CDI (carbonyldiimidazole) and
DEPC (diethyl cyanophosphate). As to the amount of the condensing agent used, the condensing agent
may be used in an amount properly chosen in the range of 1 mole to excess moles per mole of the
aromatic amide derivative of the general formula (VI-1) or the general formula (VI-2).
[0032] The base usable in the reaction includes, for example, organic bases such as triethylamine,
pyridine, etc., and inorganic bases such as potassium carbonate, etc. As to the amount of the base used,
the base may be used in an amount properly chosen in the range of 1 mole to excess moles per mole of
the aromatic amide derivative of the general formula (VI-1) or the general formula (VI-2).
[0033] As to the reaction temperature, the reaction can be carried out at 0 DEG C to the boiling point
of the inert solvent used. Although the reaction time is varied depending on the scale of reaction, the
reaction temperature, etc., it ranges from several minutes to 48 hours.
[0034] After completion of the reaction, the desired compound is isolated from the reaction system
containing the desired compound by a conventional method, and if necessary, purified by
recrystallization, column chromatography, etc., whereby the desired compound can be produced.
99/612
[0035] Typical compounds as the aromatic diamide derivative of the general formula (I) or a salt
thereof are listed in Table 1 or Table 2 but they are not intended in any way to limit the scope of the
present invention. In the following tables, Me indicates methyl, Et ethyl, Pro propyl, Bu butyl, Ph
phenyl, Pyr pyridyl, and c- an alicyclic hydrocarbon.
EMI47.1
EMI47.2
EMI48.1
EMI49.1
EMI50.1
EMI51.1
EMI52.1
EMI53.1
EMI54.1
EMI55.1
EMI56.1
EMI57.1
EMI58.1
EMI59.1
EMI60.1
EMI61.1
EMI62.1
EMI63.1
EMI64.1
EMI65.1
EMI66.1
EMI67.1
>;tb;>;TABLE; Id=Table 2 Columns=10
>;tb;Title: (Z>;1;=Z>;2;=O, R>;2;=R>;3;=H)
>;tb;
>;tb;Head Col 1: No
>;tb;Head Col 2: -A>;1;-B-R>;1;
>;tb;Head Col 3: Q>;1;
>;tb;Head Col 4: Q>;2;
>;tb;Head Col 5: Q>;3;
>;tb;Head Col 6: Q>;4;
>;tb;Head Col 7: Q>;5;
100/612
>;tb;Head Col 8: Xn
>;tb;Head Col 9: Ym
>;tb;Head Col 10: Melting point DEG C
>;tb;2-1>;SEP;CH(Me)CH2OCONHEt>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;3Cl>;SEP;2-Me-4-OCF3
>;tb;2-2>;SEP;CH(Me)CH2OCON(Et)2>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;3Cl>;SEP;2-Me-4-CF2CF3
>;tb;2-3>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;3Cl>;SEP;2-Me-4-CF2CF3>;SEP;85
>;tb;2-4>;SEP;C(Me)2CH2OCONHMe>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;3Cl>;SEP;2-Me-4-CF(CF3)2
>;tb;2-5>;SEP;CH(Me) CH2OCONHEt>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;H>;SEP;2Me-4-CF(CF3)2>;SEP;100
>;tb;2-6>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;3Br>;SEP;2-Me-4-CF3
>;tb;27>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;H>;SEP;2-Cl4-OCF3
>;tb;2-8>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;H>;SEP;2Me-4-CF2CF3
>;tb;2-9>;SEP;CH (Me) CH2OCONHEt>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;H>;SEP;2Me-4-OCF3
>;tb;210>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;H>;SEP;2-Me-4CF2CF3
>;tb;2-11>;SEP;CH (Me)
CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;H>;SEP;2-Me-4CF(CF3)2>;SEP;94
>;tb;2-12>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;H>;SEP;2Et-4-CF(CF3)2
>;tb;2-13>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;H>;SEP;2Me-4-CF(CF3)2>;SEP;103
>;tb;214>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;H>;SEP;2-Cl-4CF3
>;tb;2-15>;SEP;CH (Me)
CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;H>;SEP;2-Me-4-OCF3
>;tb;2-16>;SEP;C (Me) 2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;3I>;SEP;2-Me-4-CF2CF3
>;tb;2-17>;SEP;CH(Me)CH2OCONHEt>;SEP;N>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;H>;SEP;2Me-4-OCF3
>;tb;218>;SEP;CH(Me)CH2OCON(Et)2>;SEP;N>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;H>;SEP;2-Me-4CF2CF3
>;tb;2-19>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;N>;SEP;C>;SEP;N>;SEP;C>;SEP;H>;SEP;2Me-4-CF(CF3)2
>;tb;2-20>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-CF3
>;tb;2-21>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Cl-4-CF3
>;tb;2-22>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF3
>;tb;2-23>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Cl-4-OCF3
>;tb;2-24>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;4-CF2CF3
>;tb;2-25>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-CF2CF3
101/612
>;tb;2-26>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Cl-4-CF2CF3
>;tb;2-27>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-OMe-4-CF2CF3
>;tb;2-28>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;4-CF(CF3)2>;SEP;97
>;tb;2-29>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;6I>;SEP;4-CF(CF3)2>;SEP;119
>;tb;2-30>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3Cl>;SEP;2-Me-4-CF(CF3)2
>;tb;2-31>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;Br>;SEP;2-Me-4-CF(CF3)2
>;tb;2-32>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-CF(CF3)2>;SEP;204
>;tb;2-33>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;6I>;SEP;2-Me-4-CF(CF3)2>;SEP;140
>;tb;2-34>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-CF(CF3)2
>;tb;2-35>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-CF(CF3)2>;SEP;176
>;tb;2-36>;SEP;CH(Me)CH2NHCO2Et>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3-I>;SEP;2Me-4-CF(CF3)2
>;tb;2-37>;SEP;CH(Me)CH2NHCOEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3-I>;SEP;2Me-4-CF(CF3)2
>;tb;2-38>;SEP;CH(Me)CH2NHSO2Et>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3-I>;SEP;2Me-4-CF(CF3)2
>;tb;2-39>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Cl-4-CF(CF3)2>;SEP;188
>;tb;2-40>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Cl-4-CF(CF3)2
>;tb;2-41>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Cl-4-CF(CF3)2
>;tb;2-42>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Cl-4-CF(CF3)2
>;tb;2-43>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-OMe-4-CF(CF3)2
>;tb;2-44>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-OMe-4-CF(CF3)2
>;tb;2-45>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-OMe-4-CF(CF3)2
>;tb;2-46>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-OMe-4-CF(CF3)2
>;tb;2-47>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCH(CF3)2>;SEP;197
>;tb;248>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;H>;SEP;2-Me-4OCH(CF3)2>;SEP;168
>;tb;2-49>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCH(CF3)2>;SEP;226
>;tb;2-50>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCH(CF3)2>;SEP;210
>;tb;2-51>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCH(CF3)2>;SEP;213
>;tb;2-52>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;6I>;SEP;2-Me-4-OCH(CF3)2>;SEP;222
>;tb;2-53>;SEP;CH(Me)CH2NHCO2Me>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCH(CF3)2
>;tb;2-54>;SEP;CH(Me)CH2NHCOMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3-I>;SEP;2Me-4-OCH(CF3)2
102/612
>;tb;2-55>;SEP;CH(Me)CH2NHSO2N(Me)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCH(CF3)2
>;tb;2-56>;SEP;CH(Me)CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCHF2
>;tb;2-57>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCHF2
>;tb;2-58>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCHF2
>;tb;2-59>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHF2
>;tb;2-60>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHF2
>;tb;2-61>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHF2
>;tb;2-62>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHFCF3
>;tb;2-63>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHFCF3
>;tb;2-64>;SEP;CH(Me)CH2OCONHEt>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHFCF3
>;tb;2-65>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHFCF3
>;tb;2-66>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHFCF3
>;tb;2-67>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2CHFCF3
>;tb;2-68>;SEP;CH(Me)CH2OCONHEt>;SEP;N>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCF2
>;tb;2-69>;SEP;CH(Me)CH2OCON(Et)2>;SEP;C>;SEP;N>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-CF2CF3
>;tb;2-70>;SEP;CH(Me)CH2OCONHCH2Ph>;SEP;C>;SEP;C>;SEP;N>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-CF(CF3)2
>;tb;2-71>;SEP;C(Me)2CH2OCONHMe>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;N>;SEP;3I>;SEP;2-Cl-4-CF(CF3)2
>;tb;2-72>;SEP;CH (Me) CH2OCONH -CH2(4-(CMe)Ph)>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3-I>;SEP;2-Me-4-OCH(CF3)2>;SEP;201
>;tb;2-73>;SEP;CH(Me)CH2OP(=S) -(OMe)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;3I>;SEP;2-Me-4-OCH(CF3)2>;SEP;157
>;tb;2-74>;SEP;CH(Me)CH2OP(=S) -(CMe)2>;SEP;C>;SEP;C>;SEP;C>;SEP;C>;SEP;N>;SEP;6I>;SEP;2-Me-4-OCH(CF3)2>;SEP;134
>;tb;>;/TABLE;
[0036] Table 3 shows >;1;H-NMR data of compounds having a physical property expressed by the
word "amorphous" in Table 1.
>;tb;>;TABLE; Id=Table 3 Columns=2
>;tb;
>;tb;Head Col 1: No.
>;tb;Head Col 2: >;1;H-NMR[CDCl3/TMS, delta values (ppm)]
>;tb;>;SEP;80>;SEP;1.33(d,3H), 2.37(s,3H), 3.91(dd,1H), 3.96(dd,1H), 4.55(m,1H), 6.32(d,1H),
6.78(d,2H), 6.94(dd,1H), 7.22(m,3H), 7.39(d,1H), 7.41(s,1H), 7.81(d,1H), 7.99(d,1H), 8.21(d,1H),
8.41(s,1H).
>;tb;>;SEP;98>;SEP;1.17(d,3H), 1.75-1.90(m,4H), 2.40(s,3H), 3.10-3.42(m,4H), 4.02(dd,1H),
4.22(dd,1H), 4.32(m,1H), 6.89(d,1H), 7.22(dd,1H), 7.42(s,1H), 7.44(d,1H), 7.81(d,1H), 7.97(d,1H),
8.34(d,1H), 8.48(s,1H).
>;tb;>;SEP;117>;SEP;1.26(dt,6H), 1.28(d,3H), 2.38(s,3H), 4.08(m,6H), 4.39(s,1H), 6.79(d,1H),
7.23(dd,1H), 7.41(s,1H), 7.43(d,1H), 7.81(d,1H), 7.99(d,1H), 8.31(d,1H), 8.42(s,1H).
>;tb;>;/TABLE;
103/612
[0037] Agricultural and horticultural chemicals, in particular, agricultural and horticultural
insecticides, which contain as an active ingredient the aromatic diamide derivative of the general
formula (I) or salt thereof of the present invention are suitable for controlling various insect pests such
as agricultural insect pests, forest insect pests, horticultural insect pests, stored grain insect pests,
sanitary insect pests, nematodes, etc., which are injurious to paddy rice, fruit trees, vegetables, other
crops, flowers and ornamental plants, and the like. They have a powerful insecticidal effect, for
example, on LEPIDOPTERA including summer fruit tortrix (Adoxophyes orana fasciata), smaller tea
tortrix (Adoxophyes sp.), Manchurian fruit moth (Grapholita inopinata), oriental fruit moth (Grapholita
molesta), soybean pod borer (Leguminivora glycinivorella), mulberry leafroller (Olethreutes mori), tea
leafroller (Caloptilia thevivora), Caloptilia sp. (Caloptilia zachrysa), apple leafminer (Phyllonorycter
ringoniella), pear barkminer (Spulerrina astaurota), common white (Piers rapae crucivora), tabacco
budworm (Heliothis sp.), codling moth (Laspey resia pomonella), diamondback moth (Plutella
xylostella), apple fruit moth (Argyresthia conjugella), peach fruit moth (Carposina niponensis), rice
stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), tabacco moth (Ephestia
elutella), mulberry pyralid (Glyphodes pyloalis), yellow rice borer (Scirpophaga incertulas), rice
skipper (Parnara guttata), rice armyworm (Pseudaletia separata), pink borer (Sesamia inferens),
common cutworm (Spodoptera litura), beet armyworm (Spodoptera exigua), etc.; HEMIPTERA
including aster leafhopper (Macrosteles fascifrons), green rice leafhopper (Nephotettix cincticeps),
brown rice planthopper (Nilaparvata lugens), whitebacked rice planthopper (Sogatella furcifera), citrus
psylla (Diaphorina citri), grape whitefly (Aleurolobus taonabae), sweetpotato whitefly (Bemisia
tabaci), greenhouse whitefly (Trialeurodes vaporariorum), turnip aphid (Lipaphis erysimi), green peach
aphid (Myzus persicae), Indian wax scale (Ceroplastes ceriferus), cottony citrus scale (Pulvinaria
aurantii), camphor scale (Pseudaonidia duplex), San Jose scale (Comstockaspis perniciosa), arrowhead
scale (Unaspis yanonensis), etc.; COLEOPTERA including root-lesion nematode (Pratylenchus sp.),
soybean beetle (Anomala rufocuprea), Japanese beetle (Popillia japonica), tobacco beetle (Lasioderma
serricorne), powderpost beetle (Lyctus brunneus), twenty-eight-spotted ladybird (Epilachna
vigintiocto-punctata), adzuki bean weevil (Callosobruchus chinensis), vegetable weevil (Listroderes
costiro-stris), maize weevil (Sitophilus zeamais), boll weevil (Anthonomus gradis gradis), rice water
weevil (Lissorhoptrus oryzophilus), cucurbit leaf beetle (Aulacophora femoralis), rice leaf beetle
(Oulema oryzae), striped flea beetle (Phyllotreta striolata), pine shoot beetle (Tomicus piniperda),
Colorado potate beetle (Leptinotarsa decemlineata), Mexican beetle (Epilachna varivestis), corn
rootworm (Diabrotica sp.), etc.; DIPTERA including melon fly (Dacus(Zeugodacus) cucurbitae),
oriental fruit fly (Dacus(Bactrocera) dorsalis), rice leafminer (Agromyza oryzae), onion maggot (Delia
antiqua), seedcorn maggot (Delia platura), soybean pod gall midge (Asphondylia sp.), muscid fly
(Musca domestica), house mosquito (Culex pipiens pipiens), etc.; and TYLENCHIDA including coffee
root-lesion nematode (Pratylenchus coffeae), potato cyst nematode (Globodera rostochiensis), rootknot nematode (Meloidogyne sp.), citrus nematode (Tylenchulus semipenetrans), Aphelenchus sp.
(Aphelenchus avenae), chrysanthemum foliar nematode (Aphelenchoides ritzemabosi), etc.
[0038] The agricultural and horticultural chemical, in particular, agricultural and horticultural
insecticide, which contains as an active ingredient the aromatic diamide derivative of the general
formula (I) or salt thereof of the present invention has a marked insecticidal effect on the aboveexemplified insect pests injurious to paddy field crops, upland crops, fruit trees, vegetables, other
crops, flowers and ornamental plants, and the like. Therefore, the desired effect of the agricultural and
horticultural chemical, in particular, agricultural and horticultural insecticide of the present invention
can be obtained by applying the agricultural and horticultural chemical to the paddy field water, stalks
and leaves of fruit trees, vegetables, other crops, flowers and ornamental plants, soil, etc., at a season at
which the insect pests are expected to appear, before their appearance or at the time when their
appearance is confirmed.
[0039] The agricultural and horticultural chemical of the present invention is generally prepared into
conveniently usable forms according to an ordinary manner for preparation of agrochemicals.
[0040] That is, the aromatic diamide derivative of the general formula (I) or a salt thereof and,
optionally, an adjuvant are blended with a suitable inert carrier in a proper proportion and prepared into
a suitable preparation form such as a suspension, emulsifiable concentrate, soluble concentrate,
wettable powder, granules, dust, tablets or the like through dissolution, dispersion, suspension, mixing,
impregnation, adsorption or sticking.
104/612
[0041] The inert carrier usable in the present invention may be either solid or liquid. As a material
usable as the solid carrier, there can be exemplified soybean flour, cereal flour, wood flour, bark flour,
saw dust, powdered tobacco stalks, powdered walnut shells, bran, powdered cellulose, extraction
residue of vegetables, powdered synthetic polymers or resins, clays (e.g. kaolin, bentonite, and acid
clay), talcs (e.g. talc and pyrophyllite), silica powders or flakes (e.g. diatomaceous earth, silica sand,
mica and white carbon [synthetic, high-dispersion silicic acid, also called finely divided hydrated silica
or hydrated silicic acid, some of commercially available products contain calcium silicate as the major
component]), activated carbon, powdered sulfur, pumice, calcined diatomaceous earth, ground brick,
fly ash, sand, calcium carbonate, calcium phosphate and other inorganic or mineral powders, chemical
fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium
chloride), and compost. These carriers may be used alone or as a mixture thereof.
[0042] A material usable as the liquid carrier is selected from materials that have solubility in
themselves or which are without such solubility but are capable of dispersing an active ingredient with
the aid of an adjuvant. The following are typical examples of the liquid carrier and can be used alone or
as a mixture thereof: water, alcohols (e.g. methanol, ethanol, isopropanol, butanol and ethylene glycol),
ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and
cyclohexanone), ethers (e.g. ethyl ether, dioxane, Cellosolve, dipropyl ether and tetrahydrofuran),
aliphatic hydrocarbon (e.g. kerosene and mineral oils), aromatic hydrocarbons (e.g. benzene, toluene,
xylene, solvent naphtha and alkylnaphthalenes), halogenated hydrocarbons (e.g. dichloroethane,
chloroform, carbon tetrachloride and chlorobenzene), esters (e.g. ethyl acetate, diisopropyl phthalate,
dibutyl phthalate and dioctyl phthalate), amides (e.g. dimethylformamide, diethylformamide and
dimethylacetamide), nitriles (e.g. acetonitrile), and dimethyl sulfoxide.
[0043] The following are typical examples of the adjuvant, which are used depending upon purposes
and used alone or in combination is some cases, or need not to be used at all.
[0044] To emulsify, disperse, dissolve and/or wet a compound as active ingredient, a surfactant is
used. As the surfactant, there can be exemplified polyoxyethylene alkyl ethers, polyoxyethylene
alkylaryl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resonates, polyoxyethylene
sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonates, naphthalene sulfonic
acid condensation products, ligninsulfonates and higher alcohol sulfate esters.
[0045] Further, to stabilize the dispersion of a compound as active ingredient, tackify it and/or bind
it, the adjuvants exemplified below may also be used, namely, there may also be used adjuvants such as
casein, gelatin, starch, methyl cellulose, carboxymethyl cellulose, gum arabic, poly(vinyl alcohol)s,
turpentine, bran oil, bentonite and ligninsulfonates.
[0046] To improve the flowability of a solid product, the following adjuvants may also be used,
namely, there may be used adjuvants such as waxes, stearates, alkyl phosphates, etc.
[0047] Adjuvants such as naphthalenesulfonic acid condensation products and polycondensates of
phosphates may be used as a peptizer for dispersible products.
[0048]
Adjuvants such as silicone oils may also be used as a defoaming agent.
[0049] The content of the compound as active ingredient may be varied as required, and the
compound as active ingredient may be used in a proportion properly chosen in the range of 0.01 to 90
parts by weight per 100 parts of the agricultural and horticultural insecticide. For example, in dusts or
granules, the suitable content of the compound as active ingredient is from 0.01 to 50 % by weight. In
emulsifiable concentrates or flowable wettable powders, it is also from 0.01 to 50 % by weight.
[0050] The agricultural and horticultural chemical, in particular, agricultural and horticultural
insecticide of the present invention is used to control a variety of insect pests in the following manner:
it is applied to a crop on which the insect pests are expected to appear, or a site where appearance or
growth of the insect pests is undesirable, as it is or after being properly diluted with or suspended in
water or the like, in an amount effective for control of the insect pests.
105/612
[0051] The applying dosage of the agricultural and horticultural insecticide of the present invention is
varied depending upon various factors such as a purpose, insect pests to be controlled, a growth state of
a plant, tendency of insect pests appearance, weather, environmental conditions, a preparation form, an
application method, an application site and application time. It may be properly chosen in the range of
0.001 g to 10 kg, preferably 0.01 g to 1 kg, (in terms of the compound as active ingredient) per 10 ares
depending upon purposes.
[0052] The agricultural and horticultural chemical, in particular, agricultural and horticultural
insecticide of the present invention may be used in admixture with other agricultural and horticultural
insecticides, acaricides, nematicides, fungicides, biotic pesticides or the like in order to expand both
spectrum of controllable insect pest species and the period of time when effective application are
possible or to reduce the dosage. Furthermore, the agricultural and horticultural chemical of the present
invention may be used in admixture with herbicides, plant growth regulators, fertilizers or the like,
depending upon application situations.
[0053] As the other agricultural and horticultural insecticides, acaricides and nematicides, which are
used for the above purpose, there can be exemplified agricultural and horticultural insecticides,
acaricides and nematicides, such as Ethion, Trichlorfon, Metamidophos, Acephate, Dichlorvos,
Mevinphos, Monocrotophos, Malathion, Dimethoate, Formothion, Mecarbam, Vamidothion,
Thiometon, Disulfoton, Oxydeprofos, Naled, Methylpatathion, Fenitrothion, Cyanophos, Propaphos,
Fenthion, Prothiofos, Profenofos, Isofenphos, Temephos, Phenthoate, Dimethylvinphos,
Chlorfenvinphos, Tetrachlorvinphos, Phoxim, Isoxathion, Pyraclofos, Methidathion, Chlorpyrifos,
Chlorpyrifos-methyl, Pyridaphenthion, Diazinon, Pirimiphosmethyl, Phosalone, Phosmet,
Dioxabenzophos, Quinalphos, Terbuphos, Ethoprophos, Cadusafos, Mesulfenfos, DPS (NK-0795),
Phosphocarb, Fenamiphos, Isoamidophos, Fosthiazate, Isazophos, Ethoprophos, Fostietane,
Dichlofenthion, Thionazin, Sulprofos, Fensulfothion, Diamidafos, Pyrethrin, Allethrin, Prallethrin,
Resmethrin, Permethrin, Tefluthrin, Bifenthrin, Fenpropathrin, Cypermethrin, alpha -Cypermethrin,
Cyhalothrin, lambda -Cyhalothrin, Deltamethrin, Acrinathrin, Fenvalerate, Esfenvalerate,
Flucythrinate, Fluvalinate, Cycloprothrin, Ethofenprox, Halfenprox, Silafluofen, Fluvalinate,
Methomyl, Oxamyl, Thiodicarb, Aldicarb, Alanycarb, Cartap, Metolcarb, Xylylcarb, Propoxur,
Phenoxycarb, Fenobucarb, Ethiophencarb, Fenothiocarb, Bifenazate, BPMC, Carbaryl, Pirimicarb,
Carbofuran, Carbosulfan, Furathiocarb, Benfuracarb, Aldoxycarb, Diafenthiuron, Diflubenzuron,
Teflubenzuron, Hexaflumuron, Novaluron, Lufenuron, Flufenoxuron, Chlorfluazuron, Fenbutatin
oxide, tricyclohexyltin hydroxide, sodium oleate, potassium oleate, Methoprene, Hydroprene,
Binapacryl, Amitraz, Dicofol, Chroro-benzilate, Bromopropylate, Tetradifon, Bensultap, Benzoximate,
Tebufenozide, Methoxyfenozide, Chromafenozide, Propargite, Acequinosyl, Endosulfan, Diofenolan,
Chlorfenapyl, Fenpyroximate, Tolfenpyrad, Fipronil, Tebufenpyrad, Triazamate, Etoxazole,
Hexythiazox, nicotine sulfate, Nitenpyram, Acetamiprid, Thiacloprid, Imidacloprid, Thiamethoxam,
Clothianidin, Nidinotefuran, Fluazinam, Pyriproxyfen, Hydramethylnon, Pyrimidifen, Pyridaben,
Cyromazin, TPIC (tripropyl isocyanurate), Pymetrozin, Clofentezin, Buprofedin, Thiocyclam,
Fenazaquin, Chinomethionate, Indoxacarb, Polynactin complexes, Milbemectin, Abamectin,
Emamectin-benzoate, Spinosad, BT (Bacillus thuringiensis), Azadirachtin, Rotenone, hydroxypropyl
starch, Levamisole hydrochloride, Metam-sodium, Morantel tartrate, Dazomet, Trichlamide, Pasteuria
penetrans, Monacrosporium-phymatophagum, etc. As the agricultural and horticultural fungicides used
for the same purpose as above, there can be exemplified agricultural and horticultural fungicides such
as sulfur, lime sulfur, copper sulfate basic, Iprobenfos, Edifenfos, Tolclofos-methyl, Thiram,
Polycarbamate, Zineb, Maneb, Mancozeb, Propineb, Thiophanate, Thiophanate methyl, Benomyl,
Iminoctadin acetate, Iminocutadin albecylate, Mepronil, Flutolanil, Pencycuron, Furametpyl,
Thifluzamide, Metalaxyl, Oxadixyl, Carpropamid, Dichlofluanid, Flusulfamide, Chlorothalonil,
Kresoxim-methyl, Fenoxanil (NNF-9425), Himexazol, Etridiazol, Fluoroimide, Procymidone,
Vinclozolin, Iprodione, Triadimefon, Triflumizole, Bitertanol, Ipconazole, Fluconazole, Propiconazole,
Diphenoconazole, Myclobutanil, Tetraconazole, Hexaconazole, Tebuconazole, Imibenconazole,
Prochloraz, Pefurazoate, Cyproconazole, Isoprothiolane, Fenarimol, Pyrimetanil, Mepanipyrim,
Pyrifenox, Fluazinam, Triforine, Diclomezine, Azoxystrobin, Thiadiazin, Captan, Probenazole,
Acibenzolar-S-methyl (CGA-245704), Fthalide, Tricyclazole, Pyroquilon, Chinomethionat, Oxolinic
acid, Dithianon, Kasugamycin, Validamycin, Polyoxin, Blasticidin, Streptomycin, etc. Similarly, as the
herbicides, there can be exemplified herbicides such as Glyphosate, Sulfosate, Glyfosinate, Bialaphos,
Butamifos, Esprocarb, Prosulcarb, Benthiocarb, Pyributycarb, Asulam, Linulon, Dymron, Bensulfuron
methyl, Cyclosulfamuron, Cinosulfuron, Pyrazosulfuron ethyl, Azimsulfuron, Imazosulfuron,
106/612
Tenylchlor, Alachlor, Pretilachlor, Clomeprop, Etobenzanid, Mefenacet, Pendimethalin, Bifenox,
Acifluorfen, Lactfen, Cyhalofop-butyl, Ioxynil, Bromobutide, Alloxydim, Setoxydim, Napropamide,
Indanofan, Pyrazolate, Benzofenap, Pyraflufen-ethyl, Imazapyl, Sulfentrazone, Cafenstrole,
Bentoxazon, Oxadiazon, Paraquat, Diquat, Pyriminobac, Simazine, Atrazine, Dimethametryn,
Triazyflam, Benflesate, Flutiacet-methyl, Quizalofop-ethyl, Bentazon, calcium peroxide, etc.
[0054] As to the biotic pesticides, the same effect as above can be expected by using the agricultural
and horticultural chemical of the present invention in admixture with, for example, viral formulations
obtained from nuclear polyhedrosis virus (NPV), granulosis virus (GV), cytoplasmic polyhedrosis virus
(CPV), entomopox virus (EPV), etc.; microbial pesticides utilized as insecticides or nematicides, such
as Monacrosporium phymatophagum, Steinernema carpocapsae, Steinernema kushidai, Pasteuria
penetrans, etc.; microbial pesticides utilized as fungicides, such as Trichoderma lignorum,
Agrobacterium radiobactor, nonpathogenic Erwinia carotovora, Bacillus subtilis, etc.; and biotic
pesticides utilized as herbicides, such as Xanthomonas campestris, etc.
[0055] In addition, the agricultural and horticultural chemical of the present invention can be used in
combination with biotic pesticides including natural enemies such as Parasitic wasp (Encarsia
formosa), Parasitic wasp (Aphidius colemani), Gall-mildge (Aphidoletes aphidimyza), Parasitic wasp
(Diglyphus isaea), Parasitic mite (Dacnusa sibirica), Predatory mite (Phytoseiulus persimilis),
Predatory mite (Amblyseius cucumeris), Predatory bug (Orius sauteri), etc.; microbial pesticides such
as Beauveria brongniartii, etc.; and pheromones such as (Z)-10-tetradecenyl=acetate. (E,Z)-4,10tetradecadienyl= acetate.(Z)-8-dodecenyl=acetate.(Z)-11-tetradecenyl= acetate.(Z)-13-icosen-10-one,
(Z)-8-dodecenyl= acetate.(Z)-11-tetradecenyl=acetate (Z)-13-icosen-10-one.14-methyl-1-octadecene,
etc.
[0056] Typical examples of the present invention are described below but they should not be
construed as limiting the scope of the invention.
EXAMPLES
Production Example 1
(1-1). Production of 3-iodo-N-(4-heptafluoroisopropyl-2-methylphenyl)phthalamic acid
[0057] A solution of 3.5 g of 4-heptafluoro-isopropyl-2-methylaniline in 3 ml of acetonitrile was
slowly dropped into a suspension of 3.5 g of 1-iodophthalic anhydride in 30 ml of acetonitrile under
ice-cooling. After completion of the dropwise addition, the reaction was carried out with stirring at
room temperature for 3 hours. After completion of the reaction, the crystals precipitated were collected
by filtration and washed with a small volume of acetonitrile to obtain 4.0 g of the desired compound.
[0058] Physical property: m.p. 174 - 181 DEG C. Yield: 57%.
(1-2). Production of 3-iodo-N-(4-heptafluoroisopropyl-2-methylphenyl)phthalisoimide
[0059] To a suspension of 2.0 g of 3-iodo-N-(4-heptafluoroisopropyl-2-methylphenyl)phthalamic
acid in 10 ml of toluene was added 1.1 g of trifluoroacetic anhydride, and the reaction was carried out
with stirring at room temperature for 30 minutes. After completion of the reaction, the solvent was
distilled off under reduced pressure to obtain 2.0 g of a crude product as the desired product. The
desired product obtained was used in the subsequent reaction without purification.
[0060]
>;1;H-NMR [CDCl3/TMS, delta values (ppm)]
107/612
2.4(s, 3H), 7.3(d, 1H), 7.4(m, 2H), 7.5(t,
1H), 8.1(d, 1H), 8.2(d, 1H)
(1-3). Production of 3-iodo-N>;1;-(4-heptafluoroisopropyl-2-methylphenyl)-N>;2;-[1-methyl-2-(N,Ndimethyl sulfamoylamino)ethyl]phthalamide (compound No. 45)
[0061] In 30 ml of acetonitrile was dissolved 0.4 g of 3-iodo-N-(4-heptafluoroisopropyl-2methylphenyl)-phthalisoimide, followed by adding thereto 0.2 g of N,N-dimethylamino-N'-(2aminopropyl)sulfonamide, and the resulting mixture was stirred at room temperature for 5 hours. After
completion of the reaction, the reaction mixture was poured into ice water, followed by extraction with
ethyl acetate. The organic layer was washed with an aqueous sodium chloride solution, dried over
anhydrous magnesium sulfate and then distilled under reduced pressure to remove the solvent, and the
resulting residue was purified by silica gel column chromatography to obtain 0.2 g of the desired
compound.
[0062]
Physical property: m.p. 95 DEG C. Yield: 40%.
Production Example 2
Production of 3-iodo-N>;1;-(4-heptafluoroisopropyl-2-methylphenyl)-N>;2;-[1-methyl-2(ethylaminocarbonyloxy)ethyl]phthalamide (compound No. 96)
[0063] In 30 ml of acetonitrile was dissolved 0.55 g of 6-iodo-N-[1-methyl-2(ethylaminocarbonyloxy)ethyl]-phthalisoimide, followed by adding thereto 0.38 g of 4heptafluoroisopropyl-2-methylaniline, and the resulting mixture was stirred at room temperature for 3
hours. After completion of the reaction, the reaction mixture was poured into ice water, followed by
extraction with ethyl acetate. The organic layer was washed with an aqueous sodium chloride solution,
dried over anhydrous magnesium sulfate and then distilled under reduced pressure to remove the
solvent, and the resulting residue was purified by silica gel column chromatography to obtain 0.36 g of
the desired compound.
[0064] Physical property: m.p. 185 DEG C. Yield: 38%.
Production Example 3
(3-1). Production of 3-iodo-N-(4-heptafluoroisopropyl-2-methylphenyl)phthalimide
[0065] To a suspension of 2.7 g of 3-iodophthalic anhydride in 30 ml of acetic acid was added 2.7 g
of 4-heptafluoroisopropyl-2-methylaniline, and the resulting mixture was heated under reflux for 3
hours.
[0066] After completion of the reaction, the solvent was distilled off under reduced pressure from the
reaction mixture, and the resulting residue was purified by silica gel column chromatography to obtain
4.8 g of the desired compound.
[0067]
Yield: 89%.
108/612
(3-2). Production of 3-iodo-N>;1;-(4-heptafluoroisopropyl-2-methylphenyl)-N>;2;-[3-t-butoxycarbonyl
aminopropyl)phthalamide (compound No. 20)
[0068] In 20 ml of dioxane was dissolved 0.5 g of 3-iodo-N-(4-heptafluoroisopropyl-2methylphenyl)-phthalimide, followed by adding thereto 0.25 g of t-butyl N-(3-aminopropyl)carbamate
and two drops of trifluoroacetic acid, and the resulting mixture was stirred at room temperature for 10
hours. After completion of the reaction, the reaction mixture was poured into ice water, followed by
extraction with ethyl acetate. The organic layer was washed with an aqueous sodium chloride solution,
dried over anhydrous magnesium sulfate and then distilled under reduced pressure to remove the
solvent, and the resulting residue was purified by silica gel column chromatography to obtain 0.2 g of
the desired compound.
[0069] Physical property: m.p. 145 DEG C. Yield: 30%.
[0070] Typical formulation examples and test examples of the present invention are described below
but they should not be construed as limiting the scope of the invention.
[0071] In the formulation examples, parts are all by weight.
Formulation Example 1
>;tb;>;TABLE; Columns=2
>;tb;Each compound listed in Table 1 or Table 2>;SEP;50 parts
>;tb;Xylene>;SEP;40 parts
>;tb;Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate>;SEP;10 parts
>;tb;>;/TABLE;
[0073] An emulsifiable concentrate was prepared by mixing uniformly the above ingredients to effect
dissolution.
Formulation Example 2
>;tb;>;TABLE; Columns=2
>;tb;Each compound listed in Table 1 or Table 2>;SEP;3 parts
>;tb;Clay powder>;SEP;82 parts
>;tb;Diatomaceous earth powder>;SEP;15 parts
>;tb;>;/TABLE;
[0075]
A dust was prepared by mixing uniformly and grinding the above ingredients.
Formulation Example 3
>;tb;>;TABLE; Columns=2
>;tb;Each compound listed in Table 1 or Table 2>;SEP;5 parts
>;tb;Mixed powder of bentonite and clay>;SEP;90 parts
>;tb;Calcium lignin sulfonate>;SEP;5 parts
>;tb;>;/TABLE;
[0077] Granules were prepared by mixing the above ingredients uniformly, and kneading the
resulting mixture together with a suitable amount of water, followed by granulation and drying.
Formulation Example 4
>;tb;>;TABLE; Columns=2
109/612
>;tb;Each compound listed in Table 1 or Table 2>;SEP;20 parts
>;tb;Mixture of kaolin and synthetic, high-dispersion silicic acid>;SEP;75 parts
>;tb;Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate>;SEP;5 parts
>;tb;>;/TABLE;
[0079]
A wettable powder was prepared by mixing uniformly and grinding the above ingredients.
Test Example 1
Insecticidal effect on diamondback moth (Plutella xylostella)
[0080] Adult diamondback moths were released and allowed to oviposit on a Chinese cabbage
seedling. Two days after the release, the seedling having eggs deposited thereon was immersed for
about 30 seconds in a liquid chemical prepared by diluting a preparation containing each compound
listed in Table 1 or Table 2, as an active ingredient to adjust the concentration to 50 ppm. After airdrying, the seedling was allowed to stand in a room thermostated at 25 DEG C.
[0081] Six days after the immersion in the liquid chemical, the hatched insects were counted and the
mortality was calculated according to the following equation, whereby the insecticidal effect was
judged according to the criterion shown below. The test was carried out with three replications of 10
insects.
EMI90.1
Criterion for judgment
A --- mortality 100%
B --- mortality 99% to 90%
C --- mortality 89% to 80%
D --- mortality 79% to 50%
[0083] As a result of the above test, it was found that the following compounds had an insecticidal
activity rated B or higher: compound Nos. 1 to 122, 127 to 130, 133 to 136, 139, 140, 142 to 145, 148,
149, 152, 153, 157, 161, 165, 167 to 173, 182 to 185, 194, 198, 199, 204, 205, 210 to 212, 214 to 216,
222, 223, 229, 230, 235, 236, 243, 247, 259, 260, 263 to 272, 274, 275, 278 to 280, 284 to 290, 293,
297, 308, 311, 312, 317 to 322, 2-3, 2-5, 2-11, 2-13, 2-28, 2-29, 2-32, 2-33, 2-35, 2-39, 2-47 to 2-52, 272, 2-73 and 2-74.
Test Example 2
Insecticidal effect on common cutworm (Spodoptera litura)
[0084] A piece of cabbage leaf (cultivar: Shikidori) was immersed for about 30 seconds in a liquid
chemical prepared by diluting a preparation containing each compound listed in Table 1 or Table 2, as
an active ingredient to adjust the concentration to 50 ppm. After air-drying, the piece was placed in a
plastic Petri dish with a diameter of 9 cm and inoculated with second-instar larvae of common
cutworm, after which the dish was closed and then allowed to stand in a room thermostated at 25 DEG
110/612
C. Eight days after the inoculation, the dead and alive were counted and the mortality was calculated
according to the following equation, whereby the insecticidal effect was judged according to the
criterion shown in Test Example 1. The test was carried out with three replications of 10 insects.
EMI91.1
[0085] As a result of the above test, it was found that the following compounds had an activity rated
B or higher: compound Nos. 1, 2, 6 to 9, 12 to 16, 19, 22, 28, 29, 33 to 36, 38 to 45, 48, 50, 51, 54 to
57, 59, 62 to 72, 74, 76 to 78, 81 to 86, 88, 90 to 113, 116, 117, 129, 130, 133, 134, 139, 142, 144, 148,
152, 153, 172, 184, 229, 247, 272, 274, 279, 286, 287, 289, 290, 2-32, 2-35, 2-39, 2-47, 2-49 to 2-51,
2-72 and 2-73.
Test Example 3
Insecticidal effect on smaller tea tortrix (Adoxophyes sp.)
[0086] Tea leaves were immersed for about 30 seconds in a liquid chemical prepared by diluting a
preparation containing each compound listed in Table 1 or Table 2, as an active ingredient to adjust the
concentration to 50 ppm. After air-drying, the tea leaves were placed in a plastic Petri dish with a
diameter of 9 cm and inoculated with larvae of smaller tea tortrix, after which the dish was allowed to
stand in a room thermostated at 25 DEG C and having a humidity of 70%. Eight days after the
inoculation, the dead and alive were counted and the insecticidal effect was judged according to the
criterion shown in Test Example 1. The test was carried out with three replications of 10 insects.
[0087] As a result of the above test, it was found that the following compounds had an activity rated
B or higher: compound Nos. 1 to 4, 6 to 10, 12 to 16, 19 to 26, 28 to 45, 48 to 51, 54 to 60, 62 to 72, 74
to 78, 80 to 117, 129, 130, 133 to 136, 139, 140, 142, 144, 145, 148, 149, 152, 153, 170, 182, 184, 210,
247, 265, 272, 274, 279, 284, 286, 287, 289, 290, 317, 322, 2-32, 2-35, 2-39, 2-47, 2-49 to 2-51, 2-72
and 2-73.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of EP1241159
1. An aromatic diamide derivative represented by the general formula (I):
EMI93.1
(wherein A>;1; is a (C1-C8)alkylene group; a substituted (C1-C8)alkylene group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, (C1C6)alkylthio(C1-C6)alkyl groups, (C1-C6)alkoxycarbonyl groups and phenyl group; a (C3C8)alkenylene group; a substituted (C3-C8)alkenylene group having one or more substituents which
may be the same or different and are selected from halogen atoms, cyano group, nitro group, halo(C1C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo
(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, (C1-C6)alkylthio(C1-C6)alkyl groups,
(C1-C6)alkoxycarbonyl groups and phenyl group; a (C3-C8)alkynylene group; or a substituted (C3C8)alkynylene group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkylsulfonyl groups, (C1-C6)alkylthio (C1-C6)alkyl groups, (C1-C6)alkoxycarbonyl groups and
phenyl group,
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any of the saturated carbon atoms in the above-mentioned (C1-C8)alkylene group, substituted (C1C8)alkylene group, (C3-C8)alkenylene group, substituted (C3-C8)alkenylene group, (C3C8)alkynylene group or substituted (C3-C8)alkynylene group being able to have a (C2-C5)alkylene
group bonded thereto as a substituent, to form a (C3-C6)cycloalkane ring, and any two of the carbon
atoms in the above-mentioned (C1-C8)alkylene group, substituted (C1-C8)alkylene group, (C3C8)alkenylene group and substituted (C3-C8)alkenylene group being able to form a (C3C6)cycloalkane ring or a (C3-C6)cycloalkene ring together with an alkylene group or an alkenylene
group,
B is -O- or -N(R>;4;)- (wherein R>;4; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl
group; a (C3-C6) alkenyl group; a halo (C3-C6) alkenyl group; a (C3-C6)alkynyl group; a (C3C6)cycloalkyl group; a (C1-C6)alkylcarbonyl group; a halo(C1-C6)alkylcarbonyl group; a (C1C6)alkoxycarbonyl group; a phenylcarbonyl group; a substituted phenylcarbonyl group having on the
ring one or more substituents which may be the same or different and are selected from halogen atoms,
cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo
(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, and di (C1-C6)alkylamino groups whose (C1-C6)alkyl
groups may be the same or different; a phenyl(C1-C4)alkoxycarbonyl group; a substituted phenyl(C1C4)alkoxycarbonyl group having on the ring one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, and
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different; a phenyl(C1C4)alkyl group; or a substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups,
(C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono (C1C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6)alkoxycarbonyl groups),
R>;1; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy (C1C4)alkyl group; a (C1-C4)alkylthio(C1-C4)alkyl group; a (C2-C6)alkenyl group; a halo(C2-C6)alkenyl
group; a (C3-C6)alkynyl group; a halo(C3-C6)alkynyl group; a (C3-C6)cycloalkyl group; a halo(C3C6)cycloalkyl group; a phenyl group; a substituted phenyl group having one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups,
(C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1-C4)alkyl group; a substituted phenyl(C1C4)alkyl group having on the ring one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a
heterocyclic group; a substituted heterocyclic group having one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups,
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; -P(=W>;1;) (-OR>;5;) (-OR>;6;) (wherein W>;1; is an oxygen atom or a
sulfur atom, and each of R>;5; and R>;6;, which may be the same or different, is a hydrogen atom; a
(C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy(C1-C4)alkyl group; a (C1C4)alkylthio(C1-C4)alkyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-
112/612
C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl(C1-C4)alkyl group; a
substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6) alkoxy groups, halo (C1-C6) alkoxy groups, (C1-C6) alkylthio
groups, halo (C1-C6) alkylthio groups, (C1-C6) alkylsulfinyl groups, halo (C1-C6) alkylsulfinyl
groups, (C1-C6) alkylsulfonyl groups, halo (C1-C6) alkylsulfonyl groups, mono(C1-C6)alkylamino
groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and
(C1-C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups,
further, R>;5; being able to bind to R>;6; to form a 5- to 8-membered ring that may contain one or
two atoms which may be the same or different and are selected from oxygen atom, sulfur atom and
nitrogen atom, between adjacent carbon atoms constituting the ring); -C(=W>;1;)-N(R>;5;)(R>;6;)
(wherein W>;1;, R>;5; and R>;6; are as defined above, R>;5; being able to bind to R>;6; to form a 5to 8-membered ring that may contain one or two atoms which may be the same or different and are
selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting
the ring, and R>;5; being able to bind to R>;4; to form a 5- to 8-membered ring that may contain two or
three atoms which may be the same or different and are selected from oxygen atom, sulfur atom and
nitrogen atom, between adjacent carbon atoms constituting the ring); -C(=W>;1;)-R>;5; (wherein
W>;1; and R>;5; are as defined above); -C(=W>;1;)-W>;1;-R>;7; (wherein W>;1;s, which may be the
same or different, are as defined above, and R>;7; is a (C1-C6)alkyl group; a halo(C1-C6)alkyl group;
a (C1-C4)alkoxy(C1-C4)alkyl group; a (C1-C4)alkylthio(C1-C4)alkyl group; a phenyl group; a
substituted phenyl group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a phenyl (C1-C4)alkyl group; a substituted phenyl(C1-C4)alkyl group
having on the ring one or more substituents which may be the same or different and are selected from
halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups,
(C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; or a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups); -SO2-R>;7; (wherein R>;7; is as defined above); -SO2-N(R>;5;)(R>;6;)
(wherein R>;5; and R>;6; are as defined above, R>;5; being able to bind to R>;6; to form a 5- to 8membered ring that may contain one or two atoms which may be the same or different and are selected
from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the
ring, and R>;5; being able to bind to R>;4; to form a 5- to 8-membered ring that may contain three or
four atoms which may be the same or different and are selected from oxygen atom, sulfur atom and
nitrogen atom, between adjacent carbon atoms constituting the ring); -N(R>;5;)(R>;6;) (wherein R>;5;
and R>;6; are as defined above, R>;5; being able to bind to R>;6; to form a 5- to 8-membered ring that
may contain one or two atoms which may be the same or different and are selected from oxygen atom,
sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the ring, and R>;5; being
able to bind to R>;4; to form a 5- to 8-membered ring that may contain two or three atoms which may
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be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom, between
adjacent carbon atoms constituting the ring); or -N=C(R>;5;)R>;6; (wherein R>;5; and R>;6; are as
defined above, R>;5; being able to bind to R>;6; to form a 5-to 8-membered ring that may contain one
or two atoms which may be the same or different and are selected from oxygen atom, sulfur atom and
nitrogen atom, between adjacent carbon atoms constituting the ring); in the case of B being -N(R>;4;)-,
R>;1; being able to be -OR>;5; (wherein R>;5; is as defined above), -C(W>;2;)-N(R>;5;)R>;6;
(wherein W>;2; is =CH-NO2, =N-NO2 or =N-CN, and R>;5; and R>;6; are as defined above, R>;5; or
R>;6; being able to bind to R>;4; to form a 5- to 8-membered ring that may contain two or three atoms
which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom,
between adjacent carbon atoms constituting the ring) or -C(W>;2;)-W>;1;-R>;7; (wherein W>;1;,
W>;2; and R>;7; are as defined above, R>;7; being able to bind to R>;4; to form a 5-to 8-membered
ring that may contain two or three atoms which may be the same or different and are selected from
oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the ring), and
R>;1; being able to bind to A>;1; to form a 5- to 8-membered ring that may contain one or two atoms
which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom,
between adjacent carbon atoms constituting the ring,
each of R>;2; and R>;3;, which may be the same or different, is a hydrogen atom, a (C3C6)cycloalkyl group or -A>;2;-R>;8; (wherein A>;2; is -C(=O)-, -C(=S)-, -C(=NR>;9;)-(wherein R>;9;
is a hydrogen atom, a (C1-C6)alkyl group, a (C1-C6)alkoxy group, a mono(C1-C6)alkylamino group, a
di(C1-C6)alkylamino group whose (C1-C6)alkyl groups may be the same or different, a (C1C6)alkoxycarbonyl group, a phenyl group, or a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups), a (C1-C8)alkylene group, a halo
(C1-C8)alkylene group, a (C3-C6)alkenylene group, a halo(C3-C6)alkenylene group, a (C3C6)alkynylene group or a halo(C3-C6)alkynylene group,
(1) in the case of A>;2; being -C(=O)-, -C(=S)-or -C(=NR>;9;)- (wherein R>;9; is as defined above),
R>;8; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C3-C6)cycloalkyl
group; a halo(C3-C6)cycloalkyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic group; a substituted
heterocyclic group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; or A>;3;-R>;10; (wherein A>;3; is -O-, -S- or -N(R>;11;)- (wherein R>;11; is a hydrogen atom; a (C1C6)alkylcarbonyl group; a halo(C1-C6)alkylcarbonyl group; a (C1-C6)alkoxycarbonyl group; a
phenylcarbonyl group; a substituted phenylcarbonyl group having one or more substituents which may
be the same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl
groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups,
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a phenyl(C1-C4)alkoxycarbonyl group; or a substituted phenyl(C1C4)alkoxycarbonyl group having on the ring one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-
114/612
C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups), and R>;10; is a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C3C6)alkenyl group; a halo(C3-C6)alkenyl group; a (C3-C6)alkynyl group; a halo(C3-C6)alkynyl group;
a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkylcarbonyl group; a halo (C1C6)alkylcarbonyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1C4)alkyl group; a substituted phenyl(C1-C4)alkyl group having one or more substituents which may be
the same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl
groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6) alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups),
(2) in the case of A>;2; being a (C1-C8)alkylene group, a halo(C1-C8)alkylene group, a (C3C6)alkenylene group, a halo(C3-C6)alkenylene group, a (C3-C6)alkynylene group or a halo(C3C6)alkynylene group, R>;8; is a hydrogen atom; a halogen atom; a cyano group; a nitro group; a (C3C6)cycloalkyl group; a halo (C3-C6)cycloalkyl group; a (C1-C6)alkoxycarbonyl group; a phenyl
group; a substituted phenyl group having one or more substituents which may be the same or different
and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo
(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; a substituted heterocyclic group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; or -A>;4;-R>;12; (wherein A>;4; is O-, -S-, -SO-, -SO2-, -N(R>;11;)- (wherein R>;11; is as defined above), -C(=O)-, or -C(=N-OR>;13;)
(wherein R>;13; is a hydrogen atom, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a (C3C6)alkenyl group, a halo(C3-C6)alkenyl group, a (C3-C6)alkynyl group, a halo (C3-C6) alkynyl group,
a (C3-C6)cycloalkyl group, a phenyl (C1-C4)alkyl group, or a substituted phenyl(C1-C4)alkyl group
having on the ring one or more substituents which may be the same or different and are selected from
halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups),
(i) in the case of A>;4; being -O-, -S-, -SO-, -SO2- or -N(R>;11;)- (wherein R>;11; is as defined
above), R>;12; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C3-C6)alkenyl
group; a halo(C3-C6)alkenyl group; a (C3-C6)alkynyl group; a halo(C3-C6)alkynyl group; a (C3C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkylcarbonyl group; a halo (C1C6)alkylcarbonyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
115/612
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1C4)alkyl group; a substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6) alkoxy groups,
(C1-C6)alkylthio groups, halo (C1-C6) alkylthio groups, (C1-C6) alkylsulfinyl groups, halo (C1-C6)
alkylsulfinyl groups, (C1-C6) alkylsulfonyl groups, halo (C1-C6) alkylsulfonyl groups, mono(C1C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups,
(ii) in the case of A>;4; being -C(=O)- or -C(=NOR>;13;) (wherein R>;13; is as defined above),
R>;12; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C2-C6)alkenyl group;
a halo(C2-C6)alkenyl group; a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1C6)alkoxy group; a halo (C1-C6) alkoxy group; a (C1-C6)alkylthio group; a halo(C1-C6)alkylthio
group; a mono (C1-C6) alkylamino group; a di (C1-C6) alkylamino group whose (C1-C6)alkyl groups
may be the same or different; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenylamino group; a substituted
phenylamino group having on the ring one or more substituents which may be the same or different and
are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a phenyloxy group; a substituted phenyloxy group having on the ring one
or more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6) alkoxy groups, (C1-C6) alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenylthio group; a substituted
phenylthio group having on the ring one or more substituents which may be the same or different and
are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups)),
further, R>;2; being able to bind to A>;1; or R>;1; to form a 5- to 8-membered ring that may contain
one to three atoms which may be the same or different and are selected from oxygen atom, sulfur atom
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and nitrogen atom, between adjacent carbon atoms constituting the ring, each of Q>;1; through Q>;5; is
a carbon atom or a nitrogen atom,
each of Xs, which may be the same or different, is a halogen atom; a cyano group; a nitro group; a
(C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxycarbonyl group; a phenyl
group; a substituted phenyl group having one or more substituents which may be the same or different
and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; a substituted heterocyclic group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; or -A>;5;-R>;14; (wherein A>;5; is O-, -S-, -SO-, -SO2-, -C(=O)-, -C(=NOR>;13;) (wherein R>;13; is as defined above), a (C1C6)alkylene group, a halo(C1-C6)alkylene group, a (C2-C6)alkenylene group, a halo(C2C6)alkenylene group, a (C2-C6)alkynylene group or a halo(C3-C6)alkynylene group,
(1) in the case of A>;5; being -O-, -S-, -SO- or -SO2-, R>;14; is a halo(C3-C6)cycloalkyl group; a
halo(C3-C6)cycloalkenyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic group; a substituted
heterocyclic group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;6;-R>;15; (wherein A>;6; is a (C1-C6)alkylene group, a halo(C1C6)alkylene group, a (C3-C6)alkenylene group, a halo(C3-C6)alkenylene group, a (C3-C6)alkynylene
group or a halo(C3-C6)alkynylene group, and R>;15; is a hydrogen atom; a halogen atom; a (C3C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group;
a substituted phenyl group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; or A>;7;-R>;16; (wherein A>;7; is -O-, -S-, -SO- or -SO2-, and R>;16; is a (C1-C6)alkyl group; a
halo(C1-C6)alkyl group; a (C3-C6)alkenyl group; a halo(C3-C6)alkenyl group; a (C3-C6)alkynyl
group; a halo(C3-C6)alkynyl group; a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a
phenyl group; a substituted phenyl group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo
(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
117/612
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups),
(2) in the case of A>;5; being -C(=O)- or -C(=NOR>;13;)- (wherein R>;13; is as defined above),
R>;14; is a (C1-C6)alkyl group; a halo (C1-C6)alkyl group; a (C2-C6)alkenyl group; a halo(C2C6)alkenyl group; a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxy group;
a (C1-C6)alkylthio group; a mono (C1-C6)alkylamino group; a di(C1-C6)alkylamino group whose
(C1-C6)alkyl groups may be the same or different; a phenyl group; a substituted phenyl group having
one or more substituents which may be the same or different and are selected from halogen atoms,
cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo
(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenylamino group; a substituted
phenylamino group having on the ring one or more substituents which may be the same or different and
are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups,
(3) in the case of A>;5; being a (C1-C6)alkylene group, a halo(C1-C6)alkylene group, a (C2C6)alkenylene group, a halo(C2-C6)alkenylene group, a (C2-C6)alkynylene group or a halo(C3C6)alkynylene group, R>;14; is a hydrogen atom; a halogen atom; a (C3-C6)cycloalkyl group; a halo
(C3-C6)cycloalkyl group; a (C1-C6)alkoxycarbonyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;8;-R>;17; (wherein A>;8; is -O-, -S-, -SO- or -SO2-, and R>;17; is
a (C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo
(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6) alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6) alkylamino groups, di (C1C6) alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;9;-R>;18; (wherein A>;9; is a (C1-C6)alkylene group, a halo(C1C6)alkylene group, a (C2-C6)alkenylene group, a halo(C2-C6)alkenylene group, a (C2-C6)alkynylene
group or a halo(C3-C6)alkynylene group, and R>;18; is a hydrogen atom; a halogen atom; a (C3-
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C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a (C1-C6)alkoxy group; a halo(C1-C6)alkoxy
group; a (C1-C6)alkylthio group; a halo(C1-C6)alkylthio group; a (C1-C6)alkylsulfinyl group; a
halo(C1-C6)alkylsulfinyl group; a (C1-C6) alkylsulfonyl group; a halo (C1-C6) alkylsulfonyl group; a
phenyl group; a substituted phenyl group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6) alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6) alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups,
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a phenyloxy group; a substituted phenyloxy group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenylthio group; a substituted
phenylthio group having one or more substituents which may be the same or different and are selected
from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo (C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a
heterocyclic group; or a heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups)), n is an integer of 0 to 4,
further, two adjacent Xs on the aromatic ring being able to be taken together to represent a fused ring
that may have one or more substituents which may be the same or different and are selected from
halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups,
(C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo
(C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose
(C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups,
each of Ys, which may be the same or different, is a halogen atom; a cyano group; a nitro group; a
(C3-C6)cycloalkyl group; a halo(C3-C6)cycloalkyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups,
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;5;-R>;14; (wherein A>;5; and R>;14; are as defined above),
further, two adjacent Ys on the aromatic ring being able to be taken together to represent a fused ring
that may have one or more substituents which may be the same or different and are selected from
halogen atoms; (C1-C6)alkyl groups; halo(C1-C6)alkyl groups; (C1-C6)alkoxy groups; halo(C1C6)alkoxy groups; (C1-C6)alkylthio groups; halo(C1-C6)alkylthio groups; (C1-C6)alkylsulfinyl
groups; halo (C1-C6)alkylsulfinyl groups; (C1-C6)alkylsulfonyl groups; halo(C1-C6)alkylsulfonyl
groups; phenyl group; substituted phenyl groups having one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
119/612
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; heterocyclic groups; and substituted heterocyclic groups having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups,
m is an integer of 1 to 5, and each of Z>;1; and Z>;2; is an oxygen atom or a sulfur atom} or a salt
thereof.
2. An aromatic diamide derivative or a salt thereof according to claim 1, wherein A>;1; is a (C1C8)alkylene group; a substituted (C1-C8)alkylene group having one or more substituents which may be
the same or different and are selected from halogen atoms, cyano group, nitro group, halo(C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, (C1-C6)alkylthio (C1-C6)alkyl groups,
(C1-C6)alkoxycarbonyl groups and phenyl group; a (C3-C8)alkenylene group; a substituted (C3C8)alkenylene group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkylsulfonyl groups, (C1-C6)alkylthio (C1-C6)alkyl groups, (C1-C6)alkoxycarbonyl groups and
phenyl group; a (C3-C8)alkynylene group; or a substituted (C3-C8)alkynylene group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, halo (C1-C6) alkyl groups, (C1-C6) alkoxy groups, halo (C1-C6)alkoxy groups,
(C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, (C1C6)alkylthio(C1-C6)alkyl groups, (C1-C6)alkoxycarbonyl groups and phenyl group,
any of the saturated carbon atoms in the above-mentioned (C1-C8)alkylene group, substituted (C1C8)alkylene group, (C3-C8)alkenylene group, substituted (C3-C8)alkenylene group, (C3C8)alkynylene group or substituted (C3-C8)alkynylene group being able to have a (C2-C5)alkylene
group bonded thereto as a substituent, to form a (C3-C6)cycloalkane ring, and any two of the carbon
atoms in the above-mentioned (C1-C8)alkylene group, substituted (C1-C8)alkylene group, (C3C8)alkenylene group and substituted (C3-C8)alkenylene group being able to form a (C3C6)cycloalkane ring or a (C3-C6)cycloalkene ring together with an alkylene group or an alkenylene
group,
B is -O- or -N(R>;4;)- (wherein R>;4; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl
group; a (C3-C6)alkenyl group; a halo (C3-C6)alkenyl group; a (C3-C6)alkynyl group; a (C3C6)cycloalkyl group; a (C1-C6)alkylcarbonyl group; a halo(C1-C6)alkylcarbonyl group; a (C1C6)alkoxycarbonyl group; a phenylcarbonyl group; a substituted phenylcarbonyl group having on the
ring one or more substituents which may be the same or different and are selected from halogen atoms,
cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, and di (C1-C6)alkylamino groups whose
(C1-C6)alkyl groups may be the same or different; a phenyl(C1-C4)alkoxycarbonyl group; a
substituted phenyl(C1-C4)alkoxycarbonyl group having on the ring one or more substituents which
may be the same or different and are selected from halogen atoms, cyano group, nitro group, (C1C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1C6)alkylamino groups, and di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same
or different; a phenyl(C1-C4)alkyl group; or a substituted phenyl(C1-C4)alkyl group having on the ring
120/612
one or more substituents which may be the same or different and are selected from halogen atoms,
cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo
(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups),
R>;1; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy(C1C4)alkyl group; a (C1-C4)alkylthio(C1-C4)alkyl group; a (C2-C6)alkenyl group; a halo(C2-C6)alkenyl
group; a (C3-C6)alkynyl group; a halo(C3-C6)alkynyl group; a (C3-C6)cycloalkyl group; a halo(C3C6)cycloalkyl group; a phenyl group; a substituted phenyl group having one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups,
(C1-C6) alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups, mono (C1C6) alkylamino groups, di (C1-C6) alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6) alkoxycarbonyl groups; a phenyl(C1-C4) alkyl group; a substituted phenyl(C1C4)alkyl group having on the ring one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a
heterocyclic group; a substituted heterocyclic group having one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; -P(=W>;1;) (-OR>;5;) (-OR>;6;) (wherein W>;1; is an oxygen atom or a
sulfur atom, and each of R>;5; and R>;6;, which may be the same or different, is a hydrogen atom; a
(C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy(C1-C4)alkyl group; a (C1C4)alkylthio (C1-C4)alkyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1-C4)alkyl group; a
substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups,
di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups, R>;5; being able to bind to R>;6; to
form a 5- to 8-membered ring that may contain one or two atoms which may be the same or different
and are selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms
constituting the ring); -C(=W>;1;)-N(R>;5;)(R>;6;) (wherein W>;1;, R>;5; and R>;6; are as defined
above, R>;5; being able to bind to R>;6; to form a 5- to 8-membered ring that may contain one or two
atoms which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen
atom, between adjacent carbon atoms constituting the ring, and R>;5; being able to bind to R>;4; to
form a 5- to 8-membered ring that may contain two or three atoms which may be the same or different
and are selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms
121/612
constituting the ring); -C(=W>;1;)-R>;5; (wherein W>;1; and R>;5; areas defined above); -C(=W>;1;)W>;1;-R>;7; (wherein W>;1;s, which may be the same or different, are as defined above, and R>;7; is
a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy(C1-C4)alkyl group; a (C1C4)alkylthio(C1-C4)alkyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1-C4)alkyl group; a
substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups); -SO2-R>;7; (wherein R>;7; is as
defined above); -SO2-N(R>;5;)(R>;6;) (wherein R>;5; and R>;6; are as defined above, R>;5; being
able to bind to R>;6; to form a 5- to 8-membered ring that may contain one or two atoms which may be
the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom, between
adjacent carbon atoms constituting the ring, and R>;5; being able to bind to R>;4; to form a 5- to 8membered ring that may contain three or four atoms which may be the same or different and are
selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting
the ring); -N(R>;5;) (R>;6;) (wherein R>;5; and R>;6; are as defined above, R>;5; being able to bind to
R>;6; to form a 5- to 8-membered ring that may contain one or two atoms which may be the same or
different and are selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon
atoms constituting the ring, and R>;5; being able to bind to R>;4; to form a 5- to 8-membered ring that
may contain two or three atoms which may be the same or different and are selected from oxygen
atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the ring); or N=C(R>;5;)R>;6; (wherein R>;5; and R>;6; are as defined above, R>;5; being able to bind to R>;6; to
form a 5-to 8-membered ring that may contain one or two atoms which may be the same or different
and are selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms
constituting the ring); in the case of B being -N(R>;4;)- (wherein R>;4; is as defined above), R>;1;
being able to be -OR>;5; (wherein R>;5; is as defined above), -C(W>;2;)-N(R>;5;)R>;6; (wherein
W>;2; is =CH-NO2, =N-NO2 or =N-CN, and R>;5; and R>;6; are as defined above, R>;5; or R>;6;
being able to bind to R>;4; to form a 5- to 8-membered ring that may contain two or three atoms which
may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom,
between adjacent carbon atoms constituting the ring) or -C(W>;2;)-W>;1;-R>;7; (wherein W>;1;,
W>;2; and R>;7; are as defined above, R>;7; being able to bind to R>;4; to form a 5- to 8-membered
ring that may contain two or three atoms which may be the same or different and are selected from
oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the ring), and
R>;1; being able to bind to A>;1; to form a 5- to 8-membered ring that may contain one or two atoms
which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom,
between adjacent carbon atoms constituting the ring,
each of R>;2; and R>;3;, which may be the same or different, is a hydrogen atom or a (C1-C3)alkyl
group, each of Q>;1; through Q>;5; is a carbon atom or a nitrogen atom, each of Xs, which may be the
same or different, is a halogen atom, a nitro group, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a
(C2-C6)alkenyl group, a halo(C2-C6)alkenyl group, a (C2-C6)alkynyl group, a halo(C2-C6)alkynyl
group, a (C1-C6)alkoxy group, a halo(C1-C6)alkoxy group, a (C1-C6)alkylthio group, a halo(C1C6)alkylthio group, a (C1-C6)alkylsulfinyl group, a halo (C1-C6)alkylsulfinyl group, a (C1C6)alkylsulfonyl group or a halo(C1-C6)alkylsulfonyl group,
two adjacent Xs on the aromatic ring being able to be taken together to represent a fused ring that
may have one or more substituents which may be the same or different and are selected from halogen
122/612
atoms, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups and halo(C1-C6)alkylsulfonyl
groups, n is an integer of 0 to 2,
each of Ys, which may be the same or different, is a halogen atom; a cyano group; a nitro group; a
(C3-C6)cycloalkyl group; a halo (C3-C6)cycloalkyl group; a phenyl group; a substituted phenyl group
having one or more substituents which may be the same or different and are selected from halogen
atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkyl-sulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a heterocyclic
group; a substituted heterocyclic group having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkyl-sulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; or -A>;5;-R>;14; (wherein A>;5; and R>;14; are as defined above),
two adjacent Ys on the aromatic ring being able to be taken together to represent a fused ring that
may have one or more substituents which may be the same or different and are selected from halogen
atoms; (C1-C6)alkyl groups; halo(C1-C6)alkyl groups; (C1-C6)alkoxy groups; halo (C1-C6)alkoxy
groups; (C1-C6)alkyl-thio groups; halo(C1-C6)alkylthio groups; (C1-C6)alkyl-sulfinyl groups;
halo(C1-C6)alkylsulfinyl groups; (C1-C6)alkylsulfonyl groups; halo (C1-C6)alkylsulfonyl groups;
phenyl group; substituted phenyl groups having one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkyl-thio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkyl-sulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; heterocyclic groups; and substituted heterocyclic groups having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1C6)alkoxy groups, (C1-C6)alkyl-thio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkyl-sulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups, m is an integer of 1 to 5, and each of
Z>;1; and Z>;2; is an oxygen atom or a sulfur atom.
3. An aromatic diamide derivative or a salt thereof according to claim 2, wherein A>;1; is a (C1C8)alkylene group; a substituted (C1-C8)alkylene group having one or more substituents which may be
the same or different and are selected from halogen atoms, cyano group, nitro group, halo(C1-C6)alkyl
groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkyl-thio groups, halo(C1C6)alkylthio groups, (C1-C6)alkyl-sulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, (C1-C6)alkylthio (C1-C6)alkyl groups,
(C1-C6)alkoxycarbonyl groups and phenyl group; a (C3-C8)alkenylene group; a substituted (C3C8)alkenylene group having one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, halo (C1-C6)alkyl groups, (C1-C6)alkoxy
groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkylsulfonyl groups, (C1-C6)alkyl-thio(C1-C6)alkyl groups, (C1-C6)alkoxycarbonyl groups and
phenyl group; a (C3-C8)alkynylene group; or a substituted (C3-C8)alkynylene group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, (C1C6)alkyl-thio(C1-C6)alkyl groups, (C1-C6)alkoxycarbonyl groups and phenyl group,
123/612
any of the saturated carbon atoms in the above-mentioned (C1-C8)alkylene group, substituted (C1C8)alkylene group, (C3-C8)alkenylene group, substituted (C3-C8)alkenylene group, (C3C8)alkynylene group or substituted (C3-C8)alkynylene group being able to have a (C2-C5)alkylene
group bonded thereto as a substituent, to form a (C3-C6)cycloalkane ring, and any two of the carbon
atoms in the above-mentioned (C1-C8)alkylene group, substituted (C1-C8)alkylene group, (C3C8)alkenylene group and substituted (C3-C8)alkenylene group being able to form a (C3C6)cycloalkane ring or a (C3-C6)cycloalkene ring together with an alkylene group or an alkenylene
group,
B is -O- or -N(R>;4;)- (wherein R>;4; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl
group; a (C3-C6)talkenyl group; a halo (C3-C6)alkenyl group; a (C3-C6)alkynyl group; a (C3C6)cycloalkyl group; a (C1-C6)alkylcarbonyl group; a halo(C1-C6)alkylcarbonyl group; a (C1C6)alkoxycarbonyl group; a phenylcarbonyl group; a substituted phenylcarbonyl group having on the
ring one or more substituents which may be the same or different and are selected from halogen atoms,
cyano group, nitro group, (C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, (C1-C6)alkyl-thio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1C6)alkylsulfonyl groups, mono (C1-C6)alkylamino groups, and di (C1-C6)alkylamino groups whose
(C1-C6)alkyl groups may be the same or different; a phenyl (C1-C4)alkoxycarbonyl group; a
substituted phenyl(C1-C4)alkoxycarbonyl group having on the ring one or more substituents which
may be the same or different and are selected from halogen atoms, cyano group, nitro group, (C1C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkyl-sulfonyl groups, mono(C1C6)alkylamino groups, and di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same
or different; a phenyl(C1-C4)alkyl group; or a substituted phenyl(C1-C4)alkyl group having on the ring
one or more substituents which may be the same or different and are selected from halogen atoms,
cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1C6)alkyl-sulfonyl groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups),
R>;1; is a hydrogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy (C1C4)alkyl group; a (C1-C4)alkylthio(C1-C4)alkyl group; a (C2-C6)alkenyl group; a halo(C2-C6)alkenyl
group; a (C3-C6)alkynyl group; a halo(C3-C6)alkynyl group; a (C3-C6)cycloalkyl group; a halo(C3C6)cycloalkyl group; a phenyl group; a substituted phenyl group having one or more substituents
which may be the same or different and are selected from halogen atoms, cyano group, nitro group,
(C1-C6)alkyl groups, halo (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups,
(C1-C6)alkyl-thio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkyl-sulfinyl groups, halo(C1C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkylsulfonyl groups, mono (C1C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or
different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1-C4)alkyl group; a substituted phenyl(C1C4)alkyl group having on the ring one or more substituents which may be the same or different and are
selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio
groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups,
halo (C1-C6)alkyl-sulfonyl groups, mono (C1-C6)alkylamino groups, di(C1-C6)alkylamino groups
whose (C1-C6)alkyl groups may be the same or different, and (C1-C6)alkoxycarbonyl groups; a
heterocyclic group; a substituted heterocyclic group having one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo(C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo(C1-C6)alkyl-sulfonyl groups, mono(C1-C6)alkylamino groups, di(C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; -P(=W>;1;) (-OR>;5;) (-OR>;6;) (wherein W>;1; is an oxygen atom or a
sulfur atom, and each of R>;5; and R>;6;, which may be the same or different, is a hydrogen atom; a
(C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy(C1-C4)alkyl group; a (C1C4)alkylthio(C1-C4)alkyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-
124/612
C6)alkoxy groups, (C1-C6)alkyl-thio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkyl-sulfinyl
groups, halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl
groups, mono (C1-C6)alkylamino groups, di (C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl (C1-C4)alkyl group; a
substituted phenyl(C1-C4)alkyl group having on the ring one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, (C1-C6)alkylthio groups,
halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups, (C1C6)alkylsulfonyl groups, halo (C1-C6)alkyl-sulfonyl groups, mono (C1-C6)alkylamino groups, di (C1C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkyl-sulfonyl
groups, mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups, R>;5; being able to bind to R>;6; to
form a 5- to 8-membered ring that may contain one or two atoms which may be the same or different
and are selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms
constituting the ring); -C(=W>;1;)-N(R>;5;) (R>;6;) (wherein W>;1;, R>;5; and R>;6; are as defined
above, R>;5; being able to bind to R>;6; to form a 5- to 8-membered ring that may contain one or two
atoms which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen
atom, between adjacent carbon atoms constituting the ring, and R>;5; being able to bind to R>;4; to
form a 5- to 8-membered ring that may contain two or three atoms which may be the same or different
and are selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms
constituting the ring); -C(=W>;1;)-R>;5; (wherein W>;1; and R>;5; areas defined above); -C(=W>;1;)W>;1;-R>;7; (wherein W>;1;s, which may be the same or different, are as defined above, and R>;7; is
a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C1-C4)alkoxy(C1-C4)alkyl group; a (C1-C4)
alkylthio(C1-C4)alkyl group; a phenyl group; a substituted phenyl group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)
alkoxy groups, (C1-C6) alkylthio groups, halo(C1-C6)alkylthio groups, (C1-C6)alkyl-sulfinyl groups,
halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6)alkylsulfonyl groups,
mono(C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the
same or different, and (C1-C6)alkoxycarbonyl groups; a phenyl(C1-C4)alkyl group; a substituted
phenyl(C1-C4)alkyl group having on the ring one or more substituents which may be the same or
different and are selected from halogen atoms, cyano group, nitro group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1-C6)alkoxy groups, (C1-C6)alkylthio
groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl groups, halo (C1-C6)alkylsulfinyl groups,
(C1-C6)alkylsulfonyl groups, halo (C1-C6)alkyl-sulfonyl groups, mono (C1-C6)alkylamino groups, di
(C1-C6)alkylamino groups whose (C1-C6)alkyl groups may be the same or different, and (C1C6)alkoxycarbonyl groups; a heterocyclic group; or a substituted heterocyclic group having one or
more substituents which may be the same or different and are selected from halogen atoms, cyano
group, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6)alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkylsulfinyl
groups, halo (C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo (C1-C6)alkyl-sulfonyl
groups, mono (C1-C6)alkylamino groups, di(C1-C6)alkylamino groups whose (C1-C6)alkyl groups
may be the same or different, and (C1-C6)alkoxycarbonyl groups); -SO2-R>;7; (wherein R>;7; is as
defined above); -SO2-MR>;5;)(R>;6;) (wherein R>;5; and R>;6; are as defined above, R>;5; being
able to bind to R>;6; to form a 5- to 8-membered ring that may contain one or two atoms which may be
the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom, between
adjacent carbon atoms constituting the ring, and R>;5; being able to bind to R>;4; to form a 5- to 8membered ring that may contain three or four atoms which may be the same or different and are
selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting
the ring); -N(R>;5;) (R>;6;) (wherein R>;5; and R>;6; are as defined above, R>;5; being able to bind to
R>;6; to form a 5- to 8-membered ring that may contain one or two atoms which may be the same or
different and are selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon
atoms constituting the ring, and R>;5; being able to bind to R>;4; to form a 5- to 8-membered ring that
may contain two or three atoms which may be the same or different and are selected from oxygen
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atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the ring); or N=C(R>;5;)R>;6; (wherein R>;5; and R>;6; are as defined above, R>;5; being able to bind to R>;6; to
form a 5-to 8-membered ring that may contain one or two atoms which may be the same or different
and are selected from oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms
constituting the ring); in the case of B being -N(R>;4;)- (wherein R>;4; is as defined above), R>;1;
being able to be -OR>;5; (wherein R>;5; is as defined above), -C(W>;2;)-N(R>;5;)R>;6; (wherein
W>;2; is =CH-NO2, =N-NO2 or =N-CN, and R>;5; and R>;6; are as defined above, R>;5; or R>;6;
being able to bind to R>;4; to form a 5- to 8-membered ring that may contain two or three atoms which
may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom,
between adjacent carbon atoms constituting the ring) or -C(W>;2;)-W>;1;-R>;7; (wherein W>;1;,
W>;2; and R>;7; are as defined above, R>;7; being able to bind to R>;4; to form a 5- to 8-membered
ring that may contain two or three atoms which may be the same or different and are selected from
oxygen atom, sulfur atom and nitrogen atom, between adjacent carbon atoms constituting the ring), and
R>;1; being able to bind to A>;1; to form a 5- to 8-membered ring that may contain one or two atoms
which may be the same or different and are selected from oxygen atom, sulfur atom and nitrogen atom,
between adjacent carbon atoms constituting the ring,
each of R>;2; and R>;3;, which may be the same or different, is a hydrogen atom or a (C1-C3)alkyl
group, each of Q>;1; through Q>;4; is a carbon atom, each of Xs, which may be the same or different,
is a halogen atom, a nitro group, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a (C2-C6)alkenyl
group, a halo (C2-C6)alkenyl group, a (C2-C6)alkynyl group, a halo(C2-C6)alkynyl group, a (C1C6)alkoxy group, a halo(C1-C6)alkoxy group, a (C1-C6)alkylthio group, a halo(C1-C6)alkylthio
group, a (C1-C6)alkylsulfinyl group, a halo (C1-C6)alkylsulfinyl group, a (C1-C6)alkylsulfonyl group
or a halo(C1-C6)alkylsulfonyl group,
two adjacent Xs on the aromatic ring being able to be taken together to represent a fused ring that
may have one or more substituents which may be the same or different and are selected from halogen
atoms, nitro group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo (C1C6) alkoxy groups, (C1-C6)alkylthio groups, halo (C1-C6) alkylthio groups, (C1-C6) alkylsulfinyl
groups, halo (C1-C6) alkylsulfinyl groups, (C1-C6) alkylsulfonyl groups and halo (C1-C6)
alkylsulfonyl groups, n is an integer of 0 to 2,
Q>;5; is a carbon atom or a nitrogen atom, each of Ys, which may be the same or different, is a
halogen atom; a (C1-C6)alkyl group; a halo(C1-C6)alkyl group; a (C3-C6)cycloalkyl group; a halo(C3C6)cycloalkyl group; a (C1-C6)alkoxy group; a halo (C1-C6)alkoxy group; a (C1-C6)alkylthio group;
a halo(C1-C6)alkylthio group; a (C1-C6)alkylsulfinyl group; a halo (C1-C6)alkylsulfinyl group; a (C1C6)alkylsulfonyl group; a halo (C1-C6)alkylsulfonyl group; a halo(C1-C6)alkoxyhalo (C1-C6)alkoxy
group; a phenyl group; a substituted phenyl group having one or more substituents which may be the
same or different and are selected from halogen atoms, cyano group, halo (C1-C6)alkyl groups, halo
(C1-C6)alkoxy groups, halo (C1-C6)alkylthio groups, halo (C1-C6)alkylsulfinyl groups and halo(C1C6)alkylsulfonyl groups; a phenyloxy group; a substituted phenyloxy group having one or more
substituents which may be the same or different and are selected from halogen atoms, cyano group,
halo(C1-C6)alkyl groups, halo(C1-C6)alkoxy groups, halo(C1-C6)alkylthio groups, halo(C1C6)alkylsulfinyl groups and halo(C1-C6)alkylsulfonyl groups; a pyridyloxy group; or substituted
pyridyloxy group having one or more substituents which may be the same or different and are selected
from halogen atoms, cyano group, halo(C1-C6)alkyl groups, halo(C1-C6)alkoxy groups, halo(C1C6)alkylthio groups, halo(C1-C6)alkylsulfinyl groups and halo (C1-C6)alkylsulfonyl groups,
two adjacent Ys on the aromatic ring being able to be taken together to represent a fused ring that
may have one or more substituents which may be the same or different and are selected from halogen
atoms, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy
groups, (C1-C6)alkyl-thio groups, halo (C1-C6)alkylthio groups, (C1-C6)alkyl-sulfinyl groups,
halo(C1-C6)alkylsulfinyl groups, (C1-C6)alkylsulfonyl groups, halo(C1-C6) alkylsulfonyl groups,
phenyl group, and substituted phenyl groups having one or more substituents which may be the same or
different and are selected from halogen atoms, halo(C1-C6)alkyl groups, halo(C1-C6)alkoxy groups,
halo(C1-C6)alkylthio groups, halo(C1-C6)alkylsulfinyl groups and halo(C1-C6)alkylsulfonyl groups,
m is an integer of 1 to 3, and each of Z>;1; and Z>;2; is an oxygen atom.
4. An agricultural and horticultural chemical comprising an aromatic diamide derivative or a salt
thereof according to any one of claims 1 to 3 as an active ingredient.
126/612
5. An agricultural and horticultural chemical according to claim 4, which is an agricultural and
horticultural insecticide.
6. A method for applying an agricultural and horticultural chemical, characterized by applying an
agricultural and horticultural chemical according to claim 4 to a crop to be protected or the growth
environment of the crop to be protected, in an effective dosage for protecting useful crops against
insect pests.
7. A method for applying an agricultural and horticultural chemical according to claim 5 which is an
agricultural and horticultural insecticide.Data supplied from the esp@cenet database - Worldwide
127/612
7. GB1013457
- 12/15/1965
PHOSPHORUS-CONTAINING PESTICIDES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1013457
Inventor(s):
WILDGRUBE WOLFGANG (--); MEISNER DIETER (--); BORN MANFRED (--)
Applicant(s):
WOLFEN FILMFAB VEB (--)
E Class: C07F9/165B
Application Number:
GB19630047259 (19631129)
Priority Number: GB19630047259 (19631129)
Family: GB1013457
Abstract:
Abstract of GB1013457
Pesticidally - active phosphorus containing compounds are obtained by reacting an ester of pentavalent
phosphorus of the general formula >;FORM:1013457/C2/1; in which R1, R11 and R111 are the same
or different alkyl and aryl radicals and X1 and X2 are sulphur or oxygen atoms, at least one X being a
sulphur atom, is reacted with a sulphur halide at an elevated temperature. Suitable sulphur halides
include sulphur dichloride and disulphur dichloride and suitable phosphorus esters of the above
formula include trimethyl thiophosphate, tri-n-propyl thiophosphate and O-p-chlorophenyl-O,Odimethyl thiophosphate. When disulphur dichloride is used the mol. ratio of ester to sulphur halide
advantageously lies at 2 : 1 : in the case of sulphur dichloride, the ratio is 1 : 1 to 2 : 1. A catalyst such
as copper powder or copper compounds may be present. For the use of the compounds in insecticidal
compositions (see Division A5).ALSO:Pesticidal compositions comprise a solid or liquid diluent and a
phosphorus compound obtained by the reaction of an ester of pentavalent phosphorus of the general
formula: >;FORM:1013457/A5-A6/1; where R1, R11 and R111 are the same or different alkyl or aryl
radicals and X1 and X2 are oxygen or sulphur atoms, at least one X being a sulphur atom, with a
sulphur halide. (see Division C2). An example is given where the compounds are tested for their
activity against house flies, cornbeetles and rice beetle larvae.Description:
Description of GB1013457
COMPLETE SPECIFICATIONPhosphorus-Containing Pesticides
We, VEBFARBENFABRIK WOLFENA of
Wolfen Kreis Bitterfeld, Germany, aCorpera- tion organised under the laws of Eastern Germany, do
hereby declare the invention, for which we pray that a patent may be granted to us, and the method by
which it is to be performed, to be particularly described in and by the followingstatement:
The present invention is concerned with new phosphorus-containing pesticides and with the
production thereof.
In the literature there are described various reactions of esters of trivalent phosphorus with sulphur
halides. Thus, for example, dialkyl phosphites react with sulphur chlorides to give bis - (dialkyl phosphoryl) - sulphides (see
German Patent Specification No. 820,001) or to give the corresponding disulphides (see
Ettel and M. Zbirovski, Chem. Listy,50, 12614/1956; U.S. Patent Specification No.
2,630,450)
Tetraalkyl thiopyrophosphates, i.e. compounds of the general formula[(RO)2PO!]2S, together with
other products, are formed from triallyl phosphites and sulphur chlorides, the intermediate formation of
asulphenyl chlorides being assumed (see J.Michalski et al., Chem.
128/612
and Ind., 1052/1962; A. C. Poshkus and J. E.
Herweh, J.A.C.S., 84, 555/1962; Chem. and
Ind., 1316/1961).
We have now found, surprisingly, that esters of pentavalent phosphorus of the general formula:
2 (RO),P = S + S,Cl, >; ;
Because of the thermal lability of the reaction products, they cannot be purified by distillation. The
inertness of sulphur-free esters of pentavalent phosphorus leads one to the assumption that the abovementioned reaction proceeds viasulphenyl chlorides or thiosulphenyl chlorides.
Paper chromatographic investigations shew that the reaction products consist of a mixture of various
phosphoric acid esters whichprobEMI1.1
in which R1, R'1 and R111 are the same or different alkyl or aryl radicals and X1 andX2 are sulphur
or oxygen atoms, at least one of X1 and X, being a sulphur atom, react with sulphur halides to give
products which are very suitable as active materials for insecticidallyactive preparations.
The sulphur halide is expediently converted at elevated temperatures in the presence of an inert solvent
in such a manner that the halogen is eliminated as alkyl halide, while the sulphur is more or less
completely precipitated, depending on the conditions.
In the case of the use of disulphur dichloride, the mol ratio of ester to sulphur halide advantageously
lies at 2: 1, having regard to the yield and the insecticidal effectiveness of the reaction product; in the
case of sulphur dichloride, the ratio is1:1 to 2: 1.
The addition of copper powder or of a copper compound as catalyst results in an easier splitting off of
the alkyl halide and of the sulphur. The reaction which takes place is exemplified by the following
equation: 2RCl + 2 S+ [(RO)2.POS]2 ably contains the correspondingdisulphides.
The following Examples are given for the purpose of illustrating the present invention:
EXAMPLE 1.
156 g. (1.0 mol) trimethyl thionophosphate in 400 ml. chlorobenzene are mixed with 70 g. (0.5
mol)sulphur dichloride. After the addition of 0.5 g. copper powder, the reaction mixture is heated, with
stirring, for one hour at800C. and the temperature then increased in the course of Z hours to11(120 C.
45g. (0.9 mol) methyl chloride condense in a connected cold-trap.
Thechiorobenrene solution is distilled at 1000C./12 mm. Hg. down to a residue. After filtering off 31
g. (1 mol) sulphur with suction, there is obtained 132 g. of a red-brown product which is only slightly
soluble in water. By distillation in a high vacuum, there can be isolated about20i% of volatile
components which mainly consist of trimethyl thiophosphate.
Increasing the proportion of disulphur dichloride brings about an increasing formation of resinous
products which are difficultly soluble in common organic solvents. A redudon of the reaction
temperature to600C. leads to a reduction in the amount of methyl chloride formed and the formation of
less effective insecticidal compounds.
EXAMPLE 2.
When carrying- out the reaction described in
Example 1 but without the addition of the copper powder, there are obtained 0.9 mol methyl chloride
but only 0.3 mol sulphur.
There remains behind 135 g. of a brown residue which differs from that of Example 1 by a lower
insecticidal activity.
EXAMPLE 3.
129/612
A solution of 156 g. (1.0 mol) trimethyl thionophosphate in 400 ml. chlorobenzene is mixeddropwise
with 102 g. (1.0 mol) sulphur dichloride, whereby the temperature increases to 550C. After subsidence
of the reaction, the reaction mixture is slowly heated to800 C.
and, after one hour, heatedfrrther to110 1200C. This temperature is maintained for two hours. About
0.75 mol methyl chloride are collected, as well as 0.16 mol hydrogen chloride, which indicates
chlorination reactions.
After distilling the residue at 1000C./12 mm. Hg. and separating off 15 g. sulphur, there are obtained
120 g. of a dark red-brown product.
EXAMPLE 4.
From 78 g. (0.5 mol) trimethyl thiolphosphate in 200 ml.chloroberizene and 35 g.
(0,25 mol)sulphur dichloride, there are obtained, when working as in Example 1, 47 g.
of a dark brown product, as well as 20 g.
methyl chloride (0.4 mol).
EXAMPLE 5.
Analogously to Example 1, from 96 g. (0.4 mol) tri-n-propyl thionophosphate and 27 g.
(0.2 mol) disulphur dichloride, there areob- tained 60 g. of a brown oil. There are also formed 13 g.
sulphur and 31 g. (0.4 mol) npropyl chloride.
EXAMPLE 6.
Using the method described in Example 1, from 100 g. (0.4 mol)O-p-chlorophenyl-O,O dimethyl
thionophosphate and 27 g. (0.2 mol) disulphur dichloride, in the presence of copper powder, there are
obtained 80 g. of a dark residue. There are also obtained 10 g. sulphur and 16 g. (0.32 mol) methyl
chloride.
EXAMPLE 7.
The testing of the compounds for insecticidal effectiveness was carried out on house flies (Musca
domestica) and corn beetles(Sito; philus granarius) in acetone solution and on rice beetle larvae
(Tribolium confusum) in wheat meal. In the case of testing against house flies and corn beetles, a
solution of the active material in acetone was applied to filter papers and, after evaporation of the
acetone, the pests werecontacted with the filter papers. In the case of the rice beetle larvae, the active
material was mixed with wheat meal and the larvae placed thereon. The evaluation on corn beetles.
was carried out after 18 hours and on rice beetle larvae after 2 (a) and 10O days, respectively. The
results obtained are set out in the following Table:
Conc. of Inability
active Degree of to fly
material effective- after
Product Used againstin % ness in % minutes
Example 1 M. domestica 1.0 10
0.1 30
S. granarius 1.0 100
0.1 100
T. confusum 0.05 75 (a) 100 (b)
0.01 75 (a) 100 (b)
Example 2 M. domestica 1.0 70
0.1 70*
S. granarius 1.0 90
130/612
0.1 65
T. confusum 0.1 75 (a) 100 (b)
0.05 65 (a)
98 (b)
Example 3 M. domestica 1.0 30
0.1 150
S. granarius 1.0 95
0.1 90
T. confusum 0.1 75 (a) 100 (b)
0.05 75 (a) 100 (b)
Example 4 M. domestica 1.0 75
0.1 10*
S. granarius 1.0 90
0.1 0
T. confusum 0.5 75 (a)
99 (b)
0.2 40 (a) 90 (b)
Example 5 M. domestica 1.0 130
0.1 75*
S. granarius 1.0 90
0.1 10
T. confusum 0.1 25 (a)
95 (b)
0.051 (a) 50 (b)
* indicates evaluation made after 5 hours.
The products according to the present invention may be used as insecticides in admixture with solid or
liquid diluents or carriers.
WHAT WEAIM IS:1. Process for the production of new, pesticidally-active products, wherein an ester of pentavalent
phosphorus of the general formula:
EMI3.1
in whichR1, R11 and R111 are the same or different alkyl or aryl radicals and X1 and X2
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB1013457
**WARNING** start of CLMS field may overlap end of DESC **.
Conc. of Inability
active Degree of to fly
material effective- after
Product Used againstin % ness in % minutes
Example 1 M. domestica 1.0 10
0.1 30
S. granarius 1.0 100
0.1 100
T. confusum 0.05 75 (a) 100 (b)
0.01 75 (a) 100 (b)
Example 2 M. domestica 1.0 70
0.1 70*
S. granarius 1.0 90
0.1 65
T. confusum 0.1 75 (a) 100 (b)
0.05 65 (a)
131/612
98 (b)
Example 3 M. domestica 1.0 30
0.1 150
S. granarius 1.0 95
0.1 90
T. confusum 0.1 75 (a) 100 (b)
0.05 75 (a) 100 (b)
Example 4 M. domestica 1.0 75
0.1 10*
S. granarius 1.0 90
0.1 0
T. confusum 0.5 75 (a)
99 (b)
0.2 40 (a) 90 (b)
Example 5 M. domestica 1.0 130
0.1 75*
S. granarius 1.0 90
0.1 10
T. confusum 0.1 25 (a)
95 (b)
0.051 (a) 50 (b)
* indicates evaluation made after 5 hours.
The products according to the present invention may be used as insecticides in admixture with solid or
liquid diluents or carriers.
WHAT WEAIM IS:1. Process for the production of new, pesticidally-active products, wherein an ester of pentavalent
phosphorus of the general formula:
EMI3.1
in whichR1, R11 and R111 are the same or different alkyl or aryl radicals and X1 and X2
are sulphur or oxygen atoms, at least one of
X1 and X2 being a sulphur atom, are reacted at an elevated temperature with a sulphur halide.
2. Process according to claim 1, wherein the reaction is carried our at a temperature of more than70 C.
3. Process according to claim 1 or 2, wherein the sulphur halide is sulphurchloride or disulphur
dichloride.
4. Process according to claim 3, wherein the ester is reacted withsulphur dichioride in a mol ratio
of2:1 or with sulphurchloride in a mol ratio of1:1 to 2: 1.
5. Process according to any of the preceing claims, wherein the reaction is catalysed by copper
powder or a copper compound.
6. Process according to claim 1 for the production of pesticidally-active products,sab- stantially as
hereinbefore described and with reference to any of Examples 1 to 6.
7. Pesticidally-active products, whenever produced by the process according to any of claims 1 to 6.
8. Pesticidal compositions containing a product according to claim 7 and a solid or liquid diluent or
carrier.Data supplied from the esp@cenet database - Worldwide
132/612
8. GB1084595
- 9/27/1967
METHOD OF COMBATTING FUNGI
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1084595
Inventor(s):
SCHEINPFLUG HANS (--); JUNG HERBERT (--); LORENZ WALTER (--);
SCHMIDT KARL-JULIUS (--)
Applicant(s):
BAYER AG (--)
E Class: A01N57/06; C07F9/09A7; C07F9/12; C07F9/165A7; C07F9/18; C07F9/32C4; C07F9/32C7;
C07F9/40C4; C07F9/40C7
Application Number:
GB19650029457 (19650712)
Priority Number: DE1964F043630 (19640731)
Family: GB1084595
Equivalent:
NL6509921; BE667592
Abstract:
Abstract of GB1084595
A fungitoxic composition, which is especially useful in combatting fungi causing diseases on rice and
other cultivated plants, contains an ester of the general formula: >;FORM:1084595/A5-A6/1; in
admixture with a solid diluent or carrier, or in admixture with an organic solvent and an emulsifying
agent capable of producing a stable emulsion when diluted with water, or in admixture with water
containing an auxiliary solvent and/or an emulsifying agent. In the general formula, R and R\sv (which
may be the same or different) are alkyl or alkoxy radicals containing 1-6 carbon atoms; X is a cyano or
thiocyano radical, or an alkyl mercapto or alkylcarbonyl radical containing 1-4 carbon atoms; Y is one
or two hydrogen or halogen atoms or an alkyl or alkoxy radiccal containing 1-4 carbon atoms; A and B
(which may be the same or different) are oxygen or sulphur; and n is zero or one. The compositions
may take the form of emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents
or granulates. Adjuvants which may be employed in preparing the compositions include solvents (e.g.
benzene, xylene, chlorobenzenes, mineral oil fractions, methanol, ethanol, butanol, ethanolamine,
dimethyl formamide or water), solid carrier materials (e.g. kaolins, alumina, chalk, talc, highly
dispersed silicic acid or silicates), emulsifiers (e.g. polyoxyethylene-fatty acid esters, polyoxyethylenefatty alcohol ethers, or alkyl or aryl sulphonates) and dispersing agents (e.g. lignin, sulphite waste
liquors and methyl cellulose).Description:
Description of GB1084595
COMPLETE SPECIFICATION
Method ofCombating Fungi
We,FARBENFABRIKEN BAYER AKTIEN
GESELLSCHAFT, a body corporate orgamsed under the laws of Germany, of Leverkusen,
Germany, do hereby declare the invention, for which we pray that a patent may be granted to us and the
method by which it is to be performed, to be particularly described in and by the followingstatement:
The present invention is concerned with new methods of combatting fungi.
According to the present invention there is provided a method of combatting fungi or of preventing
fungal growth, in which there is applied to a fungus habitat a composition containing at least one ester
of the generalformula:
EMI1.1
133/612
wherein R and R', which may be the same or different, are alkyl or alkoxy radicals containing 1 to 6
carbon atoms;
X is a cyano or thiocyano radical, or an alkylmercapto or alkylcarbonyl radical containing 1 to 4
carbon atoms;
Y is one or two hydrogen or halogen atoms or an alkyl or alkoxy radical containing 1 to 4 carbon
atoms;
A and B, which may be the same or different, are oxygen or sulphur;
and n has the value zero or one,
in admixture with a solid diluent or carrier, or in admixture with an organic solvent and an emulsifying
agent capable of producing a stable emulsion when diluted with water, or in admixture with water
containing an auxiliary solvent and/or an emulsifying agent.
R and R' preferably stand for the same or different alkyl or alkoxy radicals containing 1 to 4 carbon
atoms, such as methyl, ethyl, n- and isopropyl, sec.- and tert.-butyl radicals, whereby these radicals,
according to the above definition, can also be attached to the phosphorus atom via oxygen; X signifies,
besides the cyano or thiocyano group, in particular a methylmercapto or acetyl radical, while Y
preferably represents a hydrogen or chlorine atom or a methyl or methoxy radical.
We have found that compounds of the above-given general formula exhibit a strong fungitoxic action
and a broad spectrum of activity. Because of their low toxicity towards warm-blooded animals, they are
outstandingly suitable for combatting undesired fungal growth and good compatibility for higher plants
permits their use as plant protection agents against fungus diseases.
The esters to be used in the method according to the present invention have proved to be especially
useful in combatting rice diseases.
They show an excellent protective and, in some cases, also curative action against
Piricularia oryzae on rice.
Furthermore, the method of the invention is very effective against various fungi causing diseases on
rice and other cultivated plants.
The active esters possess an especial action against the following types of fungi:Cochiobodus
miyabeanus, Species of Mycosphaerella, Corticium, Cerospora, Alternaria andBotrytis.
The esters to be used in the method according to the present invention also have a fungitoxic effect
against fungi which attack the plants from the soil and, in part, cause tracheomycoses, such asFusarium
cub en se,
Fusarim dianthi,Verticillium alboairum and
Phialophoracinerescens,
Esters of the generalformula:
EMI2.1
(II) and esters of the generalformula:
EMI2.2
have proved to be especially fungitoxic.
In the last-mentioned formulae, the symbols
R and R' have the same meanings as above,
Z stands for a cyano or thiocyano group and
Z1 for a hydrogen atom or one or two
chlorine atoms.
Some of the active compounds to be used in the method according to the present invention have
already been described in the !iterature; they can be produced in known manner, for example, by the
reaction of appropriatedialkylphosphoric, -- thionophosphoric, phosphonic, thionophosphonic,
phosphinic, or thionophosphinic acid halides with the appropriately substituted phenols or by the
reaction of dialkyl phosphites, thiolphosphites, phosphonites, thiolphosphonites, phosphinites or
thiophosphinites with aromatic thiocyanates according to the method of United
Kingdom Patent Specification No. 992,159.
134/612
They can also be obtained fromdiallyl thiolor -thionothiolphosphoricthiol or -thionothiolphosphonic or
-thiol or -thionothiolphosphonic acid salts and the appropriately nuclear-substituted benzyl halides.
When the fungitoxic agents are used in the method according to the present invention, they can be
used individually or in combination with one another. They can also be mixed with other plant
protective agents, such as fungicides, herbicides, insecticides and bactericides.
The esters to be used in the method according to the present invention are employed in the form of the
usual compositions such as emulsifiable concentrates, spray powders, pastes, soluble powders, dusting
agents and granulates. These are produced in known manner, for example, by extending the active
materials with solvents and/or carriers, possibly with the simultaneous use of emulsifying and/or
dispersing agents (cf. Agricultural
Chemicals, March, 1960, pages35-38).
Adjuvants for this purpose are mainly: solvents, such as optionally chlorinated aromatic hydrocarbons
(e.g. xylene, benzene and chlorobenzenes), paraffins, (e.g. mineral oil fractions), alcohols (e.g.
methanol, ethanol and butanol), amines (e.g. ethanolamine), dimethyl formamide and water; solid
carrier materials, for example, natural and synthetic mineral powders (kaolins, alumina, chalk, talc,
highlydispersed silicic acid and silicates); emulsifiers, such as nonionic and anionic emulsifiers (e.g.
polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, alkyl sulphonates and aryl
sulphonates); and dispersing agents, such as lignin, sulphite waste liquors and methyl cellulose.
As mentioned above, the active compounds to be used in the method according to the present
invention can be present in the aforesaid compositions in admixture with known active substances.
In general, compositions contain between 0.1 and 95 percent by weight of active ester, preferably 0.5
to90%.
The compositions for use in the method according to the present invention are used in the usual
manner, for example, by spraying, dusting, atomising or vapourising. The active esters can be used,
depending upon the purpose, in a concentration of 5 to0.0005%.
In individual cases, it is, however, possible or even necessary to go below or to exceed this range of
concentration.
The following Examples are given for the purpose of illustrating the present invention:
EXAMPLES
A. Piricularia Test
A liquid preparation of active compoundcontaining:
1 part by weight acetone (solvent)
0.05 part by weight sodium oleate (dis
persing agent)
0.2 part by weight gelatine and
98.75 parts by weight water is prepared as follows:
The amount of active compound required for the desired concentration in the spray liquor is mixed
with the stated amount of solvent and the concentrate obtained diluted with the stated amount of water
containing the other additives and the dispersing agent.
Thirty rice plants, which are about 14 days old, are sprayed with the spray liquor until dripping wet
The plants remain in a greenhouse at a temperature of 22 to 240C. and at a relative atmospheric
humidity of about 70%, until dry. They are then inoculated with an aqueous suspension of 100,000 to
200,000 spores/ ml. of Piriculariaoryzae and placed in a chamber at 24 to 260C. and at a relative
atmospheric humidity of 100%.
Five days after inoculation, the degree of infestation of all the leaves of the treated plants which were
present at the time of inoculation is determined as a percentage of the untreated but also inoculated
control plants. 0% means that no infestation occurred and 100% that the infestation is exactly the same
as that of the control plants.
135/612
The test results obtained can be seen from the Table 1.
B. Piricularia Test
A solid preparation of the active compoundcontaining:
10 parts by weight acetone (solvent) and 100 parts by weight dust base consisting
of
95.5% calcium carbonate
4.0% silicic acid
0.5% magnesium stearate is prepared as follows:
The amount of active compound required for the desired concentration of the active compound in the
dusting agent is mixed with the stated amount of solvent, and the concentrate obtained is triturated in a
mortar with the stated amount of dust base until the solvent has evaporated.
Thirty rice plants which are about 14 days old are dusted with this agent. They are then inoculated
with an aqueous suspension of 100,000 to 200,000 spores/ml. ofPiriculana oryzae and placed in a
chamber at a temperature of24-260C. and at a relative atmospheric humidity of 100%.
Five days after inoculation, the infestation of all the leaves of the treated plants, which were present at
the time of inoculation, are determined as a percentage of the untreated but also inoculated control
plants. 0% means that no infestation occurred and 100% means that the infestation is exactly the same
as that of the control plants.
The test results obtained can be seen from
Table 1.
C.Piricularia Test
Examination of the curative effect:
In the test with the liquid as well as with the solid preparation of the active compound, the curative
effect of the compounds to be used according to the invention is determined, in addition to the
protective effect. To determine the protective effect, the method is exactly the same as that described
for the other test. For determining the curative effect, the test is only modified in that the active
compounds are here applied not before, but 24 hours after, inoculation. Compounds which
are effective according to this method of carrying out the test are capable of destroying the fungus
after infection and thus have a curative effect.
TABLE 1
Piricularia Test
Infestation in percentage of the infestation
of the untreated control with an active
compound concentration of
No. Active Compound (Constitution) 0.1 0.05 0.01 0.005 0.001*
EMI4.1
>;tb; >;SEP; S
>;tb; 1 >;SEP; (C2-o)-S-CCN >;SEP; liquid >;SEP; soli >;SEP; 0 >;SEP; 50
>;tb; >;SEP; I >;SEP; solid >;SEP; 0 >;SEP; 50
>;tb; t10. >;SEP; 0 >;SEP; liquid >;SEP; 0 >;SEP; 3
>;tb; >;SEP; sCH70 >;SEP; solid >;SEP; 33 >;SEP; 46
>;tb; >;SEP; O >;SEP; CI,
>;tb; 3 >;SEP; (c)1io)oC)\cL >;SEP; liquid >;SEP; 6 >;SEP; 10
>;tb; >;SEP; 2 >;SEP; solid >;SEP; 0 >;SEP; 3
>;tb; >;SEP; CL
>;tb; 4 >;SEP; (ciio)po\ >;SEP; o >;SEP; T >;SEP; liquid >;SEP; 0 >;SEP; 0
>;tb; >;SEP; Ct4
>;tb; >;SEP; 0
>;tb; liquid >;SEP; 8
>;tb; 5 >;SEP; C21-)5O2P-S >;SEP; p >;SEP; solid >;SEP; 15
136/612
>;tb; >;SEP; CN
>;tb; >;SEP; 0 >;SEP; liquid >;SEP; 12
>;tb; solid >;SEP; (CZCISoXCS-SCN >;SEP; soli >;SEP; 25
>;tb; 6 >;SEP; 2 >;SEP; l52-St4
>;tb; >;SEP; S
>;tb; >;SEP; (c25o)?"- >;SEP; s-cIA-\ >;SEP; liquid >;SEP; 1 >;SEP; 27 >;SEP; 25
>;tb; 7 >;SEP; 2 >;SEP; solid >;SEP; 13 >;SEP; 27
>;tb; >;SEP; CN
>;tb; >;SEP; Cf"
>;tb; >;SEP; O >;SEP; - >;SEP; liquid >;SEP; 0 >;SEP; 37
>;tb; 8 >;SEP; (-CH30)2 >;SEP; sc1. >;SEP; solid >;SEP; 12
>;tb;
TABLE 1 (cont.)
Piricularia Test
Infestation in percentage of the infestation
of the untreated control with an active
compound concentration of
No. Active Compound (Constitution) 0.1 0.05 0.01 0.005 0.001*
EMI5.1
>;tb; >;SEP; 0
>;tb; >;SEP; tC4RsO)2PS-CH
>;tb; >;SEP; 9 >;SEP; liquid >;SEP; 3
>;tb; >;SEP; solid >;SEP; 19
>;tb; 10 >;SEP; (CHs42P >;SEP; 5-EF129 >;SEP; solid >;SEP; 3
>;tb; >;SEP; CN >;SEP; solid >;SEP; 25
>;tb; >;SEP; 0
>;tb; 11 >;SEP; (C21 >;SEP; IsO)2. >;SEP; (C2Hs6) >;SEP; liquid >;SEP; 0 >;SEP; 63
>;tb; P-S-C'A2
>;tb; >;SEP; N >;SEP; solid >;SEP; 54
>;tb; >;SEP; (c2H50)S
>;tb; 12 >;SEP; - >;SEP; - >;SEP; / >;SEP; \4 >;SEP; liquid >;SEP; 0
>;tb; >;SEP; solid >;SEP; \ >;SEP; soli >;SEP; 46
>;tb; >;SEP; S
>;tb; 13 >;SEP; (CHg0)2F- >;SEP; S-( >; H29 >;SEP; liquid >;SEP; 0 >;SEP; 50
>;tb; >;SEP; solid >;SEP; 50
>;tb; >;SEP; CN
>;tb; >;SEP; o >;SEP; Cs
>;tb; 14 >;SEP; fl >;SEP; H30)1. >;SEP; /\ >;SEP; -S >;SEP; liquid >;SEP; 0 >;SEP; 75
>;tb; >;SEP; (c\\3d)2?-s- >;SEP; c2 >;SEP; solid >;SEP; 7 >;SEP; 27
>;tb; >;SEP; CU3
>;tb; >;SEP; liquid >;SEP; 0 >;SEP; 75
>;tb; 15 >;SEP; >;SEP; C832) >;SEP; 43 >;SEP; CH30 >;SEP; solid >;SEP; 25 >;SEP; 25
>;tb; >;SEP; H.3o)2 >;SEP; ?-C
>;tb; * Blank spaces in these columns indicate that no test was made.
EXAMPLE
Mycelium growth test
The following nutrient medium is used:
20 parts by weight powdered agar-agar
30 parts by weight malt extract
950 parts by weight distilled water
Ratio of solvent to nutrient medium:
parts by weight acetone
100 parts by weight agar nutrient medium
The amount of active compound required for the desired concentration of the active compound in the
nutrient medium is mixed with the stated amount of the solvent. The concentrate obtained is thoroughly
mixed in the stated ratio with the liquid nutrient medium which has a temperature of about420 C., and
137/612
then poured into Petri dishes of 9 cm. diameter. Control dishes without the active compound are also
provided.
When the nutrient medium has cooled and solidified, the dishes are inoculated with the fungi specified
in Table 2, and incubated at about 210C.
Evaluation is carried out after4-10 days, dependent upon the rate of growth of the fungi. For
evaluation, the radial mycelium growth on the treated nutrient media is compared with the growth on
the control medium.
The evaluation of the mycelium growth is made as follows:
0 no mycelium growth
1 very strong inibition of growth
2 medium inhibition of growth
3 slight inhibition of growth
4 growth equal to that of untreated control
The active compounds, their concentrations and the results obtained can be seen from the following
Table (Table 2): TABLE 2
Mycelium growth test Fungi*
EMI7.1
>;tb; >;SEP; IrIue!p >;SEP; 'J
>;tb; >;SEP; dsdxo >;SEP; umFrsnI >;SEP; oc
>;tb; >;SEP; asnaqn3J
>;tb; >;SEP; dsdxo >;SEP; mnrsesn >;SEP; ocu
>;tb; >;SEP; ounrst-oqle
>;tb; >;SEP; tunnUDsv2A >;SEP; N >;SEP; t >;SEP; N >;SEP; t
>;tb; >;SEP; SUa3SaJaa13
>;tb; >;SEP; BIO4douBlQa >;SEP; N >;SEP; t >;SEP; O >;SEP; t >;SEP; as
>;tb; >;SEP; smuas
>;tb; BrleuialN >;SEP; o >;SEP; Compound >;SEP; (Constitution) >;SEP; concentration >;SEP; o
>;SEP; Ohlcs
>;tb; >;SEP; . >;SEP; .u:i >;SEP; as >;SEP; as
>;tb; >;SEP; C >;SEP; .-u >;SEP; n
>;tb; >;SEP; salaup
>;tb; >;SEP; smir
>;tb; >;SEP; tojIag00
>;tb; >;SEP; e0dsos >;SEP; -*CV
>;tb; >;SEP; lt3nosd
>;tb; >;SEP; BIOdSOO143 >;SEP; ohl >;SEP; 1 >;SEP; 1 >;SEP; 0 >;SEP; 2
>;tb; >;SEP; BIWTSnW
>;tb; >;SEP; eataeqdso3dTN >;SEP; 00 >;SEP; oo >;SEP; oo
>;tb; >;SEP; snrraqlm
>;tb; >;SEP; snloqog >; >;SEP; 500 >;SEP; N >;SEP; X >;SEP; o >;SEP; N >;SEP; 0 >;SEP; 1
>;SEP; 0 >;SEP; 0 >;SEP; 2 >;SEP; 0 >;SEP; 0
>;tb; >;SEP; IplBSBS >;SEP; Orr
>;tb; >;SEP; MI >;SEP; 100 >;SEP; 0 >;SEP; 1 >;SEP; 2 >;SEP; 0 >;SEP; 1 >;SEP; 2 >;SEP; 2
>;SEP; 4 >;SEP; 4 >;SEP; 2 >;SEP; 2
>;tb; >;SEP; BrJtl"3IJd
>;tb; >;SEP; }-g- >;SEP; E
>;tb; >;SEP; 2 >;SEP; 5OzV-S >;SEP; SCM >;SEP; 100 >;SEP; 0 >;SEP; 0 >;SEP; 0 >;SEP; 3 >;SEP;
2 >;SEP; 4
>;tb; >;SEP; 8 >;SEP; Blank >;SEP; spaces >;SEP; in >;SEP; 2 >;SEP; -~ >;SEP; -~0 >;SEP; -~
>;SEP; -0~ >;SEP;
>;tb; >;SEP; >; >;SEP; 50
>;tb; >;SEP; M
>;tb; >;SEP; z >;SEP; fi
>;tb; >;SEP; = >;SEP; :: >;SEP; u2%3 >;SEP; Z >;SEP; z >;SEP; 8
138/612
>;tb; >;SEP; r >;SEP; , >;SEP; m >;SEP; os >;SEP; O=1 >;SEP; 0-0l >;SEP; .
>;tb;
>;SEP; 5 >;SEP; w >;SEP; w >;SEP; I >;SEP; T >;SEP; >;SEP; i
>;tb; >;SEP; .g >;SEP; 4 >;SEP; e >;SEP;
>;tb;Data supplied from the esp@cenet database - Worldwide
139/612
9. GB1162740
- 8/27/1969
DITHIOLPHOSPHORIC ACID TRIESTERS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1162740
Inventor(s):
SCHEINPFLUG HANS (--); SCHRADER GERHARD (--)
Applicant(s):
BAYER AG (DE)
IP Class 4 Digits: A01N
IP Class:A01N9/36
E Class: A01N57/14; C07F9/18; C07F9/177; C07F9/20
Application Number:
GB19670058682 (19671227)
Priority Number: DE1967F051410 (19670201)
Family: GB1162740
Equivalent:
NL6801062; FR1574699; BE710182; DE1300935
Abstract:
Abstract of GB1162740
1,162,740. Fungicides containing dithiolphos- phoric acid triesters. FARBENFABRIKEN BAYER
A.G. 27 Dec., 1967 [1 Feb., 1967], No.58682/67. Heading A5E. [Also in Division C2] Fungitoxic
compositions contain as active ingredient one or more compounds of the formula where R is C 1-6
alkyl, R>;SP;1>;/SP; is halogen, nitro, or C 1-@ alkyl or alkoxy, m and n are 0, 1, 2 or 3, in admixture
with a solid diluent or carrier, or a liquid diluent or carrier containing a surface- active agent. The
compositions may be formu- lated as solutions, emulsions, suspensions, powders, pastes and
granulates, and may be applied 'by squirting, scattering, spraying or atomising. Other plant [protection
agents may also be present and. the compositions are par- ticularly useful in the protection of rice
plants.Description:
Description of GB1162740
COMPLETE SPECIFICATION
Dithiolphosphoric Acid Triesters
We,FARBENFABRIKEN BAYER AKTIEN
GESELLSCHAFT, a body corporate organised under the laws of Germany, of Leverkusen,
Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly described in and by the
followingstatement:
The present invention relates to certain new dithiolphosphoric acid triesters, to a process for their
production and to their use as fungicides.
These new compounds have the general formula
EMI1.1
in which
R is a alkyl radical with 1 to 6 carbon atoms, R' is a halogen atom, a nitro group or an alkyl or alkoxy
radical with 1 to 4 carbonatoms, m is O, 1, 2 or 3and n is O, 1, 2 or 3.
From French Patent Specification No.
140/612
1,378,035 there are already known (thiono)dithiolphosphoric acid diester monoamides of the general
formula
EMI1.2
in which
R, and Rb may be hydrogen atoms, alkyl or aryl radicals,
Re or Rd may be among other things, aryl radicals, and
X is an oxygen or sulphur atom.
According to the particulars given in this
French patent specification, these compounds are suitable for the control of plant pests and plant
diseases.
The present invention also provides a process for the production of an S,S-diphenyldithiolphosphoric
acid triester of the general formula (1) which enables it to be obtained smoothly, with good yields and
in outstanding purity. In this process a phosphoric acid monoester dihalide of the formula
EMI1.3
is reacted with a thiophenol of the general formula
EMI1.4
in the form of a salt or in the presence of an acid-binding agent.
It has been found that the S,S-diphenyldithiolphosphoric acid triesters of the invention are
distinguished by outstanding fungitoxic properties and, most surprisingly, are in this respect clearly
superior to the compounds (of analogous constitution and the same direction of activity) which are
known from the abovementioned French patent specification. They therefore represent a genuine
enrichment of the art.
The course of the process of the invention is illustrated by the following reaction equation:
EMI2.1
In formulae (3) to (5) the symbols R,
R', m and n have the meaning stated earlier above, while Hal is a halogen atom.
R is preferably a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl or n
amyl radical; R' is preferably chlorine; bromine, fluorine, a nitro, a methyl or a methoxy radical. Hal is
preferably chlorine, m
is preferably 0, 1 or 2, and n is preferablyo or 1.
As examples of the phosphoric acid monoester dihalides of formula (3) there may be mentioned
cyclohexyl-, mono-, di- and trimethylcyclohexyl-phosphoric acid monoesterdichlorides. As
thiophenols of the formula (4) there may be mentioned for example: thiophenol, 2-, 3- and 4-chloro-, 4isopropyl-, 4methoxy and 4-nitro-thiophenol, 2-, 3- and 4thiocresol, and 2-bromothiocresol.
The phosphoric acid monoester dihalides to be used in the process of the present invention as starting
materials have already been described in the literature. They can be prepared according to known
methods from the phosphorus oxyhalides by reaction with the appropriate alcohols, frequently without
need for the concurrent use of acid acceptors. The crude products obtainable in this manner can in most
cases be immediately further reacted according to the present invention without previous purification
by distillation.
The reaction of the invention is carried out preferably in the presence of an inert solvent and this term
includes a diluent. Practically all inert organic solvents are suitable. Particularly good results, however,
have been obtained with aliphatic and aromatic hydrocarbons (which may be chlorinated), such as
methylene chloride, di-, tri- andtctra-chloroethylene, chloroform, carbon tetrachloride, benzine,
benzene, chlorobenzene, toluene and xylene; ethers, for example diethyl and di-n-butyl ether, dioxan,
tetrahydrofuran; aliphatic ketones and nitriles of low molecular weight, for example acetone,
methylethyl ketone, methylisopropyl ketone and methylisobutyl ketone, acetonitrile and propionitrile;
and lowboiling aliphatic alcohols, for example methanol, ethanol and isopropanol.
141/612
As already mentioned above, the reaction may be carried out in the presence of an acidbinding agent.
For this purpose all customary acid acceptors can be used, such as alkali metal hydroxides, carbonates
and alcoholates, and also tertiary organic bases, for example triethylamine, dimethylaniline,
benzyldimethylamine and pyridine. Instead of working in the presence of an acid-binding agent, it is
equally possible first to prepare a salt, preferably an alkali metal salt or an ammonium salt, of the
thiophenol concerned and then to react the salt with the appropriate phosphoric acid monoester
dihalide.
The process of the invention can be carried out successfully within a fairly wide temperature range. In
general, the work is carried out at from- 200C to the boiling point of the mixture, preferably at O to
1000C.
The reaction is preferably carried out under atmospheric pressure, but it is also possible to work at
superatmospheric or subatmospheric pressure.
When carrying out the process according to the invention, there are used, in general, two moles of the
thiophenol per mole of the phosphoric acid monoester dihalide concerned; but the former can also be
used in excess.
The phosphoric acid monoester dihalide is expediently added dropwise (generally at the temperatures
stated above) with stirring, to a solution (this term includes a suspension) of the thiophenol concerned
(or of the appropriate thiophenolate). An external cooling of the mixture is often necessary, because the
reaction is in most cases more or less strongly exothermic. Finally, it has proved expedient to continue
stirring of the reaction mixture (after combining the starting materials) for a longer period (1 to 5 hours
or overnightoptionally with heating) in order to compIete the reaction. The products of the process are
in this case obtained with particularly good yields as well as in outstanding purity.
The working up of the reaction mixture may take place according to methods known in principle by
pouring out the mixture into water, washing and drying the organic phase, distilling off the solvent andas far as is possible-fractional distillation of the residue under reduced pressure.
The dithiolphosphoric acid triesters obtainable by the process are either obtained in the form of
crystalline compounds with sharp melting paints, which can readily be further purified by
recrystallisation from the usual solvents, or they are colourless to yellow oils, some of which can be
distilled under greatly reduced pressure without decomposition. If this is not possible, the compounds
can be purified by slight distillation, that is, they can be freed from the last volatile impurities by longer
heating under reduced pressure at slightly to moderately elevated temperatures.
Examples of the compounds which can be obtained includeO-cyclohexyl-S,S -diphenyl-, -S,S-bis-(2or 4-methylphenyl)-,-S,S-bis- (4chlorophenyl)-, -S,S-bis-(2,4- or 3,4-dichloro-phenyl)-, -S,S-bis(2,4,5- or 3,4,5- or2,4,6-trichlorophenyl)-, -S,S-bis-(2- or 3- or 4-methoxyphenyl)-, -S,S-bis-(2- or 3or 4nitrophenyl)-dithiolphosphoric acid esters as well as the corresponding 0-(2- or 3- or
4methylcyclohexyl-) and0-(1,1-,1,2-,1,3- and 1,4-dimethylcyclohexyl) derivatives, as well as the
corresponding O-trimethylcylclohexyl
S,S,-diphenyl-dithiolphosphoric acid esters.
As already mentioned, the compounds of the invention have a strong fungitoxic effectiveness against a
series of fungal pathogenic agents. By reason of this fact as well as in view of their low toxicity to
warm-blooded animals they are particularly suitable for the control of undesired growth of fungi, the
good compatibility with higher plants favouringpar- ticularly their use against fungal diseases. The
compounds can be used as fungitoxic agents in plant protection against fungi of the most widely
different classes, for example Archimycetes, Phycomycetes Ascomycetes, Basidiomycetes and Fungi
Imperfecti.
The compounds have, however, given particularly good results in the control of rice diseases, since
they possess an excellent protective and curative activity against Piricularia oryzae in rice. In addition,
they can also be used for the control of further fungal pathogenic agents in rice and other cultivated
plants.
142/612
They possess a particular activity against the following species of fungi:
Cochliobolusmiyabeanus species
Mycosphaerella species
Cerospora species
Alternaria species
Corticum species
Botrytis species.
Furthermore, these active compounds show a very good activity against fungi which attack the plant
from the soil and some of which cause Tracheomycoses, such as
Fusarium cubense,
Fusarium dianthi,
Verticillium alboatrum and
Phialophora cinerescens.
When used as fungitoxic agent, the active compounds of the invention can be used either individually
or in combination with one another. Moreover, mixture with other plant protection agents, such as
other fungicides, herbicides, insecticides and bactericides is also possible.
The active compounds according to the present invention can be converted into the usual formulations,
such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in
known manner, for example by mixing the active compounds with extenders, that is, liquid or solid
diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or
dispersing agents. In the case of the use of water as an extender, organic solvents can, for example, also
be used as auxiliary solvents.
As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes or
benzene, chlorinated aromatic hydrocarbons, such as chlorobenzenes, parffins, such as mineral oil
fractions, alcohols, such as methanol or butanol, or strongly polar solvents, such as dimethyl
formamide or dimethyl sulphoxide, as well as water.
As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays,
talc or chalk, or ground synthetic minerals, such as highly-dispersed silicic acid or silicates.
Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such as
polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates and aryl sulphonates; and preferred examples of dispersing
agents include lignin, sulphite waste liquors and methyl cellulose.
As already mentioned, the active compounds according to the invention may be present in the
aforesaid formulations in admixture with known active substances.
The formulations contain, in general, from 0.1 to 95, preferably from 0.5 to 90, per cent by weight of
active compound.
Application of the active compounds or their preparations as fungitoxic agents may be made in the
usual manner, for example by squirting, scattering, spraying or atomising. The active compound is
generally applied in a concentration of 0.0005 to 5% O/o by weight, depending on the purpose
intended. This concentration range may, however, be exceeded or gone below in special cases.
The compounds of the invention can, for example, be used successfully in the so-called ultra low
volume method, in which formulations consisting almost entirely or entirely of the active ingredient are
used.
The invention also provides a fungitoxic composition containing as active ingredient a compound of
formula (I) in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier
containing a surfaceactive agent.
143/612
The invention also provides a method of combating fungus pests which comprises applying to the
fungus or a habitat thereof a compound of formula (I) alone or in the form of a composition containing
as active ingredient a compound of formula (I) in admixture with a solid or liquid diluent or carrier.
The outstanding fungitoxic activity of the
S,S - diphenylthiolphosphoric acid triesters which can be prepared according to the invention, as well
as their clear superiority in com parison with analogously structured products of the prior art, can be
seen from the following
Example A.
EXAMPLE A
Piricularia test: liquid preparation of active
compound
Solvent: 1 part by weight of acetone
Dispersing agent: 0.05 part by weight of
sodium oleate
Other additives: 0.2 part by weight of gelatin
Water: 98.75 part by weight ofH2O
The amount of active compound required for the desired concentration in the spray liquor is mixed
with the stated amount of solvent, and the concentrate is diluted with the stated amount of water
containing the stated additives.
30 rice plants about 14 days old are sprayed with the spray liquor until dripping wet. The plants remain
in a greenhouse at temperatures of 22 to24 C and a relative atmospheric humidity of about70-/ until
they are dry.
They are then inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of
Piricularia oryzae and placed in a chamber at24-260C and 100% relative atmospheric humidity.
5 days after inoculation, the infestation of all the leaves present at the time of inoculation is determined
as a percentage of the untreated but also inoculated control plants. 0% means no infestation; 100%
means that the infestation is exactly as great in the case of the control plants. This test indicates the
protective effect.
The active compounds, the concentration of the active compounds and the results can be seen from
Table A.
Test forcurative action
The above test is repeated, except that the active compounds are applied not before, but only 16 hours
after, inoculation. Substances which show an activity when the test is conducted in this manner are in a
position to kill the fungus after infection and thereby to execise a curative action.
The results can be seen from Table A.
TABLE A
Active compound Infestation as a percentage of the infestation (constitution) of the untreated control
with a concentration
of active compound (in % by weight) of
0.05 0.025
EMI4.1
>;tb; >;SEP; 0
>;tb; >;SEP; JI/ >;SEP; pr. >;SEP; 0 >;SEP; 50
>;tb; >;SEP; ( 5)2a(- >;SEP; 4y)2 >;SEP; cur. >;SEP; >;SEP; 96
>;tb; >;SEP; (2
>;tb; (known >;SEP; comparative
>;tb; preparation)
>;tb; >;SEP; >;SEP; 5t >;SEP; pr. >;SEP; O >;SEP; 0
144/612
>;tb; >;SEP; () >;SEP; p/ >;SEP; cur. >;SEP; O
>;tb; >;SEP; o >;SEP; St3CZ
>;tb; >;SEP; I' >;SEP; U >;SEP; pr. >;SEP; 0 >;SEP; 22
>;tb; >;SEP; I\9
>;tb; >;SEP; o >;SEP; 5/cH
>;tb; >;SEP; iJ/ >;SEP; 3
>;tb; >;SEP; op >;SEP; 329) >;SEP; pr. >;SEP; 6 >;SEP; 11
>;tb; >;SEP; SThDCll3
>;tb; pr. = protective action
cur. = curative action
The process of the invention is illustrated by the following Examples1-6.
EXAMPLE 1
EMI5.1
0.5 molar mixture:
110 g of thiophenol are dissolved in 500 ml of acetonitrile. To this solution are added 150 g of dried
potassium carbonate; 109 g of O-cyclohexylphosphoric acid ester dichloride are then added dropwise,
with stirring. The mixture is then stirred for several hours, and 200 ml of benzene are then added.
The reaction mixture is then diluted with 300 ml of water, the benzene layer is separated and dried over
sodium sulphate. After the benzene has been distilled off, 105 g (57% of the theory) of O-cyclohexylS,S-diphenyldithiolphosphoric acid ester are obtained. The compound crystallises from ligroin in
colourless needles of m.p.650C.
EXAMPLE 2
EMI5.2
0.5 molar mixture:
To a solution of 144 g of 4-chlorothiophenol in 600 ml of benzene there are added 102 g of
triethylamine; 108 g of O-cyclohexyl-phosphoric acid esterchloride are then added dropwise to the
reaction mixture at 10 to 150C, with stirring. The mixture is stirred for a further 4 hours at room
temperature and poured into 400 ml of ice water. The mixture is vigorously shaken, the aqueous phase
is separated and, finally, the organic layer is dried over sodium sulphate. After the solvent has been
distilled off under reduced pressure, there remains behind an oil which, when mixed with 150 ml of
cold petroleum ether, solidifies in crystalline form. 167 g (77% of the theory) of O-cyclohexyl-S,Sbis(4-chloro-phenyl)-dithiolphosphoric acid ester are obtained in the form of colourless crystal needles
of melting point 840C.
Analysis: P S Cl
Calculated for a molecular weight of 433: 7.2%; 14.8%;16.0%;
Found: 7.3%;14.1%; 16.0%.
EXAMPLE 3
EMI5.3
0.5 molar mixture:
124 g of 4-thiocresol are dissolved in 600 ml of benzene; 102 g of triethylamine are added to this
solution, and 108 g of O-cyclohexylphosphoric acid ester dichloride are then added dropwise at 10 to
150C, with stirring.
Thereafter the mixture is stirred for a further 4 hours and then worked up as described in the preceding
Example. 143 g of O-cyclohexyl - S,S - bis - (4 -methylphenyl) - dithiolphosphoric acid ester are
obtained in the form of colourless crystal needles of melting point 690C.
Analysis: P S
Calculated for a molecular weight of 392: 7.9%; 16.3%;
Found:8.1%; 16.0%.
EXAMPLE 4
EMI5.4
0.8 molar mixture:
176 g of thiophenol are dissolved in 1000 ml of benzene. To this solution are added 163 g of
triethylamine; 188 g of O-(2-methylcyclohexyl)-phosphoric acid ester dichloride are then added
145/612
dropwise to the reaction mixture, with stirring, and the mixture is further stirred for several hours at
room temperature.
The precipitated triethylammonium hydrochloride is then filtered off with suction. The filtrate is
washed once with water. The organic phase is dried over sodium sulphate and, finally, the solvent is
evaporated under reduced pressure. In this way theO-(2-methylcyclo- hexyl) - S,S diphenyldithiolphosphoric acid ester is obtained in the form of a pale yellow coloured water-insoluble
oil. The yield is 160 g (53% of the theory).
Analysis: P S
Calculated for a molecular weight of 378: 8.2%; 17.0%;
Found: 7.7%; 17.1%;
The0- (2- methylcyclohexyl) - phosphoric acid ester dichloride of the formula
EMI6.1
can be prepared e.g. as follows: 2 molar mixture:
To a solution of 308 g of phosphorus oxychloride in 600 ml of carbon tetrachloride there are added at
O to 50C, with stirring, 228 g of 2-methylcyclohexanol dissolved in 100 ml of carbon tatrachloride; the
mixture is stirred for a further 2 hours at room temperature and the solvent is then carefully distilled
off. There are obtained in this way 335 g (73% of the theory) ofO-(2-methylcyclohexyl)-phosphoric
acid ester dichloride.
EXAMPLE 5
EMI6.2
0.8 molar mixture:
176 g of thiophenol are dissolved in 1000 ml of benzene; to this solution are added first 163 g of
triethylamine and then, dropwise and with stirring, at 15 to200C, 188 g of 0-(methyl-cydohexyl)phosphoric acid ester dichloride; thereafter the mixture is stirred for a further4 hours, the precipitated
triethylammonium hydrochloride is filtered off with suction and the filtrate is washed with water.
The benzene solution is then dried over sodium sulphate and the solvent is evaporated under reduced
pressure. In this way, 220 g (73% of the theory) of0-(3-methylcyclohexyl)-S,S-diphenyldithiolphosphoric acid ester are obtained as slightly yellow, water-insoluble oil.
Analysis:P S
Calculated for a molecular weight of 378: 8.2%; 17.0%;
Found: 7.9%; 17. %
EXAMPLE 6
EMI6.3
0.6 molar mixture:
132 g of thiophenol are dissolved in 600 ml of benzene. To this solution are added 123 g of
triethylamine; 140 g ofO-(4-methyl- cyclo-hexyl)-phosphoric acid ester dichloride are then added
dropwise at 15 to 200C, with stirring, and the mixture is further stirred for some hours and then worked
up in the usual manner. There are so obtained 102 g (45% of the theory) ofO-(4-methylcyclohexyl)S,S- diphenyldithiolphosphoric acid ester in the form of colourless crystals which melt at 650C.
Analysis: P S
Calculated for a molecular weight of 378: 8.2%; 16.9%;
Found: 8.5%; 17.2%
WHAT WE CLAIMIS:1. S,S-diphenyldithiolphosphoric acid triesters of the generalformula:
EMI6.4
in which
R is a lower alkyl radical with 1 to 6 carbon atoms
R' is a halogen atom, a nitro group or an alkyl or alkoxy radical with 1 to 4 carbon atoms,
m is 0, 1, 2 or 3, and n is O, 1, 2 or 3.
146/612
2. Compounds according to claim 1 in which R is a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl or namyl radical.
3. Compounds according to claim 1 or 2 in which R' is chlorine, bromine, fluorine, a nitro, a methyl or
a methoxy radical.
4. Compounds according to any of claims1-3 in which m is 0, 1 or 2.
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
147/612
10. GB1165846
- 10/1/1969
ORGANOTHIO PHOSPHATES AND THEIR USE AS PLANT-GROWTHPROMOTERS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1165846
Applicant(s):
NIPPON KAYAKU KK (JP)
E Class: C07F9/18; C07F9/24A4
Application Number:
GB19670030254 (19670630)
Priority Number: JP19660042367 (19660701)
Family: GB1165846
Abstract:
Abstract of GB1165846
1,165,846. Treating grain and seeds with organothiophosphates. NIPPON KAYAKU K.K. 30 June,
1967 [1 July, 1966], No. 30254/67. Heading A2Q. [Also in Divisions C1 and C2] A method of
promoting the growth of a cultivated plant comprises applying to the seeds of such plant, e.g. cucumber
seeds, healthy rice seeds or yam seeds, a growth-promoting amount of an organo- thiophosphate
compound of formula where R 1 is alkyl, R 2 is alkoxy or mono- or dialkyl amino, R 3 is hydrogen,
fluorine, chlorine, bromine or methyl and R is halogen, alkoxy, allyloxy, alkoxyethyl, alkylthio,
allylthio, alkoxyethylthio, alkoxy- ethyloxy or one of the radicals -NR 4 R 5 or where R 4 is H or alkyl,
R 5 is H, alkyl, allyl or -C 6 H 5-n Yn, where X is oxygen or sulphur, Y is hydrogen, fluorine, chlorine,
bromine, alkyl, alkoxy, alkylthio, thiocyano, or is othiocyano, n is an integer up to 5. The compounds
are preferably applied in concentrations of 0.001 to 50 p.p.m. by weight of seeds, and may be
formulated as compositions, e.g.:- dusts and wettable powders containing specified powdered inert,
inorganic solids and/or starch; or aqueous emulsions; or solutions in specified organic
solvents.Description:
Description of GB1165846
COMPLETE SrPECIFnOATION
Organothio Phosphates and their use as Plant
Growth-Promoters
We, NIPPON KAYAKU KABUSHIKIKAISH.R, of 6,1-chome, Marunouchi, Chiyoda-ku,
Tokyo, Japan, a Japanese company, do hereby declare the invention for which we pray that a patent
may be granted to us, and the method by which it is to be performed, to be particularly described in and
by the followingstatement:
The present invention relates to new plantgrowth-promoting compositions and to a method for
promoting the growth of plants, and more especially the growth and yields of such important crops as
cereals, potatoes, and sweet potatoes. It further relates to certain new plant-growth-promoting
organothiophosphates.
Organophosphates of various types have been proposed for use as pesticides, and more especially as
aphicides or acaricides in agriculture and horticulture.
We have now found that certain known and other novel organothiophosphates possess excellent plantgrowth-promoting properties.
The invention, therefore, provides, in a first aspect, new compositions and a novel method for
prompting the growth of plants, and especially of the above-named and other important cultivated
148/612
plants. The active ingredients contained in these compositions or applied' to the seeds or tubers of the
plants in a growth-promoting amount are compounds of the general formula
EMI1.1
(I) in which
R1 represents a lower alkyl group,
R represents a lower alkoxy group or a lower monoalkylamino or dialkylamino group,
R, represents a fluorine, chlorine or bromine atom, hydrogen or methyl, and
R in a first preferred class of novel compounds, represents lower alkoxy, allyloxy, lower alkoxy-ethyl,
lower alkylthio, allylthio, lower alkoxyethylthio, lower alkoxyethyloxy or a radical
EMI1.2
wherein X represents oxygen or sulfur,
Y represents hydrogen, fluorine, chlorine or bromine,lower alkyl, lower alkoxy, lower alkyl thio,
thiocyano or isothiocyano, and
n is a number ranging from 1 to 5, but preferably 1;
or R, in another class of plant-growth-promoting compounds falling under the above formula,
represents halogen or the radical
EMI1.3
whereinRX represents hydrogen or lower alkyl, and
R, represents hydrogen, lower alkyl, allyl, or a group
EMI1.4
wherein Y and n have the same meanings as above.
Depending on the method of application used, the organothiophosphates of the above fonnula are
applied to the seeds, tubers or plant parts to be treated in concentrations of from 0.001 to 50 parts per
million, calculated on the weight of the plant material to be treated.
The term" lower" where used in this specification and in the appended claims in connection with an
aliphatic radical means that such radical has preferably not more than 5 carbon atoms.
In another aspect, the invention provides novel organothiophosphates of Formula I which pertain to
the first class of compounds falling thereunder and defined thereinbefore.
In a third aspect, the invention provides compositions for use in agriculture and horticulture which
comprise a plant-growth-promoting amount of a novel compound as defined in the said first class of
organothiophosphates falling under Formula I, in mixture with agriculturally acceptable, nonphytotoxic carriers.
In the above-described novel method, especially where carried out by dressing or soaking the seeds or
tubers of plants such as cereals, potatoes, sweet potatoes and other important crops, the
organothiophosphates of Formula I promote the elongation and the general growth of the plant body,
and increases the yields of the crops very considerably.
For example, when healthy seeds of rice are treated with the compounds of Formula I, and especially
with those of the above-mentioned preferred class thereof, the rate of elongation of the stems and roots
of the young plants is enhanced and the number of shoots is increased.
The effect of the treatment with the compounds of Formula I is long-lasting.
Moreover, we have found that the formation of shoots from unproductive stems is inhibited and the
ripening of the grains is accelerated.
The following representative compounds are named to illustrate the invention further.
Compounds pertaining to the first, preferred class:
EMI2.1
EMI2.2
149/612
EMI3.1
The following compounds pertain to the second class of compounds described hereinbefore:
EMI3.2
The following non-limitative examples illustrate the production of the compounds of
Formula I.
Temperatures are given therein by degrees
Centigrade. Percentages are given by weight.
EXAMPLE 1
11.8 g of sodium p-methoxyphenolate are added in small batches within 10 minutes to a solution of 24
g of 3 - chloro - 4 - ethoxycarbonyloxy - benzene - 1 - sulfonylchloride in 250 ml of anhydrous
benzene, with stirring at 200. The mixture is then heated to5060 and stirred for 5 to 6 more hours at
this temperature. The mixture is then filtered, the filtrate is evaporated to dryness und'er vacuo and the
residue re-dissolved in 130 ml of diethyl ether. The ether solution is filtered, the filtrate concentrated
by evaporation of the ether in vacuo and 29.7 g of 4'-methoxyphenyl3 - chioro - 4 - ethoxycarbonyloxy
- benzenesulfonate are obtained in the form of a lightyellow oil.
26.4 g of the crude ester are then dissolved in 120 ml of ethanol. 56 ml of an ethanolic 10% potassium
hydroxide solution are added dropwise to theethanolic solution at200 -with stirring, and the mixture is
then heated for 45 minutes at about 300.
The solvent is then evaporated under reduced pressure and the residue is partitioned between 250 ml
aqueous normal hydrochloric acid and 250 ml of diethyl ether. The ether solution is dried over
anhydrous sodium sulfate and evaporated to dryness. The resulting crude product is digested in 60 ml
of benzene and passed through a column charged with 50 mg of aluminium oxide (Act. I), whereupon
the column is eluted with 450 ml of benzene.
The eluate is recrystallized from benzene/ petroleum ether. 15.3 g of 4'-methoxyphenyl 3 - chloro - 4 hydroxybenzenesulfonate having a melting point ofS3--880 are thus obtained. Recrystallizationfrcm
the same solvent mixture raises the melting point to8890 .
The above-obtainedmethoxyphenyl chlorohydroxybenzene sulfonate is esterified with
O,O-dimethyl phosphoro-chloridethioate by employing the procedure described by Wagner et al in
J.med.chem. 8 p. 377 et sq. (1965) at p. 381, and there is obtained' the compound of the formula
EMI3.3
EXAMPLE 2
7 g of crude 4-hydroxy-benzene sulfinic acid and 6.35 g of4-chiorothiophenol are dissolved in 75 ml
of diethyl ether, the solution is cooledto - 50 and a solution of 6.1 g of ethyl nitrite in 20 ml of diethyl
ether is added thereto in small batches. The dark violet brown colored solution is stirred for 90 minutes
at0 and then further for 3 hours at 200 until it has become colorless. The solvent is then removed by
evaporation in vacuo and the residue is chromato graphed through a column containing 6 times its
amount of aluminium oxide (Act. I). The column is first eluted with benzene to remove4,4'-dichlorodiphenyl-disulfide which is obtained as a hypodust, and then with ethyl acetate which contains the
desired product.
The latter is recrystallized from benzene/ petroleum ether and pure 4'-chlorophenyl4-hvdroxy-benzene
thiosulfonate is obtained which has a melting point of124125o.
The latter product is then esterified withO,O-diethyl phosphoro-chloridethioate employing the
procedure described by Wagner et al, supra. The compound of Formula No. 9, supra, is thereby
obtained.
4-hydroxy-benzene-suifinic acid used as starting material in the above example is produced as follows:
53 g of 4-ethoxycarbonyloxy-benzene-sufonyichioride dissolved in 100 ml of acetone are added
dropwise within 2 hours and with stirringte a solution of 61.6 g of sodium sulfite in 500 ml of water at
150/612
200. At the same time, 37 g of sodium hydrogen carbonate are added to the solution. Stirring is then
continued for 12 hours, the solution is then clarified by filtration through Hyflo (Registered Trade
Mark) andsectioning off the acetone in a water jet vacuum. The solution is then cooled to0 and 100
ml of aqueous hydrochloric add (50 . HCI content) is added thereto. 4-ethoxcarbonyloxy-benzenesulfinic acid is obtained which is separated by suction filtration and dried for 3 hours in vacuo over
phosphorus pentoxide (M.P.7378o).
10 ml of 2-normal sodium hydroxide solution are poured onto 15 g of the crude
ethoxycarbonyloxybenzenesulfinic acid, the clear solution of about 400 resulting when gas
development ceases, is left to stand for 20 minutes and is then cooled to 100, acidified with 15 ml of
concentrated hydrochloric acid, and filtered.
The filtrate is extracted several times with a total of about 200 ml of diethyl ether, the ether solution is
dried over sodium sulfate and evaporated to dryness in vacuo. 4-hydroxybenzene-sulfinic acid is
obtained which melts at677(? with decomposition. The product must be used directly in the abovedescribed manner, for it decomposes rapidly when stored.
Other compounds falling under Formula I can be produced in a similar manner by the procedure given
in the two proceeding examples by using correspondingly substituted starting materials.
The compounds according to the invention are formulated for use in any desired way.
Generally such formulations will include the plant growth regulator in association with a suitable
carrier or diluent. Such carriers may be liquid or solid or in ointment form and are designed to aid the
application of the plant growth promoter either by way of dispersing at the location where it is to be
used, or to provide a concentrate formulation which can be made up by the user into a dispersible
preparation.
Liquid preparations thus comprise preparations of growth promoter in the form of solutions or
emulsionswhich can be used by themselves or which can be adapted to be made up with water or other
diluents to form sprays; in such cases the carrier is a solvent or emulsion base non-phytotoxic under the
condition of use. As suitable carriers for emulsions or solutions, the following materials are metioned:
Alkanols such as methanol, ethanol, and ethylene glycol, ketones e.g. methyl ethyl ketone or acetone,
ethers, aromatic compounds illustrated by benzene, xylene, and solvent naphtha, and liquid esters,
especially ethyl acetate.
Solid preparations comprise dusts and wettable powders, as well as semi-solid preparations such as
ointments. Such preparations may comprise inert solid and/or liquid diluents such as clays, kaolins,
bentonite, talcum, kieselguhr and starch, or ointment bases such as resins, lanolin, paraffins, Vaseline
(Registered.
TradeMark), bentonite, cellulose and its derivatives, pectins, polyethyleneglycol or polyalcohol esters
of fatty acids. These preparations usually contain a wetting, dispersion or emulsifying agent, as well as
stabilizers. Soaps, alkyl sulfonates, esters of fatty acids, hydroxyalkyl amines are mentioned as
surfactants suitable for use as emulsifier, dispersing agent or penetrating agent.
Moreover, the compounds according to the invention may be used, if desired, in admixture with
compatible fungicides, other plant growth promoters and/or fertilizers.
The following non-limiting examples are given to illustrate the above-described compositions. Parts
are given by weight unless expressly stated otherwise.
EXAMPLE I
By admixing 10 parts of 0,0 - diethyl - 0 (4 - dimethylsulfamoyl - phenyl) phosphorothioate with 60
parts of talcum and 30 parts of clay, and crushing, there is obtained dust composition usable as a seed
dressing agent.
EXAMPLE II
151/612
20 parts ofO,O - diethyl - 0 - [4 - (p chlorophenyl) - sulfamoylphenyl] phosphorothioate are admixed
with 60 parts of kaolin, 17 parts of diatomaceous earth, one part of alkylnaphthaline sulfonate, and 2
parts of lignin sulfonate to give a wettable powder which is readily dispersed and suspended in water to
be used as a soaking agent.
EXAMPLE III
By dissolving 20 parts ofO,O - diethyl 0- (4 - dimethylsulfamoylphenyl) phosphorothioate in 30 parts
of xylene and 33 parts of methyl-naphthalene, and admixing them with 17 parts of poly-alkylphenol
ethylene oxide gives a emulsion which is readily dispersed and suspended in water to be used for
soaking seeds therewith.
EXAMPLE IV 5 parts of O,N - dimethyl - O - (4 - dimethylsulfamoyl - phenyl) phosphoroamidothioate are dissolved in 15 parts of xylene, and 60 parts of starch and 20 parts of polyvinyl
pyrrolidone are admixed with them to formulate a pellet which is readily dispersible in water for
soaking seeds therewith.
EXAMPLE V 0.4 parts of O,O - diethyl - O - (2 - chloro 4 - isopropylsulfamoyl - phenyl) phosphorothioate are admixed with 25 parts of vaseline and 25 parts of stearyl alcohol, and as they are
being melted, one part of sodium laurylsulfonate, 12 parts of propylene glycol and 36.6 parts of
distilled water are added to make up an ointment which is used for coating seeds.>;/RTI;
The effectiveness of the compounds of present invention are illustrated by the following experiments.
EXPERIMENT 1
Growth promoting effect on young rice and cucumber seedlings
The compounds of the invention formulated as 20% emulsifiable solutions were diluted to 5 ppm and
10 ppm, respectively, with tap water. 15 ml of each solution are poured into
Petri dishes of 9 cm in diameter into which a filter paper had been placed.
20 seeds of healthy rice and cucumber are then placed on to filter paper and the dishes held in a
thermostat for 5 days at 25 C.
The results are shown in Table 1, below.
In the table the ratios of elongation of stems and roots have been calculated in percent based on the
elongation of stems and roots of untreated plants taken as 100%. The tests in columns marked by (*)
are average values of three replications.>;/RTI;
TABLE I
EMI5.1
Cucumber >;SEP; Rice
>;tb; Number >;SEP; of >;SEP; Concentration >;SEP; Ratio >;SEP; of >;SEP; elongation >;SEP; Ratio
>;SEP; of >;SEP; elongation >;SEP; Ratio >;SEP; of >;SEP; elongation >;SEP; Ratio >;SEP; of >;SEP;
elongation
>;tb; compounds >;SEP; (ppm) >;SEP; of >;SEP; roots* >;SEP; of >;SEP; stem* >;SEP; of >;SEP;
roots* >;SEP; of >;SEP; stem*
>;tb; 5 >;SEP; 182 >;SEP; 133 >;SEP; 122 >;SEP; 120
>;tb; (24) >;SEP; 10 >;SEP; 159 >;SEP; 100 >;SEP; 118 >;SEP; 129
>;tb; 5 >;SEP; 218 >;SEP; 167 >;SEP; 127 >;SEP; 144
>;tb; (25) >;SEP; 10 >;SEP; 200 >;SEP; 122 >;SEP; 148 >;SEP; 149
>;tb; 5 >;SEP; 188 >;SEP; 133 >;SEP; 126 >;SEP; 138
>;tb; (26) >;SEP; 10 >;SEP; 141 >;SEP; 120 >;SEP; 124 >;SEP; 120
>;tb; TABLE I (continued)>;/RTI;
EMI6.1
Cucumber >;SEP; Rice
152/612
>;tb; Number >;SEP; of >;SEP; Concentration >;SEP; Ratio >;SEP; of >;SEP; elongation >;SEP; Ratio
>;SEP; of >;SEP; elongation >;SEP; Ratio >;SEP; of >;SEP; elongation >;SEP; Ratio >;SEP; of >;SEP;
elongation
>;tb; compounds >;SEP; (ppm) >;SEP; of >;SEP; roots* >;SEP; of >;SEP; stem* >;SEP; of >;SEP;
roots* >;SEP; of >;SEP; stem*
>;tb; 5 >;SEP; 194 >;SEP; 130 >;SEP; 139 >;SEP; 126
>;tb; (36) >;SEP; 10 >;SEP; 159 >;SEP; 120 >;SEP; 126 >;SEP; 120
>;tb; 5 >;SEP; 141 >;SEP; 100 >;SEP; 129 >;SEP; 138
>;tb; (1) >;SEP; 10 >;SEP; 206 >;SEP; 144 >;SEP; 129 >;SEP; 138
>;tb; 5 >;SEP; 106 >;SEP; 95 >;SEP; 127 >;SEP; 122
>;tb; (2) >;SEP; 10 >;SEP; 153 >;SEP; 122 >;SEP; 133 >;SEP; 122
>;tb; 5 >;SEP; 129 >;SEP; 120 >;SEP; 116 >;SEP; 110
>;tb; (3) >;SEP; 10 >;SEP; 176 >;SEP; 144 >;SEP; 121 >;SEP; 105
>;tb; 5 >;SEP; 194 >;SEP; 156 >;SEP; 139 >;SEP; 138
>;tb; (4) >;SEP; 10 >;SEP; 200 >;SEP; 156 >;SEP; 154 >;SEP; 132
>;tb; 5 >;SEP; 182 >;SEP; 120 >;SEP; 129 >;SEP; 138
>;tb; (5)
>;tb; 10 >;SEP; 188 >;SEP; 120 >;SEP; 129 >;SEP; 155
>;tb; 5 >;SEP; 136 >;SEP; 125 >;SEP; 103 >;SEP; 100
>;tb; (6)
>;tb; 10 >;SEP; 120 >;SEP; 120 >;SEP; 100 >;SEP; 101
>;tb; 5 >;SEP; 171 >;SEP; 120 >;SEP; 107 >;SEP; 102
>;tb; (27)
>;tb; 10 >;SEP; 205 >;SEP; 122 >;SEP; 120 >;SEP; 102
>;tb; 5 >;SEP; 153 >;SEP; 133 >;SEP; 124 >;SEP; 139
>;tb; (28) >;SEP; 10 >;SEP; 141 >;SEP; 96 >;SEP; 116 >;SEP; 120
>;tb; TABLE I (continued)
EMI7.1
Cucumber >;SEP; Rice
>;tb; Number >;SEP; of >;SEP; Concentration >;SEP; Ratio >;SEP; of >;SEP; elongation >;SEP; Ratio
>;SEP; of >;SEP; elongation >;SEP; Ratio >;SEP; of >;SEP; elongation >;SEP; Ratio >;SEP; of >;SEP;
elongation
>;tb; compounds >;SEP; (ppm) >;SEP; of >;SEP; roots* >;SEP; of >;SEP; stem* >;SEP; of >;SEP;
roots* >;SEP; of >;SEP; stem*
>;tb; 5 >;SEP; 188 >;SEP; 156 >;SEP; 101 >;SEP; 155
>;tb; (9)
>;tb; 10 >;SEP; 171 >;SEP; 120 >;SEP; 100 >;SEP; 161
>;tb; 5 >;SEP; 196 >;SEP; 140 >;SEP; 136 >;SEP; 166
>;tb; (30)
>;tb; 10 >;SEP; 163 >;SEP; 122 >;SEP; 122 >;SEP; 150
>;tb; 5 >;SEP; 154 >;SEP; 133 >;SEP; 126 >;SEP; 121
>;tb; (32)
>;tb; 10 >;SEP; 145 >;SEP; 122 >;SEP; 126 >;SEP; 120
>;tb; 5 >;SEP; 166 >;SEP; 120 >;SEP; 106 >;SEP; 121
>;tb; (12)
>;tb; 10 >;SEP; 170 >;SEP; 133 >;SEP; 108 >;SEP; 130
>;tb; 5 >;SEP; 180 >;SEP; 144 >;SEP; 119 >;SEP; 121
>;tb; (14)
>;tb; 10 >;SEP; 205 >;SEP; 166 >;SEP; 128 >;SEP; 115
>;tb; 5 >;SEP; 153 >;SEP; 133 >;SEP; 135 >;SEP; 126
>;tb; (18)
>;tb; 10 >;SEP; 159 >;SEP; 122 >;SEP; 118 >;SEP; 114
>;tb; 5 >;SEP; 160 >;SEP; 140 >;SEP; 111 >;SEP; 102
>;tb; (20)
>;tb; 10 >;SEP; 145 >;SEP; 130 >;SEP; 131 >;SEP; 120
>;tb; 5 >;SEP; 154 >;SEP; 120 >;SEP; 116 >;SEP; 124
>;tb; (23)
153/612
>;tb; 10 >;SEP; 136 >;SEP; 118 >;SEP; 109 >;SEP; 113
>;tb; Sodium >;SEP; N- >;SEP; 5 >;SEP; 176 >;SEP; 122 >;SEP; 105 >;SEP; 145
>;tb; (1-naphthyl)
>;SEP; Phthalamide >;SEP; 10 >;SEP; 182 >;SEP; 100 >;SEP; 116 >;SEP; 128
>;tb; Untreated >;SEP; - >;SEP; 100 >;SEP; 100 >;SEP; 100 >;SEP; 100
>;tb; control
>;tb;
The above table shows that compounds of
Formula I used as active ingredient in seed dressings promote the elongation of roots and stems of the
rice plants.
EXPERIMENT 2
Pot test
Healthy rice seeds were coated with 5%, 2% and 1%, respectively, of their total weight, of a dust
which contained 10% of O,O - diethyl - O - (4 - dimethylsulfamoyl - phenyl) phosphorothioate
(Compound No. 24) and, a second series of seed batches with the aforesaid amounts, respectively, of a
dust which contained10% of 0,0 - diethyl - 0- (4 phenyl thiosulfonylphenyl) phosphorothioate
(Compound No. 4).
Pots filled with gravel and pots filled with soil of a rice paddy were prepared for this test. In the case
of gravel-culture, nutrient solutions known as " balanced solution for gravel-culture " were exchanged
once a week.
Gravel-culture conditions were the same as the conditions of growing the paddy seedlings, except that
the paddy soil was moistened with tap water. Dressed seeds of rice were sown into 20 boles at the rate
of 2 grains per hole, and cultivated at 280Ct 300C in the greenhouse. 45 days after sowing, the length
of roots, height of grasses, number of shoots, fresh weight of stems and leaves, and fresh weight of
roots were measured.
The results are shown in Table II below.
TABLE II
EMI9.1
>;tb; - >;SEP; o- >;SEP;
>;tb; >;SEP; td
>;tb; >;SEP; sOOOOOOO >;SEP; 0
>;tb; >;SEP; 3 >;SEP; o >;SEP; o >;SEP; cs >;SEP; o >;SEP; o >;SEP; vo >;SEP; m >;SEP; o >;SEP;
o >;SEP; ; >;SEP; ~ >;SEP; N >;SEP; \ >;SEP; o
>;tb; >;SEP; O >;SEP; H >;SEP; O >;SEP; e >;SEP; O >;SEP; 00 >;SEP; O >;SEP; N >;SEP; N
>;SEP; N >;SEP; \ >;SEP; b >;SEP; O
>;tb; >;SEP; =o >;SEP; Wo >;SEP; cs >;SEP; e >;SEP; cs >;SEP; ~, >;SEP; >; >;SEP; >; >;SEP; ~l
>;SEP; H >;SEP; H >;SEP; H >;SEP; H
>;tb; >;SEP; C
>;tb; >;SEP; Ratio >;SEP; of >;SEP; Height >;SEP; of >;SEP; Length >;SEP; of >;SEP; Number
>;SEP; of >;SEP; Fresh >;SEP; weight >;SEP; of >;SEP; Fresh >;SEP; weight >;SEP; of
>;tb; >;SEP; Lu
>;tb; >;SEP; g >;SEP; Q >;SEP; >;SEP; o >;SEP; o >;SEP; 200.0*
>;tb; >;SEP; 3 >;SEP; 2.5 >;SEP; >; >;SEP; 145.5 >;SEP; 8 >;SEP; 245.0 >;SEP; 312.5
>;tb; >;SEP; OS >;SEP; >; >;SEP; H >;SEP; H >;SEP; H >;SEP; H >;SEP; H >;SEP; >; >;SEP; H
>;tb; . >;SEP; . >;SEP; ~
>;tb; >;SEP; m >;SEP; s >;SEP; 116.5 >;SEP; o >;SEP; 201.5 >;SEP; 264.0 >;SEP; 306.0
>;tb; >;SEP; S >;SEP; 110.0 >;SEP; 132.5 >;SEP; o >;SEP; d >;SEP; 285.5
>;tb; >;SEP; .U >;SEP; \0 >;SEP; 0 >;SEP; 0s >;SEP; \0 >;SEP; 0 >;SEP; CD >;SEP; O >;SEP; H
>;SEP; H >;SEP; ~I >;SEP; >; >;SEP; vO >;SEP; O
>;tb; >;SEP; Z;0 >;SEP; H >;SEP; N >;SEP; >; >;SEP; >; >;SEP; 100.0 >;SEP; 100.0 >;SEP; H
>;tb; >;SEP; 5.0 >;SEP; 105.0 >;SEP; 110.5 >;SEP; 115.0 >;SEP; 125.0 >;SEP; 120.0
>;tb; >;SEP; 6 >;SEP; 6 >;SEP; o
154/612
>;tb; >;SEP; 165.0 >;SEP; 195.5 >;SEP; 196.0
>;tb; >;SEP; cu
>;tb; JP >;SEP; >;SEP; O >;SEP; UG >;SEP; O >;SEP; UE >;SEP; O >;SEP; O >;SEP; O >;SEP; O
>;SEP; O >;SEP; UE >;SEP; O >;SEP; O >;SEP; o >;SEP; o >;SEP; O; >;SEP;
>;tb; >;SEP; .bo >;SEP; = >;SEP; 100.0 >;SEP; = >;SEP; = >;SEP; " >;SEP; " >;SEP; " >;SEP; o
>;SEP; - >;SEP; o >;SEP; o
>;tb; >;SEP; ms >;SEP; H >;SEP; >; >;SEP; >; >;SEP; H >;SEP; H >;SEP; H >;SEP; ~ >;SEP; H
>;SEP; H >;SEP; H >;SEP; H >;SEP; H >;SEP; H >;SEP; H
>;tb; >;SEP; o >;SEP; b >;SEP; >;SEP; ur >;SEP; O >;SEP; O >;SEP; In >;SEP; O >;SEP; I >;SEP;
O >;SEP; ur >;SEP; o >;SEP; o >;SEP; uo >;SEP; o
>;tb; >;SEP; 5 >;SEP; uo >;SEP; N >;SEP; >; >;SEP; m >;SEP; N >;SEP; >; >;SEP; m >;SEP; CS
>;SEP; H >;SEP; m >;SEP; CS >;SEP; H
>;tb; >;SEP; Mt
>;tb; >;SEP; X >;SEP; g >;SEP; E >;SEP; t >;SEP; W >;SEP; 8 >;SEP; g
>;tb; >;SEP; t >;SEP; ; >;SEP; ;
>;tb; >;SEP; U
>;tb; >;SEP; (Xpped >;SEP; as >;SEP; o >;SEP; llos)
>;tb; >;SEP; am1lno-laaslD >;SEP; amx >;SEP; Ismplo >;SEP; l
>;tb; *average of two replications #ratio compound to 100 for untreated control plants
This Table shows that the compounds of Formula I have growth promoting properties and also
especially promote the number of shoots.
EXPERIMENT 3
Emulsifiable solutions containing 20% of
O,O - diethyl - O - (4 - dimethylsulfamoylphenyl) phosphorothioate (compound No. 24) and O,N dimethyl - O - [4 - (p - methylthiophenyl) sulfamoyl-phenyl] phosphoroamidothioate (compound No.
33), prepared as described in Example III were each diluted to aqueous 0.02%-, and 0.04%- solutions,
res- pectively. Seedlings bred in vats were soaked in the above aqueous solutions for 24 and 48 hours
respectively. Seedlings thus treated were planted in an area of 1/20 m of Wagner's pots at the rate of 3
seedlings per pot, and cultivated for 3 months. After 3 months, the average height of the plants, number
of shoots and weight of ears were determined.
TABLE III
EMI10.1
Soaking >;SEP; Height >;SEP; of >;SEP; Number >;SEP; of >;SEP; Ratio >;SEP; of >;SEP; Weight
>;SEP; of >;SEP; Ratio >;SEP; of
>;tb; No. >;SEP; of >;SEP; compound >;SEP; conc. >;SEP; % >;SEP; time >;SEP; (hrs.) >;SEP; plants
>;SEP; (cm) >;SEP; shoots >;SEP; shoots >;SEP; ears >;SEP; (g) >;SEP; weight
>;tb; (24) >;SEP; 500 >;SEP; 24 >;SEP; 78.5* >;SEP; 24.5* >;SEP; 116.6* >;SEP; 4.8* >;SEP; 145.5*
>;tb; 48 >;SEP; 73.0 >;SEP; 23.0 >;SEP; 109.5 >;SEP; 4.5 >;SEP; 136.4
>;tb; 1,000 >;SEP; 24 >;SEP; 74.5 >;SEP; 21.0 >;SEP; 100.0 >;SEP; 4.5 >;SEP; 136.4
>;tb; 48 >;SEP; 82.5 >;SEP; 24.6 >;SEP; 116.7 >;SEP; 5.2 >;SEP; 157.6
>;tb; (33) >;SEP; ,500 >;SEP; 24 >;SEP; 76.0 >;SEP; 22.0 >;SEP; 104.7 >;SEP; 4.7 >;SEP; 143.3
>;tb; 48 >;SEP; 71.0 >;SEP; 23.0 >;SEP; 109.5 >;SEP; 4.4 >;SEP; 133.3
>;tb; 1,000 >;SEP; 24 >;SEP; 77.5 >;SEP; 21.5 >;SEP; 102.2 >;SEP; 5.0 >;SEP; 152.0
>;tb; 48 >;SEP; 81.0 >;SEP; 26.5 >;SEP; 126.2 >;SEP; 5.1 >;SEP; 154.5
>;tb; Untreated >;SEP; controls >;SEP; - >;SEP; - >;SEP; 70.5 >;SEP; 21.0 >;SEP; 100 >;SEP; 3.3
>;SEP; 100
>;tb; *average of three replications
As shown by the above table, compounds of Formula I have the property of increasing the height of
grass, the number of effective shoots and the yields over those resulting from untreated controls.
EXPERIMENT 4
Field test with rice
O,O - diethyl - O - (4 - dimethylsulfamoyl phenyl) phosphorothioate (No. 24) and O methyl - N - ethyl
- O - [2 - chloro - 4 - (p methoxyphenoxysulfonyl) - phenyl] phosphoroamidothioate (No. 17) were
formulated each as 10% dust and as 20%, emulsion in accordance with Examples I and III,
155/612
respectively. A first series of batches of healthy seeds selected by salt-water sorting was dressed with
10% dusts in the proportions of 5 percent and 2.5%, respectively, calculated on the total weight of the
seeds.
A second series of batches of healthy seeds selected by salt-water sorting was soaked for 24 hours in
aqueous 0.02% or 0.04% solutions prepared from the 20%-emulsions by dilution with tap water. Seeds
thus treated were sown on May 11 of the test year and planted on
June 10, and the state of growth was observed on September 10 of the same year and the yields of 100
stems were weighted. The results are shown in Table IV below.>;/RTI;
TABLE IV
EMI11.1
Number >;SEP; of >;SEP; Number >;SEP; of >;SEP; Weight >;SEP; of >;SEP; Ratio >;SEP; of
>;tb; Compound >;SEP; Height >;SEP; of >;SEP; effective >;SEP; unproductive >;SEP; Weight
>;SEP; of >;SEP; whole >;SEP; Weight >;SEP; of >;SEP; grain
>;tb; No. >;SEP; Dosage >;SEP; plants >;SEP; (cm) >;SEP; shoots >;SEP; shoots >;SEP; ears >;SEP;
(g) >;SEP; grains >;SEP; (g) >;SEP; grains >;SEP; (g) >;SEP; weight
>;tb; 5% >;SEP; 105.1 >;SEP; 52 >;SEP; 2 >;SEP; 3.1 >;SEP; 1,182 >;SEP; 1,119 >;SEP; 177.3
>;tb; (24)
>;tb; 2.5% >;SEP; 106.5 >;SEP; 48 >;SEP; 4 >;SEP; 2.9 >;SEP; 1,012 >;SEP; 967 >;SEP; 153.2
>;tb; 5% >;SEP; 103.4 >;SEP; 51 >;SEP; 4 >;SEP; 3.0 >;SEP; 1,176 >;SEP; 1,099 >;SEP; 174.2
>;tb; (17)
>;tb; 2.5% >;SEP; 106.0 >;SEP; 46 >;SEP; 5 >;SEP; 2.9 >;SEP; 994 >;SEP; 930 >;SEP; 147.3
>;tb; 0.04% >;SEP; 95.5 >;SEP; 40 >;SEP; 11 >;SEP; 2.6 >;SEP; 735 >;SEP; 701 >;SEP; 111.1
>;tb; (24)
>;tb; 0.02% >;SEP; 98.6 >;SEP; 46 >;SEP; 7 >;SEP; 2.8 >;SEP; 916 >;SEP; 845 >;SEP; 133.9
>;tb; 0.04% >;SEP; 96.0 >;SEP; 39 >;SEP; 13 >;SEP; 2.5 >;SEP; 660 >;SEP; 640 >;SEP; 101.4
>;tb; (17)
>;tb; 0.02% >;SEP; 97.4 >;SEP; 46 >;SEP; 6 >;SEP; 2.9 >;SEP; 939 >;SEP; 907 >;SEP; 143.7
>;tb; Untreated
>;tb; controls >;SEP; - >;SEP; 96.3 >;SEP; 33 >;SEP; 13 >;SEP; 2.5 >;SEP; 678 >;SEP; 631 >;SEP;
100.0
>;tb; As shown in Table IV, the compounds of Formula I promote the growth of the plants and number
of shoots and increase the yields of rice grown from treated seeds.
Experiment 5
Field test with yams (Dioscorea Batatas)
With 10% dust of O,O - diethyl - O - (4 dimethylsulfamoylphenyl) phosphorothioate (compound No.
24) and of O,O - diethyl - O [4 - (p - chloro - phenylthio) - sulfonylphenyl] phosphorothioate
(compound No. 9) seeds of yams were treated in the proportion of 2.5% to 5%, calculated on the
weight of the seeds.
The seeds were planted on April 23, and the number of yams and yields were observed on
December 7, of the test year.
The results are shown in Table V below.>;/RTI;
TABLE V
EMI12.1
Compound >;SEP; Dosage >;SEP; Number >;SEP; of >;SEP; Number >;SEP; of >;SEP; Total >;SEP;
Ratio >;SEP; of >;SEP; total
>;tb; No. >;SEP; (%) >;SEP; large >;SEP; yams >;SEP; small >;SEP; yams >;SEP; Total >;SEP;
weight >;SEP; (g) >;SEP; weight
>;tb; 5.0 >;SEP; 23 >;SEP; 4 >;SEP; 27 >;SEP; 4,116 >;SEP; 164.6
>;tb; (24)
156/612
>;tb; 2.5 >;SEP; 17 >;SEP; 12 >;SEP; 29 >;SEP; 2,833 >;SEP; 113.3
>;tb; 5.0 >;SEP; 21 >;SEP; 7 >;SEP; 28 >;SEP; 3,517 >;SEP; 140.6
>;tb; (9)
>;tb; 2.5 >;SEP; 19 >;SEP; 9 >;SEP; 28 >;SEP; 2,964 >;SEP; 118.6
>;tb; Untreated >;SEP; - >;SEP; 12 >;SEP; 15 >;SEP; 27 >;SEP; 2,500 >;SEP; 100.0
>;tb; The compounds of the inventions promote the growth of yams, and increase the yields as shown
in Table V.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of GB1165846
WHAT WE CLAIMIS:1. A method of promoting the growth of a cultivated plant, comprising applying to the seeds of such
plant a growth promoting amount of a compound of the formula
EMI13.1
in which formula:
R1 represents lower alkyl,
R, represents lower alkoxy or lower monoor di- alkyl-substituted amino,
R, represents hydrogen, fluorine, chlorine or bromine or methyl, and
R represents halogen, lower alkoxy, allyloxy, lower alkoxyethyl, lower alkylthio, allylthio, lower
alkoxyethylthio, lower alkoxyethyloxy, or one of the radicals
EMI13.2
in which radicals
R4 represents hydrogen or lower alkyl, and
R represents hydrogen, lower alkyl, allyl, or the grouping
EMI13.3
X represents oxygen or sulfur,
Y represents hydrogen, fluorine, chlorine or bromine, lower alkyl, lower alkoxy, lower alkylthio,
thiocyano or isothiocyano, and n represents an integer of at most 5, the term "lower" being as
hereinbefore defined.
2. A method as defined in claim 1, wherein theamount of said compound ranges from about 0.001
ppm to 50 ppm calculated on the weight of the treated seeds.
3. A method as defined in claim 1, wherein the treated seeds are those of a cereal.
4. A method as defined in claim 1, wherein the treated seeds are those of rice.
5. A method as defined in claim 1, wherein the treated seeds are those of yams.
6. A compound of the formula
EMI13.4
in which formula:
R, represents lower alkyl,
R2 represents lower alkoxy or lower monoor di- alkyl-substituted amino,
R, represents hydrogen, fluorine, chlorine or bromine or methyl, and
R represents lower alkoxy, allyloxy, lower alkoxy-ethyl, lower alkylthio, allylthio, lower
alkoxyethylthio, lower alkoxyethoxy or the radical
EMI13.5
in which radical
X represents oxygen or sulfur,
Y represents hydrogen, fluorine, chlorine or bromine, lower alkyl, lower alkoxy, lower alkylthio,
thiocyano or isothiocyano, and
n represents an integer of at most 5, the term"lower" being as hereinbefore defined.
7. A compound as defined in claim 6, wherein R1 is ethyl,R, is ethoxy, R3 is hydrogen and R is
EMI13.6
8. A compound as defined in claim 6, wherein R, is ethyl, R2 is ethoxy,R, is hydrogen andRis
157/612
EMI13.7
9. A compound as defined in claim 6, whereinR1 is methyl, R2 is ethylamino, R, is chlorine in 2position and' R is
EMI13.8
10. A plant-growth-promoting composition containing as active substance at least one
organothiophosphate of the general formula
EMI14.1
as defined in claim 1, in admixture with suitable agriculturally acceptable carriers thereof.
11. A plant-growth-promoting composition containing as active substance at least one new
organothiophosphate of the general formula defined in claim 6, in admixture with a suitable
agriculturally acceptable carrier.Data supplied from the esp@cenet database - Worldwide
158/612
11. GB1168317
- 10/22/1969
GB1168317
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1168317
IP Class 4 Digits: A01N
IP Class:A01N
E Class: A01N57/06; C07F9/165A7; C07F9/40C7
Application Number:
GBD1168317 (19670609)
Priority Number: DE1966F049434 (19660610)
Family: GB1168317
Equivalent:
NL6708075; ES341592; BE699714
Abstract:
Abstract of GB1168317
1,168,317. Fungicides containing thiolphos- phoric acid esters. FARBENFABRIKEN BAYER A.G. 9
June, 1967 [10 June, 1966; 16 Aug., 1966; 2 Dec., 1966], No. 26685/67. Heading ASE. [Also in
Division C2] A fungicidal composition comprises a phos- phorus ester of the general formula:- wherein
R 1 is C 1 -C 4 alkyl and R 2 is a C 1 -C 4 alkoxy radical in admixture with a solid diluent or carrier.
The composition may also contain a surface active agent and may be in the form of a solution,
emulsion, suspension, powder, paste or granulate and an organic solvent may also be used when water
is used as diluent. Application may be by squirting, dusting, spraying or atomising and other plant
protection agents may also be present e.g. herbicides, insecticides, bactericides or other fungicides. The
compositions are particularly useful for application to rice plants subject to fungal attack.Description:
Description of GB1168317
COMPLETE SPECIFICATION
Thiolphosphoric (-Phosphonic) Acid Esters
We,FARBENFABR3:REN BAYER AKTIENGELSCHAFT, a body corporate organised under the
laws of Germany,uf Leverkusen, Germany, do hereby declare the invention, forwhich we pray that a
patent may be granted to us, and the method by which it is to be performed, to be particularly described
in and by the followingstatement:
The present invention relates to new fungitoxic thiolphosphoric (-phosphonic) acid esters and to their
preparation and use. These compounds have the generalformula:
EMI1.1
in which R, stands for an alkyl radical with 1 to 4 carbon atoms, andR2 stands for an alkyl radical
with 1 to 4 carbon atoms or analkoxy radical with 1-4 carbon atoms.
In U.S. Patent Specification No. 2,690,450, thiolphosphoric acid aryl esters are already described
which possess parasiticidal properties, in particular insecticidal properties, but also fungicidal
properties. From this publication, however, it emerges only that the above-mentioned compounds are
suitable as fungicides for the control of brown rot (Sclerotinia fructicola) and early blight (Alternaria
solani). However, from U.S. Patent
Specification No. 2,690,450 it cannot be learned whether the compounds disclosed there possess also
an effectiveness which would in practice be adequate against fungoid pathogenic agents on rice plants,
particularly the fungus Piricularia oryzae.
159/612
We have found that the new thiol-phosphoric (phosphonic acid esters of formula (1) are distinguished
by outstanding fungitoxic properties, particularly in regard to fungoid pathogenic agents on rice plants.
Surprisingly, they are in this respect distinctly superior to the known active compounds of analogous
constitut;on already proposed for the same purpose. The new compounds therefore represent a
substantial enrichment of the art.
We have also found that thiol-phosphoric (-phosphonic) acid esters of formula (1) are obtained
smoothly and with good yields when halomethylnaphthalenes of the formula:EMI1.2
are reacted with thiol-phosphoric (-phosphonic) acids of the general formula:
EMI1.3
in the form of the corresponding salts or in the presence of acid-binding agents.
The course of the process of the invention can be represented by the followingequation:
EMI2.1
In all the above formulae, thesymbols, R1 and R2 have the meaning stated earlier above, while Hal
stands for a halogen atom.
Preferably, R1 stands for a methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl or sec.-butyl radical;
preferably, R2 stands for one of these radicals or a methoxy ethoxy, npropoxy, or isopropoxy, nbutoxy,isobutoxy or sec.-butoxy radical.
The halomethylnaphthalenes used in the process are known from the literature and can readily be
prepared, even on an industrial scale.
The following is a list of some of the thiolphosphoric (-phosphonic) acid salts which may be used as
starting substances: Ammonium, potassium or sodium,O,O-dimethyl, -diethyl, -diethyl, -di-isopropyl,
-di-sec.-butyl, Omethyl-O-ethyl, O-methyl andO-ethyl-O-n- and -isopropyl, O-methyl-O-n- and sec.
butyl,O-ethyl-O-n and sec.-butyl, O-isopropyl-Osec.-butyl thiolphosphate.
The process of the invention is carried out preferably in the presence of inert solvents.
Examples thereof are hydrocarbons and chlorinated hydrocarbons, such as methylene chloride,
chloroform, carbon tetrachloride, benzene, toluene, xylenes, chlorbenzenes, and also ethers, for
example diethyl or dibutyl ether, dioxan, tetrahydrofuran, and low-boiling aliphatic ketones and
nitriles, for example acetone, methylethyl ketone, methylisopropyl ketone or methylisobutyl ketone as
well as acetonitrile or proprionitrile.
As already mentioned above, the salts (preferably the alkali metal or ammonium salts) of the thiolphosphoric (-phosphonic) acids may serve as starting substances for the reaction of the invention.
In one alternative of the process, it is possible, instead of starting from the salts, to use the
corresponding free acids and to react these in the presence of acid-binding agents.
Particularly suitable acid acceptors include alkali metal carbonates or alcoholates, such as potassium or
sodium carbonate, methylate or ethylate, and also tertiary bases, such as trethylamine, dimethylaniline
orpyridiae.
The reaction temperatures can be varied within a fairly wide range. In general, the work is carried out
at 30 to80 C, preferably at 40 to 700C.
In carrying out the processaccording to the invention equimolar amounts of halomethylnaphthalene
and thiol-phosphoric (-phosphonic) acid salt (or a mixture of the free acid concerned and the acidbinding agent) are generally used.
It has proved expedient to add, with stirring at the above-mentioned temperatures, the
halomethylnaphthalene to the already prepared solution or suspension of the thiolphosphoric (-
160/612
phosphonic) acid salt in a suitable solvent and then, in order to complete the reaction, to stir the
mixture further for a longer period (for example 1 to 3 hours), optionally with heating.
The working up of the mixture may take place in a manner which is known in principle by filtration of
themixture, evaporation of the solvent, taking up of the oily, precipitated reaction product in another,
water-immiscible organic solvent, preferably one of the abovementioned chlorinated hydrocarbons,
washing of the organic layer until there is a neutral reactien, separation of the phases, drying of the
solution and again distilling off the solvent and, optionally, fractional distillation of the residue under
reduced pressure.
The thiol-phosphoric (-phosphonic) acid esters of the invention are obtained in most cases in the form
of colourless or pale yellow to brownish coloured, water-insoluble oils, some of which can be distilled
under greatly reduced pressure without decomposition and sometimes solidify in crystalline form after
standing for a long period.
As mentioned above, the products of the process are distinguished by a strong fungitoxic effectiveness
and a wide spectrum of activity.
Surprisingly, they possess, despite this outstanding activity against phytopathogenic fungi, only a
slighttoxidty in respect ofwarm- blooded animals (median toxicityLD,0 in the rat per os 100 to 1000
mg/kg animal). To this is to be added the excellent compatibility in respect of higher plants of the
compounds which can be prepared according to the invention. By reason of these properties, the
produets of the process are eminently suitable as plant protection agents against fungoid diseases.
Fungicides involving these active compounds can be used for the control of fungi of the most widely
different classes, for example
Archimycetes, Phycomycetes, Ascomycetes,Basidiomycetes, Fungi Imperfecti. However, the active
compounds have given particularly good results against fungoid diseases of rice, in particular those
caused by the fungus Piricularia oryzae. The active compounds have an excellent protective and
curative activity against this fungus.
In addition, they can also be used for the control of other fungoid pathogenic agents on rice and otber
cultivated plants. They possess a particular activity against the following species of fungi:
Cochliobolus miyabeanus species
Mycosphaerella species
Corticium species
Cerospora species
Alternaria species
Botrytis species
Moreover, the active compounds of the invention show a very good activity in respect of fungi which
attack the plant from the soil and some of which cause tracheomycoses, such as
Fusarium cubense,
Fusarium dianthi,
Verticillirnii alboatrum and
Phialophora cinerescens.
When the active compounds of the invention are used as fungitexic agents, they may be used
individually or in combination with one another. Furthermore, they may be mixed with other plant
protection agents, such as other fungicides, herbicides, insecticides or bactericides.
The active compounds of the invention may be applied as such.
The active compounds of the invention can be converted into the usual formulations, such as solutions,
emulsions, suspensions, powders, pastes or granulates. These may be produced in known manner, for
example by mixing the active compounds with extenders, that is liquid or solid diluents or carriers,
optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents.
In the case of the use of water as an extender, organic solvents can for example also be used as
auxiliary solvents.
161/612
As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes or
benzene, chlorinated aromatic hydrocarbons, such as chlorobenzenes, parffins, such as mineral oil
fractions, alcohols, such as methanol or butanol, or strongly polar solvents, such as dimethyl
formamide or dimethylsuiphoxide, as well as water.
As solid diluents or carriers there are preferably used ground natural minerals, such as kaolins, clays,
talc or chalk, or ground synthetic minerals, such as highly-dispersed silicic acid or silicates.
Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such as
polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates and aryl sulphonates; and preferred examples of dispersing agents
include ligninsulphite waste liquors and methyl cellulose.
As already indicated above, the active compounds of the invention may be present with other active
substances in the above formulations.
The formulations contain, in general, from 0.1 to 95 per cent by weight of active compound, preferably
from 0.5 to90%.
The active compounds of the invention and preparations thereof may be applied in customary manner,
for example by squirting, dusting, spraying, atomising.
According to the purpose for which it is to be used, the active substance may be applied in a
concentration of 0.0005 to5% for example0.01--5':6. In special cases, however, it is possible, or even
necessary, to exceed' or to go below this range of concentrations.
The invention also provides a fungitoxic composition containing as active ingredient a thiolphosphoric (-phosphonic) acid ester of formula (I) in admixture with a solid diluent or carrier or in
admixture with a liquid diluent or carrier containing a surface-active agent.
Theinvention also provides a method of combating fungi which comprises applying to a fungus
habitat a thiol-phosphoric (-phosphonic) acid ester of formula (I) alone or in the form of a composition
containing as active ingredient a compound of formula (I) in admixture with a solid or liquid diluent or
carrier.
The outstanding fungitoxic effectiveness of the thiolphosphoric acid esters according to the process, as
well as their distinct superiority compared with known products of analogous constitution and the same
direction of activity, can be seen from the following experimental testresults: EXAMPLE A
Piricularia test: liquid preparation of active compound
Solvent: 1 part by weight acetone
Dispersing agent: 0.05 part by weight sodium oleate
Other additives: 0.2 part by weight gelatin
Water: 98.75 part by weight H2O
The amount of active compound required for the desired concentration in the spray liquor is mixed
with the stated amount of solvent, and the concentrate is diluted with the stated amount of water
containing the stated additives.
30 rice plants about 14 days old are sprayed with the spray liquor until dripping wet. The plants remain
in a greenhouse at temperatures of 22 to24"C and a relative atmospheric humidity of about70l, until
they aredrop.
They are then inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of
Piricularia oryzae and placed in a chamber at24--250C and10001,0 relative atmospheric humidity.
5 days after inoculation, the infestation of all the leaves present at the time ofinecula- tion is
determined as a percentage of the untreated but also inoculated control plants.0:6 means no
infestation;100% means that the infestation is exactly as great as in the case of the control plants.
162/612
The active compounds, the concentrations of the active compounds and the results can be seen from
the followingTable:
TEST forcurative action
In addition to the protective action determined as described above, the curative action of the active
compounds of the invention is also determined.
The test for curative action differs in certain points from the test procedure described above (which
only yields evidence in respect of the protective effect) in so far as the active compounds are applied
not before, but only after 16 hoursafter, inoculation. Substances which show an activity when the test
is conduced in this manner are in a position to kill the fungus after infection and thereby to exercise a
curative action.
The results of the test for curative action can also be seen from the following Table:
TABLE
Piricularia test: liquid preparation of active compound
Infestation in % of the infestation of
the untreated control with a con
centration of active compound
Serial ffi (in%) of
No. Active compound (constitution) 0.05 0.025 0.01 0.005
EMI4.1
>;tb; >;SEP; C >;SEP; c2o ; >;SEP; o >;SEP; pr.pr. >;SEP; 0 >;SEP; 3 >;SEP; 17 >;SEP; 32
>;tb; >;SEP; C2N5o >;SEP; >; >;SEP; cur. >;SEP; 0 >;SEP; 71
>;tb; >;SEP; 2 >;SEP; 0 >;SEP; pr. >;SEP; 0 >;SEP; 0 >;SEP; 71
>;tb; >;SEP; cur. >;SEP; st >;SEP; cur. >;SEP; 58
>;tb; >;SEP; y5o
>;tb; 3 >;SEP; C2N5O0fl >;SEP; O >;SEP; pr.pr. >;SEP; 18 >;SEP; 50 >;SEP; 100
>;tb; >;SEP; cur. >;SEP; 55 >;SEP; cur. >;SEP; 100
>;tb; >;SEP; c?NjO
>;tb; >;SEP; (Comparative >;SEP; preparation >;SEP; known >;SEP; from >;SEP; U.S.
>;tb;
>;SEP; Patent >;SEP; Specification >;SEP; No. >;SEP; 2,690,450)
>;tb; 4 >;SEP; O >;SEP; n >;SEP; on >;SEP; 0 >;SEP; 25 >;SEP; 42
>;tb; >;SEP; CN3 >;SEP; cur. >;SEP; 21
>;tb;
TABLE (Continued)
Piricularia test: liquid preparation of active compound
Infestation in % of the infestion of
the untreated control with a con
centration of active compound
Serial (in%) of
No. Active compound (constitution) 0.05 0.025 0.01 0.005
EMI5.1
>;tb; C2*\11 >;SEP; Q >;SEP; pr. >;SEP; 0 >;SEP; 46 >;SEP; 85
>;tb; >;SEP; C >;SEP; P-oC9 >;SEP; cur. >;SEP; 9
>;tb; >;SEP; 6 >;SEP; p ; >;SEP; pr. >;SEP; 0 >;SEP; 5 >;SEP; 20 >;SEP; 40
>;tb; >;SEP; 0 >;SEP; cur. >;SEP; 29
>;tb; >;SEP; iC3 >;SEP; 70 ; >;SEP; cur. >;SEP; 29
>;tb; >;SEP; cw3
>;tb; >;SEP; 7 >;SEP; pr. >;SEP; 0 >;SEP; 5 >;SEP; 83
>;tb; >;SEP; 0. >;SEP; \ >;SEP; cur. >;SEP; 33
>;tb; >;SEP; K30' >;SEP; J
>;tb; >;SEP; pr. >;SEP; pr. >;SEP; 0 >;SEP; 1 >;SEP; 100
163/612
>;tb; >;SEP; cur. >;SEP; cur. >;SEP; 52
>;tb; >;SEP; C3ll7 >;SEP; 0
>;tb; >;SEP; 9 >;SEP; t >;SEP; pr. >;SEP; 5 >;SEP; 12 >;SEP; 75
>;tb; >;SEP; Also >;SEP; cur. >;SEP; 38
>;tb; >;SEP; C
>;tb;
TABLE (Continued)
Infestation in % of the infestation of
the untreated control with a con
centration of active compound
Serial (in %) of
No. Active compound (constitution) 0.05 0.025 0.01 0.005
EMI6.1
>;tb; 10 >;SEP; O >;SEP; pr. >;SEP; 6 >;SEP; 13 >;SEP; 55
>;tb; >;SEP; cur. >;SEP; cur. >;SEP; 19
>;tb; 11 >;SEP; o >;SEP; 0 >;SEP; 0 >;SEP; 33 >;SEP; 50
>;tb; >;SEP; o
>;tb; >;SEP; i4 >;SEP; Rr$I >;SEP; cur. >;SEP; 0 >;SEP; 5
>;tb;
pr. = protective action
cur = curative action
The process of the invention is illustrated by the following Examples 1 to3: EXAMPLE 1
EMI6.2
A mixture of 61.0g of the ammonium salt ofO,O-diethylthiolphosphoric acid, 250 cc methylethyl
ketone and 44.2g (0.25 mole) 1chlormethylnaphthalene (b.p. 1220C 2mm Hg) are stirred for 2 hours at
an internal temperature of 700C and filtered in the cooled state.
The filtrate is freed from the solvent under reduced pressure, the residue is dissolved in
carbontetrachloride, and the solution is washed until there is a neutral reaction. After drying thereof
over sodium sulphate and removal of the solvent under reduced pressure, there remain behind 71.2g
(91.7% of the theory) of
O,O-diethylthiolphosphoric acid S-[naphthyl (1)-methyl] ester in the form of a brownish coloured oil.
Analysis P S
Calculated for a molecular weight of 310.34: 9.98%; 10.33%;
Found: 10.20%; 10.35%.
EXAMPLE 2
EMI6.3
In manner analogous to that described in the preceding Example, from 61.0g of the ammonium salt of
O,O-diethylthiolphosphoric acid and 55.3g (0.25 mole) 2-bromomethyl- naphthalene (m.p. 62 to 63 C)
there are obtained 69.2g (89% of the theory) O,O-diethylphosphoric acid S-[naphthyl-(2)-methyl] ester
in the form of a brownish coloured, viscous oil which, on standing, gradually crystallises and then
possesses a melting point of 43 to 45 C. By recrystallisation of the crude product from petroleum ether,
colourless crystals of melting point 47 to 480C are obtained.
Analysis: P S
Calculated for a molecular weight of 310.34 9.98%;10.33%
Crude product found: 10.00%; 10.66%;
Recrystallised product found: 10.10%; 10.58%;
EXAMPLE 3
EMI7.1
164/612
A mixture of52.5g of the ammonium salt of O,O-dimethylthiolphosphoric acid, 150 cc acetonitrile
and 53.0g (0.3 mole) l-chlormethylnaphthalene is stirred for 2 hours at Analysis:
Calculated for a molecular weight of 282.30:
Found:
EXAMPLE 4
EMI7.2
In manner analogous to that described in
Analysis:
Calculated for a molecular weight of 338.41:
Found:
EXAMPLE 5
The following compounds are obtainable in an internal temperature of 700C and then filtered in the
cooled state. After removal of the solvent under reduced pressure, the residue is taken up in 100 cc
methylene chloride, and the solution is washed until there is a neutral reaction. It is then dried over
sodium sulphate and freed from the solvent under reduced pressure. There remain behind
62.0g(73.313/o of the theory) of O,O-dimethylthiolphosphoric acid S - [naphthyl -(2) - methyl] ester in
the form of a yellowish oil with the refractive index nD1.5 = 1.5898.
PS
11.0%; 11.4%;
11.0%; 11.1%; the preceding Example, by reaction of39.0g of the ammonium salt of O,Odiisopropylthiolphosphoric acid with 33.2g (0.15 mole) 2bromomethylnaphthalene there are obtained
47.0g(92.5% of the theory) ofO,O-diiso- propylthiolphosphoric acid S - [naphthyl (2) - methyl] ester
in the form of a yellowish oil with the refractive index nD235 = 1.5650.
P S 9.2%; 9.5%;
9.4%; 9.6%; a manner analogous to that of Example 3.
Analysis
Calculated (%) Found (%)
Molecular
Constitution weight Refractive index P S P S
EMI8.1
(s >;SEP; o >;SEP; uF
>;tb; >;SEP; o >;SEP;
>;tb; - >;SEP;
>;tb; oo >;SEP; N >;SEP; e
>;tb; o >;SEP; o
>;tb; o >;SEP; o
>;tb; uo >;SEP; nD215 >;SEP; o >;SEP; es
>;tb; >;SEP; a
>;tb; - >;SEP; - >;SEP; .
>;tb;
310.36 >;SEP; 8 >;SEP; X
>;tb; no >;SEP; fi >;SEP; ffi
>;tb; Analysis
Calculated (%) Found (%)
Molecular
Constitution weight Refractive index P S P S
EMI9.1
280.33 nD23.5 = 1.6076 11.1 11.4 11.2 11.6 282.30 nD23.5 = 1.5942 11.0 11.4 11.1 11.5
WHAT WE CLAIM IS:1. Thiol-phosphoric (-phosphonic) acid esters of the general formula:EMI9.2
in which R1 stands for an alkyl radical with 1 to 4 carbon atoms, and R2 stands for an alkyl radical
with 1 to 4 carbon atoms or an alkoxy radical with 1-4 carbon atoms.
165/612
2. The compound of the formula:EMI9.3
3. The compound of the formula:EMI9.4
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB1168317
**WARNING** start of CLMS field may overlap end of DESC **.
Analysis
Calculated (%) Found (%)
Molecular
Constitution weight Refractive index P S P S
EMI9.1
280.33 nD23.5 = 1.6076 11.1 11.4 11.2 11.6 282.30 nD23.5 = 1.5942 11.0 11.4 11.1 11.5
WHAT WE CLAIM IS:1. Thiol-phosphoric (-phosphonic) acid esters of the general formula:EMI9.2
in which R1 stands for an alkyl radical with 1 to 4 carbon atoms, and R2 stands for an alkyl radical
with 1 to 4 carbon atoms or an alkoxy radical with 1-4 carbon atoms.
2. The compound of the formula:EMI9.3
3. The compound of the formula:EMI9.4
4. The compound of theformula: EMI10.1
5. The compound of theformula: EMI10.2
6. The compound of the formula:EMI10.3
7. The compound of theformula: EMI10.4
8. Thc compound of the formula:EMI10.5
9. The compound of theformula: EMI10.6
10. The compound of theformula:
EMI10.7
11. The compound of theformula:
EMI10.8
12. A process for the production of a thiolphosphoric (-phosphonic) acid ester according to claim 1 in
which a halomethylnaphthalene of the general formula:EMI10.9
is reacted with a thiol-phosphoric (-phosphonic) acid of the general formula:
EMI10.10
in the form of the corresponding salt or in
the presence of an add binding agent in which
R, and R2 have the same meaning as in claim
1 and Hal is a halogen atom.
13. A process according to claim 12 in which
the reaction iscarried out at 30 to 800C.
166/612
14. A process according to claim 12 or 13
in which the reaction is carried out in the
presence of an inert solvent.
15. A process according to any of claims 12
to 14 in which the halomethylnaphthalene is
added to a solution or suspension of the thiol
phosphoric (-phosphonic) acid salt and the
resulting mixture is stirred until the reaction
is substantially complete.
16. A process according to any of claims 12
to 15, substantially as hereinbefore described
in Examples 1 or 2.
17. Thiol -phosphoric (-phosphonic) acid
esters according to claim 1 whenever prepared by a process according to any of claims 12
to 16.
18. A process according to any of claims
12 to 15, substantially as hereinbefore
described in Example 3, 4 or 5.
19. Thiol-phosphoric (-phosphonic) add
esters according to claim 1 whenever prepared
by a process according to claim 18.
20. A fungitoxic composition containing as
active ingredient a thiol-phosphoric (-phos
phonic) acid ester according to any of claims
1 to 3 or 17 in admixture with a solid diluent
or carrier or in adrnixture with a liquid diluent
or carrier containing a surface-active agent.
21. A composition according to claim 20
containing from 0.1 to 95% of the active cosound, by weight.
22. A fungitoxic composition containing as
active ingredient a thiol-phosphoric (-phos
phonic) add ester according to any of claims 4
to 11 or 19 in admixture with a solid diluent
or carrier or in admixture with a liquid
diluent or carrier containing a surface-active
agent.
23. A composition according todaim 22
containing from 0.1 to93% of the active
compound, by weight.
24. A method of combating fungi which
comprises applying to a fungus habitat a thiol
phosphoric (-phosphonic) acid ester according
to any of claims 1 to 3 or 17 alone, or in the
form of a composition containing as active
ingredient a compound according to any of claims 1 to 3 or 17 in admixture with a solid or liquid
diluent or carrier.
25. A method according to claim 24 in which a composition is used containing 0.01 to5i/ó by weight
of the active compound.
167/612
26 A method according to claim 24 or 25 in which the fungus is Piricularia oryzae,
Cochliobolus miyabeanus, Mycosphaerella,
Corticium, Cersapora, Alternaria or Betrytis.
27. A method according to any of claims 24 to 26 in which the thiol-phosphoric (-phos
phonic) acid ester is No. 1 or 2 of Example A.
28. A method according to any of claims 24 to 27 in which the active compound is applied
to rice plants.
29. A method of combating fungi which
comprises applying to fungus habitat a thiol
phosphoric (-phosphonic) acid ester according
to any of claims 4 to 11 or 19 alone or in the form of a composition containing as active ingredient a
compound according to any of claims 4 to 11 or 19 in admixture with a solid or liquid diluent or
carrier.
30. A method according to claim 29 in which a composition is used containing 0.01 to 5% by weight
of the active compound.
31. A method according to claim 29 or 30 in which the fungus is Piricularia oryzae,
Cochliobolus, miyabeanus, Mycosphaerella,
Corticium, Cerospora, Alternaria or Botrytis.
32. A method according to any of claims 29 to 31 in which the active compound is applied to rice
plants.Data supplied from the esp@cenet database - Worldwide
168/612
12. GB1168817
- 10/29/1969
NEW HALOGEN-CONTAINING PHOSPHORUS ESTERS HAVING
PESTICIDAL AND HERBICIDAL PROPERTIES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1168817
Applicant(s):
CIBA LTD (CH)
IP Class 4 Digits: C07F
IP Class:C07F9/10
E Class: C07F9/12; C07F9/18; C07F9/32C4; C07F9/40C4
Application Number:
GB19660053300 (19661129)
Priority Number: CH19650016895 (19651208)
Family: GB1168817
Equivalent:
US3492376; FR1502537; DE1542857; CH478528
Abstract:
Abstract of GB1168817
1,168,817. Pesticides containing halogena- ted phosphorus esters. CIBA Ltd. 29 Nov., 1966 [8 Dec.,
1965], No. 53300/66. Heading ASE. [Also in Division C2] A pesticidal composition comprises one or
more phosphorus esters of the formula:- wherein R 1 and R 2 are the same or different alkyl radicals
bound to phosphorus directly or through oxygen or sulphur and containing together at most 5 carbon
atoms, X is oxygen or sulphur, Hal is F, Cl, Br or I and R is a C 1 -C 4 alkyl radical, together with a
carrier. The composition may contain a solvent, di- luent, dispersant, wetting agent, an adhesive, a
fertiliser and/or another pesticide and may be in the form of an emulsion concentrate, a paste, a
wettable spray powder, a spray solu- tion in an organic solvent, dust or granules. The product have
insecticidal, acaricidal, nematocidal and microbiocidal and fungicidal properties and are particularly
useful as herb- icides, e.g. for selective weed control in rice culture.Claims:
Claims of GB1168817
WHAT WE CLAIM IS: 1. A compound having the general formula:
in which R. and R.. each represents the same or different alkyl radicals which are bound to
phosphorus directly or through oxygen or sulphur, containing together at most carbon atoms, and X
represents oxygen or sulphur, Hal represents fluorine, chlorine, bromine or iodine, and R represents an
alkyl radical containing 1 to 4 carbon atoms.
2. A compound having the general formula wherein Hal represents a chlorine, bromine or iodine
atom, and the alkyl radicals contain in all no more than 5 carbon atoms.
3. The compound having the formula (c//go)2 P Br 4. The compound having the formula (C2,'oz-Por R
-I117 wherein R, and R. are identical or different alkyl radicals bound to phosphorus directly or
through oxygen or sulphur, R, and R2 containing together at most 5 carbon atoms, and in which X
represents sulphur or oxygen and Hal is a fluorine, chlorine, bromine or iodine atom, and R represents
an alkyl radical containing 1 to 4 carbon atoms, together with a carrier.
169/612
7. A preparation as claimed in claim 6 wherein there is present one of the following:
a vehicle, a solvent, a diluent, a dispersant, a wetting agent, an adhesive, a fertilizer and/or other
pesticides.
8. A pesticidal preparation as claimed in claim 6 or 7, wherein the active ingredient is a phosphoric
acid ester of the general formula \P-0 in which Hal represents a chlorine, bromine or iodine atom and
the alkyl radicals contain 60 in all no more than 5 carbon atoms.
9. A pesticidal preparation as claimed in claim 6 or 7, wherein the active ingredient is the compound
of the formula aBr 10. A pesticidal preparation as claimed in claim 6 or 7, wherein the active ingredient
is the compound of the formula S t0 (4zA'so-jPO 11. A pesticidal preparation according to 70
1,168,817 -6 1,168,817 claim 6 and substantially -as described in Example 2 herein.
ABEL & IMRAY, Chartred Patent Agents, Quality House, Quality Court, Chancery Lane, London,
W.C.2.
Printed for Her Majesty's Stationery Office by the Courier Press, Leaniingten Spa, 1969.
Published by the Patent Office, 25 Southampton Buildings, London, W.C.2, from which copies may
be obtained.Data supplied from the esp@cenet database - Worldwide
170/612
13. GB1249607
- 10/13/1971
METHOD OF COMBATING WEEDS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1249607
Inventor(s):
AYA MASAHIRO (--); SCHRADER GERHARD (--); EUE LUDWIG (--); HACK
HELMUTH (--); HIRANE SEIICHI (--); FUKAZAWA SHIGEO KISHINO NOBUO (--)
Applicant(s):
BAYER AG (DE)
IP Class 4 Digits: A01N
IP Class:A01N9/00
E Class: C07F9/24A4
Application Number:
GB19700005605 (19700205)
Priority Number: JP19690014227 (19690227)
Family: GB1249607
Equivalent:
NL7001740; FR2032449; ES376290; DE2001773; BG17277; BE745634
Abstract:
Abstract of GB1249607
1,249,607. Combating weeds with an amido- thionophosphoric acid ester. FARBENFABRI- KEN
BAYER A.G. 5 Feb., 1970 [27 Feb., 1969], No. 5605/70. Heading A5E. A method of combating weeds
comprises applying to the weeds, or to a habitat thereof (e.g. an area of rice cultivation), the compound
of the formula alone or in admixture with a solid or liquid diluent or carrier. The O-(2-nitrophenyl)-Oethyl-N-isopropylphosphoroamidothioate may be used in conjunction with MCPA.Description:
Description of GB1249607
(54)METHOD OF tCOM!BATZG WEEDS
(71) We, FARBENFABRIKEN BAYERAKTIENGBSELLSCHAFT, a Body corporate organised
under the lawsolf Germany, of
Leverkusen, Germany, dohereby declare the invention, for which we pray that a patent may be granted
to us, and the method by which it is Ito be performed, to be particularlydescribed in and by
the'fcllowing statement: The present invention relates to the use as a herbicide of a certain amidothionophosphoric acid
ester.The invention provides a method of combating weeds which comprises applying to the weeds or a
habitat thereof the compound of the formula
EMI1.1
(I) alone or in admixture with a solid or liquid diluent or carrier.
A compound of U.S. Patent No. 3,074,790,o - (2,4 dEichlorophenyl) - O - methyl - Niso propylphosphoroamidothioate, possesses activity as a herbicide. It 'has now been found that O - (2 nitrophenyl) - O - ethyl - Nisoprophylphosphoroamidcthioate of the structural formula (I) has strong
herbicidal activity, especially against weeds in paddy fields, weeds of the Graminae family, broad
leaved weeds and perennial weeds. Moreover it shows selective herbicidal activity, for example in
exhibiting little or no phytotoxicity to rice.
According to British Patent No. 659,682, it is known that compounds of the type of that used in the
present invention possess insecticidal and fungicidal activities. However, that patent indicates only that
171/612
these compounds have insecticidal and acaricidal efficacy and are also effective for the control of
harmful fungi on plants and can be used as sprayingpreparations. There is no description of a test
example showing their efficacy, and no indication of anyherbicidal activity. There is also no mention
of the applicability of the compounds to soil or ay reason to expectherbiddal activity.
The present ivention is based on the discovery that O -(2 - nitrophenyl) - O - ethyl
N - iso -propylphosphoroamidothi@ate of formula (I) shows remarkably good selective herbicidal
efficacy when used especially as apre-emergen soil treatment herbicide in the control of weeds in
areasof crop cultivation, e.g. paddy fields.
The compound used in the present invention is obtained easily and with good yieldsby reacting 0 ethyl - N -isopropyl - amidothionophosphoric acid ester halide with 2nitrophenol, preferably in the
presence of an acid binding agent, or by reacting it with a salt of 2-nitrophenol as shown by the
following reaction scheme:
EMI1.2
(II) in which Hal is a halogen at@m, preferably a chlorine atom, and Me'is a hydrogen atom, alkali
metal atom or ammonium radical.
Example 1 illustrates the preparation of the compound used in the present invention.
EXAMPLE 1
EMI1.3
(I)
14 g (0.1 mol)of 2-nitrophenol were dissolved in 100 ml of acetonitrile and 14 g of anhydrous
potassium carbonate were added to the solution. 20.2 g (0.1 mol) ofO - ethyl
N - iso-propylamidothionophosphoric acid ester chloride were added dropwise at 5060 C, with
vigorous stirring. The inorganic salt produced was filtered off and the filtrate was distilled to remove
the solvent. The residue was dissolved in 100 ml of benzene and the benzene solution was washed
with1% aqueous solution of sodium carbonate,which was dried over anhydrouns sodium sulphate.
After distillation off of the benzene, 25.3 g of O -(2 - nitrophenyl) - O - ethyl - N isopropylphosphoroamidothi@ate were obtained.
The active compounds used according to the present invention can be converted into the usual
formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be
produced in known manner, for example by mixing the active compounds with extenders, that is, liquid
or solid diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents
and/or dispersing agents. In the case cf the use of water as an extender, organic solvents can, for
example, also be used as auxiliary sclvents.
As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylene or
benzene, chlorinated aromatic hydrocarbons, such as chlorbenzenes, paraffins, such as mineral oil
fractions, alcohols, such as methanol or butanol, or strongly polar solvents, such asmethyl formamide
or dimethylsulphoxide, as well as water.
As solid diluents or carriers, there are preferably used ground natural minerals, such as kao!ins, clays,
talc, chalk or montmorillonite, or ground synthetic minerals, such as highly-dispersed,ilicic acid or
silicates.
Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such
aspolyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example
alkylarylpolyglyccl ethers, alkyl sulphonates and aryl sulphonates; and preferred examples of
dispersing agents include lignin, sulphite waste liquors and methyl cellulose.
The compounds can be applied in admixture with such adjuvants generally used for agricultural
chemicals as spreaders, emulsifiers, wetting agents, adhesive agents, etc. Further, they can be applied
in admixture with other herbicides, for example phenoxy compounds, chlorophenol compounds,
carbamate compounds, diphenyl ether compounds, urea compounds or triazine compounds, and also
172/612
with plant growth regulators, insecticides, acaricides, hematocides, fungicides and other agricultural
chemicals and fertilizers. Mixed application especially with phenoxy herbicides, for example esters of
MCPA(2 - methyl - 4chlorophenoxy acetic acid), is effective and gives rise to synergistic effects.
Herbicidal compositions containing the active compound of the formula (I) are illustrated in
thefollowing Examplcs 2-6, in which parts and percentages are by weight.
EXAMPLE 2
5% or the compound or the rormula (I) and95% of a mixture of talc and clay were formu @@@
@@@@ @@@@@@ @@@ @@@@@@@@@ @@@ @@@@@@@ @@@ lated into a dust
by mixing and crushing, and used by dusting as such.
EXAMPLE 3
20% of thecompound of the formula (I),75% of a mixture ofZeeklite (a mixturecf 1pin by weight of
talc and 3 parts by weight of kaolin) and clay,3% of sodium alkylbenzene sulphonic acid and2% of
sodium dinaphthyl-merhane disulphonic acid are formulated into a wettable powder by mixing and
crushing and applied diluted with water.
EXAMPLE 4
20% of the compound of the formula (I),75 /O of xylol and5% of apolyoxyethylene alkyl aryl
ether"Sorpcl" (trade name orTcho
Kakaku Kogyo (K.K.) are formulated into an emulsifiable concentrate by mixing and stirring, and
applied diluted with water.
EXAMPLE 5
Thecompound cf theformula (I) is dissolved in xylol while heating. The solution is sprayed onto clay
granules while rotating and mixing so that about 10% of active ingredientis incorporated in the
granules. The granular formulation is used by scattering as such cn the surface of soil.
EXAMPLE 6
Three parts of the compound of rhe formula (1), 1.5 parts of ethyl ester of MCPA (2methyl - 4 chlorophenoxy acetic acid), and 95.5 parts of bentonite are mixed well. The mixture containing 10%cf
water is granulated. It is applied to the soil surface of paddy fields.
The compositions of the present invention generally contain0.1-95% by weight, preferably0.5.-90%
by weight, of active compound.
The application may be carried out byordinary methods, for example watering, spraying, atomizing,
dusting or scattering.
The most suitable application time is before the germination of the weeds to be eradicated.
When application is carried out mainly before the germination of cultivated plants, the general
conditions of cultivation arenct so important, tut the quantity per unit area of active compound to be
applied and the appli- cation method are important.
The quantities of the active compound to be used according to this invention may varywithin a fairly
wide range. They depend upon various factors, for example the conditions of cultivation, soil, weeds
and weather as well as the purpose of application. The compound of the present invention tends to
show nonselective herbicidalacticn when used in an amount of more than 500 g per 10 a. in paddy
fields or dry fields, but tends to show selective herbicidal action when used in smaller amounts.
Thus, this invention provides crops protested from damage by weeds by being grown in areas in
which, immediately prior to and/or during the time of the growing, the compound of the formula (I)
was applied alone or in admixture with à solid or liquid diluent or carrier.
The outstanding herbicidal action of thecompound of the present invention as well as its superiority as
a herbicide to the previously knowncompounds is clearly shown by thefollowing Examples A and B.
173/612
EXAMPLE A.
Test against weeds inpaddy fields
Test method:
After filling upl pats of1/5,000 a. with soil of paddy field, paddy riceseedlings (Kinmaze variety) at
the 3 to 4 leaves stage were transplanted under inundationconditions. After the seedings were rooted,
barnyardgrass, seeds of broad-leaved weeds and spikerush wereplanted The compoundcb the formula
(I) and certain comparison compounds formulated into emulsifiable concentrate or wettable powder
were sprayed in amountsof 500, 250 and 125 g as active ingredients per 10a.After three weeks, the
herbicidal effect against barnyardgrass, spikerush and broad-leaved weeds and the phytotoxicity to
thepaddy rice were investigated. The results are in Table A.
Valuation: Herbicidal efficacy Phytotoxicity
5 highest efficacy 5 highest phytotoxicity
4 big efficacy 4 big phytotoxicity
3 medium efficacy 3medium-big phytotoxicity
2 small efficacy 2 medium phytotoxicity
1 slightest efficacy 1 small phytotoxicity
O noefficacy 0 no phytotoxicity
TABLE A
Herbicidal efficacy against weeds of paddy fields and phytotoxicity to rice
Quantity Herbicidal effect Phytotoxicity
of active
ingredients barnyard broad-leaved
Compound g/10 a grass spikerush weeds rice
Compound of the 500 5 5 5 0 formula (I)
250 5 5 5 0
125 54-5 5 0
A 500 5 4 4 0 (Comparison)
250 4 3 3 0
125 2 1 2-1 0
PCP (Commercial 500 5 3 5 0 product;
Comparison) 250 3 0 2 0
125 1 0 0 0
NIP (Commercial 500 5 5 5 3 product;
Comparison) 250 5 5 5 1
125 3 1 2 0
Non-treatment - 0 0 0 0
Notes: 1)@road-leaved weeds are: Monochomiavaginalis@ @@tala indica@ Lindernia@@@idaria.
D@@@@@@um
junceum, etc
2) PCP: pentachlorophenol (Commercial product).
3) NIP:2,4-dichlorophenyl-4 '-nitrophenyl ether (Commercial product).
4) A: O-(2-nitrophenyl)-O-methyl-N-isopropylphosphoroamidothioate.
EXAMPLE B.
Test against weeds of upland fields
Test method:
After filling up pots of 30 x 30em with soil of diluviul-volcanic ashes, seeds of the undermentioned
weeds, upland rice (Hataminori variety) and vegetarbles were sown.
After covering with soil, the compound of the formula (I) and comparison compounds in
theformulation of the emulsifiable concentrate or wettable powder were sprayed on the surface of soil
in amounts of 400, 200 and 100 g of active ingredient per 10 a. After 3 weeks,herbiçidal efficacy
against all the kinds of weeds and phytotoxicity to upland rice and various vegetables were
investigated. The results are in Table B.
174/612
Valutttion: Herbicidalefficacy Phytotoxicity
5 highest efficacy 5 highest phytotoxicity
4 big efficacy 4 big phytotoxicity
3 medium efficacy 3medliumXbig phytotoxicity
2 small efficacy 2 medium phytotoxicity
1 slightest efficacy 1 small phytotoxicity
0 no efficacy 0 no phytotoxicity TABLE B
Test results of herbicidal efficacy against weeds of upland fields and phytoxicity of various crops
Herbicidal efficacy Phytotoxicity
Quantity of a.i. barnyard- finger- dent wild common upland Japanese
Compound g/10 a grass grass foxtail amaranth purslane rice raddish Cucumber tomato carrot
Compound of the 400 5 5 5 5 5 0 0 1 0 0 formula (I) 200 5 5 5 5 5 0 0 0 0 0
100 5 4-5 4-5 5 5 0 0 0 0 0
B 400 5 5 5 1 2 0 0 1 0 0 (Comparison) 200 4-5 4 4 0 0 0 0 0 0 0
100 3 3 3 0 0 0 0 0 0 0
CAT (Commercial 100 5 5 5 5 5 2 3 2 2 2 product; 50 4 4 5 5 5 0 1 1 1 1
Comparison)
NIP (Commercial 400 5 5 5 5 5 3 1 5 5 5 product; 200 5 5 4 5 5 0 0 2 2 3
Comparison)
Non-treatment - 0 0 0 0 0 0 0 0 0 0
Notes: 1) CAT: 2-chloro-4,6-bis (ethylamino)-1,3,5-triazine
2) B: O-(2,4-dichlorophenyl)-O-methyl-N-iso-propylphosphoroamidothioate>;/RTI;Data supplied
from the esp@cenet database - Worldwide
Claims:
Claims of GB1249607
WHAT WE CLAIMIS:1. A method of combating weeds which comprisesapplying to the weeds or ahabitat thereof the
compound of the formula
EMI6.1
(I) alone or in admixture with a solid or liquid diluent or carrier.
2. A method according to claim 1 tin which the active compound is applied to an area of crop
cultivation.
3. A method according to claim 2 in which the active compound is applied to an area of rice
cultivation.
4. A method according to any of claims 1-3 in which the weeds are any of those hereinbefcre
mentioned.
5. A method according to any of claims 1-4 in which the active compound is applied before
germination of the weeds.
6. A method according to any of claims 1-5 in which the active compound is applied in an amount of
less than 500 g. per 100 ares.
7. A method according to any of claims 1-6 in which the activecompound is applied in the form of a
compositionccntaining 0.1 to95% of the active compound, by weight.
8. Crops protected from damage by weeds by being grown in areas in which, immediately prior to or
during the time of grcwing, the compound defined in claim 1 wasapt vied aloneo in admixture with a
solid or liquid diluent or carrier.Data supplied from the esp@cenet database - Worldwide
175/612
14. GB1270419
- 4/12/1972
PROCESS FOR COMBATING INSECTS IN TEA AND RICE CULTURES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1270419
Inventor(s):
HELFENBERGER HANS (--); LUTZ KARL (--)
Applicant(s):
SANDOZ LTD (CH)
E Class: A01N57/16; C07F9/6509B4V
Application Number:
GB19690034926 (19690711)
Priority Number: CH19680011551 (19680801)
Family: GB1270419
Equivalent:
CH506244
Abstract:
Abstract of GB1270419
1,270,419. Combating insects with a thiono- phosphoric acid ester. SANDOZ Ltd. 11 July, 1969 [1
Aug., 1968], No. 34926/69. Heading A5E. [Also in Division C2] A process for combating insects in a
tea or rice culture comprises applying O,O-diethyl- thionophosphoric acid O-[quinoxalyl-(2)] ester to a
tea or rice culture.Description:
Description of GB1270419
(54) PROCESS FOR COMBATING TNSTS IN ThA A RICE
CULTURES
(71) We, SANDOZ LTD., of 35 Lichtstrasse, 4000 Basle, Switzerland, a Swiss Body
Corporate, do hereby declare the invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly described in and by the
followingstatement:
The present invention relates to the control of destructive insects in tea and rice cultures.
It is known that the insect Ectropis bhurmitra, and the insects Chilo suppressalis, Tryporyza incertulas,
Tryporyzainnotata, Chilotiara potychrysa and Sesamia inferens cause considerable damage in tea and
rice cultures respectively. Furthermore, it is known that that group of insects known as stem borers are
a particular nuisance in rice cultivation.
According to our invention we provide a process for combating insects in a tea or rice culture which
comprises applying O.O-diethylthionophosphoric acidO- [quinoxalyl-(2)] ester of formula I,
EMI1.1
to a tea or rice culture.
TheO,O,-diethyl-thionophosphoric add 0 [quinoxalyl-(2)] ester may be present in the tea or rice
culture in a manner conventional for the application of other insecticides to such cultures. Thus for
example the compound may be applied to the culture on its own or preferably in combination with an
agriculturally acceptable diluent or carrier. Suitably the compound may be applied in the form of a
dusting or spraying agent, e.g. as a solution or dispersion in water or a suitable organic solvent, e.g.
alcohol, petroleum, tar distillates etc., and preferably in combination with an emulsifying agent, e.g. a
liquid polyglycol ether derived from a high molecular weight alcohol, mercaptan or alkylphenol and an
alkylene oxide.Suitable organic solvents, e.g. ketones, aromatic, optionally halogenated hydrocarbons,
mineral oils etc., may also be added to the mixture as solution aids.
176/612
The spraying and dusting agents may contain the usual inert carrier materials, e.g. talc, diatomaceous
earth, bentonite, pumice, cellulose derivatives and the like, and the usual adhesives and wetting agents
to improve adhesiveness and wettability.
The O,O-diethyl-thionophosphoric acid 0 [quinoxalyl-(2)] ester may be present in the formulations as
a mixture with other known active agents. Formulations suitable for use in the application of a
compound of formula I to a locus generally contain between 0.01 and 95 percent, and preferably
between 0.5 and 90% by weight of active agent.
The compound of formula I may be applied to the rice culture at a dose of from 0.25 to 1 kg and
preferably from 0.5 to 0.75 kg per hectare. For the treatment of rice the compound of formula I may
also be applied by addition to the paddy water or by soaking seedlings in a composition containing the
compound of formula I.
The compound of formula I used as active agent in the process of our invention may be made by
reacting 2-hydroxy quinoxaline, or a derivative thereof in which the hydrogen of the hydroxy group is
replaced by another cation, with anO,O-diethyl thionophosphoryl halide, with the proviso that when 2hydroxy quinoxaline is used the reaction is effected inthe presence of an acid-binding agent.
The process is preferably carried out in thepresence of a solvent or diluent at a temperature of
between 20 and 1200 and preferably
between 40 and800 C. TheO,O-diethyl thionophosphoryl halide is preferably a
chloride or bromide.
The invention is illustrated, but in no waylimited by the following Examples. Where
concentrations are expressed as percentages,these are percentages by weight
EXAMPLE 1
Activity against Ectropisbhurmitra in tea
Tea bushes were sprayed with an aqueous composition made by diluting commercially available
emulsion concentrates of the comparison compounds and concentrate comprising25% ofO,O-diethylthionophosphoric acid 0 [quinoxalyl >; 2)1 ester,25% ofisooctyiphenyl decaglycol ether and 50%
acetone with water.
The concentration of active agent and the numher of Ectropis bhurmitra caterpillars after 1 and 2 weeks
are shown in the following Table 1.
TABLE 1
EMI2.1
>;tb; >;SEP; Number >;SEP; of >;SEP; caterpillars
>;tb; >;SEP; in >;SEP; 10 >;SEP; bushes >;SEP;
>;tb; >;SEP; Concentration >;SEP; 1 >;SEP; week >;SEP; 2 >;SEP; weeks
>;tb; >;SEP; Active >;SEP; agent >;SEP; % >;SEP; after >;SEP; treatment
>;tb; >;SEP; O.O-diethyl-thionosphoric >;SEP; acid >;SEP; 0
>;tb; >;SEP; [qtiinoxalyl-(2)Jester >;SEP; 0.05 >;SEP; 129 >;SEP; 98
>;tb; >;SEP; O.O-dimethyl-O-(-methyl-Pnitro- >;SEP;
>;tb; phegylythionophosphate >;SEP; 0.1 >;SEP; 1627 >;SEP; 1303
>;tb; O.O-dimethyl-0-(3-methylffillitro- >;SEP;
>;tb; >;SEP; phenyi)-t1aonophosphate >;SEP; 0.2 >;SEP; 794 >;SEP; 1216
>;tb; >;SEP; untreated >;SEP; ~ >;SEP; 2481 >;SEP; 1600
>;tb; >;SEP; o >;SEP; .>;SEP; O-dimethyl-0-(2.2-dichloro-vinyl)- >;SEP;
>;tb; >;SEP; phosphate >;SEP; 0.05 >;SEP; 719 >;SEP; 592
>;tb; >;SEP; QO-dimethy1-0-(4-methyl-mercapto-3- >;SEP;
>;tb; - >;SEP; me(ilylphenyl)-itionophosphate >;SEP; 0.1 >;SEP; 1123 >;SEP; 642
>;tb; Endlin >;SEP; (i.e. >;SEP; 1t2,3,4,10,10-Hexschloro- >;SEP; 0.01 >;SEP; 677 >;SEP; 551
>;tb; >;SEP; 6ss7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-1,4* >;SEP;
>;tb; >;SEP; eadoendo-5,8-dimethanonaphthalenc) >;SEP;
177/612
>;tb;
EXAMPLE 2
Activity in rice
.Comparable plots of rice were sprayed with sors maSde;as in Example 1 and containing 0.05% of
active agent. In Table 2 the crop in kg per hectare is given as an indication of the insecticidal effect.
TABLE 2
EMI3.1
>;tb; >;SEP; Crop
>;tb; >;SEP; Active >;SEP; agent >;SEP; kg/ha
>;tb; O.O-diethyl-thionophosphoric >;SEP; acid-O
>;tb;[quinoxalyl >; 2)] >;SEP; ester >;SEP; 5429
>;tb;O.O-dimethyl-O-(4-metJlylmercapto-3-meth >;SEP;
>;tb; phenyl)-thionophosphate >;SEP; 4740
>;tb; O. >;SEP; O-dimethyl-0-(3-methylinitrophenyl)- >;SEP;
>;tb; thionophosphate >;SEP; 4573
>;tb;O.O-dimethyl-S-(l.>;SEP; 2-dicarbethoxy-ethyl)- >;SEP;
>;tb; dithiophosphate >;SEP; 3846
>;tb; Untreated >;SEP; 2834
>;tb;
Production of >;RTI O,O-diethyl thionophosphoric
acid 0- [quinoxalyl-(2)] ester
29.2 g of2-hydroxy-quinoxaline are suspended in 200 ml of methanol, a solution of 4.6 g of sodium in
100 ml of methanol is added and the resulting solution is evaporated to dryness in a vacuum the
resulting sodium salt is suspended in 700 ml of methylisobutyl ketone and 39.3 g of 0.0diethyl thionophosphoryl choride are subsequently added to the suspension while stirring. The reaction mixture
is subsequently heated to 600C and stirred at this temperature for 15 hours. The mixture is
subsequently cooled, filtered, the filtrate is washed several times with water, dried and concentrated by
evaporation.The oily residue is taken up in 150 ml of xylene, the solution is filtered, shaken with an
ice-cold 1 N solution of sodium hydroxide and subsequently washed with water until neutral. After
drying with sodium sulph te, the solution is concentrated by evapora
tion. O.O-diethyl-thionophosphoric acid 0
[quinoxalyl-(2)] ester has a boiling point of 1420C at a pressure of3.104 mm of Hg.
WHAT WE CLAIM IS:
1. A proces for combating insects in a tea or rice culture, which comprises applying 0,0diethylthionophosphoric acid 0- quinoxalyl- (2)] ester to a tea or rice culture.
2. A process as claimed in Claim 1, wherein the O,O-diethyl-thionophosphoric acid 0
[quinoxalyl-(2)] ester is applied in combination with an agriculturally acceptable diluent or carrier.
3. A process as claimed in Claim 1 or Claim 2, wherein the 0,O-diethyl-thionophosphoric acidO[quinoxalyl-(25] ester is applied in the form of a spraying agent.
4. A process as claimed in Claim 1 or Claim 2, wherein the O,O-diethyl-thionophosphoric acidO[quinoxatyl-(2)] ester is applied in the form of a dusting agent
5. A process as claimed in any of thepre- ceding claims, wherein theO,O-diethyl-thiono- phosphoric
acid 0- [quinoxalyl-(2)] ester is applied as a formulation containing between 0.01 and95% by weight
of O,O-diethylthionophosphoric acidO-[quinoxalyl-(2)]- ester.
6. A process as claimed in Claim 5, wherein theO,O-diethylthionophosphoric acid 0 [quinoxalyl-(2)]
ester is applied as a formulation containing between 0.5 and90% by weight ofO,O-diethylthionophosphoric acidO-[quinoxalyl-(2)] ester.
7. A process as claimed in any of thepre- ceding claims, wherein the culture is a tea culture.
8. A process as claimed in any one of Claims 1 to 6, wherein the culture is a rice culture.
178/612
9. A process as claimed in Claim 8, wherein theO,O-diethyl-thionophosphoric acid 0 [quinoxalyl-(2)]
ester is applied at a dosage of from 0.25 to 1 kg per hectare.
10. A process as claimed in either of Claims 8 or 9, which comprises controlling stem borers in a rice
culture.
11. A process as claimed in any of Claims 8 to 10, which comprises controllingChilo suppressalis,
Tryporyzaincertulas, Tryporyzainnotsta, Chilotraeapolychrysa orSesamia inferens in a rice culture.
12. A process as claimed in Claim 7, which comprises controlling Extropisbhurmitra in a tea culture.
13. A process as claimed in any one of
Claims 8 to 11, wherein the O,O-diethyl
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB1270419
**WARNING** start of CLMS field may overlap end of DESC **.
TABLE 2
EMI3.1
>;tb; >;SEP; Crop
>;tb; >;SEP; Active >;SEP; agent >;SEP; kg/ha
>;tb; O.O-diethyl-thionophosphoric >;SEP; acid-O
>;tb;[quinoxalyl >; 2)] >;SEP; ester >;SEP; 5429
>;tb;O.O-dimethyl-O-(4-metJlylmercapto-3-meth >;SEP;
>;tb; phenyl)-thionophosphate >;SEP; 4740
>;tb; O. >;SEP; O-dimethyl-0-(3-methylinitrophenyl)- >;SEP;
>;tb; thionophosphate >;SEP; 4573
>;tb;O.O-dimethyl-S-(l.>;SEP; 2-dicarbethoxy-ethyl)- >;SEP;
>;tb; dithiophosphate >;SEP; 3846
>;tb; Untreated >;SEP; 2834
>;tb;
Production of >;RTI O,O-diethyl thionophosphoric
acid 0- [quinoxalyl-(2)] ester
29.2 g of2-hydroxy-quinoxaline are suspended in 200 ml of methanol, a solution of 4.6 g of sodium in
100 ml of methanol is added and the resulting solution is evaporated to dryness in a vacuum the
resulting sodium salt is suspended in 700 ml of methylisobutyl ketone and 39.3 g of 0.0diethyl thionophosphoryl choride are subsequently added to the suspension while stirring. The reaction mixture
is subsequently heated to 600C and stirred at this temperature for 15 hours. The mixture is
subsequently cooled, filtered, the filtrate is washed several times with water, dried and concentrated by
evaporation.The oily residue is taken up in 150 ml of xylene, the solution is filtered, shaken with an
ice-cold 1 N solution of sodium hydroxide and subsequently washed with water until neutral. After
drying with sodium sulph te, the solution is concentrated by evapora
tion. O.O-diethyl-thionophosphoric acid 0
[quinoxalyl-(2)] ester has a boiling point of 1420C at a pressure of3.104 mm of Hg.
WHAT WE CLAIM IS:
1. A proces for combating insects in a tea or rice culture, which comprises applying 0,0diethylthionophosphoric acid 0- quinoxalyl- (2)] ester to a tea or rice culture.
2. A process as claimed in Claim 1, wherein the O,O-diethyl-thionophosphoric acid 0
179/612
[quinoxalyl-(2)] ester is applied in combination with an agriculturally acceptable diluent or carrier.
3. A process as claimed in Claim 1 or Claim 2, wherein the 0,O-diethyl-thionophosphoric acidO[quinoxalyl-(25] ester is applied in the form of a spraying agent.
4. A process as claimed in Claim 1 or Claim 2, wherein the O,O-diethyl-thionophosphoric acidO[quinoxatyl-(2)] ester is applied in the form of a dusting agent
5. A process as claimed in any of thepre- ceding claims, wherein theO,O-diethyl-thiono- phosphoric
acid 0- [quinoxalyl-(2)] ester is applied as a formulation containing between 0.01 and95% by weight
of O,O-diethylthionophosphoric acidO-[quinoxalyl-(2)]- ester.
6. A process as claimed in Claim 5, wherein theO,O-diethylthionophosphoric acid 0 [quinoxalyl-(2)]
ester is applied as a formulation containing between 0.5 and90% by weight ofO,O-diethylthionophosphoric acidO-[quinoxalyl-(2)] ester.
7. A process as claimed in any of thepre- ceding claims, wherein the culture is a tea culture.
8. A process as claimed in any one of Claims 1 to 6, wherein the culture is a rice culture.
9. A process as claimed in Claim 8, wherein theO,O-diethyl-thionophosphoric acid 0 [quinoxalyl-(2)]
ester is applied at a dosage of from 0.25 to 1 kg per hectare.
10. A process as claimed in either of Claims 8 or 9, which comprises controlling stem borers in a rice
culture.
11. A process as claimed in any of Claims 8 to 10, which comprises controllingChilo suppressalis,
Tryporyzaincertulas, Tryporyzainnotsta, Chilotraeapolychrysa orSesamia inferens in a rice culture.
12. A process as claimed in Claim 7, which comprises controlling Extropisbhurmitra in a tea culture.
13. A process as claimed in any one of
Claims 8 to 11, wherein the O,O-diethyl
thionophosphoric acid 0-[quinoxalyl-(2)J ester is added to the paddy water.
14. A process as claimed in Claim 1 and substantially as hereinbefore described in either of Examples
1 or 2.Data supplied from the esp@cenet database - Worldwide
180/612
15. GB1402296
- 8/6/1975
FUNGICIDE FOR PLANT PROTECTION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB1402296
Applicant(s):
BASF AG (--)
IP Class 4 Digits: C07F; A01N
IP Class:A01N9/36; C07F9/24
E Class: C07F9/24
Application Number:
GB19720050290 (19721101)
Priority Number: DE19712154371 (19711102)
Family: GB1402296
Equivalent:
JP48056830; DE2154371
Abstract:
Abstract of GB1402296
1402296 Fungicidal application of Dithio- phosphoramide esters BADISCHE ANILIN- & SODAFABRIK AG 1 Nov 1972 [2 Nov 1971] 50290/72 Heading A5E [Also in Division C2] Fungicidal
processes and compositions util- ise as active ingredients a fungitoxic amount of a
dithiophosphoramide ester of the formula: where R>;SP;1>;/SP; and R>;SP;2>;/SP;, independently of
one an- other, each denote alkyl of 1 to 4 carbon atoms or, together, denote ethylene; R>;SP;3>;/SP;
and R>;SP;4>;/SP; each independently denote alkyl of 1 to 12 carbon atoms, cycloalkyl, methylsubstituted cyclo- alkyl, alkoxyalkyl, benzyl, phenyl. chloro-sub- stituted phenyl, carbamoyloxysubstituted phenyl, #-morpholinoethyl or R>;SP;3>;/SP; alternatively denoting hydrogen and/or
R>;SP;4>;/SP; denoting di- methylamino; or NR>;SP;3>;/SP;R>;SP;4>;/SP; denotes an unsubsti- tuted
or alkyl-substituted saturated mono- cyclic heterocyclic radical with a 5- or 6- membered ring. The
dithiophosphoramide esters find application in the treatment of cereals (rice, barley, oats, corn) and
bananas.Description:
Description of GB1402296
(54) FUNGICIDE FOR PLANT PROTECTION
(71) We, BADISCHE ANILIN- & SODA-FABRIK AKTIENGESELL
SCHAFT, aGerman Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do
hereby declare the invention, for which we pray that a patent may be granted to us, and the method by
which it is to be performed, to be particularly described in and by the followingstatement:
The present invention relates to fungicides for protecting plants and containingS,S-diesters of Nsubstituted phosphoramidodithioic acid S,S-dialkylamidodithiophosphates, a process for producing
these compounds and their use asfungicides.
Some of these esters have been proposed for use as defoliants, desiccants, insecticides and acaricides.
We have now found that S,S-diesters of N-substituted phosphoramidodithioic acid of the formula
EMI1.1
where R1 and R2, independently of one another, each denote alkyl of 1 to 4 carbon atoms (e.g. methyl,
ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl), or together, denote ethylene or, R3 and R4,
independently of one another, each denote alkyl of 1 to 12 carbon atoms; cycloalkyl (cyclopentyl,
cyclohexyl,cyclooctyl); cycloalkyl substituted by methyl; alkoxyalkyl; benzyl; phenyl; chloro-
181/612
substituted phenyl; phenyl substituted bycarbamoyloxy;fi-morpholinoethyl; orR3 may further denote
hydrogen, and/or R4 may denote dimethylamino, orR and R4 together with the nitrogen atom whose
substituents they are denote an unsubstituted or alkyl-substitutedmonocydic saturated (i.e. multiple
bond-free) heterocyclic radical with a 5- or 6-membered ring (e.g.morpholine, thiomorpholine,
pyrrolidine or piperidine), have a strong fungicidal action on fungus pathogens in monocotyledons,
such as cereals (e.g. barley, oats,
Indian corn, and especially rice) or bananas for instance on the fungus Piricularia oryzae.
PreferablyRs and R4 each independently denote a saturated hydrocarbon radical of not more than 12
carbon atoms optionally substituted by an alkoxy radical of 1 to 4 carbon atoms, or R4 denotes such a
radical, andR denotes hydrogen; orRa and R4 each independently denote a benzyl or phenyl radical or
a phenyl radical substituted oby 1 to 3 chlorine atoms and/or by a carbamoyloxy group, orNR3Rf
denotes an unsubstituted oralkyl-substituted piperazine group, orN (nCsH7)2.
In a useful class of compoundsRD, R2, R3 and R4 all denote hydrocarbon radicals orR3. and/orRu
may denote chlorophenyl radicals.
The compounds to be used according to the invention may readily be prepared by reacting a compound
of the formula
EMI1.2
5 10 15 20 25 30 35 whereRl and R2 have the above meanings and X denotes halogen, preferably
chlorine with an amine of the formula
EMI2.1
whereR andR' have the above meanings, preferably in the presence of a solvent, advantageously for
instance benzene or toluene, at from10 to110 C.
Without isolating theS,S-dialkylphosphorous amide, oxidation to the fungicidal
phosphoramidodithioic derivatives is then effected with an oxidant, advantageously with an aqueous
solution ofH,O,. The reaction steps are illustrated by the following scheme:
EMI2.2
The S,S-dialkylphosphorous chlorides used as starting materials are known from the literature and may
be prepared with facility (cf. Touben-Weyl, Methoden der organischen Chemie, 12/2, p 91).
The amines employed are also known and may be easily produced in substantial amounts. Generally,
the amines are used in such amounts that there are approximately two molar equivalents of the amine to
one molar equivalent of the S,S-dialkylphosphorus chloride. In the case of amines which due to their
low basicity only react sluggishly or are not easily accessible, one molar equivalent of the amine may
be replaced by triethylamine or a similar tertiary amine, e.g., pyridine, asacid-binding agent. One mole
of amine may therefore be replaced by one mole of a conventional agent which binds hydrogen
chloride.
The reaction may be carried out for instance by dripping the amine into a solution of S,Sdialkylphosphorous chloride at30 to60 C, and then stirring the reaction mixture at 10 to110 C,
preferably for example in boiling benzene at70"C, until no more amine hydrochloride separates out.
The precipitated amine hydrochloride may be suction filtered after cooling to25 C and the filtrate
oxidized, or the whole reaction mixture is reacted withH2O--.
Advantageously, oxidation in accordance with equation 2 is carried out by allowing30,b (by
weight)H,O to drip at105 to40 C into the solution ofS,S-dialkyl- phosphorous amide (with or without
amine hydrochloride) in benzene or toluene with vigorous stirring and external cooling, and
subsequently boiling for instance the benzolic solution for 1 to 4 hours under reflux to complete the
reaction.Working up is then effected by washing the organic phase, after cooling, with aqueous3% (by
weight)NaHCO solution (possibly after suction filtering the amine hydrochloride), drying overNa SOl,
and removing the solvent in vacuo atSOD to60"C by direct distillation.
The compounds are obtained in very pure form, and are mainly pale yellow to orange colored oils, or
crystalline compounds which need no further purification.
182/612
The active ingredients have a low toxcity to warmbloods and a strong fungicidal action on fungi in
monocotyledons, e.g., on Erisyphe graminis in cereals (e.g. barley and oats), Helminthosporium sp. in
barley and oats, Piricularia grisea in bananas, and
Pellicularia sasakii and Piriculariaorvzae in rice.
The plants to be protected against fungus attack are treated, e.g., sprayed or dusted, with the active
ingredient. It is also possible to treat the seed or seedlings with the active ingredient before sowing or
planting. The active ingredients are used in fungicidal amounts.
The preparation of the active ingredients is illustrated by the following example.
EXAMPLE 1
Preparation ofS,S-diisopropyl N-isopropylphosphoramidodithioatephosphate
21.7 parts by weight of S,S-diisopropylphosphorous chloride is dissolved in 100 parts by weight of
benzene. While stirring, a solution of 11.6 parts by weight of isopropylamine in 50 parts by weight of
benzene is dripped in, and the mixture is then boiled under reflux for 2 hours. After cooling, the
hydrochloride which has separated out is suction filtered. Slowly and with ice cooling, 11.5 parts by
weight of30% (by weight)H200 is added to the filtrate. Subsequently the mixture is heated under
reflux for 30 minutes with vigorous stirring. After cooling, the mixture is washed with aqueous3% (by
weight) NaHCO3 solution and dried over Na2SO1.The solvent is then evapor
ated in vacuo and the residue kept for 1 hour under an oil pump vacuum at a bath temperature of60 C.
A crystalline substance remains. The yield is 19 parts by weight (75%); melting point:63 to 65 C.
Analysis:
Calc.: C 42.4 H 8.6 N 5.5 0 6.3 P 12.1 S25,2
Found: C 43.0 H 8.6 N 5.0 P 12.1 S 25.8
The following compounds may be prepared analogously:
EMI3.1
EMI3.2
>;tb; Active
>;tb; 25
>;tb; Active >;SEP; 1 >;SEP; R2 >;SEP; R3 >;SEP; R4
>;tb; dient
>;tb; No.
>;tb;
1 >;SEP; C2H5 >;SEP; 02H5 >;SEP; H >;SEP; CH3 >;SEP; 1.5548
>;tb; 2 >;SEP; 02H5 >;SEP; 02H5 >;SEP; H >;SEP; n-C3H7 >;SEP; 1.5403
>;tb; 3 >;SEP; 02H5 >;SEP; 02H5 >;SEP; H >;SEP; i-03H7 >;SEP; 1.5385
>;tb; 4 >;SEP; 02H5 >;SEP; C2H5 >;SEP; H >;SEP; -C2H4-OC2H5 >;SEP; 1.5282
>;tb; 5 >;SEP; C2H5 >;SEP; C2H5 >;SEP; t >;SEP; 1.5461
>;tb; 6 >;SEP; C2H5 >;SEP; C2H5 >;SEP; H
>;tb; 7 >;SEP; 02H5 >;SEP; C2H5 >;SEP; H >;SEP; CH3 >;SEP; 1.5338
>;tb; 8 >;SEP; C2H5 >;SEP; C2H5 >;SEP; H >;SEP; 10 >;SEP; 1.5409
>;tb; 9 >;SEP; 02H5 >;SEP; C2H5 >;SEP; C2H5 >;SEP; n-C4H9 >;SEP; 1.5108
>;tb; 10 >;SEP; 02H5 >;SEP; C2H5 >;SEP; i-C3H7 >;SEP; n-C4H9 >;SEP; 1.5191
>;tb; 11 >;SEP; C2H5 >;SEP; C2HT >;SEP; i-C3H7, >;SEP; 1.5312
>;tb; 12 >;SEP; C2H5 >;SEP; 02H5 >;SEP; 5 >;SEP; 11 >;SEP; n-C5H11 >;SEP; 1.5017
>;tb; 13 >;SEP; C2H5 >;SEP; C2H5 >;SEP; -C2H40-CH3 >;SEP; -C2H40-CH3 >;SEP; 1.5218
>;tb;
EMI4.1
>;tb; Active
>;tb; ingre- >;SEP; R1 >;SEP; R5 >;SEP; R4 >;SEP; n25
183/612
>;tb; dient >;SEP; D
>;tb; No.
>;tb; 14 >;SEP; C2H5 >;SEP; C2H5 >;SEP; -CH2 >;SEP; t >;SEP; -CH2 >;SEP; O >;SEP; 1.5891
>;tb; 15 >;SEP; C2H5 >;SEP; i >;SEP; -CH7 >;SEP; H >;SEP; i-05H7 >;SEP; 1.5239
>;tb; 16 >;SEP; C2H5 >;SEP; i-C3H7 >;SEP; i-^3H7 >;SEP; 3"7 >;SEP; 1.5148
>;tb; 17 >;SEP; C2H5 >;SEP; i-C3H7 >;SEP; 3 >;SEP; 7 >;SEP; 3 >;SEP; 7 >;SEP; 1.5109
>;tb; 18 >;SEP; C2H5 >;SEP; i-C3H7 >;SEP; H
>;tb; 19 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; CH3 >;SEP; 1.5439
>;tb; 20 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; -CH2-CH2-OC3H7 >;SEP; 1.5244
>;tb; 21 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; -C2H4-O-C2H5 >;SEP; 1.5164
>;tb; 22 >;SEP; n-C3H7 >;SEP; n-C >;SEP; H >;SEP; H >;SEP; n-CAHg >;SEP; 1.5204
>;tb; >;SEP; 37 >;SEP; 37
>;tb; 23 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; ) >;SEP; 1.5305
>;tb; 24 >;SEP; n-C3H7 >;SEP; n-G3H7 >;SEP; H >;SEP; "-H7 >;SEP; 1.53,3
>;tb; 25 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; i-03H7 >;SEP; 1.5298
>;tb; 26 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; -C12H25 >;SEP; 1.4865
>;tb; 27 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; 0-C-NH2 >;SEP; 1.5442
>;tb; 28 >;SEP; n'C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; t >;SEP; C1 >;SEP; 1.5783
>;tb; >;SEP; Cl
>;tb; 29 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; H >;SEP; 5 >;SEP; Cl >;SEP; 1.5740
>;tb; 30 >;SEP; 3 >;SEP; 7 >;SEP; n-C3H7 >;SEP; C1
>;tb; 31 >;SEP; n-C >;SEP; H >;SEP; n-C >;SEP; H >;SEP; H >;SEP; C2H5 >;SEP; 1.5390
>;tb; >;SEP; 37 >;SEP; 37
>;tb; 32 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; 0 >;SEP; 1.5402
>;tb; 33 >;SEP; 3 >;SEP; 7 >;SEP; 3 >;SEP; 7 >;SEP; H >;SEP; 1.5742
>;tb; 34 >;SEP; n% >;SEP; n-C3 >;SEP; H7 >;SEP; H >;SEP; -CH2-CH2~ >;SEP; O >;SEP; 1.5338
>;tb; 35 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; CH3 >;SEP; CH3 >;SEP; 1.5245
>;tb;
EMI5.1
>;tb; Active
>;tb; dient >;SEP; R2 >;SEP; R3 >;SEP; R4 >;SEP; 25
>;tb; >;SEP; n; >;SEP; m.p.
>;tb; No.
>;tb; >;SEP; 37 >;SEP; 37 >;SEP; NCH3 >;SEP; 1.5293
>;tb; 36 >;SEP; n-C >;SEP; H >;SEP; n-C >;SEP; H >;SEP; H >;SEP; CH3
>;tb; >;SEP; 3
>;tb; 37 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; C2H5 >;SEP; 02H5 >;SEP; 1.5160
>;tb; 38 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; n-C >;SEP; H >;SEP; n-03H7
>;tb; 39 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; 3 >;SEP; 7 >;SEP; 3 >;SEP; 7 >;SEP; 1.5136
>;tb; 40 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; n-C4H9 >;SEP; n-C4H9 >;SEP; 1.5018
>;tb; 41 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; C2H5 >;SEP; n-C4H9 >;SEP; 1.5117
>;tb; 42 >;SEP; n-C3H7 >;SEP; n-C >;SEP; H >;SEP; CH3 >;SEP; 1.5568
>;tb; 43 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; n-C6H13 >;SEP; n-C6H13 >;SEP; 1.4855
>;tb; 44 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; ; >;SEP; 0 >;SEP; 1.5266
>;tb; >;SEP; CH
>;tb; >;SEP; ; >;SEP; CH3 >;SEP; CH;;
>;tb; 45 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; mixture: >;SEP; 5 >;SEP; 3 >;SEP; G~H?
>;tb; >;SEP; H3 >;SEP; CH3
>;tb; >;SEP; 3
>;tb; 46 >;SEP; n-C3H7 >;SEP; n-C3H7 >;SEP; 9 >;SEP; 1.5331
>;tb; 47 >;SEP; i-C3H7 >;SEP; i-C3H7 >;SEP; H >;SEP; n-C >;SEP; H >;SEP; 1.5047
>;tb; >;SEP; 37
>;tb; 48 >;SEP; i-C3H7 >;SEP; i-C3H7 >;SEP; H >;SEP; i-C3H7 >;SEP; 630 >;SEP; to >;SEP; 65 C
>;tb; 49 >;SEP; 3 >;SEP; 7 >;SEP; i-C >;SEP; H >;SEP; H >;SEP; " >;SEP; 70 >;SEP; to >;SEP; 71
>;SEP; C
>;tb; 50 >;SEP; i-C3H7 >;SEP; i-C >;SEP; H >;SEP; H >;SEP; 5 >;SEP; -C2H-0-C2H5 >;SEP; 1.5098
>;tb; 51 >;SEP; i-C3H7 >;SEP; i-C >;SEP; H >;SEP; H >;SEP; 1080 >;SEP; to >;SEP; 11000
184/612
>;tb; >;SEP; 37 >;SEP; 37 >;SEP;
>;tb; 52 >;SEP; i-C3H7 >;SEP; i-C >;SEP; H >;SEP; H >;SEP; 10 >;SEP; 740 >;SEP; to >;SEP; 75"0
>;tb; 53 >;SEP; i-C3H7 >;SEP; i-C3H7 >;SEP; CH3 >;SEP; CH3 >;SEP; 1.5291
>;tb; 54 >;SEP; i-C3H7 >;SEP; i-C3H7 >;SEP; C2H5 >;SEP; 02H5 >;SEP; 1.5075
>;tb; 55 >;SEP; i-C3H7 >;SEP; i-C3H7 >;SEP; n >;SEP; 3 >;SEP; 7 >;SEP; 3 >;SEP; 7 >;SEP; 1.5033
>;tb; 56 >;SEP; i-C3H7 >;SEP; i-C3H7 >;SEP; n-C6H13 >;SEP; n >;SEP; C6H13 >;SEP; 1.4858
>;tb; 56 >;SEP; I-CH7 >;SEP; I-CiH, >;SEP; n-C6H13 >;SEP; n-C6H13 >;SEP; 1.k858
>;tb; 57 >;SEP; i-C3H7 >;SEP; i-C >;SEP; H >;SEP; tmC >;SEP; 1.5272
>;tb; >;SEP; 3 >;SEP; 7 >;SEP; '-i
>;tb;
Active ingredient
No. R' RR R'
EMI6.1
n-C3H, n-C,H
CHr, n-C,H2
The agents according to the invention may be used as solutions, emulsions,stis- pensions or dusts. The
form of application depends entirely on the purpose for which the agents are being used; in any case it
should ensure a fine distribution of the active ingredient.
For the preparation of solutions to be sprayed direct, organic liquids of boiling point higher than150 C,
e.g. hydrocarbons having boiling points higher than1500C, e.g. tetrahydronaphthalene or alkylated
naphthalenes, or organic liquids having boiling points higher than130do and having one or more than
one functional group, e.g. the keto group, the ether group, the ester group or the amide group, this
group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of
a heterocyclic ring, may be used as spray liquids.
Aqueous formulations may be prepared from emulsion concentrates, pastes orwettable powders by
adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be
homogenized in water organic solvents by means of wetting or dispersing agents, e.g., polyethylene
oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active
ingredient, emulsifying, wetting or dispersing agent and possibly solvent.
Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier,erg.,
kieselguhr, talc, clay or fertilizers. The active ingredients may be used mixed with selective herbicides,
plant growth regulating agents or with other pesticides.
EXAMPLE 2
90 parts by weight of the compound of Example 1 is mixed with 10 parts by weight ofN-methvl-Epsrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
EXAMPLE 3
20 parts by weight of the compound of Example 1 is dissolved in a mixture consisting of 80 parts
byweight ofxylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of
oleic acid-N-monoethanolamide, 5 parts by weight of thecalcium salt of dodecylbenzenesulfonic acid,
and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring
the solution into
100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is
obtained containing0.02 0 by weight of the active ingredient.
EXAMPLE 4
20 parts by weight of the compoundcf Example 1 is dissolved in a mixture consisting of 40 parts by
weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles
of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of
ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water
and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of
the active ingredient.
EXAMPLE 5
185/612
20 parts by weight of the compound of Example 1 is dissolved in a mixture consisting of 25 parts by
weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point
between2103 and280 C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole
of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing
it therein, an aqueous dispersion is obtained containing0.02 ó by weight of the active ingredient.
EXAMPLE 6
20 parts by weight of the compound of Example 1 is well mixed with 3 parts by weight of the sodium
salt ofdiisobuty]naphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic
acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated
in a hammer mill. Byunifonnly distributing the mixture in20,000 parts by weight of water, a spray
liquid is obtained containing0.1% by weight of the active ingredient.
EXAMPLE 7
3 parts by weight of the compound of Example 1 is intimately mixed with 97 parts by weight of
particulate kaolin. A dust is obtained containing3% by weight of the active ingredient.
EXAMPLE 8
30 parts by weight of the compound of Example 1 is intimately mixed with a mixture consisting of 92
parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed
onto the surface of this silica gel. A formulation of the active ingredient is obtained having good
adherence.
EXAMPLE 9
Leaves of rice seedlings grown in pots are infected with an aqueous conidial suspension of the fungus
Piricularia oryzae. After infection the plants are placed for 24 hours in a cabinet of high humidity
(steam-saturated) and in which a temperatureof from 22" to 25"C is maintained. The plants are
subsequently sprayed to run-off with 0.1, 0.05 and0.023% (by weight) aqueous emulsions
containing80% active ingredient and 20% dispersant (dry basis). The pots are then put back in the
humid cabinet. After 5 days the disease has spread on the untreated control plants to such an extent that
the major portion of the total leaf surface is affected.
Active Leaf attack after spray
ingredient liquor treatment
No.0.1% 0.05% 0.023%
1002
2023
3002
4000
5002
6002
7003
8002
9003
10 0 0 3
11 0 0 2
12 0 0 3
13 0 0 3
14 0 0 2
15 0 2 2
16 0 2 3
17 0 2 3
18 0 0 2
19 0 2 2
20 0 0 2
21 0 0 3
22 0 0 2
24 0 2 2
25 0 2 2
186/612
26 0 0 2
28 0 0 2
30 0 0 2
31 0 0 2
32 0 2 3
33 0 2 2
34 0 2 3
35 0 2 2
Active Leaf attack after spray
ingredient liquor treatment
No. 0.1%0.05% 0.025%
36 0 2 3
37 0 2 2
38 0 0 0
39 0 2 2
40 0 0 2
41 0 0 3
43 0 0 3
44 0 0 2
45 0 0 2
46 0 0 2
48 0 2 3
49 0 0 3
52 0 0 2 53 0 2 2 2
55 0u 2
56 0 0 3
58 0 2 2
59 0 0 2
O-ethyl-S,S-diphenyl
dithiophosphate
(Comparative agent) 1 3 4
Control (untreated) 5
O=no attack, graduated down to
5=severe attack
WHAT WE CLAIM IS:
1.A process for protecting monocotyledonous plants from fungi wherein the plants or their seeds are
treated with a fungitoxic amount of an N-substituted phosphoramidodithioic ester of the formula:
EMI8.1
whereRl and R2, independently of one another, each denote alkyl of 1 to 4 carbon atoms or, together,
denote ethylene;;R and R4 each independently denote alkyl of 1 to 12 carbon atoms, cycloalkyl,
methyl-substituted cycloalkyl, alkoxyalkyl, benzyl, phenyl, chloro-substituted phenyl,carbamoyloxysubstituted phenyl,p-morphollnoethyl or, rug alternatively denoting hydrogen and/or R4 denoting
dimethylamino orN R3R4 denotes an unsubstituted or alkyl-substituted saturatedmonocyclic
heterocyclic radical with a 5- or 6-membered ring.
2. A process as claimed in claim 1 where the monocotyledonous plants are cereals.
3. A process as claimed in claim 1 where the plants are rice or bananas.
4. A process as claimed in claim 2 where the plants are cereals other than rice.
5. A process as claimed in claim 4 wherein the cereals are barley or oats.
6. A process as claimed in any preceding claim, whereR and R4 each independently denote a
saturated hydrocarbon radical of not more than 12 carbon atoms optionally substituted by an alkoxy
radical of 1 to 4 carbon atoms, or R4 denotes such a radical, and R3 denotes hydrogen.
187/612
7. A process as claimed in any of claims 1 to 5, whereR3 and R4 each independently denote a benzyl
or phenyl radical or a phenyl radical substituted by 1 to 3 chlorine atoms and/or by a carbamoyloxy
group.
8. A process as claimed in any of claims 1 to 5, where R3 is as specified in claim 6 and R4 is as
specified in claim 7.
9. A process as claimed in any of claims 1 to 5, whereN3R4 denotes an unsubstituted or alkyl
substituted morpholine, thiomorpholine, pyrrolidine or piperidine group.
10. A process as claimed in any of claims 1 to 5, whereN3R4 denotes an unsubstituted or alkylsubstituted piperazine group.
11. A process as claimed in any of claims 1 to 5 wherein R3 and R4 orN R3Rr are listed herein.
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB1402296
**WARNING** start of CLMS field may overlap end of DESC **.
Active Leaf attack after spray
ingredient liquor treatment
No. 0.1%0.05% 0.025%
36 0 2 3
37 0 2 2
38 0 0 0
39 0 2 2
40 0 0 2
41 0 0 3
43 0 0 3
44 0 0 2
45 0 0 2
46 0 0 2
48 0 2 3
49 0 0 3
52 0 0 2 53 0 2 2 2
55 0u 2
56 0 0 3
58 0 2 2
59 0 0 2
O-ethyl-S,S-diphenyl
dithiophosphate
(Comparative agent) 1 3 4
Control (untreated) 5
O=no attack, graduated down to
5=severe attack
WHAT WE CLAIM IS:
1.A process for protecting monocotyledonous plants from fungi wherein the plants or their seeds are
treated with a fungitoxic amount of an N-substituted phosphoramidodithioic ester of the formula:
EMI8.1
whereRl and R2, independently of one another, each denote alkyl of 1 to 4 carbon atoms or, together,
denote ethylene;;R and R4 each independently denote alkyl of 1 to 12 carbon atoms, cycloalkyl,
methyl-substituted cycloalkyl, alkoxyalkyl, benzyl, phenyl, chloro-substituted phenyl,carbamoyloxysubstituted phenyl,p-morphollnoethyl or, rug alternatively denoting hydrogen and/or R4 denoting
dimethylamino orN R3R4 denotes an unsubstituted or alkyl-substituted saturatedmonocyclic
heterocyclic radical with a 5- or 6-membered ring.
188/612
2. A process as claimed in claim 1 where the monocotyledonous plants are cereals.
3. A process as claimed in claim 1 where the plants are rice or bananas.
4. A process as claimed in claim 2 where the plants are cereals other than rice.
5. A process as claimed in claim 4 wherein the cereals are barley or oats.
6. A process as claimed in any preceding claim, whereR and R4 each independently denote a
saturated hydrocarbon radical of not more than 12 carbon atoms optionally substituted by an alkoxy
radical of 1 to 4 carbon atoms, or R4 denotes such a radical, and R3 denotes hydrogen.
7. A process as claimed in any of claims 1 to 5, whereR3 and R4 each independently denote a benzyl
or phenyl radical or a phenyl radical substituted by 1 to 3 chlorine atoms and/or by a carbamoyloxy
group.
8. A process as claimed in any of claims 1 to 5, where R3 is as specified in claim 6 and R4 is as
specified in claim 7.
9. A process as claimed in any of claims 1 to 5, whereN3R4 denotes an unsubstituted or alkyl
substituted morpholine, thiomorpholine, pyrrolidine or piperidine group.
10. A process as claimed in any of claims 1 to 5, whereN3R4 denotes an unsubstituted or alkylsubstituted piperazine group.
11. A process as claimed in any of claims 1 to 5 wherein R3 and R4 orN R3Rr are listed herein.
12. A process as claimed in any of claims 6 to 11, whereR1=R2.
13. A process as claimed in claim 12 where R1=R2=n-propyl.
14. A process as claimed in any of claims 1 to 5 where the N-substituted phosphoramidodithioic ester
has the formula
EMI9.1
15. A process as claimed in any of claims 1 to 5 where the
N-substituted phosphoramidodithioic ester has the formula
EMI9.2
16. A process as claimed in any preceding claim, where the N-substituted phosphoramidodithioic ester
is prepared by a process in which a compound of formula
EMI9.3
whereRt, R2,R and R4 have the meanings specified in claim 1, is reacted with an oxidising agent.
17. A process according to claim 16 whereinRT, R2; R3 and R4 have the meanings specified in claim
12 and the oxidising agent is hydrogen peroxide.
18. A process according to claim 16 or 17 wherein the compound of formula
EMI9.4
is prepared by reacting a compound of formula
EMI9.5
with a compound of formula
EMI9.6
X, denoting halogen, in the presence of an acid-binding agent which may optionally be an excess of the
compound of formula
EMI9.7
189/612
19. A process as claimed in any of claims 16 to 18, whereinR-, R2, R3 andR4 all denote hydrocarbon
radicals orR and/or R' may denote chlorophenyl radicals.
20. A process as claimed in claim 12, whereNR Ri denotes unsubstituted piperazino orN(nC H-)..
21. A process as claimed in any of claims 16 to 19 wherein the N-substituted phosphoramidodithioic
ester is prepared by a process substantially as described herein.
22. A process as claimed in any preceding claim in which the N-substituted phosphoramidodithioic
ester is applied to monocotyledonous plants infested with fungus pathogens.
23. A process as claimed in claim 22 in which the N-substituted phosphoramidodit-hioie ester is
applied to rice plants infested with Piricularia oryzae or Pellicularia sasakii or to bananas infested with
Piricularia grisea.
24. A process as claimed in claim 22 inwhich the N-substituted phosphoramidodithioic ester is
applied to cereals infested with Erisyphe graminis.
25. A process as claimed in claim 22 in which the N-substituted phosphoramidodithioic ester is
applied to barley or oats infested withErisyphe graminis or Helminthosporium.
26. A process as claimed in claim 24 or 25 in which the N-substituted phosphoramidodithioic ester is
the one in whichRl=R2=R:Rtn-propyl.
27. A fungicidal composition comprising N-substituted phosphoramidodithioic ester of the formula
EMI10.1
whereRl andRD, independently of one another, each denote alkyl of 1 to 4 carbon atoms, or together,
denote ethylene; R3 andR4 each independently denote alkyl of 1 to 12 carbon atoms, cycloalkyl,
methyl-substituted cycloalkyl, alkoxyalkyl, benzyl, phenyl, chloro-substituted phenyl,carbamoyloxysubstituted phenyl orss-morpholinoethyl or,
R1 alternatively denoting hydrogen; and/orR1 denoting dimethylamino orNR3R4 denotes an
unsubstituted oralk1-substituted saturatedmonocyclic heterocyclic radical with a 5- or 6-membered
ring, and a solid carrier, an organic liquid of boiling point higher than150 C, an emulsifying, wetting
or dispersing agent, or a fertiliser, selective herbicide plant growth-regulating agent, or another
pesticide.
28. A fungicidal composition as claimed in claim 27 wherein the N-substituted phosphoramidodithioic
ester is as specified in any of claims 6 to 21.
29. A fungicidal composition comprising an N-substituted phosphoramidodithioic ester of the formula
EMI10.2
whereRl, R2, R" andR all denote n-propyl, or where R1 and R2 both denote ethyl,R" denotes
hydrogen andR4 denotes 2-ethoxy-ethyl, and a solid carrier, an organic liquid of boiling point
above150 C, or other liquid carrier, an emulsifying, wetting or dispersing agent, or a fertiliser,
selective herbicide, growth-regulating agent, or other pesticide.
30. A fungicidal composition as claimed in claim 27, 28 or 29 and substantially as hereinbefore
described in any of Examples 2 to 8.
31. Seeds or plants to which have been applied a fungitoxic amount of an N-substituted
phosphoramidodithioic ester as specified in claim 1 or in any of claims 6 to 21, 26, 27 or 29.Data
supplied from the esp@cenet database - Worldwide
190/612
16. GB945014
- 12/18/1963
LOW TOXIC ORGANO-PHOSPHORIC ACID ESTER AND INSECTICIDAL
COMPOSITIONS CONTAINING THE SAME
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB945014
Applicant(s):
SUMITOMO CHEMICAL CO (--)
E Class: A01N57/14; C07F9/18
Application Number:
GB19610024348 (19610705)
Priority Number: JP19600033848 (19600802)
Family: GB945014
Equivalent:
US3150040; NL267465; ES269135; CH405816; NL123938C; DE1207398
Abstract:
Abstract of GB945014
The invention comprises O,O-dimethyl-O-(4-cyanophenyl) thionophosphate. It may be obtained by
reacting O,O-dimethyl chlorothionophosphate with 4-cyanophenyl or an alkali metal salt thereof. The
reaction is preferably carried out in an inert organic solvent and substantially equimolecular
proportions of the reactants are general employed. When the free 4-cyanophenyl is used the reaction is
preferably carried out in the presence of an acid binding agent, e.g. an organic base such as pyridine or
diethylamine, or an alkali metal carbonate or bicarbonate. Suitable solvents are hydrocarbons,
halogenated hydrocarbons, alcohols, ketones and ethers. A dehydrohalogenation catalyst, e.g. copper
powder or a cuprous salt may also be present. The product has insecticidal properties (see Division
A5).ALSO:An insecticidal composition comprises an inert carrier and as active ingredient O,Odimethyl O - (4 - cyanophenyl) thionophosphate (see Division C2). The invention also includes a
method of eradicating injurious insects, especially borers of rice, from a crop area containing a growing
crop which comprises applying to the crop area an insecticide comprising O,O-dimethyl O-(4cyanophenyl) thionophosphate. The insecticidal compositions may be in the form of an emulsion,
suspension, dust or oil preparation. In preparing the emulsion the active ingredient, which is stated to
have low toxicity to warm blooded animals, may be mixed with an organic solvent, e.g. benzene or
xylene, and a non-ionic surface active agent to form an emulsifiable concentrate suitable for dilution
with water before use. Wettable powders may be obtained by mixing the active ingredient with a nonionic surface active agent and a powdered carrier and are then added to water to form a suspension.
Dusts may be formed by mixing the active ingredient with a powdered carrier with or without the use
of a volatile solvent, e.g. acetone. Oil preparations may be obtained by dissolving the active ingredient
in a solvent such as deodorized kerosene if desired with the use of a co-solvent, e.g. an aromatic
hydrocarbon such as benzene, xylene or methylnaphthalene. A fungicide, herbicide or other insecticide
may also be present.Claims:
Claims of GB945014
WHAT WE CLAIM IS:1 0,0 Dimethyl O ( 4 cyanophenyl) thionophosphate.
2 A method for preparing 0,0-dimethyl0-( 4-cyanophenyl) thionophosphate which comprises
condensing 0,0-dimethyl chlorothionophosphate and a compound represented by the formula:
/ O o/ wherein M is chosen from hydrogen and alkali metals.
191/612
3 An insecticidal composition comprising an inert carrier and as the essential active ingredient O,Odimethyl-0-( 4-cyanophenyl) thionophosphate.
4 An insecticidal composition comprising an emulsion of a toxic quantity of 0,Odimethyl-O-( 4cyanophenyl) thionophosphate.
An insecticidal composition comprising Leamington Spa: Printed for Her Majesty's Stationery Office,
by the Courier Press (Leamington) Ltd -1963 Published by The Patent Office, 25 Southampton
Buildings, London, W C 2, from which copies may be obtained.
945,014Data supplied from the esp@cenet database - Worldwide
192/612
17. GB967081
- 8/19/1964
(THIO)-PHOSPHORIC (PHOSPHONIC, PHOSPHINIC) ACID ESTERS AND
PROCESSES FOR THEIR PRODUCTION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB967081
Applicant(s):
BAYER AG (--)
E Class: A01N57/06; C07F9/12; C07F9/18; C07F9/32C4; C07F9/40C4
Application Number:
GB19610039323 (19611102)
Priority Number: DE1960F032452 (19601102); DE1961F033078 (19610127); DE1961F033766
(19610426)
Family: GB967081
Equivalent:
NL270950; CH422822
Abstract:
Abstract of GB967081
Phosphorus containing esters of the formula >;FORM:0967081/C1/1; in which R,1 and R2, which may
be the same or different, are C1 or C2 alkyl or alkoxy, R is a methyl or methoxy radical in position 2 or
3, with the proviso that R1 and R2 are both alkyl radicals if R is a methyl radical in position 3 and, X is
sulphur or oxygen are claimed as novel compounds, suitable for active ingredients in insecticidal
compositions (see Division A5) and are made by reacting a phosphorus containing compound of the
formula R1R2P(X)-halogen R1, R2 and X having the meanings above and "Hal" is a halogen atom
other than fluorine, with a corresponding 4 nitrophenol, the reaction being effected in the presence of
an acid binding agent or the alkali metal salt of the nitrophenol being used. It is preferable to carry out
the reaction in an inert solvent e.g. hydrocarbons, lower aliphatic ketones, chlorbenzene, toluene,
xylene, methyl ethyl ketone. Numerous detailed examples are given. Specifications 644,616 and
655,875 are referred to.ALSO:Pesticidal compositions, suitable for use against aphids, rice stalk borers,
caterpillars, plant lice and spider mites contain a novel phosphorus containing ester (see Division C2)
of the formula >;FORM:0967081/A5-A6/1; in which R1 and R2, which may be the same or different or
C1 or C2 alkyl or alkoxy, R is a methyl or methoxy radical in position 2 or 3 with the proviso R1 and
R2 are both alkyl radicals if R is a methyl radical in position 3, and X is sulphur or oxygen, and solid or
liquid extending or diluting agent, of which class chalk, talc, bentonite and vermiculite, water
optionally in conjunction with e.g. acetone dimethyl formamide and/or non-ionic emulsifiers are
specified. Specifications 644,616 and 655,875 are referred to.Description:
Description of GB967081
COMPLETE SPECIFICATION (Thio)-Phosphoric (Phosphonic,Pliosphinic) Acid Esters
and processes for their production
We,FARBENFABRIKEN BAYER AKTIENGSELLSCHAFT, a body corporate organised under the
laws of Germany, of (22c) Leverkusen
Bayerwerk, Germany, do hereby declare the invention, for which we pray that a patent may be granted
to us, and the method by which it is to be performed to be particularly described in and by the
following statment: The present invention is concerned with new and useful phosphorus-containing esters with pesticidal,
especially insecticidal and miticidal, properties and with the production thereof.
In Specification No. 644,616, there is described and claimed a method of preparing an organic
phosphate of the generalformula: -
193/612
EMI1.1
wherein Z is sulphur or oxygen,R11 andRsl are alkyl, aralkyl or aryl radicals andm represents an
integer not greater than 3, which comprises reacting a compound of the generalformula: EMI1.2
with a nitrophenoxide of the general formula:
EMI1.3
wherein X represents an alkali-forming metal, in the presence of a solvent for the alkaliforming metal
nitrophenoxide. These organic phosphates are stated to possess general pestcontrol characteristics.
In Specification No. 655,875, there is described and claimed a pesticidal composition comprising a
mixture of one or more organic phosphates and a carrier therefor, said organic phosphates having the
generalformula:
EMI1.4
in whichR111 andR211 are alkyl, aralkyl or aryl groups, Z1 is a sulphur or oxygen atom, yl is an NH
or N-alkyl group or a sulphur or oxygen atom, and X is a hydrogen or halogen atom or an alkyl, aryl,
alkyloxy, nitro, amino, alkylamino, dialkylamino, acyl, carboalkyloxy or carboaryloxy group, said
carrier comprising at least 50% by weight of the composition, and being such that if the composition is
admixed with or contain water the resulting pH is not greater than 8.5.
We have now found a group of phosphoruscontaining esters which fall within the broad scope of the
formulae of the phosphorus-con taining esters given in the two above-mentioned
Specifications Nos. 644,616 and 655,875 but which are not specifically described in these two
Specifications. The compounds according to the present invention have a greater pesticidal actvity than
those specifically mentioned in Specifications Nos. 644,616 and 655,875.
The new compounds of the present invention may be represented by the general formula:
EMI2.1
in which R1 and R2, which may be the same or different, stand for alkyl or alkoxy radicals containing
1 or 2 carbon atoms, R stands for a methyl or methoxy radical in the 2- or 3position, with the proviso
that R1 and R2 are both alkyl radicals if R is a methyl radical in the 3-position, and X is a sulphur or
oxygen atom.
Dialkyl phosphoric or -thiophosphoric acid esters of 4-nitrophenol have already been described many
times in the literature (compare, for example, G. Schrader "DieEntsvicklung neuer Insektizide auf
Grundlage organischer
Fluor- undPhosphor-Verbindungen", 2nd edition, Verlag Chemie, Weinheim, Bergstrasse, as well as
German Patent No.
S14,152). The insecticidal properties of the named compounds are also known(see, for example,
German Patent Specification No.
811,514). Thus, theO,O-dimethyl-, as well as theO,O-diethyl - 0 - (4-nitrophenyl)-thionophosphoric
acid esters have achieved significance as pesticidal agents. Furthermore, reports have already been
made in the literature about alkyl phosphonicacid-O-alkyl-O-(4-nitro- phenyl) esters and dialkyl
phosphinic acid-O (4-nitrophenyl) esters, as well as about their applicability for the combating of plant
pests.
The disadvantage attached to the abovementioned esters of phosphorus and which renders difficult,
and in many cases even makes impossible, their practical use as pesticidal or plant protective agents, is
the relatively high toxicity of the compounds to warm-blooded animals and the danger connected
therewith for humans and domestic animals.
Various attempts have been made to reduce the toxicity of these products to warm-blooded animals by
the introduction of suitable substituents into the 4-nitrophenyl residue, without the good pesticidal
effect thereby being
Iost. Thus, for example, O,O-dimethyl-O-(chloro-4-nitrophenyl)-thionophosphoric acid ester, which
only possesses a slight toxicity to warm-blooded animals, is already known from
German Patent Specification No. 921,870. In practice, however, this ester has not achieved as great a
significanceas? for example, the
194/612
O,O-dimethyl- or the O,O-diethyl-(4-nitrophenyl)-thionophosphoric acid ester.
In accordance with the present invention it has now been found that (thio)-phosphoric (phosphonic,
phosphinic) acid esters of 2- or 3-methyl-or -methoxy-4-nitrophenol of the general formula:
EMI2.2
in which the symbols have the above said significance, are distinguished by outstanding insecticidal
properties and, in part, by an exceptionally low toxicity for warm-blooded animals. Thus, for example,
the average toxicity(LD5e) of O,O-dimethyl-O-(2-methyl4-nitrophenyl)-thionophosphoric acid ester
amounts to 11000 mg per kg in the case of rats with oral application. However, on the other hand, for
example, plant lice are already killed 100% by0.001% solutions of the ester mentioned. As was further
found, the phosphorus compounds according to the invention are especially suitable for the combating
rice pests, for example, rice stalk borers.
The above-described alteration of the biological properties of the 4-nitrophenyl esters of phosphorus
by the introduction of a methyl or methoxy group into the 2-position of the 4-nitrophenyl residue, is
surprising and makes the compounds valuable as agricultural pesticides.
The inventive (thio)-phosphoric (phosphonic, phosphinic) acid esters of 2- or 3-methyl- or -methoxy4-nitrophenyl are produced according to methods known in principle, i.e. by the reaction of the
corresponding (thio)-phosphoric (phosphonic phosphinic) acid halides (excluding the fluorides) with 2or 3-methyl- or methoxy-4-nitrophenols in the presence of acid-binding agents (e.g. alkali metal
carbonates) or with the salts (preferably alkali metal salts) of 2- or 3-methyl- or methoxy-4nitrophenols. The reaction is preferably carried out in inert, organic solvents, such as hydrocarbons or
lower aliphatic ketones.
Chlorobenzene, toluene, xylene and methyl ethyl ketone have proved to be particularly suitable for the
mentioned purpose.
The products of the process can be applied in the way commonly used for plant protection and
pesticidal agents based on phosphorus esters, i.e. preferably in combination with solid or liquid
extending or diluting agents. As solid extending agents there have proved to be particularly useful
chalk, talc, bentonite and vermiculite, while for the production of liquid formulations there may chiefly
be considered water, possibly in conjunction with a solubiliser (e.g. acetone or dimethyl formamide), as
well as a non-ionic emulsifier.
The following Examples are given for the purpose of illustrating the presentinvention:
EXAMPLE 1
EMI3.1
A solution of 46 g (0.3 mol) of 2-methyl-4nitrophenol in 500 cc of chlorobenzene is mixed with 84 g
(0.6 mol) of powdered potassium carbonate and heated for half an hour with stirring to8090 C. 47 g
(0.33 mol) of dimethyl phosphoric acid chloride are subsequently added dropwise to the mixture
whereby an exothermic reaction sets in which must be somewhat moderated, possibly by cooling. At
the end of the addition of the acid chloride, the reaction mixture is stirred for 2 hours at8090 C. the
separated salts filtered off with suction and the solvent removed by distillation in a vacuum. The
residue is taken up in benzene and first washed in water, later with a 2N solium hydroxide solution for
the removal of unreacted 2-methyl-4-nitrophenol and finally with water until a neutral reaction is
obtained. After drying the benzene layer with sodium sulphate, the solvent is distilled off and there are
obtained 60 g(76.6% of theoretical) of a 97% O,O-dimethyl-O-(2methyl-4-nitrophenyl)-phosphoric
acid ester in the form of a non-distillable red-brown oil.
Analysis:C,H12ONP Calc.: N. 5.36; P 11.86 (mol weight: 261) found: N 5.20; P 11.38
The mean toxicity(LD,,) on rats peros is 100 mg per kg animal. Aphids are killed completely with
0.0001% solutions.
EXAMPLE 2
EMI3.2
195/612
61 g (0.4 mol) of 2-methyl-4-nitrophenol are dissolved in 250 cc of methyl ethyl ketone. The solution
obtained is mixed with 112 g (0.8 mol) of powdered potassium carbonate and heated with stirring
at6070 C. for half an hour.
92 g (0.4 mol) of a 75% solution of dimethyl thiophosphoric acid chloride in xylene is subsequently
added drop wise at this temperature.
For the completion of the reaction, the reaction mixture is heated at7080 C. for 2 hours, then allowed
to cool, the separated salts filtered off with suction and washed with 250 cc of benzene. The filtrate is
washed with water until the benzene solution is colorless.
The benzene layer is then dried over sodium sulphate and the solvent distilled off. The oil which
remains behind crystallizes on cooling.
The O,O-dimethyl-O-(2-methyl4-nitrophenyl) thionophosphoric acid ester has a melting point of 550
C. Yield: 90 g (81.2% of the theoretical).
The compound possesses a mean toxicity(LDso) of 1 g per kg of rat, applied orally.
Analysis:C"Hl20 NSP (mol weight: 277.2)
Calc.: N 5.05; S 11.57; P 11.18
Found: N 4.86; S 11.28; P 10.92
Aphids are killed completely with0.001 % solutions.
EXAMPLE 3
EMI3.3
46 g (0.3 mol) of 2-methyl-4-nitrophenol and 84 g (0.6 mol) of powdered potassium carbonate are
heated in 500 cc of chlorobenzene at8090 C. for half an hour. 55 g (0.32 mol) of diethyl phosphoric
acid chloride are subsequently added dropwise to the mixture in a quarter of an hour, whereby a weakly
exothermic reaction sets in. The mixture is then heated at8090 C. for 2 hours and, after cooling, the
separated salts are filtered off with suction.
The solvent is distilled off from the filtrate in a vacuum and the residue worked up as described in
Example 1. 70 g(80.8% of theoretical) ofO. O-diethyl-O-(2-methy1-4- nitrophenyl)-phosphoric acid
ester are obtained in the form of a bright yellow oil of b.p. 1151160 C/0.01 mm Hg.
Analysis:
CllHlGOGNP calcd: N 4.84; P 10.71
found: N 4.77; P 10.62
The ester shows on rats peros aLid5, of 25 mg per kg of animal.
Aphids are killed completely with0.01% solutions.
EXAMPLE 4
EMI3.4
A mixture of 61 g (0.4 mol) of 2-methyl-4nitro-phenol and 112 g (0.8 mol) of powdered potassium
carbonate in 450 cc of methyl ethyl ketone is heated at6070 C. for half an hour. 75 g (0.4 mol) of
diethyl thiophosphoric acid chloride are subsequently added dropwise to the mixture at this temperature
and afterwards heated at7080 C. for 2 hours. After cooling, the separated salts are filtered off with
suction and the filter residue washed with 300 cc of benzene. The filtrate is washed with water and
subsequently with a 2N sodium hydroxide solution until it is scarcely yellow coloured. After again
washing with water until it shows a neutral reaction, the benzene solution is dried over sodium sulphate
and the solvent then distilled off. The O,O-diethyO-(2-methyl4-nitrophenyl) - thionophosphoric acid
ester is obtained in the form of a redbrown oil.
Yield: 99 g(81.2 ,S, of the theoretical).
Analysis:
196/612
C,,H,,O,NSP calc.: N 4.59; S 10.50; P 10.15;
found: N 4.32; S 10.80; P 10.34.
On rats per os, the compound shows aLD, of 50 mg per kg animal.
Caterpillars are killed completely with 0.1% solutions.
EXAMPLES
EMI4.1
A solution of 46 g (0.3 mol) of 2-methyl-4nitrophenol in 350 cc of methyl ethyl ketone is, after the
addition of 84 g (0.6 mol) of powdered potassium carbonate, heated to 50600 C. for half an hour. 38 g
(/0.33 mol) of dimethyl - thionophosphinic acid chloride are subsequently added dropwise to this
mixture, whereby the temperature of the reaction mixture increases to 350 C. For completion of the
reaction, the mixture is stirred at60L700 C.
for 1 hour, then allowed to cool, the separated salts filtered off with suction and the contents of the
filter washed out with 300 cc of benzene.
The filtrate is first washed with water, then with a 2N sodium hydroxide solution until it is scarcely
yellow coloured. Finally, the benzene solution is again washed with water until it shows a neutral
reaction, dried over sodium sulphate and the solvent distilled off.
The residue remaining behind is recrystallized from acetonitrile. In this manner, lemon yellow, thick
crystals of melting point 980 C. are obtained. Yield 23 g (31.2% of the theoretical).
Systemic action:0.1% solution 100%.
Aphids are killed completely with0.1 solutions.
EXAMPLE 6
EMI4.2
46 g (0.3 mol) of 2-methyl-4-nitrophenol and 46 g (0.33 mol) of powdered potassium carbonate are
stirred at 600 C. for half an hour in 300 cc of methyl ethyl ketone. 53 g (0.33 mol) ethyl
thionophosphonic acid methyl ester chloride are then added to the reaction mixture at2025 C. with
external cooling and, after the addition is completed, the mixture heated at 500 C. for 2 hours. After
cooling, the precipitated salts are filtered off with suction and washed with 500 cc of benzene. The
filtrate is washed with water until it is almost colourless. After drying the benzene solution with sodium
sulphate, the solvent is distilled off. The residue (60 g) crystallizes upon trituration with petroleum
ether. The crystal mass is filtered off with suction and the ethyl thionophosphonic acid-O-methyl-O-(2methyl-4nitrophenyl) ester is obtained in the form of a crystalline, sandy, yellowish powder.
Yield:72.5'-/o of the theoretical.
Analysis:
CloHllO NSP calc.: N 5.09; S 11.65; P 11.20;
(mol weight: 275.3) found: N 5.39; S 11.57; P 11.30;
The ester possesses a mean toxicity of 50 mg per kg of rat by oral application.
Aphids are killed completely with0.01 ?ol solutions.
EXAMPLE 7
EMI5.1
46 g (0.3 mol) of 2-methyl-4-nitrophenol and 46 g (0.33 mol) of powdered potassium carbonate in 300
cc of methyl ethyl ketone are heated with stirring to5060 C. for half an hour. 52 g (0.3 mol) of ethyl
thionophosphonic acid ethyl ester chloride are subsequently added dropwise at this temperature to the
mixture, whereby a weakly exothermic reaction sets in.
For the completion of the reaction, the reaction mixture is heated to5060 C. for 2 hours and then
worked up as described in the previous Example. 75 g (86.4% of the theoretical) of ethyl
197/612
thionophosphonic acid-O-ethyl-O-(2methyl-4-nitrophenyl) ester are obtained as an orange-coloured,
water insoluble oil of b.p.
1100 C/0.01 mm Hg.
Analysis:
CllHls04NSP (mol weight: 289.3)
calc.: N 4.84 S 11.08 P 10.71
found: N 5.00 S 11.09 P 10.31
The mean toxicity(LDso) of the compound on rats peros amounts to 25 mg per kg of animal.
Aphids are killed completely with0.001,% solutions.
EXAMPLE 8
EMI5.2
23 g (0.15 mol) of 2-methoxy-4-nitrophenol (m.p.1021030 C.) and 42 g (0.3 mol) of powdered
potassium carbonate in 200 cc of methyl ethyl ketone are heated at60-700 C.
for half an hour, whereby the cinnabar-red 2methoxy-4-nitrophenol potassium separates out.
To this mixture there is slowly added dropwise at 300 C. 19 g (0.16 mol) of dimethyl thionophosphinic
acid chloride and the reaction mixture subsequently stirred for two hours at room temperature. The
colour of the mixture then changes to pale yellow. After cooling, the separated salts are filtered off with
suction and washed out with 300 cc of benzene.
The filtrate is first washed with water, then with a dilute 2N sodium hydroxide solution and finally
again with water until it shows a neutral reaction. After drying the benzene solution over sodium
sulphate, the solvent is distilled off. As residue there remain 22 g of dimethyl thionophosphinicacid-O(2-methoxy- 4-nitrophenyl) ester as a pale yellow crystalline mass. The product is recrystallized from
ethyl acetate and the completely pure compound is obtained in the form of heavy yellow crystals of
melting point 960 C. Aphids are killed completely with 0.01% solutions.
EXAMPLE 9
EMI5.3
51 g (0.33 mol) of 2-methoxy-4-nitrophenol are dissolved in 400 cc of acetonitrile. To the solution
obtained are added 45 g of potassium carbonate and to the reaction mixture dropwise 51 g of O,Odimethyl thionophosphoric acid chloride, at 400 C., with stirring, the mixture is heated at 65 to 700 C.
for 1 hour and then mixed with 400 cc of benzene. The benzene solution is washed 3 times with 150 cc
portions of water, then dried over sodium sulphate and the solvent distilled off. 74 g (84% of the
theoretical) of O,O-dimethyl thionophosphoric acid -O-(2-methoxy-4-nitrophenyl) ester remain behind
in the form of a colourless, waterinsoluble oil which crystallises after prolonged standing and the
possesses a m.p. of 540 C.
Spider mites are killed completely with 0.01% solutions.
EXAMPLE 10
EMI5.4
To a solution of 51 g (0.33 mol) of 2methoxy-4-nitrophenol in 400 cc of acetonitrile there are added
45 g of potassium carbonate, the reaction mixture is subsequently heated to 400 C. for 20 minutes and
then treated dropwise with stirring at 400 C. with 60 g of
O,O-diethyl thionophosphoric acid chloride.
The mixture is then heated at 700 C. for 1 hour and subsequently worked up as described in Example 9.
90 g (93 % of the theoretical) ofO,O-diethyl thionophosphoric acid-O-(2-methoxy-4-nitrophenyl)
ester of b.p. 1320 C/0.01 mm Hg are obtained.
The mean toxicity(LDso) of the compound on rats peros amounts to 25 mg per kg of animal.
198/612
Spider mites are killed completely with0.001.% solutions.
EXAMPLE 11
EMI6.1
51 g (0.33 mol) of 2-methoxy4-nitrophenol are dissolved in 400 cc of acetonitrile,a5 of potassium
carbonate are then added to this solution and it is subsequently treated dropwise at 500 C. with 50 g of
methyl thionophosphonic acid-O-ethyl ester chloride. For the completion of the reaction, the mixture is
heated to 700 C. for 1 hour and then worked up as described in Example9.
76 g (87% of the theoretical) of methyl thionophosphonicacid-O-ethyl-O-(2-methoxy- 4-nitrophenyl)
ester are obtained as a colourless, crystalline product ofm.p. 730 C.
Spider mites are killed completely with0.001% solutions.
EXAMPLE 12
EMI6.2
51 g (0.33 mol) of 2-methoxy-4-nitrophenol are dissolved in 400 cc of acetonitrile. To this solution
there are added 45 g of potassium carbonate and 55 g of ethyl thionophosphonic acid-O-ethyl ester
chloride subsequently added dropwise with stirring at 400 C. to the reaction mixture, which is then
further stirred at 700
C. for 1 hour and then worked up as in Example 9. 85 g (93 % of the theoretical) of ethyl
thionophosphonic acid-O-ethyl-O-(2-methoxy4-nitrophenyl) ester are obtained in the form of a pale
yellow, crystalline product of m.p.
440 C.
The mean toxicity (LD50) of the compound on rats peros amounts to 13.8 mg. per kg. of animal.
Spider mites are killed completely with 0.001% solutions.
EXAMPLE 13
EMI6.3
76 g (0.5 mol) of3-methylA-nitrophenol and 45 g. of finely powdered potassium carbonate are
dissolved in 250 c.c. methyl ethyl ketone. To this solution there are added at 600 C. with stirring 65 g.
(0.5 mol) of dimethyl thionophosphinic acid chloride, the reaction mixture subsequently stirred at6070
C. for one hour and then poured into ice water. The oily product which separates is taken up in
benzene, the benzene solution separated off and dried with sodium sulphate.
After distilling off the solvent, the dimethyl thionophosphinicacid-O-(3-methyl4-nitro- phenyl) ester
solidifies to colourless crystals of m.p. 680 C. Yield 60 g. (49% of the theoretical).
The mean toxicity of the compound on rats peros amounts to 1,000 mg. per kg. of animal.
Plant lice are killed 100% with0.01 % solutions of the ester and spider mites and caterpillars100%
with0.1;4 solutions.
EXAMPLE 14
EMI6.4
To a solution of 23 g. (0.15 mol) of methoxyA-nitrophenol in 275 cc of toluene there are added 18 g
of finely powdered potassium carbonate and 0.5 g of copper powder and 23 g of O,O-diethyl
thionophosphoric acid chloride are subsequently added dropwise at 1000 C. to the mixture, with
stirring; for the purpose of completing the reaction, the reaction mixture is heated for 5 hours at 1000
C. The mixture is then cooled to room temperature and the separated salts filtered off with suction. The
filtrate is first washed with water, subsequently with a 5% sodium bicarbonate solution and finally
dried with sodium sulphate. After distilling off the solvent there are obtained 33 g ofO,O-diethyl-O-(3-
199/612
methuxy-4-nitrophenyl) - thionophosphoric acid ester which crystallizes after a short time and,
recrystallized from ligroin, shows a melting point of 430 C. The mean toxicity(LD,,) of the compound
on rats peros amounts to 50 mg per kg of animal. 0.05% solutions of the ester kill plant lice to 100%.
EXAMPLE 15.
EMI6.5
A mixture of 64 g (0.4 mol) of 3-methoxy4-nitrophenol, 62 g (0.44 mol) of potassium
carbonate and 400 cc of methyl ethyl ketone
are heated, with stirring, for 30 minutes at 50
to 600 C. Subsequently, 70.4 g(0.44 mol)
of potassium carbonate and 400 cc of methyl
ethyl ketone are heated, with stirring, for 30 minutes at 50 to 600 C. Subsequently, 70A g.
(0.44 mol) of O,O-dimethyl thionophosphoric acid chloride are added dropwise to the reaction
mixture at 50 to 600 C. and the latter then heated for 2 hours at 700 C. After cooling the mixture, the
separated salts are filtered off with suction and then washed with 200 cc of benzene. The filtrate is first
washed with water and then with 2N sodium hydroxide solution until it is no longer yellow coloured.
After subsequent washing with water until it is neutral, the organic phase is dried over sodium sulphate
and the solvent finally distilled off. The residue (98 g. corresponding to 83.6% of the theoretical)
crystallizes upon cooling and can be recrystallized from a petroleum ether/ether mixture.O.O-dimethylO-(3-methoxy4-nitrophenyl) - thiono - phosphoric acid ester is obtained in the form of bright yellow
leaflets of m.p. 720 C.
Analysis:
Calc. for a mol weight of 293: N: 4.78%; S: 10.93%; P: 10.57%
Found: N: 4.75%; S: 11.08%; P: 10.86%
The mean toxicity of the compound(LD50) on rats peros amounts to 50 mg/kg of animal.
Caterpillars are killed to 100% with 0.004% solutions of the ester, while plant lice are still killed to
50% with0.0008% solutions.
EXAMPLE 16.
EMI7.1
51 g (0.33 mol) of 3-methoxy-4-nitrophenol are dissolved in 400 cc of acetonitrile. To this solution
there are first added 45 g of potassium carbonate and the mixture then stirred at 400
C. for-t- hour. The reaction mixture is subsequently mixed, with further stirring, with 50 g of methyl
thiono-phosphonic acid-O-ethyl ester chloride at 30 to 400 C., stirred at 40 to 500 C. for a further hour
and then diluted with 400 cc of benzene. The benzene solution is washed three times with 150 cc
amounts of water each time, dried over sodium sulphate and the solvent evaporated. In the subsequent
fractional distillation, there are obtained 76 g (87% of the theoretical) of methyl thionophosphonicacidO-ethyl-O-(3 -methoxy-4- nitrophenyl) ester of b.p. 1280 C./0.01 mm
Hg. The mean toxicity of the compound(LD,,) on rats peros amounts to 3,75 mg per kg of animal.
Spider mites are killed completely with 0.001% solutions.
EXAMPLE 17.
EMI7.2
To a solution of 51 g (0.33 mol) of 3methoxy - 4 - nitrophenol in 400 cc of acetonitrile there are
added, with stirring, 45 g of potassium carbonate and 55 g of ethyl thionophosphonic acid-O-ethyl ester
chloride (b.p.
480 C./1 mm Hg) are subsequently added dropwise at400 C., with further stirring, to this mixture. For
the completion of the reaction, the reaction mixture is stirred for a further 1 hour at 600 C. and then
200/612
worked up as in the preceding Example. There are obtained 80 g (88% of the theoretical) of ethyl
thionophosphonicacid-O-ethyl-O-(3 -methoxy- 4-nitrophenyl)-ester which, after re-crystallization
from a ligroin/ethyl acetate mixture, melts at 700 C.
The mean toxicity of the compound(LDso) on rats peros amounts to 3.8 mg per kg of animal.
Spider mites are killed completely with 0.001% solutions.
EXAMPLE 18.
EMI7.3
A solution of 51 g (0.33 mol) of 3-methoxy4-nitrophenol in 400 cc of acetonitrile is mixed with 45 g
of potassium carbonate and subsequently stirred at 400 C. for 20 minutes. 40 g of dimethyl
thionophosphinic acid chloride (b.p. 460 C./1 mm Hg) are then added to the reaction mixture, the latter
stirred at 600 C.
for 1 hour and finally worked up as described in Example 16. There are obtained 40 g (51% of the
theoretical) of dimethyl thionophosphinic acid-O-(3 -methoxy-4-nitrophenyl)-ester in the form of a
rapidly crystallizing product.
After recrystallization from a ligroin/ethyl acetate mixture, the compound melts at 730 C.
The mean toxicity of the compound(LD,,) on rats peros amounts to 100 mg per kg of animal.
Aphids are killed completely with 0.1% solutions.
WHAT WE CLAIMIS:1) Phosphorus-containing esters of the general formula:
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
201/612
18. GB975127
- 11/11/1964
NEW CHLORINE-AND SULPHUR-CONTAINING PHOSPHATE ESTER
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=GB975127
Inventor(s):
BORN MANFRED (--); EL-HEWEHI ZAKI (--)
Applicant(s):
WOLFEN FILMFAB VEB (--)
E Class: C07F9/09A1
Application Number:
GB19620042705 (19621112)
Priority Number: GB19620042705 (19621112)
Family: GB975127
Abstract:
Abstract of GB975127
The invention comprises dimethyl (hexachloro-methyl mercaptoethyl) phosphate of the formula:
>;FORM:0975127/C1/1; and/or >;FORM:0975127/C1/2; It may be obtained by reacting
perchloromethyl mercaptan with dimethyl dichlorovinyl phosphate in the presence of benzoyl peroxide
or while irradiating with ultraviolet light. The product is probably a mixture of the two phosphates of
the above formulae and has insecticidal properties (see Division A5).ALSO:An insecticidal
composition comprises a solid or liquid carrier or diluent and dimethyl (hexachloro methylmercaptoethyl) phosphate of the formula >;FORM:0975127/A5-A6/1; and/or
>;FORM:0975127/A5-A6/2; (see Division C2). In Examples (1) and (2): a 0.1% solution of the active
ingredient is shown to be effective against house flies and corn weevils respectively; (3) the phosphate
is stirred into wheat flour in concentrations of 0.001 and 0.005% and the flour placed in small porcelain
dishes with rice weevils, a 100% kill of the latter being obtained on the tenth day; and (4) a 2% solution
of the phosphate in Polydiol 200 is shown to have a lower toxicity towards female albino rats than
dimethyl dichlorovinyl phosphate.Description:
Description of GB975127
COMPLETE SPECIFICATION
New Chlorine- andSulphur-Containsllg Phosphate Ester
We, VEB FARBENFABRIK WOLFEN, of
Wolfen,Kreis Bitterfeld, Germany, a Corporation organised under the laws of Eastern
Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly described in and by the
followingstatement:
The present invention is concerned with new, insecticidally-active compounds and with the
preparation thereof.
The chemistry of perchloromethylmercaptan, which is obtained by the chlorination of carbon
disulphide, has recently made great advances, especially since the discovery of the known fungicideN (trichloromethylthio) - tetrahydrophthalimide (Captan).
We have now found that by the addition of perchloromethylmercaptan to dimethyl dichlorovinyl
phosphate, there is obtained the new and insecticidally-active dimethyl (hexchloromethylmercaptoethyl) phosphate of theformula:
EMI1.1
202/612
Since the reaction in question involves a radical reaction mechanism, attempts were made to use
benzoyl peroxide and ultra-violet light as caralysts. It was thereby ascertained that better results are to
be obtained by irradiation with ultra-violet light
The invention also consists in a process for the production of dimethyl (hexachlormethylmercaptoethyp phosphate, wherein perchloro-methyl mercaptan is reacted with dimethyl
dichlorovinyl phosphate in the presence of benzoyl peroxide or while irradiating with ultra-violet light.
In a preferred method of preparing the new compounds, equivalent amounts of perchloromethyl
mercaptan and dimethyl dichlorovinyl phosphate are placed in a reaction vessel made from Uviol
(Trade Mark) glass and subjected to irradiation from an ultra-violet lamp. At the end of the addition
reaction, the unreacted reaction components are removed by vacuum distillarion.
The addition product obtained, which is probably a mixture of the two compounds of the above-given
formulae, possesses a high insecticidal activity and a lower mammalian toxicity than dimethyl
dichlorovinyl phosphate.
It can be used for the formulation of insecticidal compositions by admixture with solid or liquid
diluents or carriers.
The following Examples are given for the purpose of illustrating the presentinvention:
EXAMPLE 1.
A mixture of 186 g. (1 mol) perchloromethyl mercaptan and 221 g. (1 mol) dimethyl dichlorovinyl
phosphate is placed in a reaction vessel made from uviol glass and provided with a cooling jacket and
irradiated with an ultraviolet lamp for 40 hours, with warer cooling.
Thedark yellow reaction product is subsequently freed from unreacted perchloromethyl mercaptan and
dimethyl dichlorovinyl phosphate by distillation in a vacuum. The product can thereby be separated
into three fractions
Boiling point Weight 1. Perchloromethyl mercaptan32"C./3 mm. Hg. 120 g.
2. Dimethyl dichlorovinyl126"C./3 mm. Hg. 140 g.
phosphate 3. Dimethyl (hexachloro- residue 135 g.
methylmercapto ethyl)
phosphate
The residue is taken up in ether, washed neutral with water, dried over anhydrous sodium sulphate and
the ether subsequently distilled off. Yield33% of theory.
The product is a dark brown liquid which distils in a vacuum with decomposition.
EXAMPLE 2.
0.3 ml. of a 0.1% solution of the product of Example 1 are placed on a round filter paper with a
diameter of 5.5 cm. and brought into contact with house flies(Mtesca domestics) in a 100 mL
erhlenmeyer flask. Comparative tests were carried out using 0.3 ml. of0.1% solutions of other
insecticidal compounds. The following results were obtained:
Active material Inability to fly after minutesDimethyl-p,(3-dichloro- 16.1ot,,B-dibromoethyl
phosphate
Dimethyl tetrachloroethyl 16.8
Phosphate
Dimethyl dichlorovinyl 7.2 phosphate
Product of Example 1 7.1
EXAMPLE 3.
0.8 ml. of a0.1% solution of the product of Example 1 are placed on a round filter paper with a
diameter of 9 cm. and brought into contact with corn weevils(SiteAtilius granarius) in a closed petri
203/612
dish. Comparative tests were carried out using 0.8 ml. of 0.1% solutions of other insecticidal
compounds. The following results were obtained:
Killing in percent after
Active material 3 hrs. 5 hrs.24 hrs.
Dimethyl-p,p-dichloro- 75.0 75.0 76.5oc,5-dibromoethyl phosphate
Dimethyl tetrachloroethyl 75.0 75.0 76.5 phosphate
Dimethyl dichlorovinyl 75.0 75.2 78.5 phosphateProduct of Example 1 75.0 75.0 76.5
EXAMPLE 4.
The product of Example 1 is stirred into wheat flour in concentrations of0.001 and0.005% and the
flour placed in small porcelain dishes with rice weevils(Tiibolium confusum).
Comparative tests were carried out using the same concentrations of other active materials.
The following results were obtained:
Percentage kill
Concentration initial final
Active material in % value valueDimethyl-(3,f3-dichloro 0.001 27.1 68.3cc,,8-dibromoethyl
phosphate 0.005 73.4 100.0
Dimethyl tetrachloroethyl 0.001 75.0 100.0 phosphate 0.005 75.0 100.0
Dimethyl dichlorovinyl 0.001 75.4 100.0 phosphate 0.005 75.4 100.0
Product of Example 1 0.001 75.0 100.0
0.005 75.4 100.0
The above test was carried out over a period of 10 days, the initial value being the average kill on the
first and second days of the test and the final value being the kill on the tenth and final day.
EXAMPLE 5.
For the toxicological testing of the product of Example 1, a2% solution thereof in Polydiol 200 was
used. The testing was carried out on female albino rats with a weight of100 # 5 g. On the basis of the
investigations, the toxicity value, according to the formula ofBehrens andKarber, was found to
be:LDs9 = 150 mg./kg. rat by oral administration.
The product of Example 1 possesses a lower mammalian toxicity than dimethyldichloro- vinyl
phosphate.
WHAT WE CLAIMIS:1. Dimethyl(hexachloro-methylmercapto ethyl) phosphate of theformula:
EMI3.1
2. Process for the production of dimethyl (hexachloro - methylmercaptoethyl) phosphate, wherein
perchloromethyl mercaptan is reacted with dimethyl dichlorovinyl phosphate in the presence of
benzoyl peroxide or while irradiating with ultra-violet light.
3. Process for the production of dimethyl (hexachloro - methylmercaptoethyl) phosphate, substantially
as hereinbefore described and with reference to Example 1.
4. Dimethylhexachloro - methylmercapto ethyl) phosphate, whenever produced by the process
according to claim 2 or 3.
5. Insecticidal compositions containing dimethyl(hexachloro -methyimercaptoethyl) phosphate as
daimed in Claim 1, together with a solid or liquid diluent or carrier.
**WARNING** end of DESC field may overlap start of CLMS **.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of GB975127
204/612
**WARNING** start of CLMS field may overlap end of DESC **.
EXAMPLE 4.
The product of Example 1 is stirred into wheat flour in concentrations of0.001 and0.005% and the
flour placed in small porcelain dishes with rice weevils(Tiibolium confusum).
Comparative tests were carried out using the same concentrations of other active materials.
The following results were obtained:
Percentage kill
Concentration initial final
Active material in % value valueDimethyl-(3,f3-dichloro 0.001 27.1 68.3cc,,8-dibromoethyl
phosphate 0.005 73.4 100.0
Dimethyl tetrachloroethyl 0.001 75.0 100.0 phosphate 0.005 75.0 100.0
Dimethyl dichlorovinyl 0.001 75.4 100.0 phosphate 0.005 75.4 100.0
Product of Example 1 0.001 75.0 100.0
0.005 75.4 100.0
The above test was carried out over a period of 10 days, the initial value being the average kill on the
first and second days of the test and the final value being the kill on the tenth and final day.
EXAMPLE 5.
For the toxicological testing of the product of Example 1, a2% solution thereof in Polydiol 200 was
used. The testing was carried out on female albino rats with a weight of100 # 5 g. On the basis of the
investigations, the toxicity value, according to the formula ofBehrens andKarber, was found to
be:LDs9 = 150 mg./kg. rat by oral administration.
The product of Example 1 possesses a lower mammalian toxicity than dimethyldichloro- vinyl
phosphate.
WHAT WE CLAIMIS:1. Dimethyl(hexachloro-methylmercapto ethyl) phosphate of theformula:
EMI3.1
2. Process for the production of dimethyl (hexachloro - methylmercaptoethyl) phosphate, wherein
perchloromethyl mercaptan is reacted with dimethyl dichlorovinyl phosphate in the presence of
benzoyl peroxide or while irradiating with ultra-violet light.
3. Process for the production of dimethyl (hexachloro - methylmercaptoethyl) phosphate, substantially
as hereinbefore described and with reference to Example 1.
4. Dimethylhexachloro - methylmercapto ethyl) phosphate, whenever produced by the process
according to claim 2 or 3.
5. Insecticidal compositions containing dimethyl(hexachloro -methyimercaptoethyl) phosphate as
daimed in Claim 1, together with a solid or liquid diluent or carrier.Data supplied from the esp@cenet
database - Worldwide
205/612
19. JP52051028
- 4/23/1977
HERBICIDE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP52051028
Inventor(s):
AYA MASAHIRO (--); SAITOU JIYUNICHI (--); KUME TOYOHIKO (--);
YASUI HITOSHI (--)
Applicant(s):
NIHON TOKUSHU NOYAKU SEIZO KK (--)
IP Class 4 Digits: C07F; A01N
IP Class:A01N9/36; C07F9/56; C07F9/58
E Class: C07F9/165A1; C07F9/553A7; C07F9/59E
Application Number:
JP19750126322 (19751022)
Priority Number: JP19750126322 (19751022)
Family: JP52051028
Equivalent:
US4132542; NL7611602; GB1527173; FR2328716; ES452592; DE2647481;
DD128336; BE847539; IE43805L; IE43805; GR63122; CS195315
Abstract:
Abstract of JP52051028
PURPOSE:Selective herbicides of organic phosphates effective for controlling weeds of Gramineae,
broadleaf weeds and perennual weeds in paddy fields by soil or post-emergennce treatment without
exerting damages to applied rice plants.Description:
Description of corresponding document: US4132542
This invention relates to new organic phosphoric acid esters having an excellent herbicidal activity and
their use in controlling harmful weeds. The invention also relates to herbicidal compositions
comprising the organic phosphoric acid ester as an active ingredient and to herbicidal method
employing such compounds.
Canadian Patent Specification No. 710,340 discloses that a compound of the formula ##STR2##
possesses a herbicidal activity.
The novel organophosphosphoric esters of the invention are of the formula ##STR3## in which R@1 is
lower alkyl (e.g. of up to 6 carbon atoms), cyclohexyl or phenyl;
R@2 is lower alkyl (e.g., of up to 6 carbon atoms);
R@3 is alkylene of up to 6 carbon atoms; and
X and Y are independently selected from oxygen and sulfur.
We have discovered that the specific O-phosphoric acid ester type compounds of formula (I) above
exhibit a very good weed-killing effect especially on paddy field weeds, such as gramineous weed,
broadleaf weed and perennial weeds and display selective herbicidal action causing no phytotoxicity to
cultured plants and thus is superior to conventional materials of this type. Particularly, the present
invention is based on the discovery that the specific compounds of formula (I) exhibit superior
herbicidal efficacy when used as either in pre-emergence or post-emergence treatment in paddy fields.
206/612
Preferably, for best activity, R@1 is C1 -C4 alkyl (namely, methyl, ethyl, n- or isopropyl or n-, iso-,
sec.- or tert.-butyl), cyclohexyl or phenyl, R@2 is C1 -C4 alkyl and R@3 is 1-methylpentamethylene
or hexamethylene.
The present invention also provides a process for the preparation of a compound of the formula (I), in
which (a) a phosphoryl chloride of the general formula ##STR4## in which R@1, R@2, X and Y have
the meanings stated above, is reacted with a glycolic acid amide of the general formula ##STR5## in
which R@3 has the meaning stated above, and
M@1 is hydrogen, an alkali metal atom or an ammonium group, preferably hydrogen, sodium or
potassium, or (b), provided Y is to be sulphur, a thiophosphate of the general formula ##STR6## in
which R@1, R@3 and X have the meanings stated above, and
M@2 is an alkali metal atom or an ammonium group, preferably sodium, potassium or ammonium,
is reacted with a halide of the general formula
Hal-R@2
(V),
in which
R@2 has the meaning given above, and
Hal is a halogen atom, preferably chlorine or bromine.
When O-ethyl-S-n-propyldithiophosphoryl chloride and glycolic acid N-(2-methylpiperidide) are used
as starting materials in process variant (a), the course of the reaction can be illustrated by the following
equation: ##STR7##
When potassium O-ethyl-O-(N-2-methylpiperidinocarbonylmethyl)thiophosphate and methyl chloride
are used as starting materials in process variant (b), the course of the reaction can be illustrated by the
following equation: ##STR8##
Examples of the phosphoryl chlorides of the formula (II) include O-ethyl-S-n-propyldithiophosphoryl
chloride, O-isopropyl-S-ethylthiolphosphoryl chloride, O-ethyl-S-methylthiolphosphoryl chloride, Osec.-butyl-S-ethylthiolphosphoryl chloride, O-cyclohexyl-S-methylthiolphosphoryl chloride, O-phenylS-ethylthiolphosphoryl chloride and O-phenyl-O-ethylphosphoryl chloride.
Examples of the glycolic acid amides of the formula (III) include glycolic acid 2-methylpiperidide,
glycolic acid hexamethyleneimide and the potassium or sodium salts thereof.
Process variant (a) may be effected in the presence of an acid-binding agent, especially when M@1 is
hydrogen. Any of the customary acid acceptors may be used for this purpose, for example a hydroxide,
carbonate, bicarbonate or alcoholate of an alkali metal, or a tertiary amine, for example triethylamine,
diethylaniline or pyridine.
Alternatively, the need for an acid-binding agent can be dispensed with, by employing the glycolic acid
amide in the form of an alkali metal salt or an ammonium salt.
Examples of the thiophosphates of the formula (IV) include potassium, sodium or ammonium O-ethylO-(2-methylpiperidinocarbonylmethyl)dithio-, O-ethyl-O-(2-methylpiperidinocarbonylmethyl)thio-, Oisopropyl-O-(2-methylpiperidinocarbonylmethyl)thio-, O-sec.-butyl-O-(2methylpiperidinocarbonylmethyl)thio-, O-cyclohexyl-O-(2-methylpiperidinocarbonylmethyl)thio- and
O-phenyl-O-(2-methylpiperidinocarbonylmethyl)thiophosphates.
Examples of the halides of the formula (V) include methyl chloride, methyl bromide, ethyl chloride,
ethyl bromide, n-propyl chloride and n-propyl bromide.
The preparative process, whether variant (a) or variant (b), is preferably carried out in the presence of a
solvent or diluent, preferably an inert organic solvent.
Examples of suitable solvents and diluents include water; aliphatic, alicyclic and aromatic
hydrocarbons (which may be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin,
benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride,
207/612
trichloroethylene and chlorobenzene; ethers such as diethyl ether, methyl ethyl ether, di-isopropyl
ether, dibutyl ether, propylene oxide, dioxan and tetrahydrofuran; ketones such as acetone, methyl ethyl
ketone, methyl isopropyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile
and acrylonitrile; alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; esters
such as ethyl acetate and amyl acetate; acid amides such as dimethyl formamide and dimethyl
acetamide; and sulfones and sulfoxides such as dimethyl sulfoxide and sulfolane. Bases such as
pyridine can serve as a solvent and, in process variant (a), also as acid-binding agents.
Both process variants can be carried out over a wide temperature range. Generally, the reaction is
effected at temperatures between -20 DEG C. and the boiling point of the mixture, preferably between
0 DEG and 100 DEG C. Furthermore, the reaction is preferably effected at normal pressures, although
it is also possible to effect the reaction under an elevated or reduced pressure.
The compounds of the present invention exhibit an excellent weed-killing activity, especially against
weeds that occur in paddy fields, or other crops such as soy beans, sugar beets, cotton etc., for example
gramineous weeds, broadleaved weeds and perennial weeds. By "weeds" in the broadest sense are
meant all unwanted plants growing in cultivated or uncultivated areas.
The present compounds are superior to conventional herbicides and to the structurally analogous
compound of the formula (VI) in that they show an excellent selective herbicidal effect, when used in
appropriate amounts, whether they are used in pre-emergence or in post-emergence treatments.
The compounds of the present invention, when used in appropriate amounts, exhibit little or no
phytotoxicity towards crop plants, especially rice plants. In this respect they appear to be better than
conventional compounds such as PCP or NIP (2,4-dichlorophenyl-4'-nitrophenyl ether), which are
widely used as herbicides in rice fields. The present compounds also show but little toxicity to warmblooded animals.
The present compounds exhibit a non-selective herbicidal action when used in large amounts (say, 6-30
kg of active compound per hectare) but exhibit excellent selective herbicidal action when used in
smaller amounts (say, 0.1-6 kg per hectare). Thus, they are active against the following weeds:
dicotyledons, such as Rotala indica Koehne, Lindernia pyxidaria L., and Polygonum persicaria L.; and
monocotyledons, such as Echinochloa crus-galli Beauvois, Monochoria vaginalis Presl, Eleocharis
acicularis L., Cyperus microiria Steudel, Sagittaria pygmaea Miquel, Potamogeton distinctus Bennett
and Alisma canaliculatum Braun and Bouche.
It should be noted that each of the above-named plants is merely a typical example of the stated genus;
the present compounds are effective against other species of weeds in the same genus.
The active compounds can be converted into the customary formulations, such as solutions, emulsions,
wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules,
aerosols, suspension-emulsion concentrates, and formulations used with burning equipment, such as
fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV (ultra-lowvolume) cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds
with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use
of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming
agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as
auxiliary solvents.
As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes,
toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as
chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or
paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers
and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or
208/612
strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as
water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal
temperatures and pressures, for example aerosol propellants, such as halogenated hydrocarbons, for
example freon.
As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays,
talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals,
such as highly-dispersed silicic acid, alumina or silicates.
Preferred examples of emulsifying and foam-forming agents include non-ionic and anionic emulsifiers,
such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example
alkylarylpolyglycol ethers, alkyl sulphonates, alkyl suphates and aryl sulphonates as well as albumin
hydrolyzation products; and preferred examples of dispersing agents include lignin sulphite waste
liquors and methyl cellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders,
granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the
formulations.
The active compounds according to the invention, as such or in their formulations, can (in order to
reinforce and supplement their spectrum of action in accordance with the intended use) be combined
with other herbicidal active compounds. The active compounds according to the invention can also be
used as a mixture with other active compounds, such as fungicides, insecticides and acaricides.
The formulations in general contain 0.1 to 95 percent by weight of active compound, preferably 0.5 to
90 percent by weight.
The active compounds can be used as such, in the form of their formulations or in the application forms
prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and
granules. They may be applied in the customary manner, for example by spraying, atomising, dusting,
scattering, mixing with soil, coating, fumigation, vaporising and watering.
The compositions may be diluted for actual application, and the amount of active compound used can
vary within substantial ranges. In general, the ready-to-use preparations contain 0.01 to 20%,
preferably 0.05 to 10%, by weight, of the active compound.
The active compounds can also be applied using the ULV method, whereby it is possible to apply
compositions that are 95% by weight active compound or even to use the active compound by itself.
In general, the active compound is applied to an area of agriculture in an amount of 0.1 to 10 kg per
hectare, preferably 0.3 to 6 kg per hectare. However, it is possible to employ application rates outside
the broader range.
The present invention also provides a herbicidal composition containing as active ingredient a
compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or
in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating weeds which comprises applying to the
weeds, or to a habitat thereof a compound of the present invention alone or in the form of a
composition containing as active ingredient a compound of the present invention in admixture with a
diluent or carrier.
The present invention further provides crops protected from damage by weeds by being grown in areas
in which immediately prior to and/or during the time of the growing a compound of the present
invention was applied alone or in admixture with a diluent or carrier.
209/612
It will be seen that the usual methods of providing a harvested crop may be improved by the present
invention.
The herbicidal compositions of this invention are illustrated by the following Examples, in which the
active compounds are identified by the number of the corresponding preparative Example. Parts are by
weight.
EXAMPLE (I)
Fifteen parts of compound No. 2, 80 parts of a mixture of siliceous earth and kaolin (at a ratio of 5:1)
and 5 parts of an emulsifier (a polyoxyethylene alkylphenylether) were mixed by pulverization, thereby
forming a wettable powder. The resulting wettable powder was diluted with water and applied by
spraying.
EXAMPLE (II)
Thirty parts of compound No. 6, 30 parts of xylene, 30 parts of methylnaphthalene and 10 parts of a
polyoxyethylene alkylphenylether were mixed by stirring, thereby forming an emulsifiable concentrate.
The resulting concentrate was diluted with water before being applied by spraying.
EXAMPLE (III)
Two parts of compound No. 4 and 98 parts of a mixture of talc and clay (at a ratio of 1:3) were mixed
by pulverization, thereby forming a dusting agent.
EXAMPLE (IV)
1.5 parts of compound No. 3, 0.5 part of isopropyl hydrogen phosphate (PAP), and 98 parts of a
mixture of talc and clay (at a ratio of 1:3) were mixed by pulverization, thereby forming a dusting
agent.
EXAMPLE (V)
Twenty-five parts of water were added to a mixture comprising 10 parts of compound No. 1, 10 parts
of bentonite, 78 parts of a mixture of talc and clay (at a ratio of 1:3) and 2 parts of lignin sulfonate.
The resulting mixture was compacted well and then finely divided into granular form of 20-40 mesh,
by means of an extruder granulator, and dried at 40 DEG-50 DEG C., thereby forming a granular agent.
EXAMPLE (VI)
Ninety-five parts of clay particles having a particle size distribution of0.2 to 2 mm were charged into a
rotary mixer, and 5 parts of compound No. 7 dissolved in an organic solvent were sprayed onto said
particles in the mixer during rotation. After the product had been rendered homogeneous, it was dried
at 40 DEG-50 DEG C., thereby giving a granular agent.
EXAMPLE (VII)
0.5 part of compound No. 8, 20 parts of a mixture of high-boiling-point aromatic compounds and 9.5
parts of kerosine were mixed by stirring, thereby giving an oil preparation.
The herbicidal activity of the present compounds is illustrated by the following biotest Examples.
Again, each of the compounds of this invention is identified by the number of the corresponding
preparative Example.
EXAMPLE A
Pre-emergence treatment under flooded conditions against paddy-field weeds (pot test)
210/612
Production of the active-compound preparation
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of benzyloxypolyglycol ether
The preparation of the active compound was obtained by mixing one part by weight of the active
compound with the above-stated amounts of solvent and emulsifier. The emulsifiable concentrate
obtained in this manner was then diluted with water to the required concentration.
Test Method:
Wagner pots (0.0002 are) were charged with soil from a paddy field. Two rice plants (Kinmaze variety)
at the two- or three-leaved stage (about 10 cm high) were transplanted into each pot. In addition,
Echinochloa crus-galli, Cyperus sp., Eleocharis acicularis L. and seeds of various broad-leaved weeds
(including Monochoria vaginalis Presl, Rotala indica Koehne, and Lindernia pyxidaria L.) were also
planted and the whole was maintained in a wet condition. Two days after transplantation, each pot was
flooded with water to a depth of 3 cm. The active-compound preparation was then applied at a
prescribed dosage.
After this treatment, water was allowed to leak out of each pot for two days at a rate of 2-3 cm per day.
Thereafter, each pot was maintained in a flooded condition to a depth of 3 cm. Four weeks after the
treatment with the active-compound preparation, the herbicidal efficacy and the phytotoxicity towards
the rice plants were evaluated, in comparison with untreated control pots, on the following scales.
Herbicidal efficacy
5 - more than 95%
4 - more than 80%
3 - more than 50%
2 - more than 30%
1 - more than 10%
0 - 10% or less
Phytotoxicity towards rice plants
5 - more than 90% (plant completely injured)
4 - more than 50%
3 - more than 30%
2 - 30% or less
1 - less than 10%
0 - 0% (no phytotoxicity)
The test results are shown below in Table A.
>;tb;
Table A
>;tb;__________________________________________________________________________
>;tb;Pre-emergence treatment under flooded conditions.
>;tb;
Dosage rate of
>;tb;
Herbicidal Efficacy
>;tb;Compound
>;tb;
active compound
>;tb;
Echinochloa
>;tb;
Eleocharis
>;tb;
Cyperus
>;tb;
Broadleaved
>;tb;
Phytotoxicity
>;tb;No. (kg/ha) crus-galli
>;tb;
acicularis
>;tb;
sp. weeds Rice plants
>;tb;__________________________________________________________________________
>;tb;1
4
5
5 5 5
0
211/612
>;tb;
2
5
5 5 5 0
>;tb;
1
5
5 5 5 0
>;tb;2
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
5
5 5 5 0
>;tb;3
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
5
5 5 5
0
>;tb;4
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
5
4 5 5 0
>;tb;5
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
4
4 5 4 0
>;tb;6
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
5
5 5 5 0
>;tb;7
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
5
5 5 5 0
>;tb;8
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
5
5 5 5 0
>;tb;(VI) 4
5
5 5 3
4
>;tb;Comparison
>;tb;
2
4
4 4 2 3
>;tb;compound
>;tb;
1
3
3 4 0 1
>;tb;__________________________________________________________________________
>;tb; NOTE: The comparison compound is described in Canadian Patent 710,340 and
>;tb; has the formula
>;tb; ##STR9##
EXAMPLE B
Post-emergence treatment under flooded conditions against paddy-field weeds (pot test)
Production of the active-compound preparation
The active-compound preparation was obtained in the manner described in Example A.
Test method
Wagner pots (0.0002 are) were charged with soil from a paddy field. Two rice plants (Kinmaze variety)
at the two- or three-leaved stage (about 10 cm high) were transplanted into each pot. In addition,
Echinochloa crus-galli, Cyperus sp., Eleocharis acicularis L. and seeds of various broad-leaved weeds
(including Monochoria vaginalis Presl, Rotala indica Koehne and Lindernia pyxidaria L.) were also
planted and the whole was maintained in a wet condition.
The active-compound preparation was applied when the Echinochloa crus-galli had grown to the twoleaved stage (about 7-9 days after being planted). At the time of the treatment with the activecompound preparation, each pot was flooded to a depth of 6 cm.
After this treatment, water was allowed to leak from each pot for two days at a rate of 2 to 8 cm per
day. Thereafter, each pot was maintained in a flooded condition, to a depth of 3 cm. Four weeks after
treatment, the herbicidal efficacy and the phytotoxicity towards the rice plants were evaluated, in
comparison with untreated control pots, on the scales given in Example A.
The results obtained are given below in Table B.
212/612
>;tb;
Table B
>;tb;__________________________________________________________________________
>;tb;Post-emergence treatment under flooded conditions
>;tb;
Dosage rate of
>;tb;
Herbal Efficacy
>;tb;Compound
>;tb;
active compound
>;tb;
Echinochloa
>;tb;
Eleocharis
>;tb;
Cyperus
>;tb;
Broadleaved
>;tb;
Phytotoxicity
>;tb;No. (kg/ha) crus-galli
>;tb;
acicularis
>;tb;
sp. weeds Rice plants
>;tb;__________________________________________________________________________
>;tb;1
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
5
5 5 5 0
>;tb;2
4
5
5 5 5
0
>;tb;
2
5
5 5 5 0
>;tb;
1
5
4 5 4 0
>;tb;6
4
5
5 5 5
0
>;tb;
2
5
5 5 5
0
>;tb;
1
5
5 4 4 0
>;tb;(VI) 4
4
4 5 3
4
>;tb;Comparison
>;tb;
2
3
2 3 0 3
>;tb;compound
>;tb;
1
1
1 2 0 0
>;tb;__________________________________________________________________________
>;tb; NOTE: The comparison compound is described in Canadian Patent No. 710,340
>;tb; and has the formula
>;tb; ##STR10##
>;tb; The process for preparing the compounds of the invention is illustrated in the following preparative
Examples.
EXAMPLE 1 ##STR11##
2.8 g of anhydrous potassium carbonate were added to a solution comprising 4.4 g (0.02 mole) of Oethyl-S-n-propyldithiophosphoryl chloride, 3.2 g (0.02 mole) of glycolic acid-2-methylpiperidide and
20 ml of toluene. The resulting solution was then stirred at 30-35 DEG C. for 18 hours. After
completion of the reaction, the reaction mixture was cooled to room temperature and washed with
water, a 5 % aqueous potassium hydroxide solution and water in that order. The organic layer was
separated and collected, and then dried with anhydrous sodium sulfate. After removal of toluene by
distillation there were obtained 5.5 g of O-ethyl-S-n-propyl-O-(2-methylpiperidinocarbonylmethyl)
phosphorodithioate. This final product had a refractive index nD@20 of 1.5310.
EXAMPLE 2 ##STR12##
To a solution comprising 4.1 g (0.02 mole) of O-isopropyl-S-ethylthiophosphoryl chloride, 3.2 g (0.02
mole) of glycolic acid-2-methylpiperidide and 20 ml of toluene there were added 2.1 g (0.02 mole) of
triethylamine at 20-30 DEG C., and the resulting solution was stirred for 1 hour. Thereafter, it was
stirred at 50-60 DEG C. for 1 hour and then at 80 DEG C. for 1 hour. After completion of the reaction,
the reaction mixture was cooled to room temperature and washed with water, dilute hydrochloric acid,
a 5% aqueous sodium hydroxide solution and water in that order. The organic layer was separated and
collected. By following the procedure of Example 1 there were obtained 5.5 g of O-isopropyl-S-ethyl-
213/612
O-(2-methylpiperidonocarbonylmethyl) phosphorothioate. This product had a refractive index nD@20
of 1.4967.
The compounds shown in Table 1 below were prepared by methods analogous to those of the
preceding Examples.
>;tb;
Table 1
>;tb;__________________________________________________________________________
>;tb; ##STR13##
>;tb;Compound
Refractive Index
>;tb;No. R@1 R@2
>;tb;
R@3
X Y nD@20
>;tb;__________________________________________________________________________
>;tb;3 C2 H5
>;tb;
CH3
>;tb;
##STR14## O S 1.4985
>;tb;
##STR15##
>;tb;
C2 H5
>;tb;
##STR16## O S 1.4942
>;tb;5
>;tb;
##STR17##
>;tb;
CH3
>;tb;
##STR18## O S 1.5120
>;tb;6
>;tb;
##STR19##
>;tb;
C2 H5
>;tb;
##STR20## O S 1.5412
>;tb;7
>;tb;
##STR21##
>;tb;
C2 H5
>;tb;
##STR22## O O 1.5095
>;tb;8
>;tb;
##STR23##
>;tb;
C2 H5
>;tb;
CH2 CH2 CH2 CH2 CH2 CH2
>;tb;
O O 1.5556
>;tb;__________________________________________________________________________
it will be understood that the specification and examples are illustrative but not limitative of the present
invention and that other embodiments within the spirit and scope of the invention will suggest
themselves to those skilled in the art.Data supplied from the esp@cenet database - Worldwide
214/612
20. JP53003527
- 1/13/1978
METHOD OF RESTRAINING WEED GROWTH IN RICE FLELD USING
ALKYL*AMINOCARBONYL*PHOSPHONATE SALT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP53003527
Inventor(s):
JIEEMUSU NOTSUKUSU REINORUZU (--)
Applicant(s):
DU PONT (--)
IP Class 4 Digits: C07F; A01N
IP Class:A01N9/36; C07F9/58; C07F9/44; C07F9/65
E Class: A01N57/18; C07F9/40A9Q
Application Number:
JP19770012210 (19770208)
Priority Number: US19760699934 (19760625)
Family: JP53003527
Equivalent:
US4084952
Abstract:
Abstract not available for JP53003527
Abstract of corresponding document: US4084952
Alkyl(aminocarbonyl)phosphonate salts are added to rice cultures in order to control problem
herbaceous plant growth.Description:
Description of corresponding document: US4084952
BACKGROUND OF THE INVENTION
A broad range of alkyl(aminocarbonyl)phosphonate salts is disclosed in U.S. Pat. No. 3,846,512. These
compounds are extremely useful as plant growth regulants.
The presence of undesired vegetation in rice is an especially important problem for the world at this
time. Faced with the current world situation, wherein food shortages are acute in many different areas,
it is most important not to lose a portion of a valuable crop such as rice because of the presence of this
undesired vegetation. In particular, two kinds of herbaceous weeds, arrowhead, Sagittaria sp. and
nutsedge, Cyperus serotinus or rotundus are especially troublesome for rice crops. In the past, these
herbaceous weeds have been extremely difficult to control. Thus, a need exists for a particularly
effective compound which will control the growth of these weeds and prevent them from damaging a
significant part of the rice crop.
SUMMARY OF THE INVENTION
According to this invention, it has unexpectedly been discovered that a compound of Formula I may be
utilized for the post-harvest control of arrowhead, Sagittaria sp. and nutsedge Cyperus serotinus or
rotundus. ##STR1## wherein R1 is alkyl of 1 through 8 carbon atoms, chloroalkyl of 1 through 8
carbon atoms containing up to 3 chlorine atoms, bromoalkyl of 1 through 8 carbon atoms containing up
to 3 bromine atoms, alkoxy alkyl of from 3 through 10 carbon atoms, total, alkenyl of 2 through 8
carbon atoms, alkynyl of 3 through 4 carbon atoms, phenyl or benzyl;
215/612
R2 and R3 can be the same or different and each can be hydrogen, alkyl of 1 through 4 carbon atoms,
hydroxy alkyl of 2 through 4 carbon atoms, alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through
4 carbon atoms; R2 and R3 can be taken together to form a ring wherein R2 and R3 taken together are -(CH2)2 --O--(CH2 O2 -- or --(CH2)n -- where n is 4, 5 or 6 or one of R2 and R3 can be ##STR2##
where R4 is hydrogen or alkyl of 1 through 4 carbon atoms and R5 is hydrogen or alkyl of 1 through 4
carbon atoms, and
M is hydrogen, sodium, lithium, potassium, calcium, magnesium, zinc, manganese, barium or
##STR3## where R6, R7 and R8 can be the same or different and each can be hydrogen, alkyl of 1
through 4 carbon atoms or hydroxy alkyl of 2 through 4 carbon atoms; and R9 is hydrogen, alkyl of 1
through 12 carbon atoms, ##STR4## where R4 is hydrogen or alkyl of 1 through 4 carbon atoms and
R5 is hydrogen or alkyl of 1 through 4 carbon atoms or benzyl.
Preferred for their high biological activity are those compounds of formula I where, independently:
(a) R1 is alkyl of 1 through 4 carbon atoms or alkenyl of 3 through 4 carbon atoms,
(b) R2 and R3 are both equal to hydrogen,
(c) M is ammonium or an alkali metal such as sodium, lithium or potassium.
More preferred for their higher activity are those compounds of formula I where R1 is alkyl of 1
through 4 carbon atoms, R2 and R3 are both hydrogen and M is ammonium or an alkali metal such as
sodium, lithium or potassium.
Specifically preferred for their outstanding herbicidal activity are:
(a) Ammonium ethyl (aminocarbonyl) phosphonate m.p. 173 DEG-176 DEG C
(b) Ammonium methyl (aminocarbonyl) phosphonate m.p. 148 DEG-152 DEG C.
PREPARATION OF THE COMPOUND
The compounds of the instant invention may be prepared according to the process disclosed in U.S.
Pat. 3,846,512, the disclosure of which is herein incorporated by reference.
Basically, the process involves the following equation: ##STR5##
FORMULATION OF THE COMPOUNDS
The growth controlling compositions of the present invention can be prepared by admixing at least one
of the compounds of this invention with pest control adjuvants or modifiers to provide compositions in
the form of dusts, water-soluble powders, solutions, granules or pellets.
Compositions of the invention may contain as a conditioning agent, one or more surface-active agents,
sometimes called surfactants, in amounts sufficient to render a given composition containing the
compound of this invention readily soluble in water or capable of wetting foliage efficiently.
The surface-active agent used in this invention can be a wetting, dispersing or an emulsifying agent
which will assist dispersion and solution of the active compound. The surface-active agent or surfactant
can include such anionic, cationic and non-ionic agents as have heretofore been generally employed in
plant control compositions of similar type. Suitable surface-active agents are set forth, for example, in
"Detergents and Emulsifiers", 1975 Annual by John W. McCutcheon, Inc.
In general, less than 10% by weight of the surface-active agent will be used in compositions of this
invention and ordinarily the amount of surface-active agents will range from 1-5% but may even be
less than 1% by weight.
Additional surface-active agents can be added to the formulations to increase the ratio of
surfactant:active ingredient up to as high as 5:1 by weight. Such compositions may have a greater
effectiveness than can be expected from a consideration of the activity of the components used
separately. When used at higher rates, it is preferred that the surfactant be present in the range of onefifth to five parts surfactant for each one part of active agent.
WATER-SOLUBLE POWDERS
216/612
Water-soluble powders are compositions containing the water-soluble active material, an inert solid
extender which may or may not be water-soluble, and optionally one or more surfactants to provide
rapid wetting and solution. A buffer, which may also function as an extender, can be present to
improve formulation stability and control the pH of the final spray solution.
The classes of extenders suitable for the water-soluble powder formulations of this invention are the
natural clays, diatomaceous earth, synthetic mineral fillers derived from silica and silicate, starch,
sugar, and inorganic salts. Most preferred fillers for this invention are kaolinites, attapulgite clay,
montmorillonite clays, synthetic silicas, synthetic magnesium silicate, calcium sulfate dihydrate, and
disodium hydrogen phosphate.
Suitable surfactants for use in such compositions are those listed by J. W. McCutcheon in "Detergents
and Emulsifers", 1975 Annual. Among the more preferred surfactants are the non-ionic and anionic
types, and those most suitable for the preparation of the dry, soluble products of this invention are solid
forms of compounds known to the art as wetters and dispersants. Occasionally a liquid, non-ionic
compound classified primarily as an emulsifier may serve as both wetter and dispersant.
Most preferred wetting agents are alkylbenzene- and alkylnaphthalene-sulfonates, sulfated fatty
alcohols, amines or acid amides, long-chain acid esters of sodium isethionate, esters of sodium
sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils
and ditertiary acetylenic glycols. Preferred dispersants are methylcellulose, polyvinyl alcohol lignin
sulfonates, polymeric alkylnaphthalenesulfonates, sodium naphthalenesulfonate, polymethylene
bisnaphthalenesulfonate, and sodium N-methyl-N-(long chain acid)taurates.
Wetting and dispersing agents in these preferred water-soluble compositions of this invention are
usually present at concentrations of from about 0.5 weight percent to 5 weight percent. The inert
extender then completes the formulation. Where needed, 0.1 weight percent to 1.0 weight percent of
the extender may be replaced by a corrosion inhibitor or an anti-foaming agent or both.
Thus, water-soluble formulations of the invention will contain from about 25 to 95 weight percent
active material, from 0.5 to 2.0 weight percent wetting agent, from 0.25 to 0.5 weight percent
dispersant, and from 4.25 to 74.25 weight percent inert extender, as these terms are described above.
When the water-soluble powder contains a corrosion inhibitor or an anti-foaming agent or both, the
corrosion inhibitor will not exceed about 1 percent of the composition, and the anti-foaming agent will
not exceed about 0.5 percent by weight of the composition, both replacing equivalent amounts of the
inert extender.
SOLUTION CONCENTRATES
The aqueous solution concentrates are prepared by mixing a water-soluble active compound of this
invention with water. A portion of the water may be replaced with methanol, ethanol, isopropanol,
ethylene glycol, cellosolve or methyl cellosolve. Surfactants and buffering agents can optionally be
present.
These aqueous solution concentrates will contain from 15 to 60 percent active ingredient and from 40
to 85 percent water or mixture of water and hydroxylated organic solvent. Surfactants, corrosion
inhibitors, buffering and antifoam agents may also be included in which case they may replace up to 10
percent of the solvent system.
DUSTS
Dusts are dense powder compositions which are intended for application in dry form, in accordance
with the preferred compositions and methods of the invention. Dusts are characterized by their freeflowing and rapid settling properties so that they are not readily windborne to areas where their
presence is not desired. They contain primarily an active material and a dense, free-flowing, solid
extender.
217/612
Their performance is sometimes aided by the inclusion of a wetting agent, and convenience in
manufacture frequently demands the inclusion of an inert, adsorptive grinding aid. For the dust
compositions of this invention, the inert extender may be either of vegetable or mineral origin, the
wetting agent is preferably anionic or non-ionic and suitable adsorptive grinding aids are of mineral
origin.
Suitable classes of inert solid extenders for use in the dust compositions are those organic or inorganic
powders which possess high bulk density and are very free-flowing. They are also characterized by
possessing relatively low surface areas and are poor in liquid adsorption. Suitable classes of grinding
aids are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate.
Among ionic and non-ionic wetting agents, the most suitable are the members of the group known to
the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease of
incorporation some liquid non-ionic agents are also suitable in the dust formulations.
Preferred inert solid extenders for the dusts of this invention are micaceous talcs, pyrophyllite, dense
kaolin clays, tobacco dust and ground calcium phosphate rock.
Preferred grinding aids are attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic
calcium and magnesium silicates. Preferred wetting agents are those previously described under watersoluble powder formulations.
The inert solid extenders in the dusts of this invention are usually present in concentration of from
about 30 to 90 weight percent of the total composition. The grinding aid will usually constitute 5 to 50
weight percent of the composition, and the wetting agent will constitute from 0 to 1.0 weight percent of
the composition. Dust compositions can also contain other surfactants such as dispersing agents in
concentrations of up to about 0.5 weight percent.
The water-soluble powders described above can also be used in the preparation of dusts. While such
water-soluble powders could be used directly in dust form, it is more advantageous to dilute them by
blending with the dense dust diluent. In this manner, dispersing agents, corrosion inhibitors, and antifoam agents may also be found as components of a dust.
Thus, the dust compositions of this invention will comprise about 5 to 20 weight percent active
material, 5 to 50 weight percent adsorptive filler, 0 to 1.0 weight percent wetting agent, and about 30 to
90 weight percent dense, free-flowing dust diluent, as these terms are used herein. Such dust
formulations can contain, in addition, minor amounts of dispersants, corrosion inhibitors, and anti-foam
agents, derived from the water-soluble powders used to make the dusts.
GRANULES AND PELLETS
Under some circumstances it may be advantageous to apply the compounds of this invention in the
form of granules or pellets. Suitable carriers are natural clays, some pyrophyllites and vermiculites.
Wetting agents of the type listed by J. W. McCutcheon in "Detergents and Emulsifiers", 1975 Annual
can also be present to aid leaching of the active component.
One method of preparation suitable for both granules and pellets involves blending the active
ingredient with clays, water-soluble salts, surfactants and a small amount of water. After pelleting
and/or granulating, the formulation is dried prior to use. A second method suitable for the preparation
of granules formulation involves spraying a solution of the active material on porous, adsorptive,
preformed clay or vermiculite granules. Surfactants listed by McCutcheon can also be included in the
spray solution. After drying, the granules are ready for application.
The preferred granules or pellets will contain about 5 to 30 weight percent of active material, about 0 to
5 weight percent wetting agent and about 65 to 95 weight percent inert mineral carrier.
UTILITY
The carbamoylphosphonic salts of this invention may be used to control certain persistent weeds in rice
paddies after the harvest of one rice crop and prior to the planting of the next. These weeds, such as
218/612
arrowhead and nutsedge are not controlled by currently used selective rice herbicides. When sprayed
on the foliage of the weeds while they are growing, but after rice harvest, the phosphonates of this
invention cause retardation and prevent bud break on the vegetative propagules (stolons or tubers) of
these species. This effectively controls the plant the following season. These chemicals have little or no
effect on plants through the soil and cause no reaction in the following crop.
The compounds may be applied at rates of 1 to 20 kg/ha in sufficient carrier to distribute them
uniformly over the leaves of the weeds. Treatment must be applied while the weeds are green and
growing to insure that it will be translocated to the stolons or tubers. However, it must not be applied
before the crop is harvested.
EXAMPLE 1
Arrowhead, Sagittaria sp., was treated with ammonium ethyl(aminocarbonyl)phosphonate after water
had been drained from experimental rice pots at the rate of approximately 2-1/2 kg/ha. This treatment
caused marked growth retardation and prevented regrowth in the pots.
EXAMPLE 2
Nutsedge, Cyperus serotina, growing in experimental pots was treated with rates of ammonium
ethyl(aminocarbonyl)phosphonate at rates of 2-1/2, 5 and 10 kg/ha. Two and one-half months later the
tubers were dug from treated and control pots and their germination determined. The results are shown
below.
>;tb;______________________________________
>;tb;
Rate, Tubers
>;tb;Treatment
>;tb;
kg/ha Number Weight g.
>;tb;
Germination
>;tb;______________________________________
>;tb;Phosphonate
>;tb;
10
15
2
none
>;tb;
5
12
2
none
>;tb;
21/2 27
4
none
>;tb;Control -262
57
good
>;tb;______________________________________
EXAMPLE 3
Nutsedge, Cyperus rotundus, was treated with a foliar spray of ammonium
ethyl(aminocarbonyl)phosphonate or ammonium methyl(aminocarbonyl)phosphonate (B) in early
September. The data below were taken the last of April the next season. The results show that the
treatment effectively reduced the stand of nutsedge the next spring.
>;tb;______________________________________
>;tb;
Rate, Nutsedge at Cover
>;tb;Treatment
>;tb;
kg/ha Application on 9/9
>;tb;
Nutsedge 4/4
>;tb;______________________________________
>;tb;A
4
100
95
>;tb;
8
100
80
>;tb;
12
100
50
>;tb;B
4
100
90
>;tb;
8
100
35
>;tb;
12
100
15
>;tb;______________________________________Data supplied from the esp@cenet database Worldwide
219/612
21. JP55141495
- 11/5/1980
OOETHYL SSALKYL SSISOPROPYLPHOSPHORODITHIOLATE AND
NEMATOCIDE COMPRISING IT AS ACTIVE CONSTITUENT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP55141495
Inventor(s):
KOYANAGI MUTSUO (--); FUJITA YOSHIO (--); MUKAI KUNIO (--)
Applicant(s):
SUMITOMO CHEMICAL CO (--)
IP Class 4 Digits: C07F; A01N
IP Class:A01N57/12; C07F9/17
E Class: A01N57/12; C07F9/17
Application Number:
JP19790049208 (19790420)
Priority Number: JP19790049208 (19790420)
Family: JP55141495
Equivalent:
EP0018224; US4273769; HU184742
Abstract:
Abstract of JP55141495
NEW MATERIAL:The title compound of formula I (R is methyl or ethyl group). EXAMPLE:The
compound of formula I. USE:A nematocide against soil nematodes of the genera Heterodera (cyst
nematode), Pratylenchus (root leison nematode), and Meloidogyne (root-knot nematode), and
Aphelenchoides besseyi Christie (rice white-tip nematode), applicable during the growth of crops, with
safety and low toxicity to men and cattle, without phytotoxicity. PROCESS:A phosphorodithioate of
formula II (M is alkali metal; A is isopropyl, methyl, or ethyl group) is reacted with a halogen
compound of the formula Hal.B (Hal is halogen; B is isopropyl, methyl, or ethyl group, and when A is
isopropyl group B is methyl or ethyl group). Alternatively, a phosphorochloridothioate of formula IV is
reacted with a mercaptan of the formula HSB in the presence of a deacidification agent.Description:
Description of corresponding document: US4273769
This invention relates to an O-ethyl S-alkyl S-isopropyl phosphorodithiolate represented by the general
formula (I), ##STR1## wherein R represents methyl or ethyl group. It relates also to a nematocidal
composition comprising said dithiolate compound as an active ingredient.
The present compound represented by the general formula (I) is a novel nematocidal compound not
described in the literature, which can control a wide variety of harmful nematoda and exhibits little
phytotoxicity.
The nematocides in general use at present include D--D (a mixture of dichloropropene and
dichloropropane), EDB (ethylene dibromide), DBCP (1,2-dibromo-3-chloropropane), chloropicrin and
the like.
All of these chemicals diffuse as a gas through the soil and the nematoda die by contact with the gas.
However, in order to ensure the nematocidal effect, covering or water sealing of the field is necessary
for 7 to 14 days after application of the chemicals. Further, if a crop is transplanted or sowed while the
gas is still remaining, it will suffer from chemical injury. Accordingly, the field must be left as it is for
220/612
a long period after application of the chemicals or subjected to frequent degassing to remove the gas
from the soil. Owing to the non-cultivation period which is required or the troublesome degassing
work, an optimum sowing or planting time is often missed.
Beside the above-noted disturbance in effective utilization of the field owing to the chemical injury, a
high toxicity of chloropicrin gives rise to the pollution problem and other above-noted chemicals have
a disadvantage of high controlling chemical's cost per unit area.
The present inventors performed an investigation on the nematocidal effect of a series of
dithiolphosphate esters and as a result found that, as will become evident from the Examples herein
described, a distinguished nematocidal effect is exhibited by an ester in which the alkyl in the O-alkyl
linkage is ethyl, the alkyl in one S-alkyl linkage is isopropyl, and the alkyl in the other S-alkyl linkage
is methyl or ethyl, as compared with other esters having other alkyls closely related to those in the
former ester. Based on this finding, the present invention has been accomplished.
The compound of this invention is a compound which is safe, free from chemical injury, applicable
even during the vegetative period of the crops, is of high nematocidal activity, and of low toxicity to
man and animals. As contrasted to the conventional notion about the use of commercial nematocides,
the active ingredient of this invention is a distinguished nematocidal compound which is applicable to
the plant at any stage of growth.
The nematocide of this invention is effective in controlling a wide variety of nematoda including not
only soil nematoda such as cyst nematode, root-knot nematode and root-lesion nematode, but also other
nematoda such as rice white-tip nematode.
These O-ethyl S-alkyl S-isopropyl phosphorodithiolates are synthesized as described below.
The O-ethyl S-alkyl S-isopropyl phosophorodithiolates represented by the general formula (I) can be
prepared by any of the following methods A, B, C, D and E.
A. Synthesis by the reaction of a dithiophosphoric acid salt represented by the general formula (II),
##STR2## (wherein M represents an alkali metal atom such as, for example, potassium or sodium and
A represents isopropyl, methyl or ethyl group) with a halide of the general formula (III),
X--B
(III)
wherein X represents a chlorine, bromine or iodine atom and B represents isopropyl, methyl or ethyl
group, provided that B is methyl or ethyl group when A is isopropyl group; and B is isopropyl group
when A is methyl or ethyl group.
Among the reaction conditions, the reaction temperature is from room temperature to 100 DEG C., the
reaction time is from 30 minutes to 10 hours, and the molar ratio is 1 to 2 moles of the compound
represented by the formula (III) for 1 mole of the compound represented by the formula (II). The
reaction solvents include alcohols such as methanol and ethanol, ketones such as acetone, nitriles such
as acetonitrile, and water. When water is used as the reaction medium, the yield of the intended product
can be improved by adding 0.05 mole of a phase transfer catalyst such as tetra-n-butyl-ammonium
bromide for 1 mole of the compound of the formula (II).
B. Synthesis by the reaction of a thiophosphoric acid chloride represented by the general formula (IV),
##STR3## (wherein A is as defined above) with a mercaptan of the formula (V),
B--SH
(V)
(wherein B is as defined above) in the presence of an acid binding agent. As the acid binding agents,
mention may be made of organic bases such as triethylamine and pyridine.
The reaction conditions are such that the reaction temperature is 0 DEG to 100 DEG C., the reaction
time is 30 minutes to 10 hours and the molar ratio is 1 to 2 moles of the compound of formula (V) and
the acid binding agent for 1 mole of the compound of formula (IV). Examples of the reaction solvents
are hydrocarbons such as hexane, benzene and toluene, ethers such as ethyl ether, ketones such as
221/612
acetone and methyl isobutyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile, and
halohydrocarbons such as methylene chloride and chloroform.
C. Synthesis by the reaction of a thiophosphoric acid chloride of the above general formula (IV) with a
mercaptide of the formula (VI),
B--SM
(VI)
wherein B and M are as defined above.
The reaction conditions are such that the reaction temperature is 0 DEG to 100 DEG C., the reaction
time is 30 minutes to 10 hours, and the molar ratio is 1 to 1.1 moles of the compound of formula (VI)
for 1 mole of the compound of formula (IV). Examples of the reaction solvents are hydrocarbons such
as hexane, benzene and toluene, ethers such as ethyl ether, ketones such as acetone and methyl isobutyl
ketone, esters such as ethyl acetate, nitriles such as acetonitrile and halohydrocarbons such as
methylene chloride and chloroform.
D. Synthesis in two steps. In the first step, a phosphorochloridodithioite represented by the general
formula (VII), ##STR4## (wherein G represents methyl or ethyl group) is reacted with ethanol in the
presence of an acid binding agent under a nitrogen atmosphere to synthesize a phosphorodithioite
represented by the general formula (VIII), ##STR5## (wherein G is as defined before) and in the
second step, this compound is treated with an oxidizer.
The acid binding agent used is an organic base such as triethylamine or pyridine and the oxidizer used
is a peroxide such as hydrogen peroxide. The reaction conditions in the first step are such that the
reaction temperature is 0 DEG to 5 DEG C., the reaction time is 1 to 3 hours, and the molar ratio is 1 to
1.5 moles of ethanol and the acid binding agent for 1 mole of the compound of formula (VII). The
reaction solvents are hydrocarbons such as hexane and benzene, ketones such as acetone and methyl
isobutyl ketone, ethers such as ethyl ether, esters such as ethyl acetate, and halohydrocarbons such as
chloroform.
The reaction conditions in the second step are such that the reaction temperature is 0 DEG to 100 DEG
C., the reaction time is 30 minutes to several hours, and the molar ratio is 1 to 1.2 moles of an oxidizer
for 1 mole of the compound of formula (VII). The reaction solvents are hydrocarbons such as hexane
and benzene, and halohydrocarbons such as methylene chloride.
E. Synthesis by the reaction of a phosphorochloridodithiolate represented by the formula (IX),
##STR6## (wherein G is as defined above) with ethanol in the presence of an acid binding agent, or by
the reaction of said compound of the formula (IX) with sodium ethylate. The acid binding agent is an
organic base such as triethylamine or pyridine. The reaction conditions are such that the reaction
temperature is 0 DEG to 100 DEG C., the reaction time is 30 minutes to 10 hours, and the molar ratio
is 1 to 1.5 moles of ethanol and the acid binding agent, or 1 to 1.5 moles of sodium ethylate for 1 mole
of the compound of formula (IX). The reaction solvents are hydrocarbons such as hexane, benzene, and
toluene, ethers such as ethyl ether, ketones such as acetone and methyl isobutyl ketone, esters such as
ethyl acetate, nitriles such as acetonitrile, and halohydrocarbons such as methylene chloride and
chloroform.
>;tb;______________________________________
>;tb;Compound Structural
Physical
>;tb;No.
formula
constant
>;tb;______________________________________
>;tb;Compound (1) of this invention
>;tb;
##STR7##
nD@26.0 1.5045
>;tb;Compound (2) of this invention
>;tb;
##STR8##
nD@26.0 1.4948
>;tb;Reference compound (a) (MOCAP.RTM.)
>;tb;
##STR9##
nD@26.0 1.5015
>;tb;Reference compound (b)
>;tb;
##STR10##
nD@26.0 1.4972
>;tb;Reference compound (c)
>;tb;
##STR11##
nD@26.0 1.5037
222/612
>;tb;Reference compound (d)
>;tb;
##STR12##
nD@26.0 1.4998
>;tb;Reference compound (e)
>;tb;
##STR13##
nD@26.0 1.5015
>;tb;Reference compound (f)
>;tb;
##STR14##
nD@27.5 1.5076
>;tb;______________________________________
Typical examples of synthesis are described below.
Synthesis Example 1 [Compound (1) of this invention]
Into 100 ml of acetone, was dissolved 11.9 g of potassium O-ethyl S-isopropyl dithiophosphate. After
addition of 10.6 g of methyl iodide, the solution was refluxed for one hour with stirring. The reaction
mixture was stripped of the acetone under reduced pressure. The residue was dissolved in toluene,
washed with a 5% aqueous sodium carbonate solution, then with water, and the toluene was removed
under reduced pressure, leaving behind 8.9 g of an oily substance. This substance was subjected to
silica gel column chromatography to yield 8.0 g of O-ethyl S-methyl S-isopropyl phosphorodithiolate
in the form of pale yellowish green oil having a refractive index (nD@26.0) of 1.5045.
Elementary analysis:
>;tb;______________________________________
>;tb;
Calculated for
>;tb;
C6 H15 O2 PS2
>;tb;C%
33.63
33.45
>;tb;H%
7.06
6.92
>;tb;P%
14.45
14.28
>;tb;______________________________________
Synthesis Example 2 [Compound (2) of this invention]
Into 100 ml of toluene, was dissolved 10.2 g of O-ethyl S-isopropyl thiophosphoric acid chloride
followed by 4.7 g of ethyl mercaptan. To the solution was added dropwise 6.0 g of triethylamine at
room temperature. After having been stirred for two hours at room temperature, the reaction mixture
was washed successively with 10% hydrochloric acid, water, 5% aqueous sodium carbonate solution,
and water. The toluene was removed under reduced pressure, leaving behind 8.1 g of an oily substance.
This oily substance was subjected to silica gel column chromatography to obtain 6.7 g of 0,S-diethyl Sisopropyl phosphorodithiolate in the form of yellowish green oil having a refractive index (nD@26.0)
of 1.4949.
Elementary analysis:
>;tb;______________________________________
>;tb;
Calculated for
>;tb;
C7 H17 O2 PS2
>;tb;
Found
>;tb;______________________________________
>;tb;C%
36.83
36.64
>;tb;H%
7.51
7.39
>;tb;P%
13.56
13.28
>;tb;______________________________________
Synthesis Example 3 [Compound (1) of this invention]
A mixture comprising 21.0 g of a 50% aqueous solution of potassium O-ethyl S-methyl
dithiophosphate, 11.1 g of isopropyl iodide and 0.8 g of tetra-n-butylammonium bromide was stirred at
50 DEG C. for one hour. The reaction mixture was extracted with 50 ml of toluene. The extract was
freed from the toluene under reduced pressure, leaving behind 9.5 g of an oily substance. This
substance was subjected to silica gel column chromatography to obtain 9.0 g of O-ethyl S-isopropyl Smethyl phosphorodithiolate.
223/612
Synthesis Example 4 [Compound (2) of this invention]
To a mixture of 4.4 g of sodium ethyl mercaptide and 50 ml of methyl isobutyl ketone, was added
dropwise at 0 DEG C. 10.1 g of O-ethyl S-isopropyl thiophosphoric acid chloride. The mixture was
stirred at 0 DEG C. for one hour and treated in a manner similar to that in Synthesis Example 2 to
obtain 9.1 g of O,S-diethyl S-isopropyl phosphorodithiolate.
Synthesis Example 5 [Compound (1) of this invention]
Into 20 ml of hexane, was dissolved 9.4 g of S-isopropyl S-methyl phosphorochloridodithioite. To the
solution was added dropwise at 0 DEG to 5 DEG C. a mixture of 2.8 g of ethanol and 6.1 g of
triethylamine. The resulting reactant mixture was stirred at 0 DEG to 5 DEG C. for 2 hours. The
reaction was carried out under a nitrogen atmosphere to prevent oxidation. After removal of
triethylamine hydrochloride by filtration, the filtrate was concentrated to obtain 9.4 g of O-ethyl Sisopropyl S-methyl phosphorodithioite. This product was dissolved in 20 ml of benzene and heated
under reflux. To the solution, while being kept under reflux, was added dropwise 5.9 g of 30% aqueous
hydrogen peroxide. The mixture was stirred at 80 DEG C. for one hour and then left standing to cool
down. The organic layer was washed twice with 20 g of a 5% aqueous sodium hydroxide solution and
then twice with water. Th benzene was removed under reduced pressure, leaving behind 9.1 g of a
reaction product which, on silica gel column chromatography, yielded 8.7 g of O-ethyl S-isopropyl Smethyl phosphorodithiolate.
Synthesis Example 6 [Compound (2) of this invention]
Into 30 ml of toluene, was dissolved 10.9 g of S-ethyl S-isopropyl phosphorochloridodithiolate
followed by 2.5 g of ethanol. To the solution, was added dropwise at room temperature 5.6 g of
triethylamine. The mixture was stirred for one hour at room temperature and then treated in a manner
similar to that in Synthesis Example 2 to obtain 6.5 g of O,S-diethyl S-isopropyl phosphorodithiolate.
The compounds of this invention prepared as described above are oily substances and are formulated in
a customary way by admixing with liquid, solid, or even gaseous carriers and, if necessary, various
adjuvants to prepare oil sprays, emulsifiable concentrates, wettable powders, granules or ducts, which
are applicable in a customary way. The compounds can, of course, be applied in admixtures with other
nematocides, insecticides, herbicides, fungicides, seed disinfectants, or fertilizer, soil-improving agent.
The effectiveness of this invention is described below with reference to test examples and preparation
examples. However, the active ingredients, adjuvants, preparations, etc., are, of course, not limited to
those described in the examples.
The above-noted preparations in various forms generally contain 0.1 to 90% by weight of active
ingredients (including active ingredients other than those of this invention) and are applied usually 25
to 500 g/10 ares. However, the application rate and concentration of the active ingredient vary with the
form of preparations, stage of the plant growth, application method, locality, type of the crop, etc.
Therefore, it is not necessary to stick to the above-noted range but the compound can be applied more
freely without any adverse effect.
Test Example 1
Controlling effect on tomato root-knot nematode when applied at the period of growing.
A mixture of 500 g of soil infested with root-knot nematode (Meloidgyne sp.) and an equal amount of
non-infested soil was placed in each 1/5,000-are Wagner pot and planted with each 6 tomato seedlings
of 3 to 4 leaf age. Two days after the seedlings had sufficiently rooted, an emulsion of the present
compound (1) or (2) prepared as described in Preparation Example 1 was drenched over the soil at a
rate of 80 ml/pot (4 liters/m@2). For comparison, other pots were similarly treated using DSCP and the
compounds (a) to (f).
After 21 days from the soil treatment, growth of the tomato plant and the formation of root knot were
observed and recorded according to the following criteria. Each test was repeated three times.
224/612
>;tb;______________________________________
>;tb;Formation of root knot
>;tb;Rating Degree of formation of root knot
>;tb;______________________________________
>;tb;0
The same as in untreated, non-infested
>;tb;
soil (i.e. no formation of root knot).
>;tb;1
Slight knot formation, as compared with
>;tb;
untreated, non-infested soil.
>;tb;2
Distinctive knot formation as compared
>;tb;
with untreated, non-infested soil.
>;tb;3
Formation of a large number of root knots
>;tb;
approximating to that in untreated,
>;tb;
infested soil.
>;tb;4
Formation of root knots, in number
>;tb;
comparable to or more than that in untreated,
>;tb;
infested soil.
>;tb;______________________________________
>;tb;______________________________________
>;tb;Growth of plant
>;tb;Rating Degree of growth of tomato seedling
>;tb;______________________________________
>;tb;A
The same as or better than the seedling
>;tb;
in non-infested soil.
>;tb;B
Slightly inferior to the seedling in non>;tb;
infested soil.
>;tb;C
Distinctively inferior to the seedling
>;tb;
in non-infested soil.
>;tb;D
Majority of seedlings withered or
>;tb;
markedly undergrown.
>;tb;______________________________________
The test results were as shown in Table 1.
>;tb;
TABLE 1
>;tb;______________________________________
>;tb;
Concentration
Growth of
>;tb;
of compound Root knot tomato
>;tb;Test compound
>;tb;
(ppm)
formation seedling
>;tb;______________________________________
>;tb;Compound (1) of
>;tb;
250
0
A
>;tb;this invention
>;tb;
125
0
A
>;tb;Compound (2) of
>;tb;
250
0
B
>;tb;this invention
>;tb;
125
0
A
>;tb;Reference 250
2
B
>;tb;compound (a)
>;tb;
125
3
B
>;tb;Reference
>;tb;compound (b)
>;tb;
250
4
B
>;tb;Reference
>;tb;compound (c)
>;tb;
250
4
B-C
>;tb;Reference 250
3
C
>;tb;compound (d)
>;tb;
125
3
B
225/612
>;tb;Reference (f)
>;tb;
250
4
B-C
>;tb;compound DBCP
>;tb;
500
2
C
>;tb;______________________________________
Test Example 2
Controlling effect on tomato root-knot nematode when applied at the time of transplanting.
A mixture of 500 g of soil infested with root-knot nematode (Meloidgyne sp.) and an equal amount of
non-infested soil was placed in each 1/5,000-are Wagner pot. A granule preparation containing the
compound (1) or (2) of this invention, prepared as described in Preparation Example 3, was added to
the pot at a rate of 0.2 g/pot (1 kg/are) and uniformly mixed with the soil in the upper depth of 15 cm.
Six tomato seedlings of 3 to 4 leaf age were then transplanted to each pot. For comparison, other pots
were similarly treated using as reference a diluted DBCP emulsion and granules containing the
compounds (a), (c) and (e).
After 21 days from the soil treatment, growth of the tomato plant and the formation of root knots were
observed and recorded in the same manner as in Test Example 1. Each test was repeated three times.
The test results were as shown in Table 2.
>;tb;
TABLE 2
>;tb;______________________________________
>;tb;
Amount of
Growth of
>;tb;
preparation
>;tb;
Root knot tomato
>;tb;Test compound (kg/are) formation seedling
>;tb;______________________________________
>;tb;Compound (1) of
>;tb;this invention
>;tb;
1 (0.05) 0
A
>;tb;Compound (2) of
>;tb;this invention
>;tb;
1 (0.05) 1
A
>;tb;Reference
>;tb;compound (a) 1 (0.05) 3
B
>;tb;Reference
>;tb;compound (c) 1 (0.05) 4
B
>;tb;Reference
>;tb;compound (e) 1 (0.05) 4
C
>;tb;Reference
>;tb;compound DBCP 500 ppm 1
C
>;tb;______________________________________
>;tb; Note:
>;tb; Figures in parentheses are the amounts applied of active compounds.
In all of the test plots treated with the compound (1) or (2) of this invention, substantially no root knot
was found and the growth of tomato seedling was also good, the test results having been distinctively
superior to those in the reference plots.
Test Example 3
Controlling effect on soybean cyst nematode when applied at the time of seeding.
A mixture of 500 g of soil infested with soybean cyst nematode (Heterodera glycines) and an equal
amount of non-infested soil was placed in each 1/5,000-are Wagner pot. After the emulsion containing
the compound (1) or (2) of this invention, prepared as described in Preparation Example 1, had been
sprayed over the soil at a rate of 80 ml/pot and uniformly mixed with the soil in the upper depth of 15
cm, 10 soybeans were seeded in each pot. For comparison, the same soil mixture as used above was
treated with a DBCP emulsion or the reference compound (a).
226/612
After 30 days from the chemical treatment, the growth of each soybean plant and the cyst adhesion
were inspected. The results of inspection were recorded in the same manner as in Test Example 1. Each
test was repeated three times. The test results were as shown in Table 3.
>;tb;
TABLE 3
>;tb;______________________________________
>;tb;
Concentration
Growth of
>;tb;
of preparation
>;tb;
Adhesion soybean
>;tb;Test compound
>;tb;
(ppm)
of cyst plant
>;tb;______________________________________
>;tb;Compound (1) of
>;tb;this invention
>;tb;
100
0
A
>;tb;Compound (2) of
>;tb;this invention
>;tb;
100
0
B
>;tb;Reference
>;tb;compound (a)
>;tb;
100
3
B-C
>;tb;Reference
>;tb;compound DBCP
>;tb;
500
2
B
>;tb;______________________________________
Test Example 4
Controlling effect on root-lesion nematode by application at the time of seeding.
A mixture of 500 g of soil infested with root-rod nematode (Pratylenchus sp.) and an equal amount of
uninfested soil was placed in each 1/5,000-are Wagner pot. The pot was applied with 0.2 g/pot (1
kg/are) of a dust preparation of the compound (1) or (2) of this invention. After the dust had been
uniformly mixed with the soil in the upper depth of 15 cm, 15 carrot seeds were sowed in each pot. For
comparison, the same soil mixture as used above was treated with a DBCP emulsion or the reference
compound (d).
After 60 days from the chemical treatment, the growth of each carrot and the development of rootlesion disease spots were inspected. The inspection results were recorded in the same manner as in Test
Example 1. Each test was repeated four times. The test results were as shown in Table 4.
>;tb;
TABLE 4
>;tb;______________________________________
>;tb;
Concentra>;tb;
tion of Development
>;tb;
preparation
>;tb;
of lesion Growth of
>;tb;Test compound
>;tb;
(ppm)
spot
carrot
>;tb;______________________________________
>;tb;Compound (1) of
>;tb;this invention
>;tb;
100
0
A
>;tb;Compound (2) of
>;tb;this invention
>;tb;
100
0
A
>;tb;Reference
>;tb;compound (d)
>;tb;
100
4
B
>;tb;Reference
>;tb;compound DBCP
>;tb;
500
1
B
227/612
>;tb;______________________________________
Test Example 5
A field with the soil infested with root-knot nematode (Meloidgyne sp.) was divided by plastic plates
into test plots, each 2 m.times.1 m in area. An oil spray preparation containing the compound (1) or (2)
of this invention, prepared as described in Preparation Example 5, was injected into the test plot soil at
the points 20 cm apart from each other and at a depth of 15 cm. The injected amount of the preparation
was 2 ml for each point (about 5 liters/are). The injected spots were covered with soil and left as such
for 5 days. Thereafter, 20/m@2 of tomato seedlings of 3 to 4 leaf age were transplanted at uniform
intervals. After 28 days from the tranplanting, tomato plants were collected and inspected for the
growth. It was found that the growth in each test plot was comparable to that in the control plot where
the soild had been uninfested. The number of root knots in the test plots was zero or several at most.
On the contrary, in the plot where the soil was infested and not subjected to the chemical treatment, the
growth of tomato plant in both plant height and root length was much retarded and the formation of a
large number of root knot was observed.
Preparation Example 1
Into 50 parts of xylene, was dissolved 40 parts of the compound (1) or (2) of this invention. The
resulting solution was admixed with 10 parts of an emulsifier, Sorpol SM-200 (trademark for Toho
Chemical Co.; a mixture of anionic and nonionic surface active agents) and stirred thoroughly to obtain
a 40% emulsifiable concentrate.
Preparation Example 2
To 40 parts of the compound (1) or (2) of this invenion, was added with stirring 75 parts of Sorpol SM200 (the same as described above). To the resulting uniform mixture, were added successively 20 parts
of carplex #80 (trademark for Shionogi and Co., a fine powder of synthetic hydrated silicon oxide) and
35 parts of 300-mesh diatomaceous earth. The mixture was passed through a commercial liquidizer to
obtain a 40% wettable powder.
Preparation Example 3
To 5 parts of the compound (1) or (2) of this invention, were added 5 parts of Toyolignin CT
(trademark for Toyobo Co.; a lignin sulfonate) and 90 parts of GSM Clay (trademark for Zieklite
Kogyo Co.). The mixture was thoroughly blended by means of an attrition mill. After addition of 10%
of water, the mixture was further stirred, then granulated by means of a granulator, and dried under the
air current to obtain a 5% granule preparation.
Preparation Example 4
Into 20 parts of acetone, was dissolved 5 parts of the compound (1) or (2) of this invention. To the
mixture, were added successively 3 parts of carplex #80 (the same as mentioned before), 0.3 part of
PAP (isopropyl hydrogenphosphate) and 91.7 parts of 300-mesh talc. The mixture was thoroughly
blended by means of a liquidizer and stripped of the acetone by evaporation to obtain a 5% dust
preparation.
Preparation Example 5
A 20% oil spray preparation was obtained by dissolving 20 parts of the compound (1) or (2) of this
invention in kerosene to make up a total of 100 parts.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of corresponding document: US4273769
What is claimed is:
228/612
1. An O-ethyl S-alkyl S-isopropyl phosphorodithiolate of the formula (I), ##STR15## wherein R is
methyl or ethyl group.
2. A compound according to claim 1 wherein R is methyl.
3. A method for controlling a nematode with a nematocidally effective amount of a compound
according to claim 1.
4. A nematocidal composition comprising an inert carrier and as the active ingredient a nematocidally
effective amount of a compound according to claim 1.
5. A nematocidal composition comprising an inert carrier and as the active ingredient a nematocidally
effective amount of a compound according to claim 2.Data supplied from the esp@cenet database Worldwide
229/612
22. JP58032890
- 2/25/1983
PHOSPHONIC ESTER DERIVATIVE, ITS PREPARATION, HEBICIDE
CONTAINING THE SAME AS ACTIVE INGREDIENT
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP58032890
Inventor(s):
SASAKI MITSURU (--); YOSHIDA AKIRA (--)
Applicant(s):
SUMITOMO CHEMICAL CO (--)
IP Class 4 Digits: C07F; A01N
IP Class:A01N57/22; C07F9/40
E Class: C07F9/32A1; C07F9/40A1; A01N57/22; A01N57/24; C07F9/58G
Application Number:
JP19810131694 (19810821)
Priority Number: JP19810131694 (19810821)
Family: JP58032890
Equivalent:
EP0073040; US4470841; BR8204905
Abstract:
Abstract of JP58032890
NEW MATERIAL:A derivative of formulaI(R1 is lower alkyl; R2 is 2,4-dichlorophenyl, 4tolyfluoromethylphenyl). EXAMPLE:o,o-Diisopropylphosphonomethyl alpha=4-(2',4'dichlorophenoxy)phenoxypropionate. USE:Herbicide with high selectivity for rice and wheat.
PREPARATION:The condensation reaction between a hydroxymethylphosphonic ester derivative such
as o,o-diisopylhydroxymethyl phsophonate and an acid chloride of formula III such as alpha-4-(2',4'dichlorophenoxy)phenoxypyorpionyl chloride is conducted in a solvent such as chloroform in the
presence of a base such as pyridine.Description:
Description of corresponding document: US4470841
The present invention relates to organic phosphorous compounds, and their production and use. More
particularly, it relates to organic phosphorus compounds of the formula: ##STR2## wherein R1 is a C1
-C4 alkyl group, a phenyl group or a C1 -C4 alkoxy group, R2 is a C1 -C4 alkyl group, R3 and R4,
which are the same or different, are each a hydrogen atom, a C1 -C4 alkyl group or a phenyl group and
R5 is a 2,4-dichlorophenyl group, a 4-trifluoromethylphenyl group or a 5-trifluoromethylpyridin-2-yl
group, and their production and use a herbicides.
Among the organic phosphorus compounds (I), preferred are those wherein R1 is a C1 -C2 alkyl group,
a phenyl group or a C1 -C4 alkoxy group, R2 is a C1 -C4 alkyl group, R3 is a hydrogen atom, a C1 -C3
alkyl group or a phenyl group, R4 is a hydrogen atom or a methyl group and R5 is a 2,4-dichlorophenyl
group, a 4-trifluoromethylphenyl group or a 5-trifluoromethylpyridin-2-yl group.
It is known that certain kinds of 2-(substituted pheoxy)propionic acid derivatives, for instance,
diclofopmethyl (i.e. methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propionate), metriflufen-methyl (i.e.
methyl 2-[4-(4-trifluoromethylphenoxy)phenoxy]propionate) and fluazifop-butyl (i.e. butyl 2-[4-(5trifluoromethyl-2-pyridyloxy)phenoxy]propionate), show a herbicidal activity against Graminaceous
weeds (cf. U.S. Pat. No. 3,954,442, GB No. 1519334B, GB No. 2015995A, etc.). However, these
230/612
known compounds have a poor selectivity between said harmful weeds and the important useful plants
such as rice plant.
As a result of the extensive study, it has now been found that the organic phosphorus compounds (I) of
the invention exhibit a prominent herbicidal potency against Graminaceous weeds germinated in the
paddy field, particularly barnyard grass (Echinochloa crus-galli), while exerting no material
phytotoxicity to the transplanted paddy rice. It has also been found that the organic phosphorus
compounds (I) of the invention show an excellent herbicidal activity against the Graminaceous weeds
in the crop field by pre-emergence soil treatment as well as post-emergence foliar treatment.
Particularly, in the post-emergence treatment, they show a strong herbicidal activity against a variety of
Graminaceous weeds such as wild oat (Avena fatua), barnyard grass, green foxtail (Setaria viridis),
blackgrass (Alopecurus myosuroides), downy brome (Bromus tectorum), johnsongrass (Sorghum
halepense), large crabgrass (Digitaria sanguinalis), annual bluegrass (Poa annua), volunteer corn (Zea
mays), etc. without any material phytotoxicity to broad-leaved crop plants such as soybeans, cotton or
sugarbeet, etc. Besides, they can be safely applied to the wheat fields to exterminate or prevent wild
oat, barnyard grass, green foxtail, blackgrass, downy brome, etc. germinated therein. Thus, the organic
phosphorus compounds (I) can be used as herbicides applicable for the fields of crops and vegetables,
etc.
The organic phosphorus compound (I) can be produced by reacting a hydroxyl compound of the
formula: ##STR3## wherein R1, R2, R3 and R4 are each as defined above with an acid halide of the
formula: ##STR4## wherein X is a halogen atom (e.g. chlorine, bromine) and R5 is as defined above in
an inert solvent (e.g. water, chloroform, ether, benzene, toluene) in the presence of a base such as an
organic tertiary amine (e.g. pyridine, triethylamine, N,N-dimethylaniline) or an inorganic base (e.g.
sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate). The base may be
employed in an amount of 1 to 2 equivalents to the hydroxyl compound (II).
The reaction proceeds ordinarily at a temperature of -70 DEG C. to 50 DEG C. and can be
accomplished within a period of 10 minutes to 24 hours, although it varies depending upon the starting
materials. By usual work-up, the objective organic phosphorus compound (I) is obtainable in a high
yield. If necessary, however, purification such as column chromatography may be applied.
The hydroxyl compound (II) used as the starting material in the above reaction can be produced
according to the method as described in Howben-Weyl: Methoden der Organischen Chemie, 12 (1), p.
475 (1964). Namely, it can be produced from the reaction between aldehydes (or ketones) and
phosphonic acid or its ester.
Alternatively, the organic phosphorus compound (I) can be obtainable by reacting an acid ester of the
formula: ##STR5## wherein X' is a halogen atom (e.g. chlorine, bromine) and R1, R2, R3 and R4 are
each as defined above with a hydroxyphenyl ether of the formula: ##STR6## wherein R5 is as defined
above in an organic solvent such as ketones (e.g. acetone, methylisobutylketone), dimethylformamide
or diethylformamide in the presence of a base (e.g. sodium carbonate, potassium carbonate). The base
may be employed in an amount of 1 to 1.5 equivalents to the acid ester (IV).
The reaction proceeds ordinarily at a temperature of 50 DEG C. to the refluxing temperature of the
solvent and can be accomplished within a period of 3 to 12 hours, although it varies depending upon
the starting materials. By usual work-up, the objective organic phosphorus compund (I) is obtainable in
a high yield. If necessary, however, purification such as column chromatography may be applied.
Some embodiments of the procedures for production of the organic phosphorus compounds (I) are
illustratively shown in the following Examples.
EXAMPLE 1
O,O-Diisopropyl hydroxymethyl phosphonate (1.0 g) and pyridine (1.0 g) were dissolved in
chloroform (10 ml), and .alpha.-4-(2',4'-dichlorophenoxy)phenoxypropionyl chloride (1.7 g) was
dropwise added thereto while stirring at 0 DEG to 5 DEG C. under ice-cooling. The resultant mixture
was stirred at room temperature (ca. 20 DEG C.) for 20 hours. A 3% aqueous solution of hydrochloric
231/612
acid (30 ml) was added thereto. Thirty minutes thereafter, the reaction mixture was separated in a
separatory funnel. The chloroform layer was washed with water, dried over magnesium sulfate and
filtered. Chloroform was evaporated in vacuo, and the residue was purified by silica gel
chromatography to give 1.26 g of O,O-diisopropylphosphonomethyl .alpha.-4-(2',4'dichlorophenoxy)phenoxypropionate (Compound No. 3). nD@21.5 1.5212.
EXAMPLE 2
O,O-Diethyl hydroxymethyl phosphonate (0.5 g) and pyridine (0.5 g) were dissolved in chloroform (5
ml), and the resultant solution was cooled to -20 DEG C. .alpha.-4-(4'Trifluoromethylphenoxy)phenoxypropionyl chloride (1.1 g) was dropwise added thereto while stirring.
After allowed to stand at room temperature for 2 hours and at 50 DEG C. for 3 hours, the resulting
mixture was cooled, and a 3% aqueous solution of hydrochloric acid (20 ml) was added thereto. Thirty
minutes thereafter, the reaction mixture was separated in a separatory funnel. The chloroform layer was
washed with water, dried over anhydrous magnesium sulfate and filtered. Chloroform was evaporated
in vacuo to give 1.03 g of O,O-diethylphosphonomethyl .alpha.-4-(4'trifluoromethylphenoxy)phenoxypropionate (Compound No. 6). nD@20 1.5000.
EXAMPLE 3
O,O-Diethyl .alpha.-hydroxyethyl phosphonate (1.8 g) and triethylamine (2.0 g) were dissolved in ether
(20 ml), and the resultant solution was cooled to 10 DEG C. while stirring. .alpha.-4-(5'Trifluoromethylpyridin-2-yloxy)phenoxypropionyl chloride (3.7 g) was added thereto at 10 DEG to 20
DEG C., and the resulting mixture was allowed to stand at a room temperature for 24 hours, followed
by addition of water (20 ml). The reaction mixture was separated in a separatory funnel. The ether layer
was dried over anhydrous magnesium sulfate and filtered. Ether was evaporated in vacuo, and the
residue was purified by silica gel chromatography to give 3.5 g of .alpha.-(O,O-diethylphosphono)ethyl
.alpha.'-4-(5'-trifluoromethylpyridin-2-yloxy)phenoxypropionate (Compound No. 11). nD@24.0
1.4780.
EXAMPLE 4
.alpha.-(O,O-Diethylphosphono)benzyl .alpha.'-bromopropionate (3.8 g) and 4-(5'trifluoromethylpyridin-2-yloxy)phenol (2.6 g) were dissolved in dimethylformamide (30 ml).
Potassium carbonate (1.5 g) was added thereto. The resultant mixture was allowed to stand at 90 DEG
to 100 DEG C. for 2 hours and cooled. The reaction mixture was poured onto ice-water (50 g) and
extracted with ether (20 ml.times.3 times). The ether layer was washed with water, dried over
anhydrous magnesium sulfate and filtered. Ether was evaporated in vacuo to give 3.6 g of .alpha.-(O,Odiethylphosphono)benzyl .alpha.'-4-(5'-trifluoromethylpyridin-2-yloxy)phenoxypropionate (Compound
No. 19). nD@26.0 1.5118).
Examples of the organic phosphorus compounds (I) produced by the same manner as above are shown
in Table 1.
>;tb;
TABLE 1
>;tb;__________________________________________________________________________
>;tb; ##STR7##
>;tb;Compound
Physical
>;tb;No. R1
>;tb;
R2
>;tb;
R3
>;tb;
R4
>;tb;
R5 property
>;tb;__________________________________________________________________________
>;tb;1 CH3 O
>;tb;
CH3
>;tb;
H
H
>;tb;
##STR8## nD@24.0 1.5466
>;tb; 2 C2 H5 O
>;tb;
C2 H5
232/612
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
H
H
##STR9## nD@24.0 1.5380
3 (i)C3 H7 O
(i)C3 H7
H
H
##STR10##
nD@21.5 1.5212
4 (n)C3 H7 O
(n)C3 H7
H
H
##STR11##
nD@22.0 1.5468
5 (n)C4 H9 O
(n)C4 H9
H
H
##STR12##
nD@22.0 1.5470
6 C2 H5 O
C2 H5
H
H
##STR13##
nD@20.0 1.5000
7 (i)C3 H7 O
(i)C3 H7
CH3
H
##STR14##
nD@24.0 1.4830
8 CH3 O
CH3
CH3
H
##STR15##
nD@24.0 1.4991
9 C2 H5 O
C2 H5
CH3
H
##STR16##
nD@24.0 1.4873
10 (n)C4 H9 O
(n)C4 H9
CH3
H
##STR17##
nD@24.5 1.4850
11 C2 H5 O
C2 H5
CH3
H
##STR18##
nD@24.0 1.4780
12 (i)C3 H7 O
(i)C3 H7
H
H
##STR19##
nD@24.5 1.4958
13 (i)C3 H7 O
(i)C3 H7
233/612
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
CH3
H
##STR20##
nD@24.5 1.4770
14 (n)C4 H9 O
(n)C4 H9
CH3
H
##STR21##
nD@24.5 1.4740
15 CH3 O
CH3
CH3
H
##STR22##
nD@23.5 1.4920
16 CH3 O
CH3
##STR23##
H
##STR24##
nD@23.5 1.5273
17 C2 H5 O
C2 H5
H
H
##STR25##
nD@22.5 1.4962
18 CH3 O
CH3
CH3
CH3
##STR26##
nD@26.0 1.5092
19 C2 H5 O
C2 H5
##STR27##
H
##STR28##
nD@26.0 1.5118
20 CH3
C2 H5
H
H
##STR29##
nD@24.0 1.4790
21
##STR30##
C2 H5
H
H
##STR31##
nD@24.0 1.5120
22 C2 H5
C2 H5
H
H
##STR32##
nD@25.0 1.4920
23 C2 H5 O
C2 H5
C2 H5
H
234/612
>;tb;
##STR33##
>;tb;
n D@25.0 1.4820
>;tb; 24 C2 H5 O
>;tb;
C2 H5
>;tb;
(i)C3 H7
>;tb;
H
>;tb;
##STR34##
>;tb;
nD@25.0 1.4835
>;tb;__________________________________________________________________________
In the practical usage of the organic phosphorus compounds (I), they may be applied as such or in any
composition form such as wettable powders, emulsifiable concentrates, granules, fine granules or dusts.
For formulation of those compositions, a solid or liquid carrier or diluent may be used. As for the solid
carrier or diluent, there may be exemplified mineral powders (e.g. kaolin, bentonite, montmorillonite,
talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, synthetic hydrated
silica), vegetable powders (e.g. soybean powder, wheat flour, wooden powder, tobacco powder, starch,
crystalline cellulose), high molecular weight compounds (e.g. petroleum resin, polyvinyl chloride,
dammar gum, ketone resin), alumina, wax and the like. As for the liquid carrier or diluent, there may be
exemplified alcohols (e.g. methanol, ethanol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons
(e.g. toluene, benzene, xylene, methylnaphthalene), halogenated hydrocarbons (e.g. chloroform, carbon
tetrachloride, monochlorobenzene), ethers (e.g. dioxane, tetrahydrofuran), ketones (e.g. acetone,
methylethylketone, isophorone, cyclohexanone), esters (ethyl acetate, butyl acetate, ethylene glycol
acetate), acid amides (e.g. dimethylformamide), nitriles (e.g. acetonitrile), ether alcohols (e.g. ethylene
glycol ethyl ether), water and the like.
A surface active agent used for emulsification, dispersion or spreading may be any of the non-ionic,
anionic, cationic and amphoteric type of agents. Examples of the surface active agent include
polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters,
sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, oxyethyleneoxypropylene
polymers, polyoxyethylene alkyl phosphates, fatty acid salts, alkyl sulfates, alkyl sulfonates, alkylaryl
sulfonates, alkyl phosphates, polyoxyethylene alkyl sulfate, quaternary ammonium salts, and the like.
But the surface active agent is not of course limited to these compounds. And, if necessary, gelatin,
casein, sodium alginte, starch, agar, polyvinyl alcohol, ligninsulfonic acid, isopropyl acid phosphate,
alginates or the like may be used as auxiliary agents.
The organic phosphorus compounds (I) of the invention may be used together with other herbicides to
improve their activity as herbicides, and in some cases, a synergistic effect can be expected. As the
herbicides to be mixed with, there may be given 2,4-dichlorophenoxyacetic acid, sodium 5-[2-chloro-4(trifluoromethyl)phenoxy]-2-nitrobenzoate, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2methylthio-4,6-bis(isopropylamino)-s-triazine, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-[4-(4chlorophenoxy)phenyl]-1,1-dimethylurea, 3-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-1,1-dimethylurea,
isopropyl N-(3-chlorophenyl)-carbamate, 3,4-dichloropropionanilide, 3-cyclohexyl-5,6trimethyleneuracil, O-ethyl O-(5-methyl-2-nitrophenyl)-N-sec-butylphosphoramidothioate, 3isopropyl-1H-2,1,3-benzothiadiazin-(4)-3H-one-2,2-dioxide, disodium methanearsonate, etc.
In the herbicidal composition of the invention, the content of the organic phosphorus compounds (I)
may be from 0.5 to 90% by weight, preferably from 1 to 80% by weight.
Practical embodiments of the herbicidal composition according to the invention are illustratively shown
in the following examples wherein parts and % are by weight. The compound number of the active
ingredient corresponds to the one in Table 1.
FORMULATION EXAMPLE 1
Forty parts of Compound No. 3, 2 parts of polyoxyethylene alkylaryl ether, 30 parts of synthetic
hydrated silica and 28 parts of diatomaceous earth are well mixed while being powdered to obtain a
wettable powder.
235/612
FORMULATION EXAMPLE 2
Ten parts of Compound No. 6, 7 parts of polyoxyethylene alkylaryl ether, 3 parts of alkylarylsulfonate
and 80 parts of xylene are well mixed while being powdered to obtain an emulsifiable concentrate.
FORMULATION EXAMPLE 3
One part of Compound No. 9, 1 part of synthetic hydrated silica, 5 parts of lignin sulfonate and 93 parts
of kaolin are well mixed while being powdered. The mixture is then kneaded with water, granulated
and dried to obtain granules.
FORMULATION EXAMPLE 4
Forty parts of bentonite, 5 parts of lignin sulfonate and 55 parts of kaolin are well mixed while being
powdered. The mixture is then kneaded with water, granulated and dried to obtain granules containing
no active ingredient. Five parts of Compound No. 17 are immersed therein to obtain a granule.
FORMULATION EXAMPLE 5
Three parts of Compound No. 19, 0.5 part of isopropyl acid phosphate, 66.5 parts of kaolin and 30
parts of talc are well mixed while being powdered to obtain a dust.
FORMULATION EXAMPLE 6
Twenty parts of Compound No. 3 is mixed with 60 parts of an aqueous solution containing 3%
polyoxyethylene sorbitan monolactate and grained until the particle size of the active ingredient
becomes less than 3 microns. Twenty parts of an aqueous solution containing 3% of sodium alginate as
a dispersing agent is incorporated therein to obtain a suspension.
The dosage rate of the organic phosphorus compounds (I) may vary on the kind of preparation, sorts of
weeds or crop plants, the weather condition, etc. Generally, however, the dosage rate may be from 0.5
to 100 grams, preferably from 1 to 50 grams, of the active ingredient per are.
The application of the organic phosphorus compounds (I) as herbicides will be illustratively shown in
the following Examples wherein the herbicidal activity on weeds were evaluated as follows: the aerial
parts of the test plants were cut off and weighed (fresh weight); the percentage of the fresh weight of
the treated plant to that of the untreated plant was calculated with the latter fresh weight taken as 100;
and the phytotoxicity to crop plants and the herbicidal activity on weeds were evaluated by the standard
given in the table below. The rating values of phytotoxicity, 0 and 1, and those of herbicidal activity, 5
and 4, are generally regarded as satisfactory to protect crop plants and control weeds, respectively. The
rating values in the paddy field test alone were calculated from the dry weight of the test plants.
>;tb;______________________________________
>;tb;
Fresh weight
>;tb;
(percentage to untreated plot) (%)
>;tb;Rating Phytotoxicity to
>;tb;
Herbicidal ac>;tb;value
crop plants tivity on weeds
>;tb;______________________________________
>;tb;5
0-39
0
>;tb;4
40-59
1-10
>;tb;3
60-79
11-20
>;tb;2
80-89
21-40
>;tb;1
90-99
41-60
>;tb;0
100
61-100
>;tb;______________________________________
TEST EXAMPLE 1
236/612
Wagner's pots (1/5000 are) were filled with paddy field soil containing the seeds of barnyard grass and
broad-leaved weeds (e.g. monochoria, false pimpernel, toothcup) and flooded with water to make a
paddy field condition. Rice seedlings of the 3-leaf stage was transplanted therein and grown for 7 days.
A designed amount of the test compound formulated in a wettable powder according to Formulation
Example 1 and diluted with water was applied to the pots where the rice plants were grown up to the
4.3 leaf stage and the barnyard grass up to the 0.5-1 leaf stage. After 20 days, herbicidal activity and
phytotoxicity were examined. The results are shown in Table 2.
>;tb;
TABLE 2
>;tb;______________________________________
>;tb;Dosage
>;tb;(weight of Phyto>;tb;active in- toxicity Herbicidal activity
>;tb;Compound
>;tb;
gredient, Rice Barnyard>;tb;
Broad-leaved
>;tb;No. g/are) plant grass weed
>;tb;______________________________________
>;tb;1
20
1
5
3
>;tb;
10
0
5
3
>;tb;
5
0
4
2
>;tb;2
20
1
5
3
>;tb;
10
0
5
2
>;tb;
5
0
5
1
>;tb;3
20
1
5
4
>;tb;
10
1
5
4
>;tb;
5
0
5
3
>;tb;4
20
0
5
2
>;tb;
10
0
5
1
>;tb;
5
0
4
1
>;tb;5
20
0
5
2
>;tb;
10
0
5
1
>;tb;
5
0
4
0
>;tb;6
10
1
5
4
>;tb;
5
0
5
3
>;tb;
2.5
0
5
2
>;tb;Diclo- 20
4
5
3
>;tb;fop- 10
3
5
2
>;tb;methyl 5
1
3
1
>;tb;Metri- 10
5
5
2
>;tb;flufen- 5
5
5
1
>;tb;methyl 2.5
3
4
1
>;tb;______________________________________
TEST EXAMPLE 2
Wagner's pots (1/5000 are) were filled with paddy field soil containing the seeds of barnyardgrass and
flooded with water to make a paddy field condition. Rice seedlings of the 3-leaf stage was transplanted
therein and grown for 12 days in a greenhouse, whereby the rice seedlings grown up to the two-tillers
stage and the barnyardgrass to the 2-leaf stage. A designed amount of the test compound formulated in
an emulsifiable concentrate according to Formulation Example 2 and diluted with 5 ml of water was
applied to the pots. After 20 days, herbicidal activity and phytotoxicity were examined. The results are
shown in Table 3.
>;tb;
TABLE 3
>;tb;______________________________________
>;tb;
Dosage
>;tb;
(weight of
>;tb;
active in- Phyto- Herbicidal
>;tb;Compound gredient, toxicity activity
>;tb;No.
g/are)
Rice plant
237/612
>;tb;
Barnyardgrass
>;tb;______________________________________
>;tb;7
5
1
5
>;tb;
2.5
0
5
>;tb;
1.25
0
5
>;tb;9
5
0
5
>;tb;
2.5
0
5
>;tb;
1.25
0
5
>;tb;11
5
1
5
>;tb;
2.5
0
5
>;tb;
1.25
0
4
>;tb;12
5
2
5
>;tb;
2.5
1
5
>;tb;
1.25
0
5
>;tb;13
5
2
5
>;tb;
2.5
1
5
>;tb;
1.25
0
5
>;tb;14
5
2
5
>;tb;
2.5
0
5
>;tb;
1.25
0
5
>;tb;16
5
1
5
>;tb;
2.5
1
5
>;tb;
1.25
0
4
>;tb;17
5
2
5
>;tb;
2.5
0
5
>;tb;
1.25
0
4
>;tb;19
5
2
5
>;tb;
2.5
1
5
>;tb;
1.25
0
4
>;tb;20
5
1
5
>;tb;
2.5
1
5
>;tb;
1.25
0
5
>;tb;21
5
1
5
>;tb;
2.5
0
5
>;tb;
1.25
0
5
>;tb;Fluazifop>;tb;
5
5
5
>;tb;butyl 2.5
4
5
>;tb;
1.25
2
4
>;tb;Metriflufen>;tb;
5
5
5
>;tb;methyl 2.5
3
4
>;tb;
1.25
2
3
>;tb;______________________________________
TEST EXAMPLE 3
Plastic trays (35 cm.times.25 cm.times.15 cm) were filled with upland field soil, and the seeds of wheat
and sugarbeet and the seeds of wild oat, barnyard grass, green foxtail, blackgrass and downy brome
were sowed therein and grown for 3 weeks in a greenhouse. Each two rays were placed into a flame of
50 cm.times.100 cm.times.40 cm and a designed amount of the test compound formulated into an
emulsifiable concentrate according to Formulation Example 2 and dispersed in water with a wetting
agent was sprayed over the top by means of a small hand sprayer to the foliage of the test plants at a
spray volume of 5 liters per are. After the spraying, the test plants were grown in the greenhouse for 3
weeks, and phytotoxicity and herbicidal activity were examined. The results are shown in Table 4. At
the time of the treatment, the test plants were in a 2 to 4-leaf stage and in 5 to 15 cm heights, although
they varied depending on their kinds.
>;tb;
TABLE 4
>;tb;__________________________________________________________________________
238/612
>;tb;
Dosage
>;tb;
(weight of
>;tb;
Phyto>;tb;
active in>;tb;
toxicity
>;tb;
Herbicidal activity
>;tb;Compound
>;tb;
gredient Sugar>;tb;
Wild
>;tb;
Barnyard>;tb;
Green
>;tb;
Black>;tb;
Downy
>;tb;No. g/are)
>;tb;
Wheat
>;tb;
beet
>;tb;
oat
>;tb;
grass foxtail
>;tb;
grass
>;tb;
brome
>;tb;__________________________________________________________________________
>;tb;1
20 0 0 5 5 5 5 2
>;tb;
10 0 0 5 5 5 4 2
>;tb;
5 0 0 3 5 5 3 0
>;tb;2
20 1 0 5 5 5 5 3
>;tb;
10 1 0 5 5 5 5 3
>;tb;
5 0 0 5 5 5 3 2
>;tb;3
20 2 0 5 5 5 5 4
>;tb;
10 1 0 5 5 5 5 3
>;tb;
5 0 0 5 5 5 5 2
>;tb;4
20 1 5 5 5 5 5 3
>;tb;
10 0 0 5 5 5 4 2
>;tb;
5 0 0 4 5 5 3 1
>;tb;5
20 1 0 5 5 5 5 3
>;tb;
10 0 0 5 5 5 5 3
>;tb;
5 0 0 5 5 5 3 1
>;tb;6
10 5 1 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 5
>;tb;8
10 5 0 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 5
>;tb;9
10 5 0 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 5
>;tb;10 10 5 1 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 5
>;tb;11 10 5 0 5 5 5 5 5
>;tb;
2.5 5 0 5 5 4 5 5
>;tb;12 10 5 0 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 5
>;tb;15 10 5 1 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 4
>;tb;18 10 5 0 5 5 5 5 5
>;tb;
2.5 5 0 5 5 3 5 4
>;tb;21 10 5 1 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 5
>;tb;22 10 5 0 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 5
>;tb;23 10 5 0 5 5 5 5 5
>;tb;
2.5 5 0 5 5 5 5 5
>;tb;24 10 5 1 5 5 5 5 5
239/612
>;tb;
2.5 5 0 5 5 4 5 5
>;tb;Diclofop>;tb;
40 4 1 5 5 5 5 3
>;tb;methyl 20 2 0 5 5 5 4 2
>;tb;
10 2 0 4 5 5 4 2
>;tb;
5 1 0 3 5 5 2 1
>;tb;Metriflufen>;tb;
20 5 1 5 5 5 5 5
>;tb;methyl 10 5 1 5 5 5 5 4
>;tb;
5 5 0 5 5 5 4 3
>;tb;
2.5 5 0 3 5 5 3 2
>;tb;Fluazifop>;tb;
10 5 1 5 5 5 5 5
>;tb;butyl 2.5 5 0 5 5 4 5 3
>;tb;__________________________________________________________________________
TEST EXAMPLE 4
Plastic trays (35 cm.times.25 cm.times.15 cm) were filled with upland field soil, and the seeds of
soybeans and cotton and the seeds of barnyard grass, volunteer corn, green foxtail, johnsongrass and
large crabgrass were sowed therein and grown for 2 to 3 weeks in a greenhouse. Each two rays were
placed into a flame of 50 cm.times.100 cm.times.90 cm and a designed amount of the test compound
formulated into an emulsifiable concentrate according to Formulation Example 2 and dispersed in
water with a wetting agent was sprayed over the top by means of a small hand sprayer to the foliage of
the test plants at a spray volume of 5 liters per are. After the spraying, the test plants were grown in the
greenhouse for 3 weeks, and phytotoxicity and herbicidal activity were examined. The results are
shown in Table 5. At the time of the treatment, the test plants were in a 1 to 4-leaf stage and in 2 to 20
cm heights, although they varied depending on their kinds.
>;tb;
TABLE 5
>;tb;__________________________________________________________________________
>;tb;Dosage
>;tb;(weight of
Herbicidal activity
>;tb;
active inGreen Large
>;tb;Compound
>;tb;
gredient,
>;tb;
Phytotoxicity
>;tb;
Barnyard>;tb;
Volunteer
>;tb;
fox>;tb;
Johnson>;tb;
crab>;tb;No. g/are)
>;tb;
Soybean
>;tb;
Cotton
>;tb;
grass corn tail
>;tb;
grass
>;tb;
grass
>;tb;__________________________________________________________________________
>;tb;1 20 0 0 5 5 5 2 5
>;tb;
5 0 0 5 3 5 0 3
>;tb;2 20 0 0 5 5 5 3 5
>;tb;
5 0 0 5 5 5 2 4
>;tb;3 20 0 0 5 5 5 4 5
>;tb;
5 0 0 5 5 5 3 4
>;tb;4 20 0 0 5 5 5 4 5
>;tb;
5 0 0 5 5 5 3 3
>;tb;5 20 0 0 5 5 5 4 5
>;tb;
5 0 0 5 5 5 3 5
>;tb;6 10 0 0 5 5 5 5 5
240/612
>;tb;
2.5 0 0 5 5 5 5 5
>;tb;8 10 0 0 5 5 5 5 5
>;tb;
2.5 0 0 5 5 5 5 5
>;tb;9 10 1 0 5 5 5 5 5
>;tb;
2.5 0 0 5 5 5 5 5
>;tb;10 10 1 0 5 5 5 5 5
>;tb;
2.5 0 0 5 5 5 5 5
>;tb;11 10 0 0 5 5 5 5 5
>;tb;
2.5 0 0 5 5 4 5 5
>;tb;12 10 0 0 5 5 5 5 5
>;tb;
2.5 0 0 5 5 5 5 5
>;tb;15 10 0 0 5 5 5 5 5
>;tb;
2.5 0 0 5 4 5 5 5
>;tb;17 10 0 0 5 5 5 5 5
>;tb;
2.5 0 0 5 5 5 5 4
>;tb;18 10 0 0 5 5 5 5 5
>;tb;
2.5 0 0 5 5 3 5 4
>;tb;20 10 0 0 5 5 5 5 5
>;tb;
2.5 0 0 5 5 5 5 4
>;tb;__________________________________________________________________________
TEST EXAMPLE 5
Plastic trays (35 cm.times.25 cm.times.15 cm) were filled with upland field soil, and the seeds of
sugarbeet, cotton and soybeans and the seeds of green foxtail, johnsongrass, blackgrass, annual
bluegrass and wild oat were sowed therein. A designed amount of the test compound formulated in a
wettable powder according to Formulation Example 1 and diluted with water was sprayed to the soil
surface over the top by means of a small hand sprayer at a spray volume of 5 liters per are. After 20
days, herbicidal activity and phytotoxicity were examined. The results are shown in Table 6.
>;tb;
TABLE 6
>;tb;__________________________________________________________________________
>;tb;Dosage
>;tb;(weight of
Herbicidal acitivity
>;tb;active in- Phytotoxicity
>;tb;
Green
Annual
>;tb;Compound
>;tb;
gredient,
>;tb;
Soy- Sugar>;tb;
fox>;tb;
Johnson>;tb;
Black>;tb;
blue>;tb;
Wild
>;tb;No. g/are)
>;tb;
bean
>;tb;
Cotton
>;tb;
beet
>;tb;
tail
>;tb;
grass
>;tb;
grass
>;tb;
grass
>;tb;
oat
>;tb;__________________________________________________________________________
>;tb;6 20 0 0 0 5 5 5 5 5
>;tb;
5 0 0 0 4 5 5 5 5
>;tb;9 20 0 0 0 5 5 5 5 5
>;tb;
5 0 0 0 4 5 5 5 5
>;tb;11 20 0 0 0 5 5 5 5 5
>;tb;
5 0 0 0 5 5 5 5 4
241/612
>;tb;13 20 1 0 0 5 5 5 5 5
>;tb;
5 0 0 0 4 5 5 5 4
>;tb;19 20 0 0 0 5 5 5 5 5
>;tb;
5 0 0 0 5 5 5 5 4
>;tb;__________________________________________________________________________Data
supplied from the esp@cenet database - Worldwide
Claims:
Claims of corresponding document: US4470841
What is claimed is:
1. A compound of the formula: ##STR35## wherein R1 is a C1 -C4 alkyl group, a phenyl group or a
C1 -C4 alkoxy group, R2 is a C1 -C4 alkyl group, R3 and R4, which are the same or different, are each
a hydrogen atom, a C1 -C4 alkyl group or a phenyl group and R5 is a 2,4-dichlorophenyl group, a 4trifluoromethylphenyl group or a 5-trifluoromethylpyridin-2-yl group.
2. The compound according to claim 1, wherein R1 is a C1 -C2 alkyl group, a phenyl group or a C1 C4 alkoxy group, R2 is a C1 -C4 alkyl group, R3 is a hydrogen atom, a C1 -C3 alkyl group or a phenyl
group, R4 is a hydrogen atom or a methyl group and R5 is a 2,4-dichlorophenyl group, a 4trifluoromethylphenyl group or a 5-trifluoromethylpyridin-2-yl group.
3. The compound according to claim 1, which is O,O-dimethylphosphonomethyl .alpha.-4-(2',4'dichlorophenoxy)-phenoxypropionate.
4. The compound according to claim 1, which is O,O-diethylphosphonomethyl .alpha.-4-(4'trifluoromethylphenoxy)phenoxypropionate.
5. The compound according to claim 1, which is .alpha.-(O,O-dimethylphosphono)ethyl .alpha.-4-(4'trifluoromethylphenoxy)phenoxypropionate.
6. A herbicidal composition which comprises as an active ingredient a herbicidally effective amount of
the compound of the formula: ##STR36## wherein R1 is a C1 -C4 alkyl group, a phenyl group or a C1
-C4 alkoxy group, R2 is a C1 -C4 alkyl group, R3 and R4, which are the same or different, are each a
hydrogen atom, a C1 -C4 alkyl group or a phenyl group and R5 is a 2,4-dichlorophenyl group, a 4trifluoromethylphenyl group or a 5-trifluoromethylpyridin-2-yl group, and an inert carrier or diluent.
7. A method for controlling weeds which comprises applying as an active ingredient a herbicidally
effective amount of the compound of the formula: ##STR37## wherein R1 is a C1 -C4 alkyl group, a
phenyl group or a C1 -C4 alkoxy group, R2 is a C1 -C4 alkyl group, R3 and R4, which are the same or
different, are each a hydrogen atom, a C1 -C4 alkyl group or a phenyl group and R5 is a 2,4dichlorophenyl group, a 4-trifluoromethylphenyl group or a 5-trifluoromethylpyridin-2-yl group to the
area where the weeds grow or will grow.
8. A compound of the formula: ##STR38## wherein R1 is a C1 -C4 alkyl group, a phenyl group or a
C1 -C4 alkoxy group, R2 is a C1 -C4 alkyl group, and R3 and R4, which are the same or different, are
each a hydrogen atom, a C1 -C4 alkyl group or a phenyl group.
9. The compound according to claim 8, which is O,O-diethylphosphonomethyl .alpha.-4-(5'trifluoromethylpyridin-2-yloxy)phenoxypropionate.
10. The compound according to claim 8, wherein R1 is a C1 -C4 alkyl group.
11. The compound according to claim 8, wherein R1 is a phenyl group.
12. The compound according to claim 8, wherein R1 is a C1 -C4 alkoxy group.
13. The compound according to claim 8, wherein R3 and R4 are each a hydrogen atom or a C1 -C4
alkyl group.
242/612
14. The compound according to claim 8, wherein R3 and R4 are each a hydrogen atom or a phenyl
group.
15. The compound according to claim 8, wherein R3 and R4 are each a C1 -C4 alkyl group or a phenyl
group.
16. A herbicidal composition which comprises as an active ingredient a herbicidally effective amount
of the compound of claim 8, and an inert carrier or diluent.
17. A method for controlling weeds which comprises applying as an active ingredient a herbicidally
effective amount of the compound of claim 8 to the area where the weeds grow or will grow.
18. The compound according to claim 8, wherein R3 is a hydrogen atom, a C1 -C3 alkyl group or a
phenyl group and R4 is a hydrogen atom or a methyl group.
19. The method of claim 17, wherein said compound is applied to a rice field.
20. The method of claim 17, wherein said compound is applied to a wheat field.Data supplied from the
esp@cenet database - Worldwide
243/612
23. JP58039692
- 3/8/1983
ORGANIC PHOSPHORIC ESTER DERIVATIVE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=JP58039692
Inventor(s):
ISHIKAWA HIROMICHI (--); KITAORI KAZUHIKO (--); MORIYAMA
SATORU (--); CHIYOUNO TADASHI (--); UCHIYAMA TSUGIO (--)
Applicant(s):
HOKKO CHEM IND CO (--)
IP Class 4 Digits: C07F; A01N
IP Class:A01N57/22; C07F9/28
E Class: A01N57/22; C07F9/40C1
Application Number:
JP19810138322 (19810904)
Priority Number: JP19810138322 (19810904)
Family: JP58039692
Equivalent:
US4443439
Abstract:
Abstract of JP58039692
NEW MATERIAL:An organic phosphoric ester derivative expressed by formulaI (R>;1; is lower
alkyl; R>;2; is H, lower alkyl or unsaturated lower alkyl; R>;3; is lower alkyl or unsaturated lower
alkyl). EXAMPLE:O-Ethyl O-(N-methoxyacetimidoyl)-phenylthionophosphonate. USE:An
insecticide, acaricide and nematocide exhibiting the activity against green rice leafhopper, etc. having
developed resistance to various organophosphorus insecticides and carbamate insecticides with low
toxicity to mammals. PROCESS:An O-alkyl-phenylthionophosphonyl halide expressed by formula II
(Hal is halogen) is reacted with an alkyl acylhydroxamate expressed by formula III to give the
compound expressed by formulaI. The reaction is preferably carried out in the presence of a base, e.g.
NaOH, in an inert organic solvent, e.g. benzene, at 0-120 deg.C.Description:
Description of corresponding document: US4443439
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to new phosphonic acid ester derivatives and, more particularly, to new
phenylthionophoshonic acid O,O-di-esters having a high insecticidal activity, high miticidal activity
and high nematocidal activity in combination. This invention also relates to a process for the
production of these new phosphonic acid ester derivatives, as well as to an insecticidal, miticidal and
nematocidal composition containing the above-mentioned new compound as active ingredient.
2. Description of the Prior Art
Many kinds of organo-phosphorus compounds having insecticidal activity, miticidal activity and/or
nematocidal activity are known. Thus, O-(N-alkoxy-benzimidoyl)-(thiono)phosphoric(phosphonic)acid esters having insecticidal and miticidal activities are disclosed in Japanese
patent application prepublication "Kokai" No. Sho 47-9149 (corresponding to U.S. Pat. No. 3,760,041),
Japanese patent application prepublication "Kokai" No. Sho 49-13335 (corresponding to U.S. Pat. No.
244/612
3,872,185) and Japanese patent application prepublications "Kokai" No. Sho 49-132244 and No. Sho
50-64436. O-(N-Alkoxy-substituted alkylimidoyl)-(thiono)phsphoric acid esters are also known to
have insecticidal and miticidal activities as disclosed in Japanese patent application prepublications
"Kokai" No. Sho 50-6724 and No. Sho 52-33627.
Amongst the insect pests, rice stem borer, brown planthoppers, rice leafhoppers, common cutworms
and aphids may be mentioned as the main insect pests which are predominantly infesting aquatic rice
plants cultivated in the submerged field or the crops cultivated in upland fields in recent years. For the
purpose of combating these main insect pests, there have been applied large quantities of insecticides
of the organo-phosphorus compound type, insecticides of the carbamate compound type, insecticides of
the chlorinated compound type and others since a long time ago. In these years, there occurs an
objectionable phenomena that the main insect pests have gained a resistance against the known
insecticidal compounds which have extensively been used in the crop fields.
SUMMARY OF THE INVENTION
An object of this invention is to provide a new insecticide of organophosphorus compound type to
which the resistance is not yet gained by the main insect pests of the crop fields. Another object of this
invention is to provide a new insecticide of organophosphorus compound type which exhibits a higher
insecticidal activity than that of the organophosphorus insecticides conventionally used in the crop
fields. Further objects of this invention will be clear from the following descriptions.
We, the present inventors, have synthetized a number of new organophosphonic acid esters and studied
their physiological properties. As a result, we have now found that amongst the new organophosphonic
acid esters, phenylthionophosphonic acid O,O-di-esters of the general formula: ##STR2## wherein R1
is a lower alkyl group; R2 is a hydrogen atom, a lower alkyl group or an unsaturated lower alkyl group;
and R3 is a lower alkyl group or an unsaturated lower alkyl group exhibit a high insecticidal activity, a
high miticidal activity and a high nematocidal activity in combination, and that the new compounds of
formula (I) show a remarkably high insecticidal activity against the "resistant" strains of insect pests
such as green rice leafhopper which have developed the resistance to various kinds of the known
organophosphorus type insecticides and of the known carbamate type insecticides.
According to a first aspect of this invention, therefore, there are provided as new compounds
phenylthionophosphonic acid O,O-di-esters of the general formula: ##STR3## wherein R1 denotes a
lower alkyl group; R2 denotes a hydrogen atom, a lower alkyl group or an unsaturated lower alkyl
group; and R3 denotes a lower alkyl group or an unsaturated lower alkyl group. The term "an
unsaturated lower alkyl group" means inclusively "a lower alkenyl group" and "a lower alkynyl group".
The term "lower" means that the concerned group contains 1 to 6 carbon atoms and preferably contains
1 to 4 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
According to a specific embodiment of the first aspect of this invention, therefore, there are provided
new compounds of the general formula: ##STR4## wherein R4 is an alkyl group containing 1-6 carbon
atoms, R5 is a hydrogen atom, an alkyl group containing 1-6 carbon atoms, an alkenyl group
containing 2-6 carbon atoms or an alkynyl group containing 2-6 carbon atoms, and R6 is an alkyl group
containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms or an alkynyl group
containing 2-6 carbon atoms.
More specifically, in formula (I'), R4 is methyl or ethyl group; R5 is hydrogen, methyl, ethyl, n-propyl,
i-propyl, n-butyl, vinyl, propenyl or ethynyl group; and R6 is methyl, ethyl, i-propyl, vinyl, allyl or
propargyl group.
According to a preferred embodiment of the first aspect invention, there are provided as new
compounds phenylthionophosphonic acid O,O-di-esters of the formula: ##STR5## wherein R7 is an
alkyl group of 1-4 carbon atoms, an alkenyl group of 2-4 carbon atoms or an alkynyl group of 2-4
carbon atoms.
More specifically, in formula (I"), R7 is methyl, ethyl, i-propyl, allyl or propargyl group.
245/612
Although the new compounds of general formula (I), (I') or (I") according to this invention have a
chemical structure similar to that of the known O-(N-alkoxy-benzimidoyl)-(thiono)phosphoric(phosphonic)acid esters and O-(N-alkoxy-substituted alkylimidoyl)-(thiono)phosphoric acid
esters taught in the chemical literature above-referred to, it has been found that the new compounds of
this invention are remarkably superior to the known, similar compounds in the insecticidal activity,
miticidal activity and nematocidal activity. Besides, it is observed that the pesticidal activities of the
new compounds of this invention are much more rapid and lasting than those of the known, similar
compounds and are systemic in nature which makes it possible to achieve the desired pesticidal effect
on pests inhabiting on the earth by applying the compounds to aquatic surface or soil. In addition, the
new compounds of this invention advantageously exhibit little or no toxicity to mammalian animals
and do not exhibit any phyto-toxicity to crop plants at all.
Representative examples of the new compounds of formula (I), (I') or (I") according to this invention
are listed in Table 1 below, together with the structural formulae, boiling point and optical refractive
index thereof.
>;tb;
TABLE 1
>;tb;__________________________________________________________________________
>;tb;Compound
Boiling point
>;tb;
Refractive
>;tb;No. Structural formula ( DEGC./mmHg)
>;tb;
index (nD@24)
>;tb;__________________________________________________________________________
>;tb;
##STR6##
105.about.108/0.01
>;tb;
1.5389
>;tb; 2
>;tb;
##STR7##
103.about.105/0.01
>;tb;
1.5364
>;tb; 3
>;tb;
##STR8##
104.about.107/0.01
>;tb;
1.5328
>;tb; 4
>;tb;
##STR9##
110.about.112/0.01
>;tb;
1.5291
>;tb; 5
>;tb;
##STR10##
109.about.112/0.01
>;tb;
1.5288
>;tb; 6
>;tb;
##STR11##
113.about.115/0.01
>;tb;
1.5280
>;tb; 7
>;tb;
##STR12##
110.about.114/0.015
>;tb;
1.5409
>;tb; 8
>;tb;
##STR13##
112.about.116/0.015
>;tb;
1.5393
>;tb; 9
>;tb;
##STR14##
107.about.110/0.015
>;tb;
1.5492
>;tb; 10
>;tb;
##STR15##
105.about.108/0.01
>;tb;
1.5333
>;tb; 11
>;tb;
##STR16##
108.about.111/0.01
>;tb;
1.5276
>;tb; 12
>;tb;
##STR17##
112.about.115/0.015
>;tb;
1.5411
>;tb; 13
246/612
>;tb;
##STR18##
106.about.109/0.015
>;tb;
1.5497
>;tb; 14
>;tb;
##STR19##
98.about.102/0.007
>;tb;
1.5394
>;tb; 15
>;tb;
##STR20##
97.about.100/0.007
>;tb;
1.5490
>;tb; 16
>;tb;
##STR21##
101.about.104/0.007
>;tb;
1.5302
>;tb; 17
>;tb;
##STR22##
98.about.102/0.007
>;tb;
1.5479
>;tb;__________________________________________________________________________
Chemical designations of Compounds Nos. 1 to 17 given in Table 1 above are as follows:
(1) O-ethyl,O-(N-methoxyformimidoyl)phenylthionophosphonate (Compound No. 1);
(2) O-ethyl,O-(N-methoxyacetimidoyl)phenylthionophosphonate (Compound No. 2);
(3) O-ethyl,O-(N-methoxypropionimidoyl)phenylthionophosphonate (Compound No. 3);
(4) O-ethyl,O-(N-methoxy-n-butyrimidoyl)phenylthionophosphonate (Compound No. 4);
(5) O-ethyl,O-(N-ethoxy-i-butyrimidoyl)phenylthionophosphonate (Compound No. 5);
(6) O-ethyl,O-(N-methoxyvalerimidoyl)phenylthionophosphonate (Compound No. 6);
(7) O-ethyl,O-(N-methoxyacrylimidoyl)phenylthionophosphonate (Compound No. 7);
(8) O-ethyl,O-(N-methoxycrotonimidoyl)phenylthionophosphonate (Compound No. 8);
(9) O-ethyl,O-(N-ethoxypropionimidoyl)phenylthionophosphonate (Compound No. 9);
(10) O-ethyl,O-(N-ethoxyacetimidoyl)phenylthionophosphonate (Compound No. 10);
(11) O-ethyl,O-(N-i-propoxyacetimidoyl)phenylthionophosphonate (Compound No. 11);
(12) O-ethyl,O-(N-allyloxyacetimidoyl)phenylthionophosphonate (Compound No. 12);
(13) O-ethyl,O-(N-propargyloxyacetimidoyl)phenylthionophosphonate (Compound No. 13);
(14) O-methyl,O-(N-methoxyacetimidoyl)phenylthionophosphonate (Compound No. 14);
(15) O-methyl,O-(N-ethoxycrotonimidoyl)phenylthionophosphonate (Compound No. 15);
(16) O-methyl,O-(N-i-propoxyacetimidoyl)phenylthionophosphonate (Compound No. 16); and
(17) O-methyl,O-(N-allyloxyacetimidoyl)phenylthionophosphonate (Compound No. 17).
The new compounds of general formula (I), (I') or (I") according to this invention can be produced by a
process which is shown by the following reaction equation: ##STR23## in which R1, R2 and R3 have
the same meanings as defined above and Hal denotes a halogen atom such as chlorine or bromine.
According to a second aspect of this invention, therefore, there is provided a process for the production
of a phenylthionophosphonic acid O,O-di-ester of the general formula: ##STR24## wherein R1
denotes a lower alkyl group; R2 denotes a hydrogen atom, a lower alkyl group or an unsaturated lower
alkyl group; and R3 denotes a lower alkyl group or an unsaturated lower alkyl group, which comprises
reacting a phenylthionophosphonic halide of the general formula: ##STR25## wherein Hal denotes a
halogen atom and R1 has the same meaning as defined above with a hydroxamate of the general
formula: ##STR26## wherein R2 and R3 have the same meanings as defined above.
In the process of this invention, the reaction may be conducted in the presence of a base acting as an
acid-binding agent, if required. The base available for this purpose includes inorganic bases, for
example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkali metal
carbonate such as sodium carbonate or potassium carbonate; an alkali metal alcoholate such as sodium
methoxide; sodium hydride; metallic sodium; as well as organic bases, for example, a tertiary amine
such as triethylamine, dimethylaniline, pyridine and the like which have been employed conventionally
as the acid-binding agents. The reaction is conducted preferably in an inert organic solvent which may
be, for example, aliphatic or aromatic hydrocarbons such as benzene, toluene, xylene, and petroleum
benzine; chlorinated aliphatic or aromatic hydrocarbons such as carbon tetrachloride, methylene
chloride, chloroform and chlorobenzene; ketones such as acetone, methyl ethyl ketone, methyl
isopropyl ketone and methyl isobutyl ketone; ethers such as diethylether, dibutylether, tetrahydrofuran
and dioxane; and nitriles such as acetonitrile and propionitrile.
247/612
The reaction temperature may vary within a wide range and usually be in a range of 0 DEG C. to 120
DEG C. and preferably in a range of 20 DEG C. to 80 DEG C. The reaction may proceed under
atmospheric pressure, though the reaction may be conducted under an elevated pressure, if desired. The
reactants of the formulae (II) and (III) may preferably be present in a substantially equimolar
proportion in the reaction mixture.
The new compounds of this invention are effective to combat a wide variety of insect pests such as
insects sucking as the bait the body juice of plants or animals; and insects chewing a portion of plants
or animals or a material of vegetable or animal origin, as well as acarine pests and nematodes. The
insect and acarine pests which may be combatted with the new compounds of this invention include
those associated with agriculture (including the growing of crops for food and fibre, horticulture and
animal husbandry), such as the insect and acarine pests infesting the growing plants, those associated
with forestry, the storage of products of vegetable origin, such as grains, fruits and timber, and also the
pests associated with the transmission of diseases of man and animals, such as houseflies and
mosquitos. The new compounds of this invention are useful to combat a wide variety of the insect and
acarine pests as mentioned below.
Thus, the pests which may be combatted with the new compounds of this invention include: Coleoptera
insect pests such as azuki bean weevil (Callosobruchus chinensis), maize weevil (Sitophilus zeamais),
red flour beetle (Tribolium castaneum), twenty-eight-spotted ladybird (Henosepilachna
vigintioctopunctata) and barley wireworm (Agriotes fuscicollis); Lepidopterous insect pests such as
gypsy moth (Lymantria dispar), common cabbageworm (Pieris rapae), common cutworm (Spodoptera
litura), rice stem borer (Chilo suppressalis), summer fruit tortrix (Adoxophyes orana fasciata) and
almond moth (Ephestia cautella); Hemipterous insect pests such as green rice leafhopper (Nephotettix
cincticeps), brown rice planthopper (Nilaparvata lugens), small rice plant-hopper (Laodelphax
striattellus), comstock mealybug (Pseudococcus comstocki), green peach aphid (Myzus persicae), and
apple aphid (Aphis pomonella); Orthopterous insect pests such as German cockroach (Blattella
germanica), American cockroach (Periplaneta americana), and African mole cricket (Gryllotalpa
africana); Dipterous insect pests such as house fly (Musca domestica), yellow-fever mosquito (Aedes
aegypti), seedcorn maggot (Hylemya platura) and smaller house mosquiot (Culex tritaeniorhynchus);
and Thripidae insect pests such as southern yellow thrips (Thrips palmi). The acarine pests which may
be combatted with the new compounds of this invention include: carmine spider mite (Tetranychus
cinnabarinus), two-spotted spider mite (Tetranychus urticae), citrus red mite (Panonychus citri) and
pink citrus rust mite (Aculops pelekassi) and the like. The nematodes which may be combatted with the
new compounds of this invention include: southern root-knot nematode (Meloidogyne incognita), rice
white-tip nematode (Aphelenchoides besseyi), soybean cyst nematode (Heterodera glycines) and
others.
In use, the new compounds of this invention may be applied to the pests, to the locus of the pests, to the
habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means
of applying the pesticidal compounds, for example, by dusting or spraying. The new compounds of this
invention may be formulated into conventional formulations or preparations for pesticidal usage, by
mixing the active compound of this invention with an acceptable known diluent or carrier material.
According to a third aspect of this invention, therefore, there is provided an insecticidal, miticidal and
nematocidal composition comprising an insecticially, miticidally and/or nematocidally effective
amount of a phenylthionophosphonic acid O,O-di-ester of the general formula: ##STR27## wherein R1
denotes a lower alkyl group; R2 denotes a hydrogen atom, a lower alkyl group or an unsaturated lower
alkyl group; and R3 denotes a lower alkyl group or an unsaturated lower alkyl group, as the active
ingredient, in combination with an acceptable diluent or carrier. The compounds of formula (I) which
are used in the composition of this invention may preferably be the new compounds of general formula
(I') or (I") given above.
The pesticidal (insecticidal, miticidal and nematocidal) composition of this invention may be prepared
by formulating a new compound of general formula (I) into the form of emulsifiable concentrate,
wettable powder, flowable powder, dusting powder, driftless (DL-type) powder, granules, fine
granules, tablets, liquid preparations, etc., according to conventional formulation techniques. The
carrier materials to be used may be solid or liquid ones which have been used conventionally in the
248/612
preparations for agricultural and horticultural usages. The available carriers in the composition of this
invention are not limited to any particular one. The solid carriers available include, for example mineral
powders such as kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite,
gypsum, calcium carbonate, apatite, kieselguhr, white carbon, slaked lime, siliceous sand, ammonium
sulfate and urea; vegetable materials such as soybean powder, wheat flour, wood meal, tobacco
powder, starch and crystalline cellulose; polymeric compounds such as petroleum resin, polyvinyl
chloride, ketone resin and dammar gum; alumina, silicates, polysaccharide, colloidal silica and waxes.
The liquid carriers available include, for example, water; alcohols such as methanol, ethanol, npropanol, isopropanol, butanol, ethylene glycol and benzyl alcohol; aromatic hydrocarbons such as
benzene, toluene, xylene, ethylbenzene and methylnaphthalene; halogenated hydrocarbons such as
chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene,
trichlorofluoromethane and dichlorodifluoromethane; ethers such as ethylether, ethylene oxide, dioxane
and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl
ketone and isophorone; esters such as ethyl acetate, butyl acetate, ethylene glycol acetate and amyl
acetate; acid amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile,
propionitrile and acrylonitrile; sulfoxides such as dimethylsulfoxide; alcoholethers such as ethylene
glycol monomethylether and ethylene glycol monoethylether; aliphatic and cycloaliphatic
hydrocarbons such as n-hexane, cyclohexane, industrial gasoline (petroleum ether, solvent naphtha,
etc.) and petroleum fractions (paraffins, kerosene, gas oil, etc.).
When the active compound of this invention is formulated in the form of an emulsifiable concentrate,
wettable powder, flowable sols, etc., one or more surface active agents are used for the purposes of
emulsification, dispersion, solubilization, wetting, foaming, lubrication and/or spreading. Surface
active agents may be of nonionic, anionic, cationic and amphoteric types. Examples of the nonionic
type are polyoxyethylene alkylethers, polyoxyethylene alkylesters, polyoxyethylene
sorbitanalkylesters, sorbitan alkylesters and the like. Examples of the anionic type are alkylbenzene
sulfonates, alkylsulfosuccinates, alkyl sulfates, polyoxyethylene alkylsulfates, aryl sulfonates and the
like. Examples of the cationic type include quaternary ammonium compounds such as stearyl trimethyl
ammonium chloride and alkyl dimethylbenzyl ammonium chloride and polyoxyethylene alkylamines.
Examples of the amphoteric type are carboxylic acids of betaine type and alkyl sulfates.
Other additives which may be used as an adjuvant include polyvinyl alcohol, carboxymethylcellulose,
acasia gum, polyvinyl acetate, gelatin, casein, sodium alginate and tragacanth gum, for example.
The composition according to this invention in the form of a variety of formulations as abovementioned may contain 0.1 to 95%, preferably 0.5 to 90%, by weight, of a phenylthionophosphonic
acid O-alkyl,O-(N-alkoxyalkanoylimidoyl)ester of formula (I) according to this invention. Thus, the
composition may usually contain 0.1 to 5% by weight of the active compound when formulated in the
form of dusting powder, DL powder or fine granules, 1 to 10% by weight in the form of granules and 5
to 95% by weight in the form of wettable powder, emulsifiable concentrate or liquid preparations.
When the composition of this invention is in the form of dusting powder, DL powder, fine granules or
granules, the composition will be applied as such to plants, surfaces and/or interior of soils or aquatic
fields upon or in which pests, mites and/or nematodes are living at a rate of 2 to 5 kg per 10 ares (or at
a rate of 50 to 500 g of the active ingredient per 10 ares). For nematocidal purposes, in particular, the
composition may be applied even at a higher rate of about 500 to 10,000 g of the active ingredient per
10 ares. The composition in the form of emulsifiable concentrate, wettable powder, liquid preparations
or flowable sols may usually be diluted with water or a suitable solvent before use to give a
concentration of the active ingredient of about 5 to 1,000 ppm, preferably about 50 to 500 ppm, the
dilute formulation being usually applied at a rate of 100 to 300 l per 10 ares. Emulsifiable concentrate,
liquid preparations and flowable sols may also be applied as such or in a diluted form with a small
amount of water, i.e. in the form of a LV spray or ULV spray, at a rate of about 50 to 3000 ml per 10
ares mainly as aerial spraying agent.
The composition of this invention may further incorporate, if desired, other insecticide, miticide,
nematocide, fungicide and/or herbicide.
According to a further aspect of this invention, there is provided a method of combating insect pests,
acarine pests and/or nematode pests at a locus of infestation, which comprises treating the pests or the
249/612
locus of infestation with an insecticidally, miticidally or nematocidally effective amount of a
compound of general formula (I), (I') or (I").
The invention is now illustrated with reference to the following Examples. Examples 1 to 3 are
illustrative of the production of the new compounds of this invention; Examples 4 to 7 illustrative of
the formulations comprising the new compound of this invention; and Examples 8 to 18 are illustrative
of the pesticidal properties of the new compounds of this invention.
EXAMPLE 1
Production of Compound No. 2 of the formula: ##STR28##
To a solution of methyl acetohydroxamate (8.9 g) in methyl ethyl ketone (100 ml) was added
potassium hydroxide (5.6 g) and the mixture was heated at 50 DEG C. for 1 hour under stirring. Then,
O-ethyl-phenylthionophosphonic chloride (22.1 g) was added to the reaction mixture and the reaction
was conducted at 80 DEG C. for 5 hours under stirring. After the methyl ethyl ketone was distilled off
under a reduced pressure, benzene (200 ml) was added to the residue and the resulting solution was
washed with water (200 ml), then with a 2% aqueous sodium hydroxide solution and finally with water
until the washings became neutral. The solution thus washed was dried over anhydrous sodium sulfate,
subjected to a distillation under a reduced pressure to remove the benzene therefrom and then to a
vacuum distillation to yield O-ethyl, O-(N-methoxyacetimidoyl) phenylthionophosphonate (19.7 g;
72%).
b.p. 103 DEG-105 DEG C./0.01 mmHg; nD@24 1.5364.
EXAMPLE 2
Production of Compound No. 12 of the formula: ##STR29##
To a solution of allyl acetohydroxamate (11.5 g) in acetonitrile (100 ml) was added potassium
hydroxide (5.6 g) and the mixture was heated at 50 DEG C. for 1 hour under stirring. Then, O-ethylphenylthionophosphonic chloride (22.1 g) was added to the mixture and the reaction was conducted at
80 DEG C. for 5 hours under stirring. After the acetonitrile was distilled off under a reduced pressure,
benzene (200 ml) was added to the residue and the resulting solution was washed with water (200 ml),
then with a 2% aqueous sodium hydroxide solution and finally with water until the washings became
neutral. The solution thus washed was dried over anhydrous sodium sulfate, subjected to a distillation
under a reduced pressure to remove the benzene therefrom and then to a vacuum distillation to yield Oethyl, O-(N-allyloxyacetimidoyl) phenylthionophosphonate (16.2 g; 54%).
b.p. 112 DEG-115 DEG C./0.015 mmHg; nD@24 1.5411
EXAMPLE 3
Production of Compound No. 1 of the formula: ##STR30##
To a solution of methyl formhydroxamate (7.5 g) in tetrahydrofuran (100 ml) was added sodium
hydride (4.0 g as 60% suspension in oil) under ice-cooling and the mixture was stirred at room
temperature for 10 minutes. Then, O-ethyl-phenylthionophosphonic chloride (22.1 g) was added to the
mixture and the reaction was conducted at 65 DEG C. for 2 hours under stirring. The reaction solution,
after the addition of benzene (200 ml) thereto, was washed with water (200 ml), then with a 2%
aqueous sodium hydroxide solution and finally with water until the washings became neutral. The
solution thus washed was dried over anhydrous sodium sulfate, subjected to a distillation under a
reduced pressure to remove the solvent used and then to a vacuum distillation to yield O-ethyl, O-(Nmethoxyformimidoyl) phenylthionophosphonate (19.2 g; 74%).
b.p. 105 DEG-108 DEG C./0.01 mmHg; nD@24 1.5389.
EXAMPLE 4
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Emulsifiable concentrate
40 Parts (by weight) of the Compound No. 2 prepared in the Example 1, 20 parts (by weight) of an
emulsifying agent consisting of the condensation product of ethylene oxide with fatty alcohols
(available as a trade-name "Solpol 700H", a product of Toho Chemical Industry Company, Japan), and
40 parts (by weight) of xylene were mixed together uniformly to give an emulsifiable concentrate
which may be diluted with water upon use to give a sprayable emulsion.
EXAMPLE 5
Wettable powder
25 Parts (by weight) of the Compound No. 11 listed in Table 1, 15 parts (by weight) of white carbon
(finely divided silica), 3 parts (by weight) of calcium ligninesulfonate, 2 parts (by weight) of a
polyoxyethylene-nonylphenylether as the non-ionic emulsifier, 5 parts (by weight) of diatomaceous
earth and 50 parts (by weight) of clay were ground together and mixed uniformly with each other in a
mixer to give a wettable powder which may be dispersed in water upon use.
EXAMPLE 6
Dusting powder
1.5 Parts (by weight) of the Compound No. 14 listed in Table 1 was mixed well with 98.5 parts (by
weight) of clay, followed by grinding to small particle size. A dusting powder was obtained, which was
directly be applied by a known dusting device.
EXAMPLE 7
Granules
5 Parts (by weight) of the Compound No. 2, 1.5 parts (by weight) of lauryl sulfate, 1.5 parts of calcium
ligninesulfonate and 67 parts of kaolin were admixed with 15 parts (by weight) of water, followed by
kneading in a kneader and granulation in a granulator. The granules so shaped were then dried in a
fluidizing drier to give granules which may directly be applied to the soil.
EXAMPLE 8
This Example illustrates the test of estimating the insecticidal activity of test compounds against rice
stem borer.
Aquatic rice plants of average height of about 50 cm which had been grown in a pot having an area of
1/10,000 ares at the soil surface were infested with 30 larvae of rice stem borer (Chilo suppressalis)
which had just hatched from the eggs. 5 Days after the infestation, the rice plants and the larvae were
sprayed with the composition under test which was prepared by diluting with water the wettable
powder of this invention made according to the preceding Example 5 to the concentration of the active
compound as indicated in Table 2 below. The composition was sprayed by means of a spraygun and
was applied at the rate of application of 50 ml per three pots. 5 Days after the spraying, the rice plants
were dissected and the numbers of the dead larvae and the surviving larvae were counted, respectively,
and percent of mortality was assessed. The tests were conducted with three replicates for a particular
value of the concentration of the active compound under test, and the average of % mortality was
calculated. The results (expressed as averaged % mortality) are set out in Table 2 below.
>;tb;
TABLE 2
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Concentration of active Compound
>;tb;
sprayed (ppm)
>;tb;Test Compounds
>;tb;
100
50
251/612
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
95
>;tb;Compound No. 2
>;tb;
100
100
>;tb;Compound No. 3
>;tb;
100
95
>;tb;Compound No. 4
>;tb;
100
93
>;tb;Compound No. 5
>;tb;
100
93
>;tb;Compound No. 6
>;tb;
100
93
>;tb;Compound No. 7
>;tb;
100
95
>;tb;Compound No. 8
>;tb;
100
95
>;tb;Compound No. 9
>;tb;
100
93
>;tb;Compound No. 10
>;tb;
100
95
>;tb;Compound No. 11
>;tb;
100
100
>;tb;Compound No. 12
>;tb;
100
100
>;tb;Compound No. 13
>;tb;
100
93
>;tb;Compound No. 14
>;tb;
100
95
>;tb;Compound No. 15
>;tb;
100
95
>;tb;Compound No. 16
>;tb;
100
95
>;tb;Compound No. 17
>;tb;
100
95
>;tb;Comparative 78
47
>;tb;Compound A
>;tb;Comparative 60
35
>;tb;Compound B
>;tb;Comparative 73
55
>;tb;Compound C
>;tb;Comparative 78
47
>;tb;Compound D
>;tb;Comparative 80
60
>;tb;Compound E
>;tb;Comparative 80
57
>;tb;Compound F
>;tb;Comparative 100
67
>;tb;Compound G
>;tb;Comparative 80
57
>;tb;Compound H
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________
Compound Nos. 1 to 17 as above are identical to those listed in Table 1 before. The same reference is
made in the following tables in this specification.
>;tb;______________________________________
>;tb;Comparative compound A:
252/612
>;tb;
##STR31##
>;tb;
(see U.S. Pat. No. 3,760,041)
>;tb; Comparative compound B:
>;tb;
##STR32##
>;tb;
(see U.S. Pat. No. 3,760,041)
>;tb; Comparative compound C:
>;tb;
##STR33##
>;tb;
(see U.S. Pat. No. 3,872,185)
>;tb; Comparative compound D:
>;tb;
##STR34##
>;tb;
(see U.S. Pat. No. 3,872,185)
>;tb; Comparative compound E:
>;tb;
##STR35##
>;tb;
(see Japanese patent application
>;tb;
prepublication "Kokai"
>;tb;
Sho 49-132244)
>;tb; Comparative compound F:
>;tb;
##STR36##
>;tb;
(see Japanese patent application
>;tb;
prepublication "Kokai"
>;tb;
Sho 50-64436)
>;tb; Comparative compound G:
>;tb;
##STR37##
>;tb;
(see Japanese patent application
>;tb;
prepublication "Kokai"
>;tb;
Sho 50-6724)
>;tb; Comparative compound H:
>;tb;
##STR38##
>;tb;
(see Japanese patent application
>;tb;
prepublication "Kokai"
>;tb;
Sho 52-33627)
>;tb;______________________________________
EXAMPLE 9
This Example illustrates the test of estimating the insecticidal activity of test compounds against red
flour beetle.
A sheet of filter paper placed on the bottom of a glass Petri dish of 9 cm diameter was sprayed with 1
ml of the composition under test which was prepared by diluting with water the emulsifiable
concentrate of this invention made in the Example 4, to the concentration of the active compound
indicated in Table 3 below. Twenty adult red flour beetles (Tribolium castaneum) were then placed into
the dish and the dish was kept in a constant-temperature room at 25 DEG C. 24 Hours later, the number
of the dead insects was counted and % mortality was assessed. The tests were conducted with three
replicates for a particular value of the concentration of the active compound under test, and the average
of % mortality was calculated. The results (expressed as the averaged % mortality) are given in Table 3
below.
>;tb;
TABLE 3
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Concentration of active compound
>;tb;
sprayed (ppm)
>;tb;Test Compounds
>;tb;
300
100
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
97
>;tb;Compound No. 2
>;tb;
100
100
253/612
>;tb;Compound No. 3
>;tb;
100
90
>;tb;Compound No. 4
>;tb;
100
97
>;tb;Compound No. 5
>;tb;
100
90
>;tb;Compound No. 6
>;tb;
100
90
>;tb;Compound No. 7
>;tb;
100
97
>;tb;Compound No. 8
>;tb;
100
90
>;tb;Compound No. 9
>;tb;
100
97
>;tb;Compound No. 10
>;tb;
100
90
>;tb;Compound No. 11
>;tb;
100
100
>;tb;Compound No. 12
>;tb;
100
100
>;tb;Compound No. 13
>;tb;
100
90
>;tb;Compound No. 14
>;tb;
100
97
>;tb;Compound No. 15
>;tb;
100
97
>;tb;Compound No. 16
>;tb;
100
97
>;tb;Compound No. 17
>;tb;
100
90
>;tb;Comparative 77
43
>;tb;compound A
>;tb;Comparative 77
40
>;tb;compound B
>;tb;Comparative 83
43
>;tb;compound C
>;tb;Comparative 83
65
>;tb;compound D
>;tb;Comparative 83
58
>;tb;compound E
>;tb;Comparative 77
50
>;tb;compound F
>;tb;Comparative 100
67
>;tb;compound G
>;tb;Comparative 83
50
>;tb;compound H
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 10
This Example illustrates the test of estimating the effect of the test compounds for controlling
"resistant" strains of green rice leafhopper.
Aquatic rice plants of an average height of about 40 cm were planted in a pot of square cross-section (6
cm.times.6 cm) and made of black colored polyvinyl chloride. These aquatic rice plants were treated by
dusting thereon the dusting powder of this invention made in the Example 6, at the rate of application
of the active compound as indicated in Table 4 below. After the dusting treatment, the treated rice
254/612
plants were covered with a cylindrical box of 11 cm diameter in the cross-section and made of
polyvinyl chloride. Twenty adult female green rice leafhoppers (Nephotettix cincticeps) of 3 days old
after the emergence of such "resistant" strain which showed the resistance against the known organophosphorus type insecticides and against the known carbamate-type insecticides were released into and
confined in the cylindrical box containing the treated aquatic rice plants. The rice plants-cultivating
pot, together with the covering cylindrical box of polyvinyl chloride, was kept in a constanttemperature room at 25 DEG C. 48 Hours after the releasing of the insects, percent of the mortality was
assessed. The tests were conducted with three replicates for a particular value of the concentration of
the active compound under test, and the average of % mortality was calculated. The results (expressed
as averaged % mortality) are set out in Table 4 below.
>;tb;
TABLE 4
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Rate of application of active
>;tb;
compound (g/10 ares)
>;tb;Test Compounds
>;tb;
15
5
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
95
>;tb;Compound No. 2
>;tb;
100
100
>;tb;Compound No. 3
>;tb;
100
93
>;tb;Compound No. 4
>;tb;
100
95
>;tb;Compound No. 5
>;tb;
100
93
>;tb;Compound No. 6
>;tb;
100
93
>;tb;Compound No. 7
>;tb;
100
97
>;tb;Compound No. 8
>;tb;
100
93
>;tb;Compound No. 9
>;tb;
100
95
>;tb;Compound No. 10
>;tb;
100
93
>;tb;Compound No. 11
>;tb;
100
98
>;tb;Compound No. 12
>;tb;
100
98
>;tb;Compound No. 13
>;tb;
100
93
>;tb;Compound No. 14
>;tb;
100
95
>;tb;Compound No. 15
>;tb;
100
97
>;tb;Compound No. 16
>;tb;
100
97
>;tb;Compound No. 17
>;tb;
100
93
>;tb;Comparative 73
37
>;tb;Compound A
>;tb;Comparative 67
23
>;tb;Compound B
>;tb;Comparative 67
37
>;tb;Compound C
>;tb;Comparative 73
20
255/612
>;tb;Compound D
>;tb;Comparative 90
47
>;tb;Compound E
>;tb;Comparative 73
33
>;tb;Compound F
>;tb;Comparative 93
50
>;tb;Compound G
>;tb;Comparative 87
33
>;tb;Compound H
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 11
This Example illustrates the test of estimating the effect of test compounds for controlling green peach
aphid.
Young seedlings of egg plant were cultivated in a pot of square cross-section (6 cm.times.6 cm), and
these young egg plants were infested with 20 adult wingless green peach aphids (Myzus persicae)
which had been reared over some successive generations. The infested egg plant was kept in a
constant-temperature room for 24 hours. After the aphids on the egg plant started to reproduce, the egg
plant with the infesting green peach aphids was sprayed with the composition under test which was
prepared by diluting with water the emulsifiable concentrate of this invention made in the Example 4 to
the concentration of the active compound as indicated in Table 5 below. The composition was applied
at the rate of 30 ml per pot. The pot was subsequently kept in a constant-temperature room at 25 DEG
C. 5 Days after the spraying, the number of the green peach aphids which was infesting the egg plant
was counted, and percent of mortality was calculated. The tests were conducted with three replicates
for a particular value of the concentration of the active compound under test, and the average of %
mortality was calculated.
The results (expressed as averaged % mortality) are given in Table 5 below.
>;tb;
TABLE 5
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Concentration of active compound
>;tb;
sprayed (ppm)
>;tb;Test Compounds
>;tb;
100
50
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
90
>;tb;Compound No. 2
>;tb;
100
100
>;tb;Compound No. 3
>;tb;
100
90
>;tb;Compound No. 4
>;tb;
100
90
>;tb;Compound No. 5
>;tb;
100
90
>;tb;Compound No. 6
>;tb;
100
90
>;tb;Compound No. 7
>;tb;
100
90
>;tb;Compound No. 8
>;tb;
100
90
>;tb;Compound No. 9
>;tb;
100
90
>;tb;Compound No. 10
256/612
>;tb;
100
90
>;tb;Compound No. 11
>;tb;
100
98
>;tb;Compound No. 12
>;tb;
100
94
>;tb;Compound No. 13
>;tb;
100
90
>;tb;Compound No. 14
>;tb;
100
90
>;tb;Compound No. 15
>;tb;
100
90
>;tb;Compound No. 16
>;tb;
100
90
>;tb;Compound No. 17
>;tb;
100
90
>;tb;Comparative 84
59
>;tb;compound A
>;tb;Comparative 85
40
>;tb;compound B
>;tb;Comparative 88
57
>;tb;compound C
>;tb;Comparative 85
51
>;tb;compound D
>;tb;Comparative 93
45
>;tb;compound E
>;tb;Comparative 92
57
>;tb;compound F
>;tb;Comparative 100
63
>;tb;compound G
>;tb;Comparative 94
57
>;tb;compound H
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 12
This Example illustrates the test of controlling housefly.
A sheet of filter paper was placed on the bottom of a glass Petri dish of 9 cm diameter, and the filter
paper was sprayed with 1 ml of a composition under test which was prepared by diluting with water the
wettable powder of this invention made in the Example 5, to a concentration of the active compound as
indicated in Table 6 below. 10 Adult houseflies (Musca domestica) of 4 days old after the emergence
were released into and confined in the covered dish. The dish containing the houseflies was kept in a
constant-temperature room at 25 DEG C. 48 Hours later, the number of dead insects was counted and
% mortality was assessed. The tests were conducted with three replicates for a particular value of the
concentration of the active compound under test, and the average of % mortality was calculated. The
results (expressed as the averaged % mortality) are set out in Table 6 below.
>;tb;
TABLE 6
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Concentration of active compound
>;tb;
sprayed (ppm)
>;tb;Test Compounds
>;tb;
300
100
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
97
>;tb;Compound No. 2
257/612
>;tb;
100
100
>;tb;Compound No. 3
>;tb;
100
97
>;tb;Compound No. 4
>;tb;
100
93
>;tb;Compound No. 5
>;tb;
100
97
>;tb;Compound No. 6
>;tb;
100
97
>;tb;Compound No. 7
>;tb;
100
97
>;tb;Compound No. 8
>;tb;
100
93
>;tb;Compound No. 9
>;tb;
100
93
>;tb;Compound No. 10
>;tb;
100
97
>;tb;Compound No. 11
>;tb;
100
100
>;tb;Compound No. 12
>;tb;
100
100
>;tb;Compound No. 13
>;tb;
100
93
>;tb;Compound No. 14
>;tb;
100
97
>;tb;Compound No. 15
>;tb;
100
97
>;tb;Compound No. 16
>;tb;
100
97
>;tb;Compound No. 17
>;tb;
100
93
>;tb;Comparative 70
43
>;tb;compound A
>;tb;Comparative 87
50
>;tb;compound B
>;tb;Comparative 87
40
>;tb;compound C
>;tb;Comparative 70
43
>;tb;compound D
>;tb;Comparative 83
43
>;tb;compound E
>;tb;Comparative 87
37
>;tb;compound F
>;tb;Comparative 93
50
>;tb;compound G
>;tb;Comparative 87
43
>;tb;compound H
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 13
This Example illustrates the test of estimating the effect of the new compounds for controlling twospotted spider mite.
Kidney-bean plants at the single true-leaf-extending stage planted in a pot of square cross-section (6
cm.times.6 cm) were infested with adult female two-spotted spider mites (Tetranychus urticae) which
were reared over some successive generations. The number of the mites infested was 20 per pot. The
258/612
infesting mites were allowed to produce the eggs on the bean plants. 24 Hours after the infestation, the
bean plants and the mites were sprayed with 30 ml/pot of the composition under test which was
prepared by diluting with water the wettable powder of this invention made in the Example 5 to a
concentration of the active compound as indicated in Table 7 below. The treated plants in the pot were
kept in a constant-temperature room at 25 DEG C. 3 Days after the spraying, the numbers of dead
mites and surviving mites were counted and the percent mortality was assessed in the same manner as
in Example 10. The tests were conducted with three replicates for a particular value of the
concentration of the active compound under test, and the average of mortality (%) was calculated. The
results (expressed as the averaged % mortality) are given in Table 7 below.
>;tb;
TABLE 7
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Concentration of active compound
>;tb;
sprayed (ppm)
>;tb;Test Compounds
>;tb;
100
50
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
95
>;tb;Compound No. 2
>;tb;
100
100
>;tb;Compound No. 3
>;tb;
100
95
>;tb;Compound No. 4
>;tb;
100
92
>;tb;Compound No. 5
>;tb;
100
99
>;tb;Compound No. 6
>;tb;
100
99
>;tb;Compound No. 7
>;tb;
100
93
>;tb;Compound No. 8
>;tb;
100
95
>;tb;Compound No. 9
>;tb;
100
95
>;tb;Compound No. 10
>;tb;
100
93
>;tb;Compound No. 11
>;tb;
100
100
>;tb;Compound No. 12
>;tb;
100
95
>;tb;Compound No. 13
>;tb;
100
95
>;tb;Compound No. 14
>;tb;
100
99
>;tb;Compound No. 15
>;tb;
100
99
>;tb;Compound No. 16
>;tb;
100
92
>;tb;Compound No. 17
>;tb;
100
99
>;tb;Comparative 75
25
>;tb;compound A
>;tb;Comparative 85
38
>;tb;compound B
>;tb;Comparative 87
50
>;tb;compound C
>;tb;Comparative 82
44
>;tb;compound D
259/612
>;tb;Comparative 63
44
>;tb;compound E
>;tb;Comparative 85
53
>;tb;compound F
>;tb;Comparative 87
63
>;tb;compound G
>;tb;Comparative 78
37
>;tb;compound H
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 14
This Example illustrates the test under submerged condition of estimating the effect of the test
compounds for controlling small brown planthopper.
Aquatic rice plants were transplanted and cultivated under the submerged condition in a pot having an
area of 1/10,000 ares at the soil surface. When the aquatic rice plants so cultivated reached a 4-leave
stage, the granules of this invention prepared in the Example 7 were scattered onto the surface of the
submerging water where the pot was immersed. The granules were applied at the rate of application of
the active compound as indicated in Table 8 below. The test plots were classified into two, the first plot
was such that two days lapsed between the application of the granules and the release of the insect
pests under test; and the second plot was such that 5 days lapsed between the application of the
granules and the release of the insect pests. The predetermined 2 or 5 days later, the pot was covered
with a cylindrical box made of a plastic resin material and having 10 cm diameter and 30 cm height.
Into the box covering the pot were released and confined therein 20 adult small brown planthoppers
(Laodelphax striattellus). 48 Hours after the release of the planthoppers, the number of the dead insects
was counted and % mortality was assessed. The tests were conducted with three replicates for a
particular value of the concentration of the active compound under test, and the average of % mortality
was calculated. The results (expressed as the averaged % mortality) are set out in Table 8 below.
>;tb;
TABLE 8
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Rate of application of active compound
>;tb;
(g/10 ares)
>;tb;
2 Days-lapsing plot
>;tb;
5 Days-lapsing plot
>;tb;Test Compounds
>;tb;
200
50
200 50
>;tb;______________________________________
>;tb;Compound No. 2
>;tb;
100
100
100 97
>;tb;Compound No. 7
>;tb;
100
90
97 90
>;tb;Compound No. 11
>;tb;
100
100
100 97
>;tb;Compound No. 12
>;tb;
100
100
100 93
>;tb;Compound No. 15
>;tb;
100
90
95 90
>;tb;Comparative
>;tb;
63
27
33 0
>;tb;compound B
>;tb;Comparative
>;tb;
93
30
37 10
>;tb;compound F
>;tb;Comparative
>;tb;
100
43
43 17
260/612
>;tb;compound G
>;tb;No treatment
>;tb;
0
0
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 15
This Example illustrates the test of estimating the effect of test compounds for controlling southern
root-knot nematode.
A quantity of soil infested by southern root-knot nematode (Meloidogyne incognita) was admixed with
a predetermined amount of the granules of this invention prepared in the Example 7 to such
concentration of the active compound as indicated in Table 9. The mixture of the soil and the granules
was stirred and mixed uniformly and then charged into a pot having an area of 1/5,000 ares. In the
treated soil charged in the pot were sown 20 seeds of tomato plant per pot. The tomato seeds were
cultivated in a greenhouse. 4 Weeks after the seed sowing, the grown roots of the young tomato plant
were withdrawn from the soil without damaging the roots, and the degree of injury of the roots was
evaluated according to the following ratings to estimate the root-knot index:
Ratings of root-knot (Degree of injury):
0--No root-knot formation (perfect control).
1--Slight root-knot formation was observed at the tip of small side-roots.
2--Root-knot formation was observed in the small side-roots but the knots formed were not yet
connected with each other.
3--Root-knot formation was observed along the whole length of the small side-roots with some knots
being connected with each other.
4--Root-knot formation was observed in the main root, too, with the many knots in the side-roots being
connected with each other.
5--The number of root-knots formed were very much great, with the knots connected with each other in
the main root and also in the side-roots (corresponding to the "control" plot where no treatment was
made).
Root-knot index was estimated according to the following equation: ##EQU1##
The tests were conducted with three replicates for a particular value of the concentration of the active
compound under test, and the average of the estimated root-knot indexes was calculated. The results
(expressed as the averaged % root-knot index) are listed in Table 9 below.
>;tb;
TABLE 9
>;tb;______________________________________
>;tb;
Root-knot Index (%)
>;tb;
Rate of application of active
>;tb;
compound (Kg/10 ares)
>;tb;Test Compound
>;tb;
3
1
>;tb;______________________________________
>;tb;Compound No. 2
>;tb;
0
8
>;tb;Compound No. 7
>;tb;
0
14
>;tb;Compound No. 11
>;tb;
0
11
>;tb;Compound No. 12
>;tb;
0
14
>;tb;Compound No. 15
>;tb;
2
21
>;tb;Comparative 27
78
>;tb;compound B
>;tb;Comparative 20
62
261/612
>;tb;compound F
>;tb;Comparative 12
63
>;tb;compound G
>;tb;No treatment 98
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 16
This Example illustrates the test of estimating the insecticidal activity of test compounds against Thrips
palmi.
A piece of the foliage of musk-melon which was cut off by means of a leaf-punch of 8 cm diameter
was immersed for 10 seconds in a volume of the composition under test which was prepared by
diluting with water the wettable powder of this invention made in the Example 5 to the concentration of
the active compound indicated in Table 10 below. The foliage piece was dried in air and then placed on
the bottom of a Petri dish of 9 cm diameter. Ten adult Thrips palmi were subsequently placed and
confined in said dish, and the dish was kept in a constant-temperature room at 25 DEG C. 48 Hours
later, the number of the dead insects was counted and % mortality was assessed. The tests were
conducted with three replicates for a particular value of the concentration of the active compound under
test, and the average of % mortality was calculated. The test results are shown in Table 10 below.
>;tb;
TABLE 10
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Concentration of active compound
>;tb;
used for treatment (ppm)
>;tb;Test Compounds
>;tb;
500
100
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
93
>;tb;Compound No. 2
>;tb;
100
100
>;tb;Compound No. 3
>;tb;
100
97
>;tb;Compound No. 4
>;tb;
100
87
>;tb;Compound No. 5
>;tb;
100
90
>;tb;Compound No. 6
>;tb;
100
90
>;tb;Compound No. 7
>;tb;
100
80
>;tb;Compound No. 8
>;tb;
100
83
>;tb;Compound No. 9
>;tb;
100
90
>;tb;Compound No. 10
>;tb;
100
100
>;tb;Compound No. 11
>;tb;
100
100
>;tb;Compound No. 12
>;tb;
100
83
>;tb;Compound No. 13
>;tb;
100
80
>;tb;Compound No. 14
>;tb;
100
100
>;tb;Compound No. 15
>;tb;
100
93
262/612
>;tb;Compound No. 16
>;tb;
100
100
>;tb;Compound No. 17
>;tb;
100
97
>;tb;Comparative 63
17
>;tb;compound A
>;tb;Comparative 37
0
>;tb;compound B
>;tb;Comparative 77
33
>;tb;compound C
>;tb;Comparative 80
30
>;tb;compound D
>;tb;Comparative 90
47
>;tb;compound E
>;tb;Comparative 87
50
>;tb;compound F
>;tb;Comparative 20
0
>;tb;compound G
>;tb;Comparative 67
0
>;tb;compound H
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 17
This Example illustrates the test of estimating the insecticidal activity of test compounds against
comstock mealybug. A piece of pumpkin to which second-instar larvae of comstock mealybug
(Pseudococcus comstocki) were infesting was immersed for 10 seconds in a volume of the composition
under test which was prepared by diluting with water the wettable powder of this invention made in the
Example 5 to the concentration of the active compound indicated in Table 11 below. After this
treatment, the pumpkin piece with the insects was placed on a sheet of filter paper covering the bottom
of a Petri dish of 9 cm diameter. The insects were confined in said dish, and the dish was kept in a
constant-temperature room at 25 DEG C. 48 Hours later, the number of the dead insects was counted
under microscope, and % mortality was assessed. The tests were conducted with three replicates for a
particular value of the concentration of the active compound under test, and the average of % mortality
was calculated. The test results are shown in Table 11 below.
>;tb;
TABLE 11
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Concentration of active compound
>;tb;
used for treatment (ppm)
>;tb;Test Compounds
>;tb;
100
30
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
96
>;tb;Compound No. 2
>;tb;
100
100
>;tb;Compound No. 3
>;tb;
100
90
>;tb;Compound No. 4
>;tb;
100
92
>;tb;Compound No. 5
>;tb;
100
97
>;tb;Compound No. 6
>;tb;
100
97
>;tb;Compound No. 7
>;tb;
100
95
263/612
>;tb;Compound No. 8
>;tb;
100
100
>;tb;Compound No. 9
>;tb;
100
94
>;tb;Compound No. 10
>;tb;
100
96
>;tb;Compound No. 11
>;tb;
100
91
>;tb;Compound No. 12
>;tb;
100
93
>;tb;Compound No. 13
>;tb;
100
90
>;tb;Compound No. 14
>;tb;
100
100
>;tb;Compound No. 15
>;tb;
100
98
>;tb;Compound No. 16
>;tb;
100
94
>;tb;Compound No. 17
>;tb;
100
96
>;tb;Comparative 80
46
>;tb;compound A
>;tb;Comparative 83
47
>;tb;compound B
>;tb;Comparative 85
51
>;tb;compound C
>;tb;Comparative 77
26
>;tb;compound D
>;tb;Comparative 92
63
>;tb;compound E
>;tb;Comparative 90
44
>;tb;compound F
>;tb;Comparative 81
40
>;tb;compound G
>;tb;Comparative 76
35
>;tb;compound H
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________
EXAMPLE 18
This Example illustrates the test of estimating the insecticidal activity of test compounds against
twenty-eight-spotted ladybird.
A piece of the foliage of egg-plant which was cut off by means of a leaf-punch of 8 cm diameter was
immersed for 10 seconds in a volume of the composition under test which was prepared by diluting
with water the wettable powder of this invention made in the Example 5 to the concentration of the
active compound indicated in Table 12 below. The foliage piece qas dried in air and then placed on the
bottom of a Petri dish of 9 cm diameter. Ten larvae of twenty-eight-spotted ladybird (Henosepilachna
vigintioctopunctata) were subsequently placed and confined in said dish, and the dish was kept in a
constant-temperature room at 25 DEG C. 48 Hours later, the number of the dead insects was counted
and % mortality was assessed. The tests were conducted with three replicates for a particular value of
the concentration of the active compound under test, and the average of % mortality was calculated.
The test results are shown in Table 12 below.
>;tb;
TABLE 12
>;tb;______________________________________
>;tb;
Mortality (%)
>;tb;
Concentration of active compound
264/612
>;tb;
used for treatment (ppm)
>;tb;Test Compounds
>;tb;
300
100
>;tb;______________________________________
>;tb;Compound No. 1
>;tb;
100
93
>;tb;Compound No. 2
>;tb;
100
100
>;tb;Compound No. 3
>;tb;
100
47
>;tb;Compound No. 4
>;tb;
100
100
>;tb;Compound No. 5
>;tb;
100
90
>;tb;Compound No. 6
>;tb;
100
97
>;tb;Compound No. 7
>;tb;
100
93
>;tb;Compound No. 8
>;tb;
100
100
>;tb;Compound No. 9
>;tb;
100
93
>;tb;Compound No. 10
>;tb;
100
100
>;tb;Compound No. 11
>;tb;
100
90
>;tb;Compound No. 12
>;tb;
100
93
>;tb;Compound No. 13
>;tb;
100
97
>;tb;Compound No. 14
>;tb;
100
100
>;tb;Compound No. 15
>;tb;
100
97
>;tb;Compound No. 16
>;tb;
100
100
>;tb;Compound No. 17
>;tb;
100
93
>;tb;Comparative 90
37
>;tb;compound A
>;tb;Comparative 43
57
>;tb;compound B
>;tb;Comparative 87
43
>;tb;compound C
>;tb;Comparative 100
60
>;tb;compound D
>;tb;Comparative 87
47
>;tb;compound E
>;tb;Comparative 93
53
>;tb;compound F
>;tb;Comparative 93
50
>;tb;compound G
>;tb;No treatment 0
>;tb;(Control)
>;tb;______________________________________Data supplied from the esp@cenet database Worldwide
Claims:
Claims of corresponding document: US4443439
265/612
What we claim is:
1. A method of combating insect pests, acarine pests and/or nematode pests at a locus of infestation,
which comprises treating the pests or the locus of infestation with an insecticidally, miticidally and/or
nematocidally effective amount of a compound of the general formula: ##STR39## wherein R1
denotes a lower alkyl group; R2 denotes a hydrogen atom, a lower alkyl group or an unsaturated lower
alkyl group; and R3 denotes a lower alkyl group or an unsaturated lower alkyl group.
2. A pesticidal composition comprising as an active ingredient an insecticidally, miticidally and/or
nematocidally effective amount of a compound of the general formula: ##STR40## wherein R1
denotes a lower alkyl group; R2 denotes a hydrogen atom, a lower alkyl group or an unsaturated lower
alkyl group and R3 denotes a lower alkyl group or an unsaturated lower alkyl group in combination
with an acceptable carrier or diluent.
3. Compounds of the general formula: ##STR41## wherein R1 denotes a lower alkyl group; R2
denotes a hydrogen atom, a lower alkyl group or an unsaturated lower alkyl group; and R3 denotes a
lower alkyl group or an unsaturated lower alkyl group.
4. Compounds of the general formula: ##STR42## wherein R4 is an alkyl group containing 1-6 carbon
atoms, R5 is a hydrogen atom, an alkyl group containing 1-6 carbon atoms, an alkenyl group
containing 2-6 carbon atoms or an alkynyl group containing 2-6 carbon atoms, and R6 is an alkyl group
containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms or an alkynyl group
containing 2-6 carbon atoms.
5. Compounds according to claim 4 wherein R4 is methyl or ethyl group; R5 is hydrogen, methyl,
ethyl, n-propyl, i-propyl, n-butyl, vinyl, propenyl or ethynyl group; and R6 is methyl, ethyl, i-propyl,
vinyl, allyl or propargyl group.
6. Compounds of the general formula: ##STR43## wherein R7 is an alkyl group of 1-4 carbon atoms,
an alkenyl group of 2-4 carbon atoms or an alkynyl group of 2-4 carbon atoms.
7. Compounds according to claim 6 wherein R7 is methyl, ethyl, i-propyl, allyl or propargyl group.
8. A compound according to claim 3 selected from: O-ethyl, O-(Nmethoxyformimidoyl)phenylthionophosphonate; O-ethyl, O-(Nmethoxyacetimidoyl)phenylthionophosphonate; O-ethyl, O-(Nmethoxypropionimidoyl)phenylthionophosphonate; O-ethyl, O-(N-methoxy-nbutyrimidoyl)phenylthionophosphonate; O-ethyl, O-(N-ethoxy-ibutyrimidoyl)phenylthionophosphonate; O-ethyl, O-(Nmethoxyvalerimidoyl)phenylthionophosphonate; O-ethyl, O-(Nmethoxyacrylimidoyl)phenylthionophosphonate; O-ethyl, O-(Nmethoxycrotonimidoyl)phenylthionophosphonate; O-ethyl, O-(Nethoxypropionimidoyl)phenylthionophosphonate; O-ethyl, O-(Nethoxyacetimidoyl)phenylthionophosphonate; O-ethyl, O-(N-ipropoxyacetimidoyl)phenylthionophosphonate; O-ethyl, O-(Nallyloxyacetimidoyl)phenylthionophosphonate; O-ethyl, O-(Npropargyloxyacetimidoyl)phenylthionophosphonate; O-methyl, O-(Nmethoxyacetimidoyl)phenylthionophosphonate; O-methyl, O-(Nethoxycrotonimidoyl)phenylthionophosphonate; O-methyl, O-(N-ipropoxyacetimidoyl)phenylthionophosphonate; and O-metyl, O-(Nallyloxyacetimidoyl)phenylthionophosphonate.Data supplied from the esp@cenet database Worldwide
266/612
24. KR8901062
- 4/22/1989
COMPOSION FOR PROTECTING CULTIVATED PLANTS FROM
PHYTOTOXIC EFECTS OF HERBICIDES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=KR8901062
Inventor(s):
BURDESKA KURT (CH); BRUNNER HANS-GEORG (CH); KABAS
GUGLIELMO (CH); FOERY WERNER (CH)
Applicant(s):
CIBA GEIGY CORP (CH)
IP Class 4 Digits: A01N; C07D
IP Class:A01N25/32; A01N57/10; C07D239/02
E Class: A01N25/32; C07D239/30B; C07D239/52; C07D239/42; C07D239/46C; C07F9/6512G
Application Number:
KR19810005105 (19811223)
Priority Number: CH19800009522 (19801223); CH19810002363 (19810408)
Family: KR8901062
Equivalent:
EP0055693; US4674229; US4493726; SU1482505; OA6972; ES8300322;
BG37221; PT74181; HU191339; DD202798; CS243465
Abstract:
Abstract of KR8901062
Phenylpyrimidines (I)[R=H, alkyl, halo, NO2, CF3, etc.; R1=H, halo, SOMe, OMe, etc.; R2=H, Me,
Ph, NMe, OEt, etc.; R3=H, halo, OEt, NHMe, SEt, etc.; n=1-5), useful as herbicide antidotes, were
prepd.. Thus, post-transplant application of 2-phenyl-4-chloropyrimidine (1kg/ha) protected rice
against the phytotoxic activity of pretilachlor (1kg/ ha) by 50%.Description:
Description of corresponding document: US4493726
The present invention relates to a method of and a composition for protecting cultivated plants from the
phytotoxic effects of herbicides. In the method of this invention, the phenylpyrimidines of the formula I
below are applied to the crops of cultivated plants simultaneously or shortly afterwards with the
herbicide, or a composition which, in addition to containing the herbicide, also contains a
phenylpyrimidine of the formula I, is applied to the crops. The invention also relates to the
compositions which contain phenylpyrimidines of the formula I.
The phenylpyrimidines of this invention have the formula I ##STR2## in which
n is an integer from 1 to 5,
R is hydrogen, halogen, cyano, nitro or hydroxyl, a C1 -C6 alkyl, C1 -C6 alkoxy or C1 -C6 alkylthio
group, which is unsubstituted or mono- or polysubstituted by halogen, C1 -C6 alkoxy, C2 -C12
alkoxyalkyl, C1 -C6 alkylcarbonyl, C1 -C6 alkylcarbonyloxy, C1 -C6 alkoxycarbonyl, C2 -C6
alkenylcarbonyl or C2 -C6 alkynylcarbonyl, di(C1 -C6)alkylamino, C1 -C6 alkylenedioxy, phosphonyl
or C1 -C6 alkylphosphonyl; or R is a C2 -C6 alkenyl or C2 -C6 alkenyloxy group or the formyl or
carboxyl group; or it is a carbonyl or carbonyloxy group which is substituted by C1 -C6 alkyl, C1 -C6
haloalkyl, C1 -C6 alkoxy, C2 -C6 alkenyl, C2 -C6 alkynyl, amino, di(C1 -C6)alkylamino, or by a 5- to
6-membered saturated heterocyclic ring which is bound through the nitrogen atom; or it is an amino
267/612
group which is unsubstituted or substituted by C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6 alkylcarbonyl; or
is an ureido radical which is unsubstituted or substituted by C1 -C6 alkyl or C1 -C6 alkoxy or it is the
sulfonyl, a C1 -C6 aklylsulfonyl, sulfamoyl, C1 -C6 alkylsulfamoyl or C1 -C6 alkylcarbonylsulfamoylrest,
R1 and R3, each independently of the other, are halogen, cyano, hydroxyl, sulfhydryl, a C1 -C6 alkyl,
C1 -C6 alkoxy or C1 -C6 alkylthio radical, which is unsubstituted or substituted by halogen or C1 -C6
alkoxy; a C2 -C6 alkenyl or C2 -C6 alkynyl radical, or a C3 -C6 cycloalkyl radical, an amino, C1 -C6
alkylamino or di(C1 -C6)alkylamino group, a 5- to 6membered saturated heterocyclic ring which is
bound through the nitrogen atom; a phenyl or phenoxy-rest and
R2 is hydrogen, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl or phenyl.
Alkyl by itself or as moiety of another substituent comprises branched or unbranched alkyl groups
which contain the indicated number of carbon atoms. Examples of such alkyl groups are: methyl, ethyl,
propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, as well as the higher homologs amyl, isoamyl,
hexyl, heptyl, octyl, together with their isomers. The alkenyl and alkynyl groups can likewise be
straight chain or branched. Cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The phenylpyrimidines of the formula I are most suitable for protecting cultivated plants such as
sorghum, rice, maize, cereals (wheat, rye, barley, oats), cotton, sugar beet, sugar cane, soybeans etc.,
from attack by aggressive agrochemicals, especially by herbicides belonging to a wide variety of
compound classes, e.g. triazines, phenylurea derivatives, carbamates, thiocarbamates, haloacetanilides,
halophenoxyacetates, substituted phenoxyphenoxyacetates and -propionates, substituted
pyridyloxyphenoxyacetates and -propionates, benzoic acid derivatives etc., where these compounds do
not have a selective action or do not act selectively enough, i.e. where they also damage the cultivated
plants to a greater or lesser extent in addition to the weeds to be controlled. The invention also relates
to compositions which contain these phenylpyrimidines of the formula I, together with herbicides.
Particularly suitable antidotes are the phenylpyrimidines of the formula I, wherein n is an integer of
from 1 to 5, R is hydrogen, halogen, cyano, nitro, hydroxyl, C1 -C6 alkyl, C1 -C6 alkoxy, C1 -C6
haloalkyl, C2 -C6 alkenyl, C2 -C6 haloalkenyl, C2 -C6 alkynyl, amino, C1 -C6 alkylamino, C1 -C6
alkylcarbonylamino, carboxy, C1 -C6 alkylcarbonyl, C1 -C6 alkoxycarbonyl, sulfonyl, C1 -C6
alkylsulfonyl, sulfamoyl, C1 -C6 alkylsulfamoyl, C1 -C6 alkylcarbonylsulfamoyl, R1 and R3
independently of each other are halogen and R2 is hydrogen or chlorine.
Important compounds are phenylpyrimidines of the formula I, wherein n is 1 and R is in the paraposition to the pyrimidine-rest and represents hydrogen, halogen, C1 -C6 alkyl, hydroxyl, C1 -C6
alkoxy; R1 and R3 are halogen and R2 is hydrogen, especially
2-phenyl-4,6-dichloropyrimidine,
2-phenyl-4,6-dibromopyrimidine,
2-para-tolyl-4,6-dichloropyrimidine,
2-(4-chlorophenyl)-4,6-dichloropyrimidine,
2-(4-methoxyphenyl)-4,6-dichloropyrimidine,
2-(4-hydroxyphenyl)-4,6-dichloropyrimidine,
2-(3-nitrophenyl)-4,6-dichloropyrimidine and
2-(3-chloro-4-fluorophenyl)-4,6-dichloropyrimidine.
Various compounds which are able to antagonise specifically the harmful effects of a herbicide on
cultivated plants have already been proposed as safeners or antidotes, i.e. compounds which protect
cultivated plants without noticeably influencing the herbicidal action on the weeds which it is desired
to control. Depending on their properties, such antidotes, also known as safeners, can be used for
pretreating the seeds of the cultivated plants (dressing seeds or seedlings) or before sowing seeds in
furrows, or as tank mixture together with the herbicide, before or after emergence of the plants.
For example, British patent specification No. 1,277,557 discloses the treatment of seed and seedlings of
wheat and sorghum with certain esters and amides of oxamic acid from attack by N-methoxymethyl2',6'-diethyl-chloroacetanilide (Alachlor). Other publications (German Offenlegungsschrift
specification Nos. 1 952 910 and 2 245 471, and French patent specification No. 2 021 611), propose
268/612
antidotes for the treatment of cereals, maize seeds and rice seeds to protect them from attack by
herbicidal thiocarbamates. In German patent specification No. 1 576 676 and U.S. Pat. No. 3,131,509,
hydroxyaminoacetanilides and hydantoins are suggested for protecting cereal seeds against carbamates
such as IPC, CIPC, etc. Further development, however, has shown all these preparations to be
unsatisfactory.
Surprisingly, phenylpyrimidines of the formula I have the property of protecting cultivated plants from
attack by aggressive agrochemicals, in particular from herbicides belonging to a wide range of
compound classes, for example chloroacetanilides, chloroacetamides, carbamates and thiocarbamates,
diphenyl ethers and nitrodiphenyl ethers, benzoic acid derivatives, triazines and triazinones,
phenylureas, nitroanilines, oxdiazolones, pyridyloxyphenoxy derivatives, phosphates and pyrazoles,
where these compounds are not tolerated or are insufficiently tolerated by the cultivated plants.
The phenylpyrimidines of this invention preferably protect herbicides belonging to the classes of the
chloroacetanilides, chloroacetamides, thiocarbamates, and phosphates.
Depending on the particular purpose, a safener or antidote of the formula I can be used for pretreating
the seeds of the cultivated plant or incorporated in the soil before or after sowing, or else applied by
itself alone or together with the herbicide before or after emergence of the plants. In principle,
therefore, the treatment of the plant or seeds can be carried out independently of the time of application
of the phytotoxic chemical. However, the treatment can also be carried out simultaneously (tank
mixture). Preemergence treatment includes both the treatment of the crop area before sowing
(ppi=preplant incorporation), and the treatment of the sown crop areas in which the plants have not yet
emerged.
The rates of application in which the antidote is employed in relation to the herbicide depend largely on
the mode of application. Where a field treatment is carried out, either as tank mixture or if herbicide
and antidote are applied separately, the ratio of antidote to herbicide is usually from 1:100 to 10:1, with
the preferred range however being from 1:5 to 8:1, most preferably 1:1.
When dressing seeds and taking similar protective measures, however, much smaller amounts of
antidote are required in comparison e.g. with the amounts of herbicide employed later per hectare of
crop area. For seed dressing, 0.1 to 10 g of antidote is usually required per kg of seeds, with the
preferred amount being from 1 to 2 g. If the antidote is to be applied shortly before sowing by seed
soaking, then e.g. antidote solutions which contain the active ingredient in a concentration of 1-10000
ppm, preferably 100-1000 ppm, are used.
Protective measures such as seed dressing with an antidote of the formula I and a possible later field
treatment with agrochemicals, normally follow at a greater interval of time. Pretreated seeds and plants
can come into contact later with different chemicals in agriculture, horticulture and forestry.
Accordingly, the invention also relates to plant protection compositions which contain, as active
ingredient, an antidote of the formula I together with conventional carriers. If appropriate or desired,
such compositions can additionally be mixed with the chemical against the action of which it is desired
to protect the cultivated plant, for example with a herbicide.
Cultivated plants within the scope of this invention are all plants which, in any form, can be harvested
(seeds, roots, stalks, tubers, leaves, blossoms) and from which extracts can be obtained (oils, sugar,
starch, protein) and which for this purpose are cultivated and tended. To these plants belong e.g. all
species of cereals such as wheat, rye, barley and oats, and also in particular rice, sorghum, cotton, sugar
beet, sugar cane, soybeans, beans and peas.
The antidote will be employed whereever it is intended to protect a cultivated plant from the
phytotoxicity of a chemical.
The following compounds are cited as examples of herbicides against whose effects it is desired to
protect cultivated plants:
269/612
Chloracetanilides: 2-chloro-2',6'-diethyl-N-(2"-propoxyethyl)acetanilide ("Propachlor"), 2-chloro-6'ethyl-N-(2"-methoxy-1"-methylethyl)-acet-o-toluidide ("Metolachlor"), 2-chloro-2',6'-diethyl-N(butoxymethyl)acetanilide ("Butachlor"), 2-chloro-6'-ethyl-N-(ethoxymethyl)acet-o-toluidide
("Acetochlor"), 2-chloro-6'-ethyl-N-(2"-propoxy-1"-methylethyl)acet-o-toluidide, 2-chloro-2',6'dimethyl-N-(2"-methoxy-1"-methylethyl)acetanilide, 2-chloro-2',6'-dimethyl-N-(2"methoxyethyl)acetanilide ("Dimethachlor"), 2-chloro-2',6'-diethyl-N-(pyrazol-1-ylmethyl)acetanilide,
2-chloro-6'-ethyl-N-(pyrazol-1-ylmethyl)acet-o-toluidide, 2-chloro-6'-ethyl-N-(3,5-dimethylpyrazol-1ylmethyl)acet-o-toluidide, 2-chloro-6'-ethyl-N-(2"-butoxy-1"-methylethyl)acet-o-toluidide
("Metazolachlor"), 2-chloro-6'-ethyl-N-(2"-butoxy-1"-(methylethyl)acet-o-toluidide, 2-chloro-2'trimethylsilyl-N-(butoxymethyl)acetanilide, 2-chloro-2',6'-diethyl-N-(methoxymethyl(acetanilide
("Alachlor") and 2-chloro-2',6'-diethyl-N-(ethoxycarbonylmethyl)acetanilide.
Chloroacetamides: N-[1-isopropyl-2-methylpropen-1yl-(1)]-N-(2'-methoxyethyl)-chloroacetamide .
Carbamates and thiocarbamates: N(3',4'-dichlorophenyl)propionanilide ("Propanil"), S-4-chlorobenzyldiethyl-thiocarbamate ("Thiobencarb"), S-ethyl-N,N-hexamethylene-thiocarbamate ("Molinate"), Sethyl-dipropyl-thiocarbamate ("EPTC"), N,N-di-sec-butyl-S-benzyl-thiocarbamate (Drepamon), S-(2,3dichloroallyl)-diisopropylthiocarbamate and S(2,3,3-trichloroallyl)-diisopropylthiocarbamate ("Di- and
Tri-allate"), 1-(propylthiocarbonyl)-decahydroquinaldine, S-4-benzyldiethylthiocarbamate and also
corresponding sulfinylcarbamates.
Diphenylethers and nitrodiphenyl ethers: 2,4-dichlorophenyl-4'-nitrophenyl ether ("Nitrofen"), 2chloro-1-(3'-ethoxy-4'-nitrophenoxy)-4-trifluoromethylbenzene ("Oxyfluorfen"), 2',4'-dichlorophenyl3-methoxy-4-nitrophenyl ether ("Chlormethoxinyl"), methyl 2-[4'-(2",4"dichlorophenoxy)phenoxy)propionate, N-(2'-methoxyethyl)-2-[5'-(2"-chloro-4"trifluoromethylphenoxy)phenoxy]pro pionamide.
Benzoic acid derivatives: methyl 5-(2',4'-dichlorophenoxy)-2-nitrobenzoate ("Bifenox"), 5-(2'-chloro4'-trifluoromethylphenoxy)-2-nitrobenzoic acid ("Acifluorfen"), 2,6-dichlorobenzonitrile
("Dichlobenil").
Triazines and triazinones: 2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine ("Prometryn"), 2,4bis(ethylamino)-6-methylthio-1,3,5-triazine ("Simetryn"), 2-(1',2'-dimethylpropylamino)-4-ethylamino6-methylthio-1,3,5-triazine ("Dimethametryn"), 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4triazin-5-one ("Metribuzin").
Phenylureas: N-(3'-isopropylphenyl)-N',N'-dimethyl urea ("Isoproturon"), N-(3',4'dimethylbenzyl)-N'4-tolyl urea ("Dimuron"), N-(3'-chloro-4'-isopropylphenyl)-N',N'-(3-methyl-pentamethylen-1,5-yl)
urea.
Nitroanilines: 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline ("Trifluralin"), N-(1'-ethylpropyl)-2,5dinitro-3,4-xylidine ("Pendimethalin").
Oxadiazolones: 5-tert-butyl-3-(2',4'-dichloro-5'-isopropoxyphenyl)-1,3,4-oxadiazol-2-one
("Oxdiazon").
Pyridyloxyphenoxy derivatives: 2-propinyl-2-[4'-(3",5"-dichloropyridyl-2"-oxy)phenoxy]-propionate.
Phosphates: S-2-methylpiperidino-carbonylmethyl-O,O-dipropylphosphoro-dithioate ("Piperophos").
Pyrazoles: 1,3-dimethyl-4-(2',4'-dichlorobenzoyl)-5-(4'-tolylsulfonyloxy)pyrazole.
The phenylpyrimidines of the formula I which act as antidotes may optionally be employed after
application of the agrochemical or also simultaneously with it.
Many phenylpyrimidines of this invention are novel, whilst others are known compounds.
Phenylpyrimidines are used as intermediates in the manufacture of dyes, in which connection attention
is drawn to e.g. British patent specification No. 1,502,912 or to published European patent application
Nos. 20 298 and 31 796. They are also known as intermediates of pharmacologically active
270/612
compounds, q.v. J. Med. Chem. 1978 (21), pp. 123-126, or they are met with elsewhere in the chemical
literature, q.v. Bull. Soc. Chem. Jap. 44 (8), pp. 2182-5.
The phenylpyrimidines of the formula I can be obtained by known synthesis routes. The 2phenylpyrimidine ring is formed e.g. by condensation of a phenylamidine with a malonic acid
derivative.
The 2-phenylpyrimidines are obtained by condensing a phenylamidine with adialkyl malonate in
alcoholic solution in the presence of a base ##STR3## and then, if desired, replacing the hydroxyl
groups of the resultant 2-phenyl-4,6-dihydroxypyrimidine of the formula IV by halogen atoms with a
halogenating agent (phosphoroxy chloride, phosphoroxy bromide, sulfuryl chloride, bromosuccinimide
etc.) and, if desired, replacing these halogen atoms in turn by further radicals R1 and R3.
If R2 is hydrogen, this can be replaced e.g. by treatment with chlorine or bromine in a polar solvent,
e.g. glacial acetic acid.
The halogen atoms in the positions 4, 5, and 6 of the pyrimidine ring can in turn be replaced, in known
manner, by alcohols, mercaptans or amines.
The following publications, for example, are cited as references: J. Chem. Soc. 1965, pp. 5467-5473, J.
prakt. Chem. 312 (1970), pp. 494-506, J. Chem. Soc. Perkin Trans.1 1977, pp. 2285-6.
Phenylpyrimidines in which R1 is an alkyl or phenyl group are obtained e.g. by condensation of a
phenylamidine with an alkyl ester of an acetoacetic acid: ##STR4## Here too the --OH group can be
replaced in known manner by a halogen atom, which in turn can be replaced by an alcohol, a thiol or an
amine.
It is also possible to prepare e.g. 2-phenyl-4,6-dichloropyrimidine and 2-phenyl-4-chloro-6hydroxypyrimidines by reaction of chlorobenzylidine-carbamoyl chlorides with an aliphatic nitrile in
the presence of hydrogen chloride: ##STR5## q.v. Bull. Soc. Chem. Japan 44 (1971), pp. 2182-2185.
2-Phenyl-4,6-dichloropyrimidine can be obtained e.g. in accordance with Ang. Chemie 89 (1977), pp.
816-817, e.g. by condensation of a N-phenyl cyanamide and a N,N-dialkyl amide in POCl3 at 100
DEG C.: ##STR6##
In the above formulae, R, R2 and n are as defined for formula I.
The synthesis of such compounds or the exchange of radicals R1, R2 and R3 by other substituents cited
in the definition are procedures which are known per se. As regards the preparation of these
compounds attention is drawn to the Examples or to the literature. A further reference is also "The
Chemistry of Heterocyclic Compounds", 16, Interscience Publishers, New York 1962, pp. 119 ff.
The compounds of formula I can be used by themselves alone or together with the compounds which it
is desired to antagonise.
The compounds of the formula I are used in unmodified form or preferably together with the adjuvants
conventionally employed in the art of formulation, and are therefore formulated in known manner to
emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders,
soluble powders, dusts, granulates, and also encapsulations in e.g. polmyer substances. Just like the
nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering
or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of
the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by
homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid
carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms,
e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl
271/612
phthalate, aliphatic hydrocarbons such as cyclohexane, or paraffins, alcohols and glycols and their
ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether;
ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl
sulfoxide or dimethyl formamide; as well as epoxidised vegetable oils such as epoxidised coconut oil
or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such
as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it
is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable
granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or
bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great
number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite
or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active
compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and
wetting properties. The term "surfactants" will also be understood as comprising mixtures of
surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active
compounds.
Suitable soaps are the alkali, alkaline earth or unsubstituted or substituted ammonium salts of higher
fatty acids (C10 -C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty
acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of
fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty
sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali, alkaline earth or unsubstituted or
substituted ammonium salts and contain a C8 -C22 alkyl radical which also includes the alkyl moiety
of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture
of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of
sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated
benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical
containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or
triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a
naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding
phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of
ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols,
or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether
groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the
alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with
polypropylene glycol, ethylenediaminepolypropylene glycol and alkylpolypropylene glycol containing
1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups
and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 glycol units per
propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil
polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol,
polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acids esters of polyoxyethylene
sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
272/612
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least
one polyglycol ether or C8 -C22 alkyl radical and, as further substituents, lower unsubstituted or
halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of
halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in the following
publications: "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood,
N.J., 1979; Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co. Inc.,
New York, 1964.
The pesticidal formulations will normally contain 0.1 to 99%, preferably 0.1 to 95%, of a compound of
the formula I, 1 to 99% of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of a
surfactant. Whereas commercial products will be preferably formulated as concentrates, the end user
will normally employ dilute formulations.
The compositions can also contain further ingredients such as stabilisers, antifoams, viscosity
regulators, binders, adhesives, as well as fertilisers or other active compounds, in order to attain special
effects.
In the following Examples parts and percentages are by weight.
Preparatory Examples
Example 1
2-p-Tolyl-4,6-bis-isopropoxypyrimidine ##STR7##
(a) 21.16 g of sodium are dissolved in anhydrous isopropanol and to this solution are added 95.64 g of
4,6-dichloro-2-p-tolylpyrimidine at 60 DEG-65 DEG C. over 15 minutes. The mixture is then heated to
the boil and refluxed for a further 4 hours to bring the reaction to completion. Excess isopropanol is
then distilled off and the residual oil is taken up in chloroform. The chloroform layer is washed with
water, dried over sodium sulfate, and filtered. The solvent is then distilled off, affording 112 g of 2-ptolyl-4,6-bis-isopropoxypyrimidine in the form of a yellowish oil which is purified by high vacuum
distillation. The boiling point is 123 DEG C./5.332 Pascal.
The starting 2-p-tolyl-4,6-dichloropyrimidine is prepared as follows:
(b) 102.3 g of p-tolylamidine hydrochloride and 99.3 g of diethyl malonate are suspended in 520 ml of
anhydrous ethanol. With good stirring and cooling, 323.7 g of a 30% solution of sodium methylate are
then run in. The reaction mixture is then heated to reflux and stirred at reflux temperature for 5 hours.
The solvent is then distilled off and the residue is taken up in 1000 ml of water, heated to 80 DEG C.,
and the somewhat turbid solution is then filtered over silica gel. The filtrate is cooled and acidified with
15% hydrochloric acid. The dense crystalline slurry is filtered and the filter residue is washed with
water and dried at 100 DEG C., affording 100-110 g of 2-p-tolyl-4,6-dihydroxypyrimidine with a
melting point of 314 DEG C. (with decompos.),
(c) 72.6 g of the dihydroxy compound, 72.6 g of N,N-dimethyl aniline and 363 g of phosphoroxy
chloride was heated to the boil and the mixture is stirred at reflux for 1 hour. Excess phosphoroxy
chloride is distilled off and then the residue is washed with iced water to remove any phosphoroxy
chloride still remaining, triturated with iced water, and filtered. The filter residue is washed with iced
water and vacuum dried at 40 DEG-50 DEG C., affording 85.9 g of 2-p-tolyl-4,6-dichloropyrimidine
with a melting point of 86 DEG-87 DEG C.
Example 2
2-p-Tolyl-4,6-bis-isopropoxy-5-bromopyrimidine ##STR8##
273/612
111.7 g of 4,6-diisopropoxy-2-p-tolylpyrimidine and 450 ml of carbon tetrachloride are heated to 70
DEG-75 DEG C. To the resultant solution is added 0.5 g of dibenzoyl peroxide, followed by the
addition, over 45 minutes, of a mixture of 1 g of azoisobutyronitrile and 70.8 g of Nbromosuccinimide. The mixture is refluxed for 2 hours to bring the reaction to completion. The
precipitated succinimide is then filtered off and excess carbon tetrachloride is removed by distillation,
affording 141 g of the title compound with a melting point of 74 DEG-75 DEG C. after purification
with methanol.
Example 3
2-p-Tolyl-4,6-dimethoxypyrimidine ##STR9##
156.1 g of a 30.5% solution of sodium methylate are stirred with 700 ml of anhydrous methanol. To the
solution are then added, over 10 minutes and with gentle cooling, 95.64 g of 2-p-tolyl-4,6dichloropyrimidine. The mixture is then heated to reflux and kept at the boil for 4 hours. The solvent is
removed by distillation and the residue is charged into 1000 ml of water. The product is triturated with
water to remove sodium chloride, isolated by filtration, washed with water and dried in the air,
affording 90.4 g of the title compound with a melting point of 61 DEG-62 DEG C.
Example 4
2p-Chlorophenyl-4,6-dihydroxypyrimidine ##STR10##
108 g of a 30% solution of sodium methylate in methanol are added over 10 minutes to a suspension of
38.2 g of 4-chlorobenzylamidine hydrochloride and 33.6 g of diethyl malonate in 175 ml of methanol,
and the mixture is subsequently refluxed for 5 hours. The solvent is then distilled off in a rotary
evaporator and the residue is taken up in 1000 ml of hot water and the solution is filtered. The filtrate is
then acidified to pH 1 and the precipitate is isolated by filtration and vacuum dried at 80 DEG C.,
affording 44 g of 2-p-chlorophenyl-4,6-dihydroxypyrimidine with a melting point of 333 DEG C.
(decompos.).
EXAMPLE 5
2p-Chlorophenyl-4,6-dichloropyrimidine ##STR11##
50 ml of phosphoroxy chloride (POCl3) are added dropwise at room temperature to 22 ml of N,Ndimethyl aniline. Then 22.3 g of 2-p-chlorophenyl-4,6-dihydroxypyrimidine are added in portions with
cooling, such that the temperature remains below 40 DEG C. The reaction mixture is stirred for 2 hours
at room temperature, then refluxed for 2 hours, and subsequently concentrated by rotary evaporation.
The residue is triturated with 500 ml of water and filtered with suction. The filter cake is dissolved in
methylene chloride and the solution is treated with fuller's earth, dried and concentrated. The residue
crystallises, giving 16.2 g of 2-p-chlorophenyl-4,6-dichloropyrimidine with a melting point of 119
DEG-120 DEG C. A sample sublimed at 80 DEG/0.02 mbar melts at 120 DEG-121 DEG C.
Example 6
2-p-Methoxyphenyl-4,6-dihydroxypyrimidine ##STR12##
338 g of a 30% solution of sodium methylate in methanol are added over 10 minutes to a suspension of
112 g of p-methoxybenzamidine hydrochloride and 101 g of diethyl malonate in 520 ml of ethanol, and
the mixture is subsequently refluxed for 5 hours. The reaction mixture is then concentrated by rotary
evaporation and the residue is dissolved in 1000 ml of warm water of 80 DEG C. The solution is
filtered and the filtrate is acidified to pH 1. The precipitate is isolated by filtration and vacuum dried at
80 DEG C., affording 109.8 g of 2-p-methoxyphenyl-4,6-dihydroxypyrimidine with a melting point of
318 DEG C. (decompos.).
Example 7
2-p-Methoxyphenyl-4,6-dichloropyrimidine ##STR13##
274/612
126 ml of phosphoroxy chloride (POCl3) and then 57 ml of N,N-dimethyl aniline are added dropwise
over 30 minutes to 54.5 g of 2-p-methoxyphenyl-4,6-dihydroxypyrimidine with cooling, such that the
temperature does not exceed 45 DEG C. The reaction mixture is then stirred for 2 hours at room
temperature and subsequently refluxed for 2 hours. The reaction mixture is then concentrated by rotary
evaporation and the residue is triturated in 2 liters of iced water. The solid product is isolated by
filtration, dissolved in 1.5 liters of methylene chloride and the solution is treated with fuller's earth and
dried. The methylene chloride solution is filtered and concentrated. The residue is recrystallised from
ethanol, affording 51 g of crystalline 2p-methoxyphenyl-4,6-dichloropyrimidine with a melting point of
127 DEG-128 DEG C.
The following compounds are prepared by procedures similar to those described in the preceding
Examples:
>;tb;__________________________________________________________________________
>;tb; ##STR14##
>;tb;No.
>;tb; (R)n
R1 R2 R3 Physical data
>;tb;
( DEGC.)
>;tb;__________________________________________________________________________
>;tb;1 (H)5
Cl
H
Cl
m.p. 95-96 DEG
>;tb;2 4-CH3
Cl
H
Cl
m.p. 86-87 DEG
>;tb;3 4-CH3
Cl
CH3 Cl
m.p.
>;tb;
153-154 DEG
>;tb; 4
>;tb; 4-CH3
Cl
>;tb;
##STR15## Cl
m.p.
>;tb;
132-133 DEG
>;tb; 5
>;tb; (H)5
Cl
H
CH3 m.p. 71-72 DEG
>;tb;6 4-CH3
Cl
H
CH3 m.p.
>;tb;
103-104 DEG
>;tb;7 4-CH3
Cl
H
OH
m.p.
>;tb;
229-234 DEG
>;tb;8 4-CH3
Cl
H
OCH3 m.p. 92-93 DEG
>;tb;9 4-CH3
Cl
CH3 OCH3 m.p.
>;tb;
143-144 DEG
>;tb;10 4-CH3
Cl
H
OC3 H7 iso
>;tb;
m.p. 55-57 DEG
>;tb; 11
>;tb; 4-CH3
Cl
H
>;tb;
##STR16## m.p. 86-87 DEG
>;tb; 12
>;tb; 4-CH3
Cl
H
>;tb;
##STR17## m.p.
>;tb;
102-104 DEG
>;tb; 13
>;tb; 4-CH3
Cl
H
NHCH3 m.p. 107 DEG
>;tb;14 4-CH3
Cl
Br
NHCH3 m.p.
>;tb;
105-107 DEG
>;tb;15 4-CH3
Cl
H
N(C2 H5)2
>;tb;
m.p. 74-75 DEG
>;tb;16 (H)5
CH3 H
OH
oil
>;tb;17 4-CH3
CH3 H
OH
m.p.
>;tb;
206-207 DEG
>;tb;18 (H)5
CH3 H
OCH3 b.p. 156-8 DEG/
>;tb;
1.33 10@3
>;tb;
.multidot. Pa
>;tb;19 4-CH3
CH3 H
OCH3 m.p. 66-67 DEG
>;tb; 20
275/612
>;tb; 4-CH3
CH3 H
>;tb;
##STR18## m.p. 90-91 DEG
>;tb; 21
>;tb; (H)5
CH3 H
OC2 H4 OCH3
>;tb;
b.p.
>;tb;
158-160 DEG/
>;tb;
13.33 Pa
>;tb;22 (H)5
CH3 H
(OC2 H4)2
>;tb;
OCH3 b.p.
>;tb;
148-150 DEG/
>;tb;
2.66 Pa
>;tb;23 4-CH3
CH3 H
OC2 H4 OCH3
>;tb;
m.p. 61-62 DEG
>;tb;24 (H)5
CH3 H
N(CH3)2
>;tb;
m.p. 55-57 DEG
>;tb;25 4-CH3
CH3 H
N(CH3)2
>;tb;
m.p. 97-98 DEG
>;tb;26 4-CH3
CH3 Br
N(CH3)2
>;tb;
m.p. 49-50 DEG
>;tb; 27
>;tb; (H)5
CH3 H
>;tb;
##STR19## m.p. 88-90 DEG
>;tb; 28
>;tb; 4-CH3
CH3 H
>;tb;
##STR20## m.p.
>;tb;
123-124 DEG
>;tb; 29
>;tb; 4-CH3
CH3 Br
>;tb;
##STR21## m.p.
>;tb;
113-114 DEG
>;tb; 30
>;tb; 4-CH3
OCH3 H
>;tb;
##STR22## m.p. 99-100 DEG
>;tb; 31
>;tb; 4-CH3
OCH3 H
OCH3 m.p. 61-62 DEG
>;tb;32 4-CH3
OCH3 CH3 OCH3 m.p. 93-94 DEG
>;tb; 33
>;tb; 4-CH3
OCH3
>;tb;
##STR23## OCH3 m.p. 214 DEG
>;tb; 34
>;tb; 4-CH3
OC2 H5
>;tb;
H
OC2 H5
>;tb;
m.p. 71 DEG
>;tb;35 4-CH3
OC3 H7 n
>;tb;
H
OC3 H7 n
>;tb;
m.p. 62 DEG
>;tb;36 4-CH3
OC3 H7 iso
>;tb;
H
OC3 H7 iso
>;tb;
b.p.
>;tb;
123 DEG/5.332
>;tb;
Pa
>;tb;
Example 1
>;tb;37 4-CH3
OC3 H7 iso
>;tb;
Br
OC3 H7 iso
>;tb;
m.p. 73-74 DEG
>;tb;
Example 2
>;tb;38 4-CH3
OC4 H9 n
>;tb;
H
OC4 H9 n
>;tb;
b.p.
276/612
>;tb;
158-161 DEG/
>;tb;
13.332 Pa
>;tb; 39
>;tb; 4-CH3
>;tb;
##STR24## H
>;tb;
##STR25## m.p.
>;tb;
125-126 DEG
>;tb; 40
>;tb; 4-CH3
SC2 H5
>;tb;
H
SC2 H5
>;tb;
m.p. 55-56 DEG
>;tb;41 4-CH3
OC2 H4 OCH3
>;tb;
H
OC2 H4 OCH3
>;tb;
oil
>;tb;42 4-CH3
OC2 H4 OCH3
>;tb;
CH3 OC2 H4 OCH3
>;tb;
oil
>;tb;43 4-CH3
OC2 H4 OCH3
>;tb;
Cl
OC2 H4 OCH3
>;tb;
m.p. 55-57 DEG
>;tb;44 4-CH3
OC2 H4 OCH3
>;tb;
Br
OC2 H4 OCH3
>;tb;
m.p. 55-56 DEG
>;tb;45 4-CH3
OC2 H4 OCH3
>;tb;
H
NHCH3 m.p. 65-66 DEG
>;tb;46 4-CH3
OC2 H4 OCH3
>;tb;
Br
NHCH3 oil
>;tb;47 4-CH3
OC2 H4 OCH3
>;tb;
H
N(C2 H5)2
>;tb;
oil
>;tb; 48
>;tb; 4-CH3
>;tb;
##STR26## H
>;tb;
##STR27## m.p.
>;tb;
125-126 DEG
>;tb; 49
>;tb; 4-CH3
Br
H
Br
m.p.
>;tb;
125-126 DEG
>;tb;50 (H)5
Br
H
Br
m.p.
>;tb;
115-118 DEG
>;tb;51 (H)5
Cl
H
OH
m.p.
>;tb;
218-221 DEG
>;tb;52 (H)5
Cl
H
SH
m.p. 150 DEG Z
>;tb;53 4-Cl
Cl
H
Cl
m.p. 120 DEG
>;tb;54 4-OCH3
Cl
H
Cl
m.p.
>;tb;
127-128 DEG
>;tb;55 4-CN
Cl
H
Cl
m.p.
>;tb;
230-232 DEG
>;tb;56 3-CF3
Cl
H
Cl
m.p. 56-57 DEG
>;tb;57 2-CH3
Cl
H
Cl
m.p. 74-75 DEG
>;tb;58 2-CH3
Cl
Cl
Cl
m.p.
>;tb;
122-125 DEG
>;tb;59 3-Cl, 4-F
Cl
H
Cl
m.p. 94-95 DEG
>;tb;60 2,6(CH3)2
>;tb;
Cl
H
Cl
m.p.
>;tb;
103-104 DEG
>;tb;61 3,4(CH3)2
>;tb;
Br
H
Br
>;tb;62 4-C3 H7 i
277/612
>;tb;
Cl
H
Cl
m.p. 63-64 DEG
>;tb;63 4-C3 H7 i
>;tb;
Cl
H
F
>;tb;64 4-Cl
F
H
F
m.p.
>;tb;
139-141 DEG
>;tb;65 2-CH3, 6-C2 H5
>;tb;
Cl
H
Cl
>;tb;66 2-CH3, 6-C2 H5
>;tb;
Cl
H
C2 H5
>;tb;67 2-Cl
Cl
H
Cl
m.p.
>;tb;
116-118 DEG
>;tb;68 3-C2 H5
>;tb;
Cl
H
Cl
>;tb;69 4-CH3
Cl
F
Cl
>;tb;70 4-F
Cl
F
Cl
>;tb;71 3-CHF2
Cl
H
Cl
>;tb;72 2,4(CH3)2
>;tb;
Br
H
Br
>;tb;73 2,3,6(CH3)3
>;tb;
Cl
H
Cl
>;tb;74 3-C3 H7i
>;tb;
Cl
H
Cl
>;tb;75 4-CHF2
Cl
H
Cl
>;tb;76 2-Cl, 4-CH3 Br
H
Br
>;tb;77 3,4(Cl)2 Cl
H
OH
>;tb;78 4-OCH2 CHCH2
>;tb;
Cl
H
Cl
m.p. 57-58 DEG
>;tb;79 4-OH
F
H
F
>;tb;80 4-COCH3 Cl
H
Cl
m.p.
>;tb;
129-130 DEG
>;tb;81 4-OCOC2 H5
>;tb;
Cl
H
Cl
>;tb;82 4-OCH(CH3)COOCH3
>;tb;
Cl
H
Cl
>;tb;83 4-OCF2 Cl Cl
H
OC2 H5
>;tb;84 4-OH
Cl
H
Cl
m.p.
>;tb;
135-137 DEG
>;tb;85 4-OCON(CH3)2
>;tb;
Cl
H
Cl
m.p.
>;tb;
191-193 DEG
>;tb;86 3-CH2 F Cl
H
Cl
>;tb;87 2-COOCH3 Cl
H
OC4 H9 n
>;tb;88 4-CH2 F Cl
H
Cl
>;tb;89 4-COOCH3 Cl
H
Cl
m.p.
>;tb;
135-140 DEG
>;tb;90 4-COOC4 H9 n
>;tb;
Cl
H
OC4 H9 n
>;tb;91 4-Cl, 2,6(OCH3)2
>;tb;
Cl
H
Cl
>;tb;92 4-CHO
Cl
H
Cl
m.p.
>;tb;
160-162 DEG
>;tb;93 3-CH2 Cl Cl
H
Cl
>;tb;94 3,5(CF3)2
>;tb;
Cl
H
Cl
>;tb;95 4-CF3
Br
H
Br
>;tb;96 4-OCHF2 Cl
H
Cl
>;tb;97 3,5(OC2 H5)2
>;tb;
Cl
H
Cl
>;tb;98 4-OC3 H7 i
278/612
>;tb;
F
H
F
>;tb;99 3-NO2
Cl
H
Cl
m.p.
>;tb;
136-138 DEG
>;tb;100
>;tb; 4-NO2
Cl
H
Cl
m.p.
>;tb;
167-168 DEG
>;tb;101
>;tb; 3-NO2, 4-CH3
>;tb;
Cl
H
Cl
>;tb;102
>;tb; 2-Cl, 4-NO2 Cl
H
Cl
>;tb;103
>;tb; 2-N(CH3)2
>;tb;
Cl
H
Cl
>;tb;104
>;tb; 3-NHCOCH3 Br
H
Br
>;tb;105
>;tb; 3-NHCOCH2 Cl
>;tb;
Cl
H
Cl
>;tb;106
>;tb; 4-OCF3
Cl
H
OC3 H7 i
>;tb;107
>;tb; 3-OCF2 Cl, 5-Cl
>;tb;
Cl
H
Cl
>;tb;108
>;tb; 2-CON(CH3)2
>;tb;
Cl
H
Cl
>;tb;109
>;tb; 4-OCF2 CHF2
>;tb;
Cl
H
Cl
>;tb;110
>;tb; 4-CONHC4 H9 n
>;tb;
Cl
H
Cl
>;tb;111
>;tb; 4-NHCOCH2 Cl
>;tb;
Cl
H
Cl
m.p.
>;tb;
196-198 DEG
>;tb;112
>;tb; 4-COCH3, 3-CH3
>;tb;
Cl
H
CH3
>;tb;113
>;tb; 3-CH2COCH3
>;tb;
F
H
OCH3
>;tb;114
>;tb; 4-COC3 H7 n
>;tb;
Cl
H
Cl
>;tb;115
>;tb; 4-OCF2 CHFCl
>;tb;
Cl
H
Cl
>;tb;116
>;tb; 2-OH
Cl
H
Cl
>;tb;117
>;tb; 4-COOCH2 CHCH2
>;tb;
Cl
H
Cl
>;tb;118
>;tb; 4-COOCH2 CCH
>;tb;
Cl
H
Cl
m.p.
>;tb;
105-109 DEG
>;tb;119
279/612
>;tb; 2-Cl, 6-CCH
Cl
H
Cl
>;tb;120
>;tb; 3-CCC(CH3)2 OCH3
>;tb;
Br
H
Br
>;tb;121
>;tb; 4-CCC(CH3)2 OH
>;tb;
Cl
H
Cl
>;tb;122
>;tb; 4-CCC(CH3)2 OCH3
>;tb;
Cl
H
Cl
>;tb;123
>;tb; 3,5(I)2, 4-OCH(CH3)COOCH3
>;tb;
Cl
H
Cl
>;tb;124
>;tb; (H)5
Cl
CF3 Cl
>;tb;125
>;tb; 4-CHCHC4 H9 n
>;tb;
Cl
H
Cl
>;tb;126
>;tb; 4Cl3
Cl
CF3 Cl
>;tb;127
>;tb; 4-OH
Br
H
Br
>;tb;128
>;tb; 4-Br
Cl
H
Cl
m.p.
>;tb;
130-131 DEG
>;tb;129
>;tb; 3-OH
Cl
H
Cl
m.p.
>;tb;
144-146 DEG
>;tb;130
>;tb; 3-OCH3
Cl
H
Cl
m.p. 97-100 DEG
>;tb;131
>;tb; 3-OCOCH2 Cl Cl
H
Cl
>;tb;132
>;tb; 2-OCH 3 Cl
H
Cl
m.p. 67-70 DEG
>;tb;133
>;tb; 2,6(F)2 Cl
H
Cl
>;tb;134
>;tb; 4-F
Cl
H
Cl
m.p.
>;tb;
102-105 DEG
>;tb;135
>;tb; 3-Cl, 4-CH3 Cl
H
Cl
m.p. 91-92 DEG
>;tb;136
>;tb; (H)5
F
H
F
m.p.
>;tb;
114-116 DEG
>;tb;137
>;tb; (H)5
F
H
Cl
m.p. 105 DEG
>;tb;138
>;tb; 2,5(Cl)2, 4-OH
>;tb;
F
H
F
>;tb;139
>;tb; 2-Cl, 4-OCH(CH3)COOC2 H5
>;tb;
Cl
H
Cl
>;tb;140
>;tb; 2,3,5(Cl)3, 4-OH
>;tb;
Cl
H
Cl
>;tb;141
>;tb; 2,3,5(Cl)3, 4-OC2 H5
>;tb;
Cl
H
Cl
>;tb;142
280/612
>;tb; 2,3,5,6(CH3)4, 4-NO2
>;tb;
Cl
H
>;tb;143
>;tb; (H)5
F
CF3 Cl
>;tb;144
>;tb; 3-SO2 N(CH3)2
>;tb;
Cl
H
>;tb;145
>;tb; 4-CSN(CH3)2
>;tb;
Cl
H
>;tb;146
>;tb; 4-C(CH3)CH2
>;tb;
Cl
H
>;tb;147
>;tb; 4-CH2 COOCH3
>;tb;
Cl
H
>;tb;148
>;tb; 4-CH2 PO(OC2 H5)2
>;tb;
Cl
H
>;tb;
>;tb;149
>;tb; 4-CH2 PO(OH)2
>;tb;
Br
H
>;tb;150
>;tb; 4-SO2 N(CH3)2, 5-CH3
>;tb;
Cl
H
>;tb;151
>;tb; 4-PO(OH)2 Br
H
>;tb;152
>;tb; 4-PO(OCH3)2
>;tb;
Cl
H
>;tb;153
>;tb; 3-PO(OCH3)2
>;tb;
Cl
H
>;tb;154
>;tb; H
SOCH3 H
>;tb;155
>;tb; 4-CH2 CHCH2
>;tb;
Cl
H
>;tb;156
>;tb; 3-CCH3
Cl
H
>;tb;157
>;tb; 2-CCH
Cl
H
>;tb;158
>;tb; 4-CCH
Cl
H
>;tb;
>;tb;159
>;tb; H
SOCH3 H
>;tb;160
>;tb; 4-C(OCH3)2 C3 H7 n
>;tb;
Cl
H
>;tb;161
>;tb; 2-CH3, 5-N(CH3)2
>;tb;
Cl
H
>;tb;162
>;tb; 2-CH3, 5-Cl Cl
H
>;tb;163
>;tb; 3-Br, 4-OH
Cl
H
>;tb;164
Cl
Cl
Cl
Cl
Cl
Cl
m.p.
110-112 DEG
Br
OC4 H9 n
Br
Cl
Cl
Cl
Cl
Cl
Cl
Cl
m.p.
168-170 DEG
Br
OCH3
Cl
Cl
OCH2 CHCH2
281/612
>;tb; 3-Br, 4-OC3 H7 n
>;tb;
Cl
H
Cl
>;tb;165
>;tb; 3-NO2 4-Cl Cl
H
Cl
m.p.
>;tb;
158-159 DEG
>;tb;166
>;tb; 3-NH2, 4-Cl Cl
H
Cl
>;tb;167
>;tb; 3-CH3, 4-NO2
>;tb;
Cl
H
Cl
m.p.
>;tb;
173-175 DEG
>;tb;168
>;tb; 3-CH3, 4-NH2
>;tb;
Cl
H
Cl
solid
>;tb;169
>;tb; 3-CH3, 4-NHCON(CH3)2
>;tb;
F
H
OCH2 CHCH2
>;tb;170
>;tb; 2-Cl, 5-CF3 Cl
H
Cl
>;tb;171
>;tb; 3-CF3, 4-Cl Cl
H
Cl
>;tb;172
>;tb; 4-CH3
SOCH3 H
Cl
>;tb;173
>;tb; 2-Cl, 5-N(CH3)2
>;tb;
Cl
H
OH
>;tb;174
>;tb; 2,6(OCH3)2, 3-NO2
>;tb;
Cl
H
Cl
>;tb;175
>;tb; 2,6(OCH3)2, 3-NH2
>;tb;
Cl
H
Cl
>;tb;176
>;tb; 2,6(OCH3)2, 3-NHCOCH3
>;tb;
Cl
H
Cl
>;tb;177
>;tb; 2-CH3, 6-C2 H5, 4-OCON(CH3)2
>;tb;
Cl
H
Cl
>;tb;178
>;tb; 3,5(I)2, 4-OH
>;tb;
Cl
H
Cl
>;tb;179
>;tb; 3,5(I)2, 4-OCH3
>;tb;
Br
H
Br
>;tb;180
>;tb; 3,5(Br)2, 4-OH
>;tb;
Cl
H
Cl
>;tb;181
>;tb; 3,5(Br)2, 4-OCH2CHCH2
>;tb;
Cl
H
Cl
>;tb;182
>;tb; 3,4,5(OCH3)3
>;tb;
Cl
H
Cl
m.p.
>;tb;
167-169 DEG
>;tb;183
>;tb; 2,3(Cl)2 Cl
H
Cl
m.p.
>;tb;
116-118 DEG
>;tb;184
>;tb; 4-CH3
F
H
SOCH3
282/612
>;tb;185
>;tb; (H)5
SOCH3 H
CN
>;tb;186
>;tb; (H)5
SCH3 H
CN
>;tb;187
>;tb; (H)5
SO2 CH3
>;tb;
H
CN
>;tb;188
>;tb; (H)5
OCOCH3
>;tb;
H
Cl
>;tb;189
>;tb; 4-CH3
CN
Cl
Cl
>;tb;190
>;tb; 3-SO2 NHCOONC3 H7 (i)
>;tb;
Cl
H
Cl
>;tb; 191
>;tb; ##STR28##
Cl
H
Cl
>;tb; 192
>;tb; ##STR29##
Br
H
Br
>;tb; 193
>;tb; ##STR30##
Cl
H
Cl
>;tb; 194
>;tb; ##STR31##
F
H
OCH3
>;tb; 195
>;tb; 3-CF3
OH
H
OH
m.p. 286 DEG C.
>;tb;196
>;tb; 4-CH3
OCH3 H
OH
>;tb;197
>;tb; 3-NH2
Cl
H
Cl
solid
>;tb;198
>;tb; 4-NH2
Cl
H
Cl
solid
>;tb;199
>;tb; 3-NHCOCH3 Cl
H
Cl
m.p.
>;tb;
228-230 DEG
>;tb;200
>;tb; 4-NHCOCH3 Cl
H
Cl
m.p.
>;tb;
190-192 DEG
>;tb;201
>;tb; 4-SO2 NHCOOCH3
>;tb;
Cl
H
Cl
>;tb;202
>;tb; 3-SO2 NCH3 COOCH3
>;tb;
Cl
H
Cl
>;tb;203
>;tb; 4-CH3.3-SO2 H
>;tb;
Cl
H
Cl
>;tb;204
>;tb; 4-CH3.3-SO2 NH2
>;tb;
Cl
H
Cl
>;tb;205
>;tb; 4-NHCONHC2 H5
>;tb;
Cl
H
Cl
>;tb;206
>;tb; 4-Cl, 3-NH2 Cl
H
Br
>;tb;207
>;tb; 3-I
Cl
H
Cl
>;tb;208
>;tb; 3-COOH
Cl
H
Cl
m.p. 250 DEG
>;tb;209
283/612
>;tb; 4-COOH
Cl
H
Cl
m.p.
>;tb;
236-238 DEG
>;tb;210
>;tb; 3-CH 3
Cl
H
OH
m.p.
>;tb;
195-200 DEG
>;tb;211
>;tb; 4-N(CH3)2
>;tb;
Cl
H
Cl
m.p.
>;tb;
150-155 DEG
>;tb;212
>;tb; 3NHCH3
Cl
H
Cl
>;tb;213
>;tb; HNHCH3
>;tb;214
>;tb; 3-NHCHO
>;tb;215
>;tb; 4-NHCHO
>;tb; 216
>;tb; ##STR32##
Cl
H
Cl
>;tb; 217
>;tb; 4-OCH2 OCH3
>;tb;
Cl
H
Cl
>;tb;218
>;tb; 4-SCH3
Cl
H
F
>;tb;219
>;tb; 3-SH
Cl
H
Cl
>;tb;220
>;tb; 4-SCH3
Cl
H
Cl
m.p.
>;tb;
109-111 DEG
>;tb;221
>;tb; 4-OCOOCH3 Cl
H
F
>;tb;222
>;tb; 3-OCOOCH3 Cl
H
Cl
>;tb;223
>;tb; 3-F
Cl
H
Cl
m.p. 72-74 DEG
>;tb;224
>;tb; 4-OC2 H4 OC2 H5
>;tb;
Cl
H
Cl
m.p. 75-77 DEG
>;tb;225
>;tb; 4-OC2 H4 OC3 H7 n
>;tb;
Cl
H
Cl
wax
>;tb;226
>;tb; 4-CH2CClCH2
>;tb;
CH3 H
Cl
>;tb;227
>;tb; 4-SO2 CH3
>;tb;
Cl
H
Cl
m.p.
>;tb;
163-165 DEG
>;tb;228
>;tb; 4-OC2 H4 OC2 H4 OC2 H5
>;tb;
Cl
H
Cl
m.p. 42-43 DEG
>;tb;229
>;tb; 4-OCH3
Br
H
Br
m.p.
>;tb;
129-131 DEG
>;tb;230
>;tb; OC6 H13n
>;tb;
Cl
H
Cl
>;tb;231
>;tb; 4-OCH2CCH Cl
H
Cl
284/612
>;tb;232
>;tb; 4-OC2 H4 N(C2 H5)2
>;tb;
Cl
H
Cl
>;tb;233
>;tb; 4-OC2 H4 Cl
>;tb;
Cl
H
Cl
>;tb;234
>;tb; 4-OC2 H4 OH
>;tb;
Cl
H
Cl
>;tb;235
>;tb; 4-OC2 H4 SCH3
>;tb;
Cl
H
Cl
>;tb;236
>;tb; 4-OC2 H4 OC2 H4 Cl
>;tb;
Cl
H
Cl
m.p. 88-89 DEG
>;tb;237
>;tb; 4-OCF3
Cl
H
Cl
>;tb;238
>;tb; 4-OC2 H5
>;tb;
Cl
H
Cl
>;tb;239
>;tb; 4-OCOCH3 Cl
H
Cl
m.p.
>;tb;
113-115 DEG
>;tb;240
>;tb; 4-OCH(CH3)COOCH3
>;tb;
Cl
H
Cl
>;tb;241
>;tb; 4-OCH(CH3)COOCH3
>;tb;
Br
H
Cl
m.p.
>;tb;
118-120 DEG
>;tb;242
>;tb; 4-OCOCHCH2 Cl
H
Cl
>;tb;243
>;tb; 4-OCOC3 H6 CHCH2
>;tb;
Cl
H
Cl
>;tb;244
>;tb; 4-OCH2 CON(CH3)2
>;tb;
Cl
H
Cl
>;tb;245
>;tb; 4-OCH2 CHCHCH3
>;tb;
Cl
H
Cl
>;tb;246
>;tb; 4-OC2 H4 CHCClCH3
>;tb;
Cl
H
Cl
>;tb;247
>;tb; (H)5
Cl
CHF2 Cl
>;tb;248
>;tb; (H)5
Cl
H
F
>;tb;249
>;tb; (H)5
Cl
H
Br
>;tb;250
>;tb; (H)5
I
H
I
>;tb;251
>;tb; 4-SOCH3 Cl
H
Cl
>;tb;252
>;tb; 4-SC2 H4 N(CH3)2
>;tb;
Cl
H
Cl
>;tb;253
>;tb; 4-SC2 H4 OCH3
285/612
>;tb;
Cl
H
Cl
>;tb;254
>;tb; 4-SC6 H13n
>;tb;
Cl
H
Cl
>;tb;255
>;tb; 4-SC2 H4 COOC4 H9
>;tb;
Cl
H
Cl
>;tb;256
>;tb; 4-SCOCH3 Cl
H
Cl
>;tb;257
>;tb; 4-SCH2 CHCH2
>;tb;
Cl
H
Cl
>;tb;258
>;tb; 4-NH2
Br
H
Br
>;tb;259
>;tb; 4-NHC6 H13n
>;tb;
Cl
H
Cl
>;tb;260
>;tb; 4-NHC3 H7i
>;tb;
Cl
H
Cl
>;tb;261
>;tb; 4-NHCH2 COOCH3
>;tb;
Cl
H
Br
>;tb;262
>;tb; 4-NHCH(CH3)CON(CH3)2
>;tb;
Cl
H
Cl
>;tb;263
>;tb; 4-NHCOCHCH2 Cl
H
Cl
>;tb;264
>;tb; 4-NHCH2CHCH2
>;tb;
Cl
H
Cl
>;tb;265
>;tb; 4-N(CH2CHCH2)2
>;tb;
Cl
H
Cl
>;tb;266
>;tb; 4-NHCHCCH
Cl
H
Cl
>;tb;267
>;tb; 4-NHCH2 CHCHC2 H5
>;tb;
Cl
H
Cl
>;tb;268
>;tb; 4-NH(CH2)4 CCH
>;tb;
Cl
H
Cl
>;tb;269
>;tb; 4-NHOCH3 Cl
H
Cl
>;tb;270
>;tb; 4-NHOCH2 CHCH2
>;tb;
Cl
H
Cl
>;tb;271
>;tb; 4-N(CH3)OCH3
>;tb;
Cl
H
Cl
>;tb;272
>;tb; 4-N(CH3)COCH3
>;tb;
Cl
H
Cl
>;tb;273
>;tb; 4-B(OCH3)COCH3
>;tb;
Cl
H
Cl
>;tb; 274
>;tb; ##STR33##
Cl
H
Cl
>;tb; 275
286/612
>;tb; ##STR34##
Cl
H
Cl
>;tb; 276
>;tb; ##STR35##
Cl
H
Cl
>;tb; 277
>;tb; ##STR36##
Cl
H
Cl
>;tb; 278
>;tb; ##STR37##
Br
H
Br
>;tb; 279
>;tb; ##STR38##
Cl
H
Cl
>;tb; 280
>;tb; ##STR39##
Cl
H
F
>;tb; 281
>;tb; 4-NHCOOCH3 Cl
H
Cl
>;tb;282
>;tb; 4-N(CH3)COOC3 H7i
>;tb;
Cl
H
Cl
>;tb;283
>;tb; 4-NHCONHCH3 Cl
H
Cl
>;tb;284
>;tb; 4-NHCON(CH3)2
>;tb;
Cl
H
Cl
>;tb;285
>;tb; 4-N(CH3)CONHCH3
>;tb;
Cl
H
Cl
>;tb;286
>;tb; 4-N(CH3)CON(CH3)OCH3
>;tb;
Cl
H
Cl
>;tb;287
>;tb; COOC6 H13 n
>;tb;
Cl
H
Cl
>;tb;288
>;tb; 4-OCOCH2 CHCHCH3
>;tb;
Cl
H
Cl
>;tb;289
>;tb; 4-CONH2 Cl
H
Cl
>;tb;290
>;tb; 4-CON(C3 H7 n)2
>;tb;
Cl
H
Cl
>;tb;291
>;tb; 4-CONHC6 H13 n
>;tb;
Cl
H
Cl
>;tb;292
>;tb; 4-OCOC2 H4 N(C2 H5)2
>;tb;
Br
H
Br
>;tb;293
>;tb; 4-CONHOCH3 Cl
H
Cl
>;tb;294
>;tb; 4-CON(CH3)2
>;tb;
Cl
H
Cl
>;tb;295
>;tb; 4-CHO
Br
H
Br
>;tb;296
>;tb; 4-COC4 H9 n
>;tb;
Cl
H
Cl
>;tb;297
>;tb; 4-COCHCHN(CH3)2
>;tb;
Cl
H
Cl
>;tb;298
>;tb; 4-CSN(C3 H7)2
287/612
>;tb;
Cl
H
Cl
>;tb;299
>;tb; 4-CSNHC6 H13 n
>;tb;
Cl
H
Cl
>;tb;300
>;tb; 4-NCHC3 H7 i
>;tb;
Cl
H
Cl
>;tb;301
>;tb; 4-NCHC6 H13 n
>;tb;
Cl
H
Cl
>;tb;302
>;tb; 4-NCH(CH3)2
>;tb;
Cl
H
Cl
>;tb; 303
>;tb; ##STR40##
Cl
H
>;tb; 304
>;tb; 4-N(CH3)CH2 OCH3
>;tb;
Cl
H
Cl
>;tb;305
>;tb; 4-SO2 NH2
>;tb;
Cl
H
Cl
>;tb;306
>;tb; 4-SO2 N(CH3)2
>;tb;
Cl
H
Cl
>;tb;307
>;tb; 4-SO2 NHC4 H9
>;tb;
Cl
H
Cl
>;tb; 308
>;tb; ##STR41##
Br
H
>;tb; 309
>;tb; 4-SO2 NHCH2 CHCH2
>;tb;
Cl
H
Cl
>;tb;310
>;tb; 4-CH(OCH3)2
>;tb;
Cl
H
Cl
>;tb;311
>;tb; 4-CH(OC2 H4 OCH3)2
>;tb;
Cl
H
F
>;tb;312
>;tb; 4-C(C4 H9 n)(OC2 H5)2
>;tb;
Cl
H
Cl
>;tb;313
>;tb; 4-C(CH3)(OCH3)2
>;tb;
Cl
H
Cl
>;tb;314
>;tb; 4-C(CH3)(OC2 H4 SCH3)2
>;tb;
Cl
H
Cl
>;tb; 315
>;tb; ##STR42##
Cl
H
>;tb; 316
>;tb; ##STR43##
Cl
H
>;tb; 317
>;tb; ##STR44##
Cl
H
>;tb; 318
>;tb; ##STR45##
Cl
H
>;tb; 319
>;tb; 4-PO(OH)OC2 H5
>;tb;
Cl
H
Cl
>;tb;320
Cl
Br
Cl
Cl
Cl
Cl
288/612
>;tb; 4-SO3 H Cl
H
>;tb;321
>;tb; 4-CF3
Cl
H
>;tb;322
>;tb; 4-CH2 Br Cl
H
>;tb;
>;tb;323
>;tb; 4-CH2 Cl Cl
H
>;tb;324
>;tb; 4-CH2 OCH3
>;tb;
Cl
H
>;tb;325
>;tb; 4-CH2 OH Cl
H
>;tb;326
>;tb; 4-CH2 OCOCH3
>;tb;
Cl
H
>;tb;
>;tb;327
>;tb; 4-CH2 OC4 H9 n
>;tb;
Cl
H
>;tb;328
>;tb; 4-CH2 SCH3
>;tb;
Cl
H
>;tb;329
>;tb; 4-CH2 N(CH3)2
>;tb;
Cl
H
>;tb;330
>;tb; 4-CHClCH3 Cl
H
>;tb;331
>;tb; 4-C2 H5
>;tb;
Cl
H
>;tb;332
>;tb; 4-C6 H13 n
>;tb;
Cl
H
>;tb;333
>;tb; 4-C5 H11 iso
>;tb;
Br
H
>;tb;334
>;tb; 4-CCCH3 Cl
H
>;tb;335
>;tb; 4-CHCH2 Cl
H
>;tb;336
>;tb; 4-CH2CHCH2
>;tb;
Cl
H
>;tb;337
>;tb; 4-CClCH2 Cl
H
>;tb;
>;tb;338
>;tb; 4-C2 H4 Cl
>;tb;
Cl
H
>;tb;339
>;tb; 4-C2 H4 N(C2 H5)2
>;tb;
Cl
H
>;tb; 340
>;tb; ##STR46##
Cl
>;tb; 341
>;tb; ##STR47##
Cl
>;tb; 342
>;tb; ##STR48##
Cl
Cl
Cl
Cl
m.p.
155-156 DEG
Cl
Cl
Cl
Cl
m.p.
108-110 DEG
Cl
Cl
Cl
F
Cl
Cl
Br
Cl
Cl
F
Cl
m.p.
128-130 DEG
Cl
Cl
H
Cl
H
Cl
H
Cl
289/612
>;tb; 343
>;tb; 4-CHCH2CH2 OCH3
>;tb;
Cl
H
Cl
>;tb;344
>;tb; 4-N(CH3)COCH2 Cl
>;tb;
Cl
H
Cl
>;tb;345
>;tb; 4-CH2 CN Cl
H
Cl
m.p.
>;tb;
151-158 DEG
>;tb;346
>;tb; 3-F
Br
H
Br
>;tb;347
>;tb; 3-Cl
Cl
H
Cl
m.p.
>;tb;
117-119 DEG
>;tb;348
>;tb; 3-NO2
Br
H
Br
m.p.
>;tb;
165-167 DEG
>;tb;349
>;tb; 3-NO2
F
H
F
>;tb;350
>;tb; 3-OC3 H7 i
>;tb;
Cl
H
Cl
>;tb;351
>;tb; 3-OCH2 CHCHCH3
>;tb;
Cl
H
F
>;tb;352
>;tb; 3-OCH2 CCH Cl
H
Cl
>;tb;353
>;tb; 3-OC2 H4 N(C2 H5)2
>;tb;
Cl
H
Cl
>;tb;354
>;tb; 3-OCH(CH3)CH2 N(C2 H5)
>;tb;
Cl
H
Cl
>;tb;355
>;tb; 3-OC2 H4 Cl
>;tb;
Cl
H
Cl
>;tb;356
>;tb; 4-CH3
Br
H
Cl
>;tb;357
>;tb; 3-OC2 H4 SC2 H5
>;tb;
Cl
H
Cl
>;tb;358
>;tb; 3-OC 2 H4 OC3 H7 n
>;tb;
Cl
H
Cl
>;tb;359
>;tb; 3-OCF3
Cl
H
F
>;tb;360
>;tb; 3-OCHF2 Cl
H
Cl
>;tb;361
>;tb; 3-OCF2 CHF2
>;tb;
Cl
H
Cl
>;tb;362
>;tb; 3-OCF2 CHFCl
>;tb;
Br
H
Br
>;tb;363
>;tb; 3-OCOC2 H5
>;tb;
Cl
H
Cl
>;tb;364
>;tb; 3-OCOCH2 Cl Br
H
Br
290/612
>;tb;365
>;tb; 3-SC2 H5
>;tb;
Cl
H
Cl
>;tb;366
>;tb; 3-SCF3
Cl
H
Cl
>;tb;367
>;tb; 3-SCHF2 Cl
H
Cl
>;tb;368
>;tb; 3-SO2 CH3
>;tb;
Cl
H
Cl
>;tb;369
>;tb; 3-SC3 H6 N(CH3)2
>;tb;
Cl
H
Cl
>;tb;370
>;tb; 3-SC3 H6 Cl
>;tb;
Cl
H
Cl
>;tb;371
>;tb; 3-SC5 H11 iso
>;tb;
Cl
H
Cl
>;tb;372
>;tb; 3-SCH2 COOC3 H7 n
>;tb;
Cl
H
F
>;tb;373
>;tb; 3-SCH2CCH Cl
H
Cl
>;tb;374
>;tb; 3-NH2
Br
H
Br
solid
>;tb;375
>;tb; 3-N(CH3)2
>;tb;
Cl
H
Cl
>;tb;376
>;tb; 3-NHC4 H9 n
>;tb;
Cl
H
Cl
>;tb;377
>;tb; 3-NHC4 H9 sek
>;tb;
Cl
H
Cl
>;tb;378
>;tb; 3-N(CH2 CCH)2
>;tb;
Cl
H
F
>;tb;379
>;tb; 3-NHCH2 CHCH2
>;tb;
Cl
H
Cl
>;tb;380
>;tb; 3-N(CH3)COCH2 Cl
>;tb;
Cl
H
Cl
>;tb;381
>;tb; 3-SO2 NHCO2 CH3
>;tb;
Cl
H
Cl
m.p.
>;tb;
160-161 DEG
>;tb;382
>;tb; 3-NHCOCHCHCH3
>;tb;
Cl
H
Cl
>;tb;383
>;tb; 3-NHOH
Br
H
Br
>;tb;384
>;tb; 3-NHOC2 H5
>;tb;
Cl
H
Br
>;tb;385
>;tb; 3-NCH3 OCH3
>;tb;
Cl
H
Cl
291/612
>;tb;386
>;tb; 3-N(C3 H7 iso)CO2 C2 H5
>;tb;
Cl
H
Cl
>;tb; 387
>;tb; ##STR49##
Cl
H
Cl
>;tb; 388
>;tb; ##STR50##
Cl
H
Cl
>;tb; 389
>;tb; 3-NHCOOC4 H9 iso
>;tb;
Cl
H
Cl
>;tb;390
>;tb; 3-NHCONHC4 H9 n
>;tb;
Cl
H
Cl
>;tb; 391
>;tb; ##STR51##
Br
H
Br
>;tb; 392
>;tb; 3-N(CH3)CON(CH3)2
>;tb;
Cl
H
Cl
>;tb;393
>;tb; 3-COOH
Cl
H
Cl
m.p. 250 DEG C.
>;tb;394
>;tb; 3-COOCH3 Cl
H
Cl
m.p.
>;tb;
190-191 DEG
>;tb;395
>;tb; 3-COOCH2 CHCH2
>;tb;
Cl
H
Cl
m.p.
>;tb;
120-121 DEG
>;tb;396
>;tb; 3-COOC3 H7 i
>;tb;
Cl
H
Cl
>;tb;397
>;tb; 3-COCH2CCC3 H 7 n
>;tb;
Cl
H
Cl
>;tb;398
>;tb; 3-CONH2 Cl
H
Cl
>;tb;399
>;tb; 3-CONHOH
Cl
H
Cl
>;tb;400
>;tb; 3-CON(CH3)2
>;tb;
Cl
H
Cl
>;tb;401
>;tb; 3-CONHCH3 Br
H
Br
>;tb;402
>;tb; 3-CONHCH2 CHCH2
>;tb;
Cl
H
F
>;tb;403
>;tb; 3-COOC3 H6 N(CH3)2
>;tb;
Cl
H
Cl
>;tb;404
>;tb; 3-CHO
Cl
H
Cl
>;tb;405
>;tb; 3-COCH3 Cl
H
Cl
>;tb; 406
>;tb; ##STR52##
Cl
H
Cl
>;tb; 407
>;tb; 3-CSNHC4 H9 n
>;tb;
Cl
H
Cl
>;tb;408
>;tb; 3-CSNHC3 H7 iso
292/612
>;tb;
Cl
H
Cl
>;tb; 409
>;tb; ##STR53##
Cl
H
Cl
>;tb; 410
>;tb; 3-NCHC3 H7 (i)
>;tb;
Cl
H
Cl
>;tb;411
>;tb; 3-NC(CH3)CH2 OCH3
>;tb;
Cl
H
Cl
>;tb;412
>;tb; 3-NCHC2 H4 OC2 H5
>;tb;
Cl
H
Cl
>;tb; 413
>;tb; ##STR54##
Cl
H
Cl
>;tb; 414
>;tb; 3-SO2 NH2
>;tb;
Cl
H
Cl
m.p.
>;tb;
207-208 DEG
>;tb;415
>;tb; 3-SO2 NHCH3
>;tb;
Cl
H
Cl
m.p.
>;tb;
174-175 DEG
>;tb;416
>;tb; 3-SO2 N(C4 H9 n)2
>;tb;
Cl
H
Cl
>;tb; 417
>;tb; ##STR55##
Cl
H
Cl
>;tb; 418
>;tb; 3-SO2 N(CH3)2
>;tb;
Cl
H
Cl
m.p.
>;tb;
144-145 DEG
>;tb;419
>;tb; 3-CH(OC2 H5)2
>;tb;
Cl
H
Cl
>;tb;420
>;tb; 3-C(CH3)(OCH3)2
>;tb;
Cl
H
Cl
>;tb;421
>;tb; 3-C(CH3)(OC2 H4 OCH3)2
>;tb;
Cl
H
Cl
>;tb; 422
>;tb; ##STR56##
Cl
H
Cl
>;tb; 423
>;tb; ##STR57##
Cl
H
Cl
>;tb; 424
>;tb; 3-PO(OC2 H5)2
>;tb;
Cl
H
Cl
>;tb;425
>;tb; 3-P(OH)2 Cl
H
Cl
>;tb;426
>;tb; 3-P(OH)OCH3 Cl
H
Cl
>;tb;427
>;tb; 3-SO3 H Cl
H
Cl
m.p. 95-96 DEG
>;tb;428
>;tb; 3-CF3
Cl
H
F
>;tb;429
>;tb; 3-CH2 CN Cl
H
Cl
>;tb;430
>;tb; 3-CH2 Cl Cl
H
Cl
293/612
>;tb;431
>;tb; 3-CH2 OC2 H5
>;tb;
Cl
H
Cl
>;tb;432
>;tb; 3-CH2 OH Br
H
Br
>;tb;433
>;tb; 3-C2 H4 SCH3
>;tb;
Cl
H
Cl
>;tb;434
>;tb; 3-C2 H4 SOCH3
>;tb;
Cl
H
Cl
>;tb;435
>;tb; 3-CHClC2 H5
>;tb;
Cl
H
F
>;tb;436
>;tb; 3-C3 H7 n
>;tb;
Cl
H
Cl
>;tb;437
>;tb; 3-C6 H13 iso
>;tb;
Cl
H
Cl
>;tb;438
>;tb; 3-CCH
Cl
H
Cl
>;tb;439
>;tb; 3-CCCH3 Cl
H
Cl
>;tb;440
>;tb; 3-CHCH2 Cl
H
Cl
>;tb;441
>;tb; 3-CClCH2 Cl
H
Cl
>;tb;442
>;tb; 3-CClCHCH3 Cl
H
Cl
>;tb;443
>;tb; 3-C2 H4 N(CH3)2
>;tb;
Cl
H
Cl
>;tb; 444
>;tb; ##STR58##
Cl
H
Cl
>;tb; 445
>;tb; 3-CHCHC3 H7 n
>;tb;
Cl
H
Cl
>;tb; 446
>;tb; ##STR59##
Cl
H
Cl
>;tb; 447
>;tb; 3-CH2 COOC2 H5
>;tb;
Cl
H
Cl
>;tb;448
>;tb; 3-CH2 CONH2
>;tb;
Br
H
Br
>;tb;449
>;tb; 3-CH3
Br
H
Br
>;tb;450
>;tb; 2-F
Cl
H
Cl
>;tb;451
>;tb; 2-OCH2 CCH Cl
H
Cl
>;tb;452
>;tb; 2-SCH3
Cl
H
Cl
>;tb;453
>;tb; 2-SH
Cl
H
Cl
>;tb;454
>;tb; 2-COOH
Cl
H
Cl
>;tb;455
294/612
>;tb; 2-COOCH3 Cl
H
Cl
>;tb;456
>;tb; 2-CH2 OH Br
H
Br
>;tb;457
>;tb; 2-CHO
Cl
H
Cl
>;tb;458
>;tb; 3-Cl, 4F
F
H
F
m.p.
>;tb;
101-103 DEG
>;tb;459
>;tb; 3-Cl, 4F
F
H
Cl
>;tb;460
>;tb; 3,4(CH3)2
>;tb;
Cl
H
Cl
>;tb;461
>;tb; 3,5(Cl)2 Cl
H
Cl
m.p.
>;tb;
175-177 DEG
>;tb;462
>;tb; 2,6(Cl)2 Cl
H
Cl
>;tb;463
>;tb; 2,3(CH3)2
>;tb;
Cl
H
Cl
>;tb;464
>;tb; 2,4(CH3)2
>;tb;
Cl
H
Cl
>;tb;465
>;tb; 3-Cl, 4-C3 H7 iso
>;tb;
Cl
H
Cl
>;tb;466
>;tb; 2-Cl, 4-CH3 Cl
H
Cl
>;tb;467
>;tb; 3,4(Cl)2 Cl
H
Cl
>;tb;468
>;tb; 3,5(OCH3)2
>;tb;
Cl
H
Cl
m.p.
>;tb;
168-172 DEG
>;tb;469
>;tb; 3-NH2, 4-CH3
>;tb;
Cl
H
Cl
>;tb;470
>;tb; 3-NHCH3, 4-CH3
>;tb;
Cl
H
Cl
>;tb;471
>;tb; 3-OH, 5-Cl
Cl
H
Cl
>;tb;472
>;tb; 3-OCHF2, 5-Cl
>;tb;
Cl
H
Cl
>;tb;473
>;tb; 3-OCH3, 5-Cl
>;tb;
Cl
H
Cl
>;tb;474
>;tb; 3-COOH, 5-Cl Cl
H
Cl
>;tb;475
>;tb; 3-COOCH3, 5-Cl
>;tb;
Cl
H
Cl
>;tb;476
>;tb; 3-CONH2, 5-Cl
>;tb;
Cl
H
Cl
>;tb;477
>;tb; 4-COCH3, 4-CH3
295/612
>;tb;
Cl
H
Cl
>;tb;478
>;tb; 2-Cl, 6-CCH
Br
H
Br
>;tb;479
>;tb; 4-SO2 N(CH3)2, 5-CH3
>;tb;
Br
H
Br
>;tb;480
>;tb; 3-CCH, 5CH3 Cl
H
F
>;tb;481
>;tb; 2-CH3, 5-N(CH3)2
>;tb;
Cl
H
Cl
>;tb;482
>;tb; 2-CH3, 5-Cl Cl
H
Cl
>;tb;483
>;tb; 3-Br, 4-OCH3
>;tb;
Cl
H
Cl
>;tb;484
>;tb; 3-CH3, 4-NHCON(CH3)2
>;tb;
Cl
H
Cl
>;tb;485
>;tb; 2SCH3, 5-NO2
>;tb;
Cl
H
Cl
>;tb;486
>;tb; 2SCH3, 5-NH2
>;tb;
Cl
H
Cl
>;tb;487
>;tb; 2Cl, 5-NO2 Cl
H
Cl
>;tb;488
>;tb; 2Cl, 5NH2 Cl
H
Cl
>;tb;489
>;tb; 3,4(OCH3)2
>;tb;
Cl
H
Cl
>;tb;490
>;tb; 3,4(OH)2 Cl
H
Cl
>;tb;491
>;tb; 2,3.Cl2 Cl
H
Cl
m.p.
>;tb;
116-118 DEG
>;tb;492
>;tb; 2,5(OCH3)2
>;tb;
Cl
H
Cl
m.p.
>;tb;
127-129 DEG
>;tb;493
>;tb; 2,5(OH)2 Cl
H
Br
>;tb;494
>;tb; 4-CN3, 3-CH3
>;tb;
Cl
H
Cl
m.p.
>;tb;
120-123 DEG
>;tb;495
>;tb; 4-OH, 3-CH3 Cl
H
Br
>;tb;496
>;tb; 4-OCH3, 3-NO2
>;tb;
Cl
H
Cl
>;tb;497
>;tb; 4-OH, 3-NO2 Cl
H
Cl
>;tb;498
>;tb; 4-OCH3, 3-NH2
>;tb;
Cl
H
Cl
>;tb;499
>;tb; 4-OH, 3-NH2 Cl
H
Cl
296/612
>;tb;500
>;tb; 3,5(OH)2 Cl
H
Cl
>;tb;501
>;tb; 2,6Cl2, 3-NO2
>;tb;
Cl
H
Cl
>;tb;502
>;tb; 2,6Cl2, 3-NH2
>;tb;
Cl
H
Cl
>;tb;503
>;tb; 2,6(OCH3)2, 4-Cl
>;tb;
Br
H
Br
>;tb;504
>;tb; 2,6(OH)2, 4-Cl
>;tb;
Br
H
Br
>;tb;505
>;tb; 3,5(J)2, 4-OCH3
>;tb;
Cl
H
Cl
>;tb;506
>;tb; 3,5(J)2, 4-OH
>;tb;
Br
H
Br
>;tb;507
>;tb; 3,5(Cl)2, 4-OCH3
>;tb;
Br
H
Br
>;tb;508
>;tb; 3,5(Cl)2, 4-OH
>;tb;
Cl
H
Cl
>;tb;509
>;tb; 2,5(Cl2), 4-OCH3
>;tb;
Cl
H
Cl
>;tb;510
>;tb; 2,5(Cl)2, 4-OH
>;tb;
Cl
H
Cl
>;tb;511
>;tb; 4F
Cl
H
Br
>;tb;512
>;tb; 3,4(OH)2 Br
H
Br
>;tb;513
>;tb; 2,6(OH)2, 3-NH2
>;tb;
Cl
H
Cl
>;tb;514
>;tb; 3-OCH2 OCH3
>;tb;
Cl
H
Cl
>;tb;515
>;tb; 3,5(OH)2, 4-OCH3
>;tb;
Cl
H
Cl
>;tb;516
>;tb; 3,4,5(OH)3 Cl
H
Cl
>;tb;517
>;tb; 2,3,4(OCH3)3
>;tb;
Cl
H
Cl
>;tb;518
>;tb; 2,3,4(OH)3 Cl
H
Cl
>;tb;519
>;tb; 2,3,5(Cl)3, 4-OCH3
>;tb;
Cl
H
Cl
>;tb;520
>;tb; (CH3)5 Cl
H
Cl
>;tb;521
>;tb; (H)5
CN
H
CN
m.p.
297/612
>;tb;
150-155 DEG
>;tb;522
>;tb; (H)5
Cl
H
CN
>;tb;523
>;tb; 4-CH3
CN
H
CN
>;tb;524
>;tb; 4-CH3
Cl
H
CN
>;tb;525
>;tb; 4-OCH3
CN
H
CN
>;tb;526
>;tb; 4-OCH
CN
H
Cl
>;tb;527
>;tb; 4-OH
CN
H
CN
>;tb;528
>;tb; 4-OH
Cl
H
CN
>;tb;529
>;tb; (H)5
SCH3 H
Cl
>;tb;530
>;tb; (H)5
SO2 CH3
>;tb;
H
Cl
>;tb;531
>;tb; (H)5
SCH3 H
Br
>;tb;532
>;tb; (H)5
SO2 CH3
>;tb;
H
Br
>;tb;533
>;tb; (H)5
SCH3 H
F
>;tb;534
>;tb; (H)5
SO2 CH3
>;tb;
H
F
>;tb;535
>;tb; (H)5
CN
Cl
Cl
>;tb;536
>;tb; 3-SCH2 CO2 CH3
>;tb;
Cl
H
Cl
>;tb;537
>;tb; (H)5
OCF3 H
Cl
>;tb;538
>;tb; 4-CH3
OCF3 H
Cl
>;tb;539
>;tb; 4-CH3
OCOCH3
>;tb;
H
Cl
m.p.
>;tb;
110-112 DEG
>;tb;540
>;tb; 4-OH, 3CH3 Cl
H
Cl
>;tb;541
>;tb; (H)5
Cl
F
Cl
>;tb;542
>;tb; (H)5
Br
F
Br
>;tb;543
>;tb; 3-CH3
Cl
H
Cl
m.p. 76-79 DEG
>;tb;544
>;tb; 3-SCH3
Cl
H
Cl
m.p.
>;tb;
103-105 DEG
>;tb;545
>;tb; 3-CCl3
Cl
H
Cl
>;tb;546
>;tb; 4-CCl3
Cl
H
Cl
>;tb;547
298/612
>;tb; 4-OH, 3-CH3 Br
H
Cl
m.p.
>;tb;
140-145 DEG
>;tb;548
>;tb; 4-SCH2 COCH3
>;tb;
Cl
H
Cl
>;tb;549
>;tb; 3-SCOCHCH2 Cl
H
Cl
>;tb;550
>;tb; 4-SCOCHCHCH3
>;tb;
Cl
H
Cl
>;tb;551
>;tb; 3-SCOCH2 C CH
>;tb;
Br
H
Br
>;tb;552
>;tb; 4-SOCH2 CHCH2
>;tb;
Cl
H
Cl
>;tb;553
>;tb; 3-SOCH2 CHCH2
>;tb;
Cl
H
Cl
>;tb;554
>;tb; 4-SOCH2 CCH F
H
Cl
>;tb;555
>;tb; 3-SOCH2 CCH Cl
H
Cl
>;tb;556
>;tb; 3-SO2 CH2 CHCH2
>;tb;
Br
H
Br
>;tb;557
>;tb; 4-SO2 CH2 CHCH2
>;tb;
Cl
H
Cl
>;tb;558
>;tb; 3-SO2 CH2 CCH
>;tb;
Cl
H
Cl
>;tb;559
>;tb; 4-SO2 CH2 CCH
>;tb;
Cl
H
Cl
>;tb;560
>;tb; 4-OCOC6 H13n
>;tb;
Cl
H
Cl
>;tb;561
>;tb; 3-OCOC5 H11 i
>;tb;
Cl
H
Cl
>;tb;562
>;tb; 4-OCONHCH3 Cl
H
Cl
m.p.
>;tb;
205-209 DEG
>;tb;563
>;tb; 3-OCONHCH3 Cl
H
Cl
m.p.
>;tb;
134-137 DEG
>;tb;564
>;tb; 4-OCON(CH3)2
>;tb;
Cl
H
Cl
m.p.
>;tb;
191-193 DEG
>;tb;565
>;tb; 4-OCONHC4 H9
>;tb;
Cl
H
Cl
>;tb;566
>;tb; 3-OCONHC3 H7 i
>;tb;
Cl
H
Cl
>;tb;567
>;tb; 4-OCOCHCH2 Cl
H
Cl
299/612
>;tb;568
>;tb; 3-OCOCHCHCH3
>;tb;
Cl
H
Cl
>;tb;569
>;tb; 4-OCOCH2 OCH3
>;tb;
Cl
H
Cl
>;tb;570
>;tb; 3-OCON(CH3)2
>;tb;
Cl
H
Cl
>;tb;571
>;tb; 4-NHCONHC4 H9 n
>;tb;
Cl
H
Cl
>;tb;572
>;tb; 4-SH
Cl
H
Cl
>;tb;573
>;tb; 3-OC2 H4 OH
>;tb;
Cl
H
Cl
>;tb;574
>;tb; 3-NHC2 H4 COOCH3
>;tb;
Cl
H
Cl
>;tb;575
>;tb; 3-Br, 4-OH
Cl
H
Cl
>;tb;576
>;tb; 3-NHCONHCH3 Cl
H
Cl
m.p.
>;tb;
234-238 DEG
>;tb;577
>;tb; 4-OCH3
OH
H
OH
m.p. 318 DEG
>;tb;__________________________________________________________________________
>;tb;
Z
FORMULATION EXAMPLES
The compounds of formula I will normally not be used by themselves in agriculture. They are used in
the form of ready-for-use formulations which can be applied either direct or diluted with water.
EXAMPLE 8
Dusts: The following substances are used to formulate (a) a 5% and (b) a 2% dust:
>;tb;______________________________________
>;tb;(a) 5 parts of 2-p-tolyl-4,6-bis-isopropoxypyrimidine
>;tb;
or of a mixture thereof with 2-chloro-2',6'>;tb;
diethyl-N--(butoxymethyl)-acetanilide
>;tb;
95 parts of talcum;
>;tb;(b) 2 parts of the above active ingredient or a mixture
>;tb;
1 part of highly dispersed silicic acid
>;tb;
97 parts of talc;
>;tb;______________________________________
The active ingredients are mixed with the carriers and ground and in this form can be processed to
dusts for application.
Example 9
Granulate: The following substances are used to formulate a 5% granulate:
>;tb;______________________________________
>;tb;5
parts of 2-p-tolyl-4,6-isopropoxy-5-bromopyrimidine
>;tb;
or of a mixture thereof with 2-chloro-2',6'-diethyl>;tb;
N--(methoxymethyl)-acetanilide
>;tb;0.25 part of epoxidised vegetable oil
300/612
>;tb;0.25 part of cetyl polyglycol ether
>;tb;3.25 parts of polyethylene glycol
>;tb;91 parts of kaolin (particle size 0.3-0.8 mm).
>;tb;______________________________________
The active ingredient or mixture is mixed with the vegetable oil and the mixture is dissolved in 6 parts
of acetone. Then polyethylene glycol and cetyl polyglycol ether are added. The resultant solution is
sprayed on kaolin and the acetone is evaporated in vacuo. A microgranular formulation of this kind can
be conveniently incorporated in seed furrows.
Example 10
Wettable powders: The following constituents are used to formulate (a) a 70%, (b) a 40%, (c) and (d) a
25% and (e) a 10% wettable powder:
>;tb;______________________________________
>;tb;(a) 70 parts of 2-p-tolyl-4,6-bis-(methoxyethyl)-5-chloro>;tb;
pyrimidine or a mixture thereof with 2-chloro>;tb;
2',6'-diethyl-N--(2"-propoxyethyl)-acetanilide
>;tb;
5 parts of sodium dibutylnaphthylsulfonate
>;tb;
3 parts of naphthalenesulfonic acid/phenolsulfonic
>;tb;
acid/formaldehyde condensate (3:2:1)
>;tb;
10 parts of kaolin
>;tb;
12 parts of Champagne chalk
>;tb;(b) 40 parts of active ingredient or mixture as above,
>;tb;
5 parts of sodium lignosulfonate
>;tb;
1 part of sodium dibutylnaphthalenesulfonate
>;tb;
54 parts of silicic acid
>;tb;(c) 25 parts of active ingredient or mixture as above
>;tb;
4.5 parts of calcium lignosulfonate
>;tb;
1.9 parts of Champagne chalk/hydroxyethyl
>;tb;
cellulose mixture (1:1)
>;tb;
1.5 parts of sodium dibutylnaphthalenesulfonate
>;tb;
19.5 parts of silicic acid
>;tb;
19.5 parts of Champagne chalk
>;tb;
28.1 parts of kaolin
>;tb;(d) 25 parts of active ingredient or mixture as above
>;tb;
2.5 parts of isooctylphenoxy polyethylene ethanol
>;tb;
1.7 parts of a Champagne chalk/hydroxyethyl
>;tb;
cellulose mixture (1:1)
>;tb;
8.3 parts of sodium aluminium silicate
>;tb;
16.5 parts of kieselguhr
>;tb;
46 parts of kaolin
>;tb;(e) 10 parts of active ingredient or mixture as above
>;tb;
3 parts of a mixture of the sodium salts of
>;tb;
saturated fatty alcohol sulfates
>;tb;
5 parts of naphthalenesulfonic acid/formaldehyde
>;tb;
condensate
>;tb;
82 parts of kaolin.
>;tb;______________________________________
The active ingredients are intimately mixed in suitable mixers with the additives and ground in
appropriate mills and rollers. Wettable powders of excellent wettability and suspension power are
obtained. These wettable powders can be diluted with water to give suspensions of the desired
concentration and can be used in particular for leaf application (to inhibit growth or for fungicidal
application).
Example 11
301/612
Emulsifiable concentrate: The following substances are used to formulate a 25% emulsifiable
concentrate:
>;tb;______________________________________
>;tb;25
parts of 2-phenyl-4-chloro-6-methylpyrimidine or
>;tb;
of a mixture thereof with 2-chloro-6'-ethyl-N->;tb;
(2"-methoxy-1"-methylethyl)-acet-o-toluidide
>;tb;2.5 parts of epoxidised vegetable oil
>;tb;10
parts of an alkylarylsulfonate/fatty alcohol
>;tb;
polyglycol ether mixture
>;tb;5
parts of dimethyl formamide
>;tb;57.5 parts of xylene.
>;tb;______________________________________
Example 12
Paste The following substances are used to formulate a 45% paste:
>;tb;______________________________________
>;tb;(a) 45 parts of 2-phenyl-4-chloro-6-hydroxypyrimidine or
>;tb;
of a mixture thereof with 2-chloro-2',6'-diethyl>;tb;
N--(methoxymethyl)-acetanilide
>;tb;
5 parts of sodium aluminium silicate,
>;tb;
14 parts of cetyl polyglycol ether with 8 moles of
>;tb;
ethylene oxide,
>;tb;
3 parts of oleyl polyglycol ether with 5 moles of
>;tb;
ethylene oxide,
>;tb;
2 parts of spindle oil,
>;tb;
10 parts of polyethylene glycol,
>;tb;
23 parts of water.
>;tb;(b) 45 parts of the above active ingredient or mixture
>;tb;
5 parts of ethylene glycol,
>;tb;
3 parts of octylphenoxy polyethylene glycol con>;tb;
taining 9-10 moles of ethylene oxide per mole of
>;tb;
octylphenol,
>;tb;
3 parts of a mixture of aromatic sulfonesulfonic
>;tb;
acids, condensed with formaldehyde as ammonium
>;tb;
salt,
>;tb;
1 part of silicone oil in form of a 75% emulsion,
>;tb;
0.1 part of a mixture of 1-(3-chloroallyl)-3,5,7>;tb;
triazo-azonium-adamantane chloride with sodium
>;tb;
carbonate (chloride value at least 11.5%),
>;tb;
0.2 part of a biopolymeric thickener containing a
>;tb;
maximum of 100 bacilli per gram,
>;tb;
42.7 parts of water.
>;tb;______________________________________
The active ingredient is intimately mixed with the adjuvants in appropriate devices and ground. By
diluting the resultant paste with water, it is possible to prepare suspensions of the desired concentration.
BIOLOGICAL EXAMPLES
The ability of the compounds of formula I to protect cultivated plants from the phytotoxic effects of
potent herbicides can be seen from the following Examples. In the test procedures, the compounds of
formula I are designated as antidotes. The protective action is indicated in percent. 0% denotes the
action of the herbicide when applied by itself; 100% denotes the desired normal growth of the
cultivated plant. A protective action of at least 10% is significant.
Example 13
Tests with antidote and herbicide in transplanted rice. Method of application: tank mixture
302/612
Rice plants are reared in soil to the 11/2- to 2-leaf stage. The plants are then transplanted in bunches
(always 3 plants together) in sandy loam in containers measuring 47 cm.times.29 cm.times.24 cm. The
surface of the soil is then covered with water to a height of 1.5 to 2 cm. Two to three days after
transplantation, the herbicide and the antidote as test substance are applied together direct to the water
as tank mixture. The protective action of the antidote is evaluated in percent 24 days after
transplantation. The plants treated with herbicide alone (no protective action) as well as the completely
untreated controls (100% growth) serve as references for the evaluation. The results are reported
below.
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethyl)-acet>;tb;anilide "Pretilachlor".
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of
Protective action
>;tb;compound
>;tb;
in kg/ha application in kg/ha
>;tb;
in %
>;tb;______________________________________
>;tb;1
1
1
50
>;tb;2
0.75
0.75
25
>;tb;49
0.75
0.75
12.5
>;tb;50
1
1
12.5
>;tb;53
1.5
1.5
25
>;tb;59
1
1
25
>;tb;84
1
1
25
>;tb;99
1
1
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(butoxymethyl)acet>;tb;anilide "Butachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of
Protective action
>;tb;compound
>;tb;
in kg/ha application in kg/ha
>;tb;
in %
>;tb;______________________________________
>;tb;2
1.5
1.5
12.5
>;tb;49
1.5
1.5
12.5
>;tb;50
1.5
1.5
25
>;tb;53
1.5
1.5
12.5
>;tb;54
1.5
1.5
12.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(methoxymethyl)acetanilide
>;tb;"Alachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha
in %
>;tb;______________________________________
>;tb;1
0.125 0.125
12
>;tb;2
0.125 0.125
25
303/612
>;tb;49
0.125 0.126
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(ethoxymethyl)cet-o-toluidide
>;tb;"Acetochlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha
in %
>;tb;______________________________________
>;tb;2
0.125 0.125
12.5
>;tb;49
0.125 0.125
12.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2,6-dinitro-N,N--dipropyl-4-trifluoromethylaniline
>;tb;"Trifluralin"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha
in %
>;tb;______________________________________
>;tb;2
2
2
12.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--4-chlorobenzyl-diethylthiocarbamate
>;tb;"Thiobencarb"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha
in %
>;tb;______________________________________
>;tb;1
8
8
50
>;tb;1
4
4
25
>;tb;1
2
2
12,5
>;tb;______________________________________
Rice is likewise protected from the phytotoxic effects of S-benzyl-N,N-diethylthiocarbamate.
Example 14
Test with antidote and herbicide in transplanted rice. Method of application: root treatment
Rice plants of the Yamabiko variety are reared in soil to the 11/2- to 2-leaf stage and then washed. The
roots only of the plants in bunches (always 3 plants together) are then immersed for 15 to 60 minutes in
a dish containing a solution of the compound to be tested as antidote in a concentration of 1000 ppm.
The plants are then transplanted in sandy loam in containers measuring 47 cm.times.29 cm.times.24
cm. The surface of the soil is then covered with water to a height of 1.5 to 2 cm. Two to three days
after transplantation, the herbicide is applied direct to the water. The protective action of the antidote is
evaluated in percent 24 days after transplantation. The plants treated with the herbicide alone (no
304/612
protective action) as well as the completely untreated controls (100% growth) serve as references for
the evaluation. The results are as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethyl)>;tb;acetanilide "Pretilachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
application
>;tb;
in kg/ha
in %
>;tb;______________________________________
>;tb;1
1000 ppm 0.75
87.5
>;tb;2
1000 ppm 1
50
>;tb;______________________________________
Example 15
Test with antidote and herbicide in transplanted rice. Application of the antidote to the plant using an
aqueous solution (drench method).
Rice plants of the Yamabiko variety are reared in seed dishes to the 11/2 to 2-leaf stage. 1 to 2 days
before transplantation, each seed dish with the rice plants is immersed in a larger dish containing a
solution of the compound to be tested as antidote in a concentration of 1000 ppm. The plants are then
transplanted in bunches (always 3 plants together) in sandy loam in containers measuring 47
cm.times.29 cm.times.24 cm. The surface of the soil is then covered with water to a height of 1.5 to 2
cm. Two to three days after transplantation, the herbicide is applied direct to the water. The protective
action of the antidote is evaluated in percent 24 days after transplantation. The plants treated with the
herbicide alone (no protective action) as well as the completely untreated controls (100% growth) serve
as references for the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethy)>;tb;acetanilide "Pretilachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
application
>;tb;
in kg/ha
in %
>;tb;______________________________________
>;tb;2
1000 ppm 1
37.5
>;tb;______________________________________
Example 16
Test with antidote and herbicide in transplanted rice. Preemergence application of the antidote.
The compound to be tested as antidote is sprayed in the form of a dilute solution to the most surface of
soil in seed dishes. Rice seeds are then sown in the dishes and reared to to the 11/2- to 2-leaf stage. The
plants are then transplanted in bunches (always 3 plants together) in sandy loam in containers
measuring 47 cm.times.29 cm.times.24 cm. The surface of the soil is then covered with water to a
height of 1.5 to 2 cm. Two to three days after transplantation, the herbicide is applied direct to the
water. The protective action of the antidote is evaluated in percent 24 days after transplantation. The
plants treated with the herbicide alone (no protective action) as well as the completely untreated
controls (100% growth) serve as references for the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propyloxyethyl)-
305/612
>;tb;acetanilide "Pretilachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha
in %
>;tb;______________________________________
>;tb;2
4
1.5
25
>;tb;______________________________________
Example 17
Test with antidote and herbicide in transplanted rice. Pre-plant incorporation method.
The compound to be tested as antidote is incorporated in the soil in seed dishes in a concentration of
100 ppm. Two days later the rice plants are reared in the treated seed dishes to the 11/2- to 2-leaf stage.
The plants are then transplanted in bunches (always 3 plants together) in sandy loam in containers
measuring 47 cm.times.29 cm.times.24 cm. The surface of the soil is then covered with water to a
height of 1.5 to 2 cm. Two to three days after transplantation, the herbicide is applied direct to the
water. The protective action of the antidote is evaluated in percent 24 days after transplantation. The
plants treated with the herbicide alone (no protective action) as well as the completely untreated
controls (100% growth) serve as references for the evaluation. The results are as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethyl)>;tb;acetanilide "Pretilachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
application
>;tb;
in kg/ha
in %
>;tb;______________________________________
>;tb;2
100 ppm 1
25
>;tb;2
100 ppm 0.75
25
>;tb;______________________________________
Example 18
Test with antidote and herbicide in transplanted rice. Postemergence application of the antidote (over
the top application).
Rice plants of the Yamabiko variety are reared in soil to the 11/2- to 2-leaf stage. The compound to be
tested as antidote is then sprayed in the form of a dilute solution over the rice plants. Two days later the
plants are then transplanted in bunches (always 3 plants together) in sandy loam in containers
measuring 47 cm.times.29 cm.times.24 cm. The surface of the soil is then covered with water to a
height of 1.5 to 2 cm. Two to three days after transplantation, the herbicide is applied direct to the
water. The protective action of the antidote is evaluated in percent 24 days after transplantation. The
plants treated with the herbicide alone (no protective action) as well as the completely untreated
controls (100% growth) serve as references for the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethyl)>;tb;acetanilide "Pretilachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
306/612
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha
in %
>;tb;______________________________________
>;tb;2
4
1.5
12
>;tb;______________________________________
The 2-phenylpyrimidines of this invention employed in the test methods described in Examples 13 to
18 also exerted a certain protective action on the transplanted rice when the following herbicides were
used instead of those indicated above: S-2-methylpiperidino-carbonylmethyl-O,Odipropylphosphorodithioate ("Piperophos"), S-ethyl-N,N-hexamethylenethiocarbamate ("Molinate"),
S-4-chlorobenzyl-diethyl-thiocarbamate ("Thiobencarb"), S-4-benzyl-diethyl-thiocarbamate, 5-tertbutyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2-one ("Oxadiazon") or N-(3,4dichlorophenyl-propionamide ("Propanil").
Example 19
Test with antidote and herbicide with rice sown in water. (The rice seeds are soaked and sown direct in
very wet, marshy or flooded soil. Application of the antidote as tank mixture).
Rice seeds are soaked for 48 hours in water. Plastic containers measuring 25 cm.times.17 cm.times.12
cm are filled with soil into which the soaked seeds are sown. The compound to be tested as antidote
and the herbicide are then sprayed together as tank mixture onto the surface of the soil. The water level
is raised gradually in accordance with the growth of the rice plants. The protective action of the
antidote is evaluated in percent 21 days later. The plants treated with herbicide alone (no protective
action) as well as the completely untreated controls (100% growth) serve as references for the
evaluation. The results are reported in the following table.
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethyl)>;tb;acetanilide "Pretilachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in kg/ha
in kg/ha action in %
>;tb;______________________________________
>;tb;1
0.25
0.25
62.5
>;tb;2
0.25
0.25
50
>;tb;49
0.25
0.25
37.5
>;tb;50
0.25
0.25
50
>;tb;53
0.25
0.25
62.5
>;tb;54
0.25
0.25
62.5
>;tb;57
0.25
0.25
50
>;tb;59
0.25
0.25
75
>;tb;64
0.25
0.25
12.5
>;tb;67
0.25
0.25
37.5
>;tb;84
0.25
0.25
75
>;tb;89
0.25
0.25
25
>;tb;99
0.25
0.25
62.5
>;tb;129 0.25
0.25
37.5
>;tb;130 0.25
0.25
62.5
>;tb;132 0.25
0.25
37.5
>;tb;134 0.25
0.25
62.5
>;tb;135 0.25
0.25
50
>;tb;158 0.25
0.25
50
>;tb;197 0.25
0.25
25
>;tb;198 0.25
0.25
62.5
307/612
>;tb;200 0.25
0.25
50
>;tb;209 0.25
0.25
25
>;tb;223 0.25
0.25
62.5
>;tb;248 0.25
0.25
62.5
>;tb;347 0.25
0.25
62.5
>;tb;381 0.25
0.25
25
>;tb;394 0.25
0.25
25
>;tb;461 0.25
0.25
37.5
>;tb;468 0.25
0.25
25
>;tb;491 0.25
0.25
75
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(butoxymethyl)>;tb;acetanilide "Butachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in kg/ha
in kg/ha action in %
>;tb;______________________________________
>;tb; 1
0.5
0.15
37.5
>;tb; 2
0.75
0.75
50
>;tb;49
0.75
0.75
50
>;tb;50
0.75
0.75
37.5
>;tb;53
0.75
0.75
62.5
>;tb;54
0.75
0.75
62.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(methoxymethyl)>;tb;acetanilide "Alachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in kg/ha
in kg/ha action in %
>;tb;______________________________________
>;tb; 1
0.03
0.03
25
>;tb; 2
0.03
0.03
12.5
>;tb;49
0.03
0.03
37.5
>;tb;50
0.03
0.03
37.5
>;tb;53
0.03
0.03
25
>;tb;54
0.03
0.03
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(2"-methoxy-1"-methylethyl)>;tb;acet-o-toluidide, "Metolachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in kg/ha
in kg/ha action in %
>;tb;______________________________________
>;tb; 1
0.03
0.03
25
308/612
>;tb; 2
0.03
0.03
12.5
>;tb;49
0.03
0.03
25
>;tb;50
0.03
0.03
12.5
>;tb;53
0.03
0.03
25
>;tb;54
0.03
0.03
12.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--ethyl-diisopropylthiocarbamate, "EPTC"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in kg/ha
in kg/ha action in %
>;tb;______________________________________
>;tb;1
1
1
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--2-methylpiperidino--carbonylmethyl-O,O--dipropyl>;tb;phosphothioate, "Piperophos"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in kg/ha
in kg/ha action in %
>;tb;______________________________________
>;tb;1
0.5
0.5
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 5-ethyl-N,N--hexamethylene-thiocarbamate
>;tb;"Molinate"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in kg/ha
in kg/ha action in %
>;tb;______________________________________
>;tb;1
2
2
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--4-chlorobenzyl-diethylthiocarbamate
>;tb;"Thiobencarb"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in kg/ha
in kg/ha action in %
>;tb;______________________________________
>;tb;1
4
4
37.5
>;tb;______________________________________
309/612
The antidote, compound 1, as well as other 2-phenylpyrimidines of this invention, were also able to
protect rice from the phytotoxic effects of S-4-benzyl-diethylthiocarbamate and 5-tert-butyl-3-(2,4dichloro-5-dichloro-5-isopropoxyphenyl)-1,3,4-oxdiazol -2-one ("Oxidiazon").
Example 20
Test with antidote and herbicide with rice sown in water. Application of the antidote while soaking the
rice seeds.
Rice seeds are soaked for 48 hours in solutions of the test antidote at a concentration of 100 ppm. The
seeds are then allowed to dry for about 2 hours until they are no longer tacky. Plastic containers
measuring 25 cm.times.17 cm.times.12 cm are filled with sandy loam to 2 cm below the edge. The
soaked seeds are sown on the surface of the soil in the containers and then very lightly covered. The
soil is kept in a moist (non-marshy) state. Then a dilute solution of the herbicide is sprayed onto the
surface of the soil. The water level is raised gradually in accordance with the growth of the plants.
Evaluation of the protective action in percent is made 21 days later. The plants treated with herbicide
alone (no protective action) as well as the completely untreated controls (100% growth) serve as
references for the evaluation. The results are reported in the following table.
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethyl)>;tb;acetanilide "Pretilachlor".
>;tb;
Herbicide
>;tb;Antidote
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
Rate of application
>;tb;
in kg/ha action in %
>;tb;______________________________________
>;tb;1
100 ppm
0.25
62.5
>;tb;2
100 ppm
0.25
75
>;tb;49
100 ppm
0.25
75
>;tb;50
100 ppm
0.25
87.5
>;tb;53
100 ppm
0.25
62.5
>;tb;54
100 ppm
0.25
62.5
>;tb;57
100 ppm
0.25
50
>;tb;59
100 ppm
0.25
62.5
>;tb;64
100 ppm
0.25
50
>;tb;67
100 ppm
0.25
50
>;tb;84
100 ppm
0.25
50
>;tb;89
100 ppm
0.25
62.5
>;tb;99
100 ppm
0.25
62.5
>;tb;128 100 ppm
0.25
50
>;tb;130 100 ppm
0.25
50
>;tb;132 100 ppm
0.25
37.5
>;tb;134 100 ppm
0.25
50
>;tb;135 100 ppm
0.25
50
>;tb;158 100 ppm
0.25
75
>;tb;197 100 ppm
0.25
62.5
>;tb;198 100 ppm
0.25
75
>;tb;200 100 ppm
0.25
75
>;tb;209 100 ppm
0.25
62.5
>;tb;223 100 ppm
0.25
25
>;tb;248 100 ppm
0.25
50
>;tb;347 100 ppm
0.25
50
>;tb;381 100 ppm
0.25
62.5
>;tb;394 100 ppm
0.25
50
>;tb;461 100 ppm
0.25
62.5
>;tb;468 100 ppm
0.25
75
>;tb;491 100 ppm
0.25
37.5
310/612
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(butoxymethyl)>;tb;acetanilide "Butachlor"
>;tb;
Herbicide
>;tb;Antidote
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
Rate of application
>;tb;
in kg/ha action in %
>;tb;______________________________________
>;tb; 1
100 ppm
0.5
50
>;tb; 2
100 ppm
0.5
50
>;tb;49
100 ppm
0.5
37.5
>;tb;50
100 ppm
0.5
50
>;tb;53
100 ppm
0.5
50
>;tb;54
100 ppm
0.5
50
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(methoxyethyl)>;tb;acetanilide "Alachlor"
>;tb;
Herbicide
>;tb;Antidote
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
Rate of application
>;tb;
in kg/ha action in %
>;tb;______________________________________
>;tb; 1
100 ppm
0.03
50
>;tb; 2
100 ppm
0.03
62.5
>;tb;49
100 ppm
0.03
50
>;tb;50
100 ppm
0.03
62.5
>;tb;53
100 ppm
0.03
62.5
>;tb;54
100 ppm
0.03
50
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(2"-methoxy-1"-methylethyl)>;tb;acet-o-toluidide, "Metolachlor"
>;tb;
Herbicide
>;tb;Antidote
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
Rate of application
>;tb;
in kg/ha action in %
>;tb;______________________________________
>;tb; 2
100 ppm
0.03
12.5
>;tb;49
100 ppm
0.03
12.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--ethyl-diisopylthiocarbamate, "EPTC"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
application
>;tb;
in kg/ha in %
>;tb;______________________________________
>;tb;1
100 ppm 0.5
12.5
311/612
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--2-methylpiperidino-carbonylmethyl-O,
>;tb;O--dipropylphosphorodithioate, "Piperophos"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
application
>;tb;
in kg/ha in %
>;tb;______________________________________
>;tb;1
1000 ppm 6.5
37.5
>;tb;1
100 ppm 6.5
37.5
>;tb;1
10 ppm 6.5
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--ethyl-N,N--hexamethylenethiocarbamate
>;tb;"Molinate"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
application
>;tb;
in kg/ha in %
>;tb;______________________________________
>;tb;1
1000 ppm 8
62.5
>;tb;1
100 ppm 8
62.5
>;tb;1
10 ppm 8
62.5
>;tb;1
1000 ppm 2
37.5
>;tb;1
100 ppm 2
37.5
>;tb;1
10 ppm 2
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--chlorobenzyl-diethiocarbamate "Thiocarb"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
application
>;tb;
in kg/ha in %
>;tb;______________________________________
>;tb;1
1000 ppm 8
37.5
>;tb;1
100 ppm 8
37.5
>;tb;1
1000 ppm 4
50
>;tb;1
100 ppm 4
50
>;tb;1
10 ppm 4
37.5
>;tb;1
1000 ppm 2
37.5
>;tb;1
100 ppm 2
25
>;tb;1
10 ppm 2
25
>;tb;______________________________________
Rice was also protected from the phytotoxic effects of S-benzyldiethylthiocarbamate and 5-tert-butyl3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxdiazol-2-one ("Oxdiazon").
Example 21
312/612
Test with antidote and herbicide with rice sown in water. Application of antidote and herbicide in
nutrient solution.
Seeds which would normally be damaged in the test concentrations of the herbicide employed are sown
in granular zonolith (expanded vermiculite) in plastic flower pots (diameter 6 cm at the top) which are
perforated at the bottom. Each pot is then placed in a second transparent plastic flower pot (diameter 7
cm at the top) which contains about 50 ml of the nutrient solution prepared with herbicide and antidote.
This nutrient solution then rises by capillary action in the filling material of the smaller pot and
moistens the seed and the germinating plant. The loss in fluid is daily replenished to 50 ml with a
Hewitt nutrient solution. Evaluation of the protective action in percent is made 3 weeks after the start
of the test. The plants treated with herbicide alone (no protective action) as well as the completely
untreated controls (100% growth) serve as references for the evaluation. The results are as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propyloxyethyl)>;tb;acetanilide, "Pretilachlor"
>;tb;Antidote
>;tb;
Rate of Herbicide Protective action
>;tb;compound
>;tb;
application
>;tb;
rate of application
>;tb;
in %
>;tb;______________________________________
>;tb;1
10 ppm 4 ppm
75
>;tb;______________________________________
Example 22
Test with antidote and herbicide with rice sown dry (20 days after sowing, when the rice plants have
attained the 3-leaf stage, the soil is flooded). Application of antidote and herbicide as tank mixture.
Rice seeds of the IR-36 variety are sown in containers measuring 47 cm.times.29 cm.times.24 cm,
covered and gently pressed firm. The test antidote and the herbicide are then sprayed together as tank
mixture onto the soil. About 20 days after sowing, when the rice plants are attained the 3-leaf stage, the
surface of the soil is covered with water to a height of 4 cm. The protective action of the antidote is
evaluated in percent 30 days after transplantation. The plants treated with herbicide alone (no
protective action) as well as the completely untreated controls (100% growth) serve as references for
the evaluation. The results are reported in the following table.
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2-',6'-diethyl-N--(2"-propyloxyethyl)>;tb;acetanilide, "Pretilachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb; 1
2
2
62.5
>;tb; 2
2
2
50
>;tb;49
2
2
50
>;tb;50
2
2
50
>;tb;53
2
2
62.5
>;tb;54
2
2
50
>;tb;59
2
2
50
>;tb;84
3
3
62.5
>;tb;99
2
2
27.5
>;tb;______________________________________
>;tb;______________________________________
313/612
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(butoxymethyl)>;tb;acetanilide, "Butachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb; 1
3
3
25
>;tb; 2
3
3
25
>;tb;49
3
3
37.5
>;tb;50
3
3
37.5
>;tb;53
3
3
25
>;tb;54
3
3
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2,6-diethyl-N--(methoxymethyl)-acetanilide
>;tb;"Alachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb; 1
0.25
0.25
37.5
>;tb; 2
0.5
0.5
25
>;tb;49
0.5
0.5
12.5
>;tb;50
0.25
0.25
25
>;tb;53
0.25
0.25
25
>;tb;54
0.5
0.5
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6-ethyl-N--(2"-methoxy-1"-methylethyl)>;tb;acet-o-toluidide, "Metolachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
3
0.75
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6-ethyl-N--(ethoxymethyl)-acet-o-toluidide
>;tb;"Acetochlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
314/612
>;tb; 1
0.25
0.25
25
>;tb; 2
0.25
0.25
12.5
>;tb;49
0.25
0.25
12.5
>;tb;50
0.25
0.25
12.5
>;tb;53
0.25
0.25
12.5
>;tb;54
0.25
0.25
12.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2,6-dinitro-N,N--dipropyl-4-trifluoromethylaniline
>;tb;"Trifluralin"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb; 1
1
1
37.5
>;tb; 2
1
1
25
>;tb;50
1
1
12.5
>;tb;53
1
1
25
>;tb;54
1
1
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2,6-dichlorobenzonitrile, "Dichlobenil"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb; 1
0.5
0.5
12.5
>;tb; 2
0.5
0.5
12.5
>;tb;49
0.5
0.5
25
>;tb;50
0.5
0.5
25
>;tb;53
0.5
0.5
25
>;tb;54
0.5
0.5
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--2,3,3-trichloroally-diisopylthiocarbamate
>;tb;"Tri-allate"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb; 1
4
4
12.5
>;tb; 2
4
4
25
>;tb;49
4
4
12.5
>;tb;50
4
4
25
>;tb;53
4
4
25
>;tb;54
4
4
25
>;tb;______________________________________
315/612
Example 23
Test with antidote and herbicide in rice sown dry. Application of the antidote as seed dressing.
Rice seeds are mixed with the test antidote in a glass container. Seeds and test compound are well
mixed by shaking and rotating. Containers measuring 47 cm.times.29 cm.times.24 cm are then filled
with sandy loam and the dressed seeds are sown therein. The seeds are covered and a dilute solution of
the herbicide is then sprayed onto the surface of the soil. About 20 days after sowing, when the rice
plants have attained the 3-leaf stage, the surface of the soil is covered with water to a height of 4 cm.
The protective action of the antidote is evaluated in percent 30 days after application of the herbicide.
The plants treated with herbicide alone (no protective action) as well as the completely untreated
controls (100% growth) serve as references for the evaluation. The results are as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propyloxyethyl)>;tb;acetanilide, "Pretilachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in g per kg of seeds
>;tb;
in kg/ha action in %
>;tb;______________________________________
>;tb;1
2g
3
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(2"-methoxy-1"-methylethyl)>;tb;acet-o-toluidide, "Metolachlor"
>;tb;
Herbicide
>;tb;Antidote
>;tb;
Rate of application
>;tb;
rate of application
>;tb;
Protective
>;tb;compound
>;tb;
in g per kg of seeds
>;tb;
in kg/ha action in %
>;tb;______________________________________
>;tb;1
1g
0.5
62.5
>;tb;______________________________________
Example 24
Test with antidote and herbicide in dry rice (the rice is sown dry and watered by natural rainfall).
Application of antidote and herbicide as tank mixture.
Rice seeds are sown in containers measuring 47 cm.times.29 cm.times.24 cm, covered, and gently
pressed firm. A dilute solution of the test antidote together with the herbicide is then sprayed as tank
mixture onto the soil. Evaluation of the protective action of the antidote is made in percent 24 days
after sowing. The plants treated with herbicide alone (no protective action) as well as the completely
untreated controls (100% growth) serve as references for the evaluation. The results are reported in the
following table.
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(2"-propoxyethyl)>;tb;acetanilide, "Pretilachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
316/612
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
2
2
62.5
>;tb;2
2
2
50
>;tb;49
2
2
50
>;tb;50
2
2
50
>;tb;53
2
2
62.5
>;tb;54
2
2
50
>;tb;59
2
2
50
>;tb;84
2
2
62.5
>;tb;99
2
2
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(butoxymethyl)>;tb;acetanilide, "Butolachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
3
3
25
>;tb;2
3
3
25
>;tb;49
3
3
37.5
>;tb;50
3
3
37.5
>;tb;53
3
3
25
>;tb;54
3
3
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-diethyl-N--(methoxymethyl)>;tb;acetanilide, "Alachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
0.25
0.25
37.5
>;tb;2
0.5
0.5
25
>;tb;49
0.5
0.5
12.5
>;tb;50
0.5
0.5
25
>;tb;53
0.25
0.25
25
>;tb;54
0.5
0.5
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(2"-methoxy-1"-methylethyl)>;tb;acet-o-toluidide, "Metolachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
317/612
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
3
0.75
37.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(ethoxymethyl)-acet-o-toluidide
>;tb;"Acetochlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
0.25
0.25
25
>;tb;2
0.25
0.25
12.5
>;tb;49
0.25
0.25
12.5
>;tb;50
0.25
0.25
12.5
>;tb;53
0.25
0.25
12.5
>;tb;54
0.25
0.25
12.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2,6-dinitro-N,N--dipropyl-4-trifluoromethylaniline
>;tb;"Trifluralin"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
1
1
37.5
>;tb;2
1
1
25
>;tb;50
1
1
12.5
>;tb;53
1
1
37.5
>;tb;54
1
1
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2,6-dichlorobenzonitrile, "Dichlobenil"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb; 1
0.5
0.5
12.5
>;tb; 2
0.5
0.5
12.5
>;tb;49
0.5
0.5
25
>;tb;50
0.5
0.5
25
>;tb;53
0.5
0.5
25
>;tb;54
0.5
0.5
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: S--2,3-dichloroally-diisopropylthiocarbamate
318/612
>;tb;"Di-allate"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb; 1
4
4
12.5
>;tb; 2
4
4
25
>;tb;49
4
4
12.5
>;tb;50
4
4
25
>;tb;53
4
4
25
>;tb;54
4
4
25
>;tb;______________________________________
Example 25
Test with antidote and herbicide in dry rice. Application of the antidote as seed dressing.
Rice seeds of the IR-36 variety are mixed with the test antidote in a glass container. Seeds and test
compound are well mixed by shaking and rotating. Containers measuring 47 cm.times.29 cm.times.24
cm are then filled with sandy loam and the dressed seeds are sown therein. The seeds are covered and
the herbicide is then sprayed onto the surface of the soil. The protective action of the antidote is
evaluated in percent 18 days after sowing. The plants treated with herbicide alone (no protective
action) as well as the completely untreated controls (100% growth) serve as references for the
evaluation. The results are as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(2"-methoxy-1"-methylethyl)>;tb;acet-o-toluidide, "Metolachlor"
>;tb;
Rate of
>;tb;
application
>;tb;
Herbicide
>;tb;Antidote
>;tb;
in g per rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
kg of seeds
>;tb;
in kg/ha in %
>;tb;______________________________________
>;tb;1
1g
0.5
62.5
>;tb;______________________________________
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2,6-diethyl-N--(2"-propoxyethyl)>;tb;acetanilide, "Pretilachlor"
>;tb;
Rate of
>;tb;
application
>;tb;
Herbicide
>;tb;Antidote
>;tb;
in g per rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
kg of seeds
>;tb;
in kg/ha in %
>;tb;______________________________________
>;tb;1
2g
3
37.5
>;tb;______________________________________
319/612
Example 26
Tests with antidote and herbicide in soybeans. Preemergence application of antidote and herbicide as
tank mixture.
Flower pots having a diameter of 6 cm at the top are filled with sandy loam and soybean seeds of the
"Hark" variety are sown therein. The seeds are covered and a dilute solution of the test antidote
together with the herbicide is then sprayed as tank mixture onto the surface of the soil. Evaluation of
the protective action in percent is made 21 days after the application of the herbicide. The plants treated
with herbicide alone (no protective action) as well as the completely untreated controls (100% growth)
serve as references for the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio>;tb;1,2,4-triazin-S--one, "Metribuzin"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
0,5
0,5
25
>;tb;______________________________________
Example 27
Test with antidote and herbicide in sorghum. Preemergence application ofantidote and herbicide as
tank mixture.
Flower pots having a diameter of 6 cm at the top are filled with sandy loam and sorghum seeds of the
"Funk G 522" variety are sown therein. The seeds are covered and a dilute solution of the test antidote
together with the herbicide is then sprayed as tank mixture onto the surface of the soil. Evaluation of
the protective action in percent is made 14 days after the application of the herbicide. The plants treated
with herbicide alone (no protective action) as well as the completely untreated controls (100% growth)
serve as references for the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(2"-methoxy-1"-methylethyl)>;tb;acet-o-toluidide, "Metolachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;468 1.5
1.5
37.5
>;tb;______________________________________
Example 28
Test with antidote and herbicide in wheat. Preemergence application of antidote and herbicide as tank
mixture.
Wheat seeds are sown in a greenhouse in plastic pots which contain 0.5 l of garden soil. The plants are
then treated postemergence in the 2-3-leaf stage with the test antidote together with the herbicide as
tank mixture. Evaluation of the protective action of the antidote in percent is made 20 days after
320/612
application. The plants treated with herbicide alone (no protective action) as well as the completely
untreated controls (100% growth) serve as references for the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: .alpha.-[4-(3',5'-dichloropyridyloxy-2'-)phenoxy]>;tb;propionic acid propinyl ester
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;54
0.5
0.5
50
>;tb;132 0.5
0.5
25
>;tb;197 0.5
0.5
25
>;tb;461 0.5
0.5
37.5
>;tb;______________________________________
Example 29
Test with antidote and herbicide in cereals. Preemergence application of antidote and herbicide as tank
mixture.
Wheat or barley seeds are sown in a greenhouse in plastic pots having a diameter at the top of 11 cm
and containing 0.5 l of garden soil. The seed are covered and a dilute solution of the test antidote
together with the herbicide is then sprayed as tank mixture onto the surface of the soil. Evaluation of
the protective action in percent is made 24 days after the application of the herbicide. The plants treated
with herbicide alone (no protective action) as well as the completely untreated controls (100% growth)
serve as references for the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-6'-ethyl-N--(2"-methoxy-1"-methylethyl)>;tb;acet-o-toluidide, "Metolachlor"
>;tb;Wheat (Farnese variety)
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;2
1
1
25
>;tb;______________________________________
>;tb;______________________________________
>;tb;Barley
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;1
1
1
25
>;tb;______________________________________
Example 30
321/612
Test with antidote and herbicide in maize. Preemergence application of antidote and herbicide as tank
mixture.
Maize seeds of the "LG 5" variety are sown in a greenhouse in plastic pots having a diameter at the top
of 11 cm and containing 0.5 l of garden soil. The seeds are covered and a dilute solution of the test
antidote together with the herbicide is then sprayed as tank mixture onto the surface of the soil.
Evaluation of the protective action in percent is made 18 days after the application of the herbicide.
The plants treated with herbicide alone (no protective action) as well as the completely untreated
controls (100% growth) serve as references for the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-dimethyl-N--(2"-methoxy-1"-methyl>;tb;ethyl)-acetanilide
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;2
2
2
25
>;tb;______________________________________
Example 31
Test with antidote and herbicide in maize. Application of the antidote as seed dressing.
Maize seeds of the "LG 5" variety are mixed with the test antidote in a glass container. Seeds and
compound are well mixed by shaking and rotation. Plastic pots have a diameter of 11 cm at the top are
then filled with garden soil and the dressed seeds are sown therein. The seeds are covered and the
herbicide is then applied preemergence. Evaluation of the protective action of the antidote in percent is
then made 18 days after the application of the herbicide. The plants treated with herbicide alone (no
protective action) as well as the completely untreated controls (100% growth) serve as references for
the evaluation. The result is as follows:
>;tb;______________________________________
>;tb;Herbicide: 2-chloro-2',6'-dimethyl-N--(methoxyethyl)>;tb;acetanilide, "Dimetolachlor"
>;tb;
Rate of Herbicide
>;tb;Antidote
>;tb;
application
>;tb;
rate of application
>;tb;
Protective action
>;tb;compound
>;tb;
in kg/ha in kg/ha in %
>;tb;______________________________________
>;tb;2
2
0.5
25
>;tb;______________________________________Data supplied from the esp@cenet database Worldwide
322/612
25. RU2109730
- 4/27/1998
PHENYLHYDRAZINE DERIVATIVES, METHOD OF CONTROLLING PESTS
AND INSECTOACARICIDONEMATOCIDAL COMPOSITION
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=RU2109730
Inventor(s):
MARK A DIKEJSER (CA); POL T MAKDONAL D (US)
Applicant(s):
UNIROYAL CHEM CO INC (US); JUNIROJAL KEMIKAL LTD JUNIROJA (CA)
IP Class 4 Digits: A01N; C07D; C07C
IP Class:A01N47/34; C07C243/28; C07C281/02; C07C337/06; C07D307/91; A01N47/24;
A01N33/26; A01N57/30
E Class: A01N37/30; A01N37/28; A01N47/02; A01N47/24; A01N47/34; A01N57/30; C07C243/28;
C07C281/02; C07C281/06; C07C311/49; C07C337/02; C07D307/91B3F; C07F9/24C9U
Application Number:
RU19940028885 (19921117)
Priority Number: US19910796506 (19911122); US19920979095 (19921120); WO1992US09855
(19921117)
Family: RU2109730
Equivalent:
US5367093; SK282306B; CZ290371
Abstract:
Abstract of RU2109730
FIELD: agriculture. SUBSTANCE: claimed invention describes compounds having structural formula
I: >;EMI ID=0.345 HE=21 WI=54 TI=CHI; wherein X, Y, R and Z are as defined in the specification.
Compounds of the present invention are effective against mites, nematodes, rice cicadas and fleas with
long feelers. The present invention also describes methods for preparing said compounds of formula I
wherein >;EMI ID=0.346 HE=6 WI=9 TI=CHI; is single or double bond. EFFECT: improved
properties of the insectoacaricidonematocidal composition. 15 cl, 8 tblTDescription:
Description of corresponding document: US5367093
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is directed to novel phenylhydrazine derivatives which exhibit activity as insecticides,
acaricides and nematicides. This invention is also directed to insecticidal, acaricidal or nematicidal
compositions comprising such compounds as well as to methods of controlling insects, acarids and
nematodes employing such compounds or compositions.
Destruction by insects, acarids and nematodes presents a serious problem to agriculture. A wide variety
of field crops are in need of protection from nematodes, acarids, and insects including such valuable
crops as soybeans, corn, peanuts, cotton, alfalfa, rice and tobacco. In addition, vegetables, such as
tomatoes, potatoes, sugarbeet, carrots, peas, and the like as well as fruits, nuts, ornamentals and seed
bed crops such as apples, peaches, almonds, citrus fruit and grapes may also require protection from the
ravages of such pests.
323/612
Consequently, the development of new, more effective pesticides including insecticides, acaricides and
nematicides represents an ongoing scientific activity. More particularly, the development of pesticides
which are effective as both ovicides and larvicides are of interest.
2. Description of Related Art
Chemical Abstracts 108(19):163280d refers to alkyl phenylhydrazinecarboxylates said to be useful as
acaricides. United States Patent 4,725,302 refers to substituted phenylhydrazines and
phenyloxadiazolinones said to be useful as pesticides. European Patent 0 067 471 refers to 7substituted 2,3-dihydrobenzofurans said to be useful as pesticides or chemical intermediates. DerWent
abstract 88-312695/44 refers to arylhydrazides of trifluoroacetic acid said to have fungicidal,
bacteriocidal, acaricidal, and antiseptic activity. Chemical Abstracts 105(17):152686c refers to various
phenylhydrazines said to have activity against insects and mites.
SUMMARY OF THE INVENTION
The instant invention relates to a compound having the structural formula (I) or (II): ##STR2##
wherein:
X is a) phenyl; lower phenylalkoxy; phenoxy; or benzyl; or b) one substituent from group a) and one or
more substituents selected from C1 -C4 alkoxy; halogen; lower alkyl; and lower alkylthio; or c) along
with the phenyl to which it is attached, forms a multiple fused ring heterocycle such as dibenzofuranyl;
Y is H, C1 -C4 alkanoyl, C1 -C4 haloalkanoyl, dialkoxyphosphoryl, alkylaminocarbonyl,
haloalkylsulfonyl, or C1 -C4 alkoxy carbonyl; and
R is H, C1 -C6 alkyl, C1 -C6 alkoxy, C3 -C6 cycloalkoxy, haloalkyl, alkoxyalkyl, arylalkoxy, alkenyl,
alkylthio, alkoxycarbonyl, alkylamino, heteroaryl, (e.g., 2-thiophenyl or 2-furyl) arylalkyl, haloalkoxy,
aryloxy, or C3 -C6 cycloalkyl; and
Z is O or S.
Further, when X includes a substituent having a phenyl ring (i.e., is phenyl, phenylalkoxy, phenoxy or
benzyl), the phenyl ring is optionally substituted with one or more of halogen, nitro, lower alkyl, lower
alkoxy, lower haloalkyl, or dialkylamino.
The instant invention further relates to pesticidal compositions comprising:
a) an effective amount of a compound having the structure of formula (I) or (II) above as an active
ingredient; and (b) an agriculturally acceptable carrier.
The present invention is also directed to a method for controlling pests such as insects, acarids or
nematodes which comprises applying an effective amount of a compound of formula (I) or (II) or of a
composition of the present invention to a locus to be protected or rid of pests.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the present invention have the structure (I) or (II) defined above. Preferred
compounds are those in which Y is hydrogen or COCF3.
The compounds having structure (I) may be prepared by reacting a substituted phenylhydrazine:
##STR3## with an acylating agent: ##STR4## wherein Z is halo or ##STR5## and an equivalent of an
HCl acceptor such as pyridine in a solvent such as toluene. The product of this reaction may be further
acylated, or converted by oxidation with an oxidizing agent such as Pd/air to form compounds having
structure (II).
The compositions of this invention comprise (a) a compound having a structure within that of formula
(I) or (II) above, and (b) a suitable carrier. Such suitable carriers may be solid or liquid in nature.
324/612
Suitable liquid carriers may be comprised of water, alcohols, ketones, phenols, toluene and xylenes. In
such formulations, additives conventionally employed in the art may be utilized such as, for example,
one or more surface active agents and/or inert diluents, to facilitate handling an application of the
resulting pesticide composition.
The pesticidal compositions may alternatively comprise solid carriers taking the form of dusts,
granules, wettable powders, pastes, aerosols, emulsions, emulsifiable concentrates, and water-soluble
solids.
For example, the pesticidal compounds of this invention may be applied as dusts when admixed with or
absorbed onto powdered solid carriers, such as mineral silicates, e.g., mica, talc, pyrophyllite and clays,
together with a surface-active dispersing agent so that a wettable powder is obtained which then is
applicable directly to the loci to be treated. Alternatively, the powdered solid carrier containing the
compound admixed therewith may be dispersed in water to form a suspension for application in such
form.
Granular formulations of the compounds, suitable for application by broadcasting, side dressing, soil
incorporation or seed treatment, are suitably prepared using a granular or pellitized form of carrier such
as granular clays, vermiculite, charcoal or corn cobs.
Alternatively, the pesticidal compounds may be applied in liquids or sprays when utilized in a liquid
carrier, such as in a solution comprising a compatible solvent such as acetone, benzene, toluene or
kerosene, or as dispersed in a suitable non-solvent medium, for example, water.
Another method of application to loci to be treated is aerosol treatment, for which the compound may
be dissolved in an aerosol carrier which is a liquid under pressure but which is a gas at ordinary
temperature (e.g., 20 DEG C.) and atmospheric pressure. Aerosol formulations may also be prepared
by first dissolving the compound in a less volatile solvent and then admixing the resulting solution with
a highly volatile liquid aerosol carrier.
For pesticidal treatment of plants (such term including plant parts), the compounds of the invention
preferably are applied in aqueous emulsions containing a surface-active dispersing agent which may be
non-ionic, cationic or anionic. Suitable surface-active agents include those known in the art, such as
those disclosed in U.S. Pat. No. 2,547,724 (columns 3 and 4). The compounds of the invention may be
mixed with such surface-active dispersing agents, with or without an organic solvent, as concentrates
for the subsequent addition of water to yield aqueous suspensions of the compounds at desired
concentration levels.
In addition, the compounds may be employed with carriers which themselves are pesticidally active,
such as insecticides, acaricides, fungicides or bactericides.
It will be understood that the amount of the pesticidally active compound in a given formulation will
depend upon the specific pest to be combatted, as well as upon the specific chemical composition and
formulation of the compound being employed, the method of applying the compound/formulation and
the locus of treatment so that the pesticidally effective amount of the compound may vary widely.
Generally, however, concentrations of the compound as the active ingredient in pesticidally effective
formulations may range from about 0.1 to about 95 percent by weight. Spray dilutions may be as low
as a few parts per million, while at the opposite extreme, full strength concentrates of the compound
may be usefully applied by ultra low volume techniques. Concentration per unit area, where plants
constitute the loci of treatment, may range between about 0.01 and about 50 pounds per acre, with
concentrations of between about 0.1 and about 10 pounds per acre preferably being employed for crops
such as corn, tobacco, rice and the like.
To combat pests, sprays of the compounds may be applied to the pests directly and/or to plants upon
which they feed or nest. The pesticidally active formulations may also be applied to the soil or other
medium in which the pests are present.
Harmful insects, nematodes and acarids attack a wide variety of plants, including both ornamental and
agricultural plants and inflict damage by consuming roots and/or foliage, withdrawing vital juices from
325/612
the plants, secreting toxins and often by transmitting diseases. The compounds of the present invention
may be advantageously utilized to minimize or prevent such damage. The specific methods of
application, as well as the selection and concentration of these compounds will, of course, vary
depending upon such circumstances as geographic area, climate, topography, plant tolerance, etc. For
specific circumstances, one skilled in the art may readily determine the proper compound,
concentration and method of application by routine experimentation.
The compounds of the invention are particularly useful as insecticides, nematicides and acaricides, for
foliar and/or soil application.
EXAMPLES
The following Examples are intended to further illustrate the invention, and are not intended to limit
the scope of the invention in any manner whatsoever.
EXAMPLE 1
Preparation of (4-methoxy-[1,1'-biphenyl]-3-yl)hydrazine hydrochloride (chemical intermediate)
To 25 g of 5-phenyl-o-anisidine were added 250 ml of water and 450 ml of concentrated hydrochloric
acid and the stirred solution was cooled to 0 DEG C. A solution of 8.6 g of sodium nitrite in 20 ml of
water was then added dropwise, maintaining a temperature of 0 DEG C. After this addition the mixture
was stirred, at 0 DEG C., for 1 hour. A solution of 113 g of stannous chloride in 200 ml of concentrated
HCl, cooled to -20 DEG C., was added to the reaction mixture and again the mixture was stirred for
one hour. The mixture was then suction filtered and the resulting solid was allowed to dry overnight.
The solid was dissolved in hot water, gravity filtered, and the filtrate cooled on ice. The crystallized
solid was then suction filtered and the product was allowed to dry overnight. The product obtained was
26 g of (4-methoxy-[1,1'-biphenyl]-3-yl)hydrazine hydrochloride.
EXAMPLE 2
Preparation of 2-(4-methoxy-[1,2'-biphenyl]-3-yl)-hydrazide of propanoic acid (Compound 18)
To 5 g of the product of Example 1 was added 100 ml of water and 40 ml of 10% sodium hydroxide
solution and the mixture was allowed to stir for 1 hour at room temperature. The mixture was then
extracted with ether and the ether extract was dried over sodium sulfate for one half hour. The ether
extract was then filtered and evaporated under reduced pressure to yield 4.6 g of the intermediate, (4methoxy-[1,1'-biphenyl]-3-yl)hydrazine.
To 4.6 g of the above intermediate, 150 ml of toluene and 1.58 g of pyridine were added and the
solution was stirred and cooled to 0 DEG C. Then, 1.84 g of propionyl chloride was added dropwise.
After addition of the propionyl chloride, the solution was stirred for 1 hour at 0 DEG C. The solution
was then washed twice, each time with 100 ml of water. The water fraction was saved and extracted
with toluene. The toluene fractions from the extraction were combined and evaporated under reduced
pressure. The resulting solid was washed with hexane and filtered. The product obtained was 3.4 g of
2-(4-methoxy-[1,1'-biphenyl]-3-yl)hydrazide of propanoic acid.
EXAMPLE 3
Preparation of 2-(4-methoxy-[1,1'-biphenyl]-3-yl)-2-(trifluoroacetyl) hydrazide of propanoic acid
(Compound 73)
To 2.25 g of the product of Example 2 was added 150 ml of methylene chloride. The solution was
stirred and cooled to 0 DEG C. Then 1.75 g of trifluoroacetic anhydride was added dropwise, the flask
stoppered, and the reaction stirred overnight. The solvent was then evaporated under reduced pressure
to yield a solid which was washed with hexane and filtered. The final product obtained was 2.7 g of 2(4-methoxy-[1.1'-biphenyl]-3-yl)-2-(trifluoroacetyl)-hydrazide of propanoic acid, with a melting point
of 126 DEG C.
EXAMPLE 4
Preparation of (4-bromo-[1,1'-biphenyl]-3-yl)hydrazine hydrochloride (chemical intermediate)
326/612
To 4 g of 4-bromo-[1,1'-biphenyl]-3-amine were added 25 ml of water and 50 ml of concentrated HCl
with stirring. The solution was cooled to 0 DEG C. A solution of 1.1 g of sodium nitrite in 6 ml of
water was then added dropwise while maintaining a temperature of 0 DEG C. After this addition, the
mixture was stirred at 0 DEG C. for one hour. A solution of 20 g of stannous chloride in 20 ml of
concentrated HCl cooled to -20 DEG C. was added to the reaction mixture and again the mixture was
stirred for one hour.
The precipitate was then suction filtered and the resulting solid was allowed to dry overnight. The
product, (4-bromo-[1,1'-biphenyl]hydrazine hydrochloride, was used in subsequent reactions without
further purification.
EXAMPLE 5
Preparation of isopropyl 2-(4-bromo-[1,1'-biphenyl]-3-yl) hydrazine carboxylate (Compound 139)
To the product of Example 4 was added 100 ml of a 10% aqueous sodium hydroxide solution and the
mixture was stirred for 30 minutes at 10 DEG C. The mixture was then extracted with ether, dried over
sodium sulfate for 2 hours, and evaporated, leaving 3 g of (4-bromo-[1,1'-biphenyl]-3-yl)hydrazine. To
3 g of the hydrazine were added 100 ml of toluene and 1.5 g of pyridine and the resulting mixture was
cooled an ice bath. Twelve ml of a 1 M solution of isopropyl chloroformate in toluene were added
dropwise. After the addition of isopropyl chloroformate, the solution was allowed to stir overnight at
room temperature. The solution was then washed twice, each time with 100 ml of water, dried over
sodium sulfate for 2 hours, and evaporated under reduced pressure.
The resulting solid was washed with hexane and recrystallized from toluene. The product obtained was
3 g of isopropyl 2-(4-bromo-[1,1'-biphenyl]-3-yl) hydrazinecarboxylate with melting point 107 DEG108 DEG C.
EXAMPLE 6
Preparation of isopropyl (4-bromo-[1 1'-biphenyl]-3-yl) diazenecarboxylate (Compound 161)
To 17 g of the product of Example 4 was added 100 ml of toluene and 0.4 g of palladium on charcoal.
The mixture was stirred overnight at room temperature, then filtered out and the toluene evaporated
under reduced pressure. The product obtained was 1.5 g of isopropyl (4-bromo-[1,1'-biphenyl]-3yl)diazene carboxylate as a red oil.
EXAMPLE 7
Preparation of 2-methoxy-3-dibenzofuranyl hydrazine (chemical intermediate)
To 10 g of 3-amino-2-methoxydibenzofuran were added 100 ml of water and 50 ml of concentrated
HCl with stirring. The solution was cooled to 0 DEG C. A solution of 3.5 g of sodium nitrite in 15 ml
of water was then added dropwise, maintaining a temperature of 0 DEG C. After this addition, the
mixture was stirred at 0 DEG C. for one hour. A solution of 40 g of stannous chloride in 50 ml of
concentrated HCl cooled to -20 DEG C. was added to the reaction mixture and the mixture was stirred
for one hour.
The precipitate was then suction filtered and the resulting solid added to a solution of 70 g sodium
hydroxide in 500 ml of water cooled in an ice bath. The mixture was then extracted with ether, dried
over sodium sulfate for 2 hours, and evaporated to a solid. The solid was washed with hexane, leaving
7 g of 2-methoxy-3-dibenzofuranyl hydrazine of mp 113 DEG-115 DEG C.
EXAMPLE 8
Preparation of isopropyl 2-(2-methoxy-3-dibenzofuranyl) hydrazinecarboxylate (Compound 141)
To 2.3 g of the product of Example 7 were added 100 ml of toluene and 1 g of pyridine and the
resulting mixture was cooled in an ice bath. Ten ml of a 1 M solution of isopropyl chloroformate in
toluene was then added dropwise. After this addition, the solution was allowed to stir overnight at room
temperature.
327/612
The solution was then washed twice, each time with 100 ml of water, dried over sodium sulfate for two
hours, and then evaporated under reduced pressure. The resulting solid was washed with hexane and
recrystallized from toluene. The product obtained was 2 g of isopropyl 2-(2-methoxy-3dibenzofuranyl) hydrazine carboxylate with mp of 178 DEG C.
EXAMPLE 9.
Preparation of isopropyl (2-methoxy-3-dibenzofuranyl) diazenecarboxylate (Compound 157)
To 1.4 g of the product of Example 7 were added 100 ml of toluene and 0.3 g of palladium on charcoal.
The mixture was stirred overnight at room temperature, filtered, and the toluene evaporated under
reduced pressure. The product obtained was 1.2 g of isopropyl (2-methoxy-3-dibenzofuranyl)
diazenecarboxylate as a red oil.
The compounds summarized in Tables 1-4B and numbered from 1-161 were prepared using essentially
the same processes as shown in the foregoing examples. Where starting compounds were not
commercially available, they were synthesized by methods well known in the art. Each of the
compounds so formed is characterized by their NMR characteristics.
>;tb;
TABLE 1
>;tb;______________________________________
>;tb; ##STR6##
>;tb;
NMR DATA
>;tb;COMFOR TABLE 1
>;tb;POUND X
R
Z (CDCL,3)
>;tb;______________________________________
>;tb; 1 2-C6H5 CH3
O s(3)1.9;
>;tb;
m(10)6.8-7.5;
>;tb;
bs(1)9.9
>;tb; 2 2-C6H5 OCH3
O s(3)3.6; s(1)6.5;
>;tb;
m(9)6.8-7.5;
>;tb;
bs(1)9.1
>;tb; 3 2-C6H5 OCH2CH3
O t(3)1.2; q(2)4.0;
>;tb;
s(1)6.5;
>;tb;
m(9)6.7-7.5;
>;tb;
bs(1)9.0
>;tb; 4 2-C6H5 C(CH3)3
O s(9)1.2;
>;tb;
m(10)6.8-7.5;
>;tb;
bs(1)9.7
>;tb; 5 2-C6H5 C5H9-c
O m(8)1.4-1.8;
>;tb;
m(1)2.4-2.8;
>;tb;
d(1)6.5;
>;tb;
m(9)6.7-7.5;
>;tb;
d(1)9.8
>;tb; 6 2-C6H5 OCH2C6H5 O s(2)5.1; s(1)6.5;
>;tb;
m(14)6.8-7.5;
>;tb;
s(1)9.8
>;tb; 7 2-C6H5 OCH(CH3)2 O d(6)1.2; m(1)4.9;
>;tb;
bs(1)5.9;
>;tb;
bs(1)6.3;
>;tb;
m(9)6.8-7.5
>;tb; 8 3-C6H5 CH3
O s(3)2.0;
>;tb;
m(9)6.8-7.5;
>;tb;
bs(1)8.7;
>;tb;
bs(1)9.7
>;tb; 9 2-CH3O, CH2Cl
O s(3)3.8; s(2)3.9;
>;tb;
5-C6H5
m(9)6.9-7.6;
>;tb;
bs(1)9.8
>;tb;10 2-CH3O, OCH3
O s(3)3.7; s(3)3.8;
>;tb;
5-C6H5
bs(1)6.2;
>;tb;
m(9)6.7-7.5
328/612
>;tb;11
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;12
>;tb;
>;tb;
>;tb;
>;tb;13
>;tb;
>;tb;
>;tb;
>;tb;14
>;tb;
>;tb;
>;tb;15
>;tb;
>;tb;
>;tb;16
>;tb;
>;tb;
>;tb;
>;tb;17
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;18
>;tb;
>;tb;
>;tb;
>;tb;19
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;20
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;21
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;22
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;23
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;24
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
OCH2CH3
O t(3)1.2; s(3)3.8;
q(2)4.2;
bs(1)6.3;
bs(1)6.4;
m(8)6.7-7.5
CH2CH2CH3 O t(3)0.9; m(2)1.5;
t(2)2.2; s(3)3.8;
m(9)6.8-7.5;
d(1)9.8
CH(CH3)2 O d(6)0.9; m(1)2.9;
s(3)3.8;
m(9)6.8-7.5
bs(1)9.8
C(CH3)3
O s(9)1.1; s(3)3.8;
m(9)6.8-7.5;
bs(1)9.8
OCH2C6H5 O s(3)3.9; s(2)5.0;
m(2)6.4;
m(8)6.9-7.6
CH2OCH3
O s(3)3.3; s(3)3.8;
s(2)4.0; bs(1)6.5;
m(8)6.7-7.5;
bs(1)8.3
C(CH3) CH2 O s(3)2.0; s(3)3.8;
s(1)5.2; s(1)5.7;
bs(1)6.5;
m(8)6.7-7.5;
bs(1)8.3
CH2CH3
O t(3)1.2; q(2)2.3;
s(3)3.8; bs(1)6.5;
m(8)6.8-7.5;
bs(1)8.3
O(CH2)3 CH3
O t(3)0.9; m(4)1.5;
s(3)3.8; t(2)4.1;
bs(1)6.5;
m(8)6.8-7.5
OCH2CH2CH3 O t(3)0.9; m(2)1.6;
s(3)3.8; t(2)4.1;
bs(1)6.3;
bs(1)6.5;
m(8)6.8-7.5
OCH2CH(CH3)2
O d(6)0.9; m(1)1.9;
s(3)3.8; d(2)3.9;
bs(1)6.3;
bs(1)6.6;
m(8)6.8-7.5
NHC3H7
S t(3)1.0; m(2)1.7;
q(2)3.6; s(3)3.9;
s(1)6.5;
m(9)6.8-7.5;
s(1)8.5
CO2CH2CH3 O t(3)1.2; s(3)3.8;
q(2)4.2;
m(8)6.8-7.5;
bs(1)8.3;
bs(1)9.8
SCH2CH3
O t(3)1.2; q(2)2.7;
329/612
>;tb;
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>;tb;25
>;tb;
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>;tb;26
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>;tb;
>;tb;27
>;tb;
>;tb;
>;tb;
>;tb;28
>;tb;
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>;tb;29
>;tb;
>;tb;
>;tb;
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>;tb;
>;tb;31
>;tb;
>;tb;
>;tb;32
>;tb;33
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;34
>;tb;
>;tb;
>;tb;35
>;tb;
>;tb;
>;tb;36
>;tb;
>;tb;
>;tb;37
>;tb;
>;tb;
>;tb;
>;tb;38
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;39
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-CH3O,
5-C6H5
2-C6H5
2-C6H5
2-CH3 O,
H
5-C6 H5
s(3)3.8;
m(9)6.8-7.5;
bs(1)9.5
OCH2CHCH2 O s(3)3.8; d(2)4.6;
m(3)5.1-6.0;
bs(1)6.3;
bs(1)6.5;
m(8)6.8-7.5
OCH(CH3)2 O d(6)1.2; s(3)3.8;
m(1)5.0;
bs(1)6.3;
bs(1)6.5;
m(8)6.8-7.5
CH2C(CH3)3 O s(9)1.0; s(2)2.1;
s(3)3.8;
bs(1)6.5;
m(8)6.8-7.5
CF2CF3
O s(3)3.8;
m(8)6.8-7.5;
bs(2)8.2
CF2Cl
O s(3)3.8;
bs(1)6.0;
m(8)6.8-7.5;
bs(1)8.2
2-C4H3S
O s(3)3.8;
m(13)6.7-7.9
H
O m(10)6.7-7.5;
bs(1)8.1;
bs(1)9.9;
CF3 O m(11)6.7-7.5
O s(3)3.9;
m(9)6.9-7.7;
bs(1)8.1;
bs(1)9.8
2-CH3 O,
CH3 O s(3)2.0; s(3)3.8;
5-C6 H5
m(10)6.8- 7.7
2-CH3 O,
CF3 O s(3)3.8;
5-C6 H5
m(10)6.8-7.7
2-CH3 O,
CHClCH3 O d(3)1.5; s(3)3.9;
5-C6 H5
q(1)
2-CH3 O,
CH2 C6 H5
O s(2)3.5; s(3)3.9;
5-C6 H5
m(15)5.8-7.4
2-CH3 O,
cyclohexyl O m(11)1.1-1.8;
5-C6 H5
s(3)3.8;
m(9)6.8-7.5;
bs(1)9.8
2-CH3 O,
OCH2 CH2 OCH3
O s(3)3.3; t(2)3.5;
5-C6 H5
s(3)3.8; t(2)4.2;
bs(1)6.3;
m(9)6.8-7.5
330/612
>;tb;40
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;41
>;tb;
>;tb;
>;tb;
>;tb;42
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;43
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;44
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;45
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;46
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;47
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;48
>;tb;
>;tb;
>;tb;49
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;50
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;51
>;tb;
>;tb;
>;tb;
2-CH3 O,
OCHClCH3
O d(3)1.8; s(3)3.8;
5-C6 H5
m(1)6.5;
m(10)6.8-7.6
2-CH3 O,
OC6 H5
O s(3)3.8;
5-C6 H5
m(15)6.5-7.8
2-C6 H5
OC3 H7
O m(5)0.8-1.7;
m(2)4.1;
bs(1)5.9
m(10)6.7-7.5
2-C6 H5
OCH4 H9
O m(7)0.8-1.7;
m(2)4.1;
bs(1)5.9
m(10)6.7-7.6
2-CH3 O,
OCHCH2 O s(3)3.8;
5-C6 H5
m(2)4.5-5.0
bs(1)6.2;
m(10)6.7-7.6
2-CH3 O,
OC(CH3)2 CCl3
O s(6)1.9; s(3)3.9;
5-C6 H5
bs(1)6.2;
m(9)6.8-7.6
2-CH3 O,
O-cyclohexylO m(8)1.0-2.2;
5-C6 H5
3-Cl
s(3)3.9;
m(10)6.5-7.5
2-CH3 O,
OCH2CH2Cl O m(2)3.6; s(3)3.8;
5-C6 H5
m(2)4.3;
bs(1)6.2
m(9)6.7-7.6
2-CH3 O,
CCl3 O s(3)3.9;
5-C6 H5
m(10)6.8-7.8
3-C6 H5
OCH2 CHCH2
O d(2)4.5;
m(3)5.0-6.0;
m(11)6.7-7.6
3-C6 H5
OCH(CH3)2
O d(6)1.2; m(1)4.9;
bs(1)6.0;
m(10)6.7-7.5
3-C6 H5
OC2 H5
O t(3)1.2; q(2)4.1;
bs(1)5.9;
331/612
>;tb;
m(10)6.7-7.6
>;tb;52 3-C6 H5
>;tb;
OC5 H11
>;tb;
O m(9)1.2-1.6;
>;tb;
m(2)4.0-4.3;
>;tb;
m(1)4.8-5.2;
>;tb;
bs(1)6.4;
>;tb;
m(9)6.8-7.6
>;tb;53 2-C6 H5
>;tb;
OC5 H11
>;tb;
O m(9)0.8-1.7;
>;tb;
m(2)3.9-4.2;
>;tb;
bs(1)5.9
>;tb;
m(10)6.7-7.5
>;tb;54 2-CH3 O,
>;tb;
OC5 H11
>;tb;
O m(9)0.8-1.7;
>;tb;
5-C6 H5
s(3)3.8; t(2)4.1;
>;tb;
bs(1)6.3;
>;tb;
m(9)6.7-7.5
>;tb;55 2-CH3 O,
>;tb;
OC6 H13
>;tb;
O m(11)0.8-1.7;
>;tb;
5-C6 H5
s(3)3.9; t(2)4.1;
>;tb;
bs(1)6.3;
>;tb;
m(9)6.7-7.5
>;tb;136 3-OCH2 C6 H5
>;tb;
C2 H5
>;tb;
O t(3)1.2; q(2)4.1;
>;tb;
s(2)5.0; bs(2)6.3;
>;tb;
m(9)6.9-7.4
>;tb;137 3-OCH2 C6 H5
>;tb;
CH(CH3)2
>;tb;
O d(6)1.3; m(1)5.0;
>;tb;
s(2)5.1; bs(2)6.5;
>;tb;
m(9)6.9-7.5
>;tb;138 3-OC6 H5
>;tb;
CH(CH3)2
>;tb;
O s(9)1.4; bs(2)6.5;
>;tb;
m(9)6.9-7.5
>;tb;139 2-Br,
CH(CH3)2
>;tb;
O d(6)1.3; m(1)5.0;
>;tb;
5-C6 H5
bs(1)6.3;
>;tb;
m(8)6.9-7.5
>;tb;140 3-OC6 H5
>;tb;
CH(CH3)2
>;tb;
O d(6)1.3; m(1)5.0;
>;tb;
bs(2)6.6;
>;tb;
m(9)6.9-7.5
>;tb;143 3-OCH2 C6 H5
>;tb;
CH3 O s(3)3.8; s(2)5.0;
>;tb;
bs(2)6.5;
>;tb;
m(9)7.0-7.5
>;tb;144 3-OCH2 C6 H5
>;tb;
CH2 CHCH2
>;tb;
O d(2)4.5;
>;tb;
m(3)5.1-6.0;
>;tb;
bs(2)6.5;
>;tb;
m(9)6.9-7.5
332/612
>;tb;145 2-CH2 C6 H5
>;tb;
C3 H7
>;tb;
O t(3)0.8; m(2)1.5;
>;tb;
s(2)3.8; m(2)3.9;
>;tb;
bs(2)6.4;
>;tb;
m(9)6.9-7.3
>;tb;146 2-CH2 C6 H5
>;tb;
CH2 CHCH2
>;tb;
O s(2)3.9; d(2)4.5;
>;tb;
m(3)5.0-5.8;
>;tb;
bs(2)6.6;
>;tb;
m(9)6.8-7.3
>;tb;147 3-OCH2 C6 H5
>;tb;
C(CH3)3
>;tb;
O s(9)1.4; s(2)5.0;
>;tb;
bs(2)6.5;
>;tb;
m(9)6.9- 7.4
>;tb;148 2-CH2 C6 H5
>;tb;
C(CH3)3
>;tb;
O s(9)1.4; s(2)3.9;
>;tb;
bs(2)6.2;
>;tb;
m(9)6.9-7.3
>;tb;149 3-OC6 H5
>;tb;
CH(CH3)C2 H5
>;tb;
O t(3)0.8; d(3)1.2;
>;tb;
m(2)1.5;
>;tb;
m(1)4.8;
>;tb;
bs(2)6.5;
>;tb;
m(9)6.9-7.4
>;tb;150 2-SCH3,
>;tb;
CH(CH3)2
>;tb;
O d(6)1.2; s(3)2.4;
>;tb;
5-C6 H5
m(1)4.9;
>;tb;
bs(2)6.6;
>;tb;
m(8)7.0-7.5
>;tb;154 2-CH3,
>;tb;
CH(CH3)2
>;tb;
O d(6)1.2; s(3)2.2;
>;tb;
5-C6 H5
m(1)4.9;
>;tb;
bs(1)5.8;
>;tb;
bs(1)6.6;
>;tb;
m(8)7.0-7.6
>;tb;155 2-OCH3,
>;tb;
CH(CH3)2
>;tb;
O d(6)1.3; s(3)3.8;
>;tb;
5-OC6 H5
m(1)4.9;
>;tb;
m(10)6.5-7.4
>;tb;______________________________________
>;tb; NOTES FOR TABLES 1-4B
>;tb; (1) S = Singlet, d = doublet, t = triplet q = quartet, m = multiplet bs >;tb; broad singlet
>;tb; (2) the number in parenthesis represents the number of protons
>;tb; (3) CD CL3 is deuterated chloroform
>;tb;
TABLE 2
>;tb;______________________________________
>;tb; ##STR7##
>;tb;COMNMR DATA FOR
>;tb;POUND X
R
TABLE 2 (CDCL,3)
>;tb;______________________________________
333/612
>;tb;56
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>;tb;64
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>;tb;65
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>;tb;
>;tb;67
>;tb;
>;tb;68
>;tb;
>;tb;69
>;tb;
>;tb;
>;tb;70
>;tb;
>;tb;
>;tb;71
>;tb;
>;tb;72
>;tb;
>;tb;73
>;tb;
>;tb;74
>;tb;
>;tb;75
>;tb;
>;tb;
>;tb;76
>;tb;
>;tb;77
>;tb;
>;tb;79
>;tb;
>;tb;78
>;tb;
>;tb;
>;tb;80
>;tb;
>;tb;
>;tb;81
>;tb;
>;tb;82
>;tb;
>;tb;
>;tb;83
2-C6H5 H
bs(1)5.8; m(9)6.8-7.5;
bs(1)8.1
2-C6H5 CH3
s(3)2.5; bs(1)6.0;
m(9)6.8-7.5
2-C6H5 OCH3
s(3)3.7; bs(1)5.7;
m(9)7.3-7.6
2-C6H5 OCH2CH3
t(3)1.2; q(2)4.2;
m(9)7.3-7.7; bs(1)9.7
2-C6H5 C(CH3)3
s(9)1.2; m(10)6.8-7.6
2-C6H5 C5H9C
m(8)1.7; m(10)6.8-7.6
2-C6H5 OCH2O6H5
s(2)5.2; bs(1)6.9;
m(9)7.3-7.6
3-C6H5 CH3
s(3)2.0; m(9)7.3-7.9;
bs(1)8.5
2-CH3O, H
s(3)3.9; b(1)5.5;
5-C6H5
m(8)7.0-7.7; bs(1)8.3
2-CH3O, CH3
s(3)2.0; s(3)3.8;
5-C6H5
bs(1)6.1; m(8)6.9-7.7
2-CH3O, OCH3
s(3)3.7; s(3)3.9;
5-C6H5
bs(1)4.2; m(8)7.3-7.8
2-CH3O, OCH2CH3
t(3)1.1; s(3)3.8,
5-C6H5
q(2)4.1; m(9)7.2-7.8
2-CH3O, N(CH3)2
s(6)3.0; s(3)3.9;
5-C6H5
m(9)7.0- 7.9
2-CH3O, CH2CH2CH3 t(3)1.0; m(2)1.7;
5-C6H5
t(2)3.0; s(3)3.9;
m(8)7.0-7.7; bs(1)8.2
2-CH3O, CH(CH3)2
d(6)1.0; m(1)2.5;
5-C6H5
s(3)3.9; bs(1)5.4;
m(8)7.0-7.9
2-CH3O, C(CH3)3
s(9)1.2; s(3)3.9;
5-C6H5
m(8)7.0-7.9; bs(1)8.3
2-CH3O, OCH2C6H5
s(3)3.8; s(2)5.1;
5-C6H5
m(8)7.1-7.8; bs(1)9.5
2-CH3O, CH2CH3
t(3)1.1; q(2); s(3)3.8;
5-C6H5
m(8)7.0-7.8; bs(1)8.1
2-CH3O, OCH2CH2CH2CH3 m(7)0.8-1.7; s(3)3.9;
5-C6H5
t(2)4.1; m(9)7.0-7.8
2-CH3O, C(CH3)CH2 s(3)2.0; s(3)3.9;
5-C6H5
m(2)5.4-5.7;
m(8)7.0-7.8; bs(1)8.3
2-CH3O, CF3
s(3)3.9; m(9)7.1-7.8
5-C6H5
2-CH3O, N(CH2CH3)2 t(6)1.2; m(4)3.3;
5-C6H5
s(3)3.8; m(9)7.0-8.0
2-CH3O, SCH2CH3
t(3)1.2; q(2)2.8;
5-C6H5
s(3)3.9; m(9)7.2-7.8
2-CH3O, CO2CH2CH3 t(3)1.3; s(3)3.8;
5-C6H5
q(2)4.2; m(8)7.0-7.9;
bs(1)9.5
2-CH3O, OCH2CHCH2 s(3)3.9; d(2)4.6;
5-C6H5
m(3)5.1-5.8;
m(9)7.0-7.7
2-CH3O, OCH(CH3)2 d(6)1.2; s(3)3.8;
5-C6H5
m(1)4.9; m(9)7.0-7.7
2-CH3O, CH2C(CH3)3 s(9)1.0; s(2)2.2;
5-C6H5
s(3)3.9; m(8)7.0-7.8;
bs(1)8.6
2-CH3O, CF2 Cl s(3)3.9; m(9)7.0-8.0
334/612
>;tb;
>;tb;84
>;tb;
>;tb;85
>;tb;
>;tb;86
>;tb;
>;tb;
>;tb;87
>;tb;
>;tb;
>;tb;88
>;tb;
>;tb;
>;tb;
>;tb;89
>;tb;
>;tb;
>;tb;90
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;91
>;tb;
>;tb;
>;tb;
>;tb;92
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;93
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;94
>;tb;
>;tb;
>;tb;
>;tb;95
>;tb;
>;tb;
>;tb;
>;tb;96
>;tb;
>;tb;
>;tb;97
>;tb;
>;tb;
>;tb;
>;tb;98
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;99
>;tb;
5-C6H5
2-CH3O, 2-C4H3S
s(3)3.9; m(12)7.0-8.0
5-C6H5
2-CH3O, 2-C4H3O
s(3)3.9; bs(1)6.5;
5-C6H5
m(11)7.0-8.0
2-CH3O, OCH2 CH3
m(6)1.3; m(4)4.2;
5-C6H5
m(9)7.0-7.8
2-CH3 O,
CH2 Cl s(3)3.9; s(2)4.0;
5-C6 H5
m(9)6.9-7.7
2-CH3 O,
CH2 C6 H5
s(2)3.7; s(3)3.8;
5-C6 H5
m(14)6.8-7.9
2-CH3 O,
cyclohexyl m(11)1.1-1.9; s(3)3.9;
5-C6 H5
m(9)6.8-7.9
2-CH3 O,
OC3 H7
t(3)1.9; m(2)1.6;
5-C6 H5
s(3)3.9; t(2)4.1;
m(9)6.9-7.8
2-CH3 O,
CH2 OCH3
s(3)3.4; s(3)3.9;
5-C6 H5
s(2)4.0; m(9)6.9-7.9
2-CH3 O,
OCH2 CH(CH3)2
d(6)0.9; m(1)1.8;
5-C6 H5
s(3)3.9; d(2)4.0;
m(9)6.9-7.8
2-C6 H5
OCH2 CH(CH3)
d(6)0.9; m(1)1.8;
d(2)3.9; bs(1)6.1;
m(9)7.2-7.7
2-CH3 O,
CH3
t(3)1.5; s(3)2.0;
5-C6 H5
s(3)4.1; m(8)6.9-7.8;
bs(1)8.3
2-CH3 O,
OCH(CH3)2
d(6)1.3; m(1)5.0;
5-C6 H 5 m(9)7.3-7.8; bs(1)10.7
2-CH3 O,
OCH2CH2Cl t(2)3.7; s(3)3.9;
5-C6 H5
t(2)4.3; m(9)6.9-7.8
2-CH3 O,
OC6 H5
s(3)3.9; m(14)6.8-7.9
5-C6 H5
2-CH3 O,
OC4 H9
m(7)0.8-1.7; m(2)4.1;
5-C6 H5
bs(1)6.2
m(9)7.2-7.6
2-C6 H5
OC3 H7
335/612
>;tb;
m(5)0.8-1.6; m(2)4.0;
>;tb;
bs(1)6.2; m(9)7.0-7.7
>;tb;100 2-CH3 O,
>;tb;
OCHCH2 s(3)3.9; m(2)4.5-5.0;
>;tb;
5-C6 H5
s(1)6.2; m(10)6.8-7.8
>;tb;101 2-CH3 O,
>;tb;
OC5 H11
>;tb;
m(9)0.8-1.6; s(3)3.8;
>;tb;
5-C6 H5
m(2)4.1-6.2;
>;tb;
m(9)6.8-7.7
>;tb;102 2-CH3 O,
>;tb;
OC6H13 m(11)0.8-1.6; s(3)3.8;
>;tb;
5-C6 H5
m(2)4.1; m(9)6.8-7.7
>;tb;______________________________________
>;tb; NOTES FOR TABLES 1-4B
>;tb; (1) S = Singlet, d = doublet, t = triplet q = quartet, m = multiplet bs >;tb; broad singlet
>;tb; (2) the number in parenthesis represents the number of protons
>;tb; (3) CD CL3 is deuterated chloroform
>;tb;
TABLE 3
>;tb;______________________________________
>;tb; ##STR8##
>;tb;COMNMR DATA FOR
>;tb;POUND Y
R
TABLE 3 (CDCL,3)
>;tb;______________________________________
>;tb;103 COCH3
CF3
s(3)2.0; s(3)3.9;
>;tb;
m(9)7.2-7.8
>;tb;104 COCH2Cl CH3
s(3)2.3; s(3)3.9;
>;tb;
s(2)4.5; m(9)7.2-7.8
>;tb;105 COCF2CF3 CH3
s(3)2.5; s(3)3.9;
>;tb;
m(9)7.0-7.6
>;tb;106 COCF2CF3 OCH3
s(3)3,4; s(3)3.9;
>;tb;
s(2)4.0; m(8)7.0-8.0;
>;tb;
bs(1)8.8
>;tb;107 COCH2CH3 CF3
t(3)1.0; m(2)2.2;
>;tb;
s(3)3.9; m(8)7.0-7.9;
>;tb;
bs(1)9.0
>;tb;108 CO2CH2CH3 CF3
t(3)1.2; s(3)3.9;
>;tb;
q(2)4.2; m(9)7.0-7.8
>;tb;109 CONHCH3 OCH2CH3 t(3)1.2; d(3)2.9;
>;tb;
s(3)3.9; m(10)7.0-7.8
>;tb;110 COCH3 CH3 s(3)2.0; s(3)3.4;
>;tb;
s(3)3.9; m(8)6.9-7.7;
>;tb;
bs(1)9.8
>;tb;111 COCF2 Cl
>;tb;
CH3 s(3)2.0; s(3)3.9;
>;tb;
m(9)6.7-7.8
>;tb;112 COCH3 CF2 CF3
>;tb;
s(3)2.0; s(3)3.9;
>;tb;
m(8)6.9-7.8; bs(1)8.9
>;tb;113 COCH3 CF2 Cl
>;tb;
s(3)2.0; s(3)3.9;
>;tb;
m(8)6.9-7.8; bs(1)8.7
>;tb;114 COCF2 CF3
>;tb;
CF3 s(3)3.9; m(9)6.9-7.9
>;tb;115 COCF2 Cl
>;tb;
CF3 s(3)3.9; m(9)6.9-7.8
>;tb;116 PO(OC2 H5)2
>;tb;
CF3 t(6)1.3; s(3)3.8;
336/612
>;tb;
>;tb;117
>;tb;
>;tb;
>;tb;118
>;tb;
>;tb;
>;tb;
>;tb;119
>;tb;
>;tb;
>;tb;
>;tb;120
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;121
>;tb;122
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;123
>;tb;
>;tb;
>;tb;
>;tb;124
>;tb;
>;tb;
>;tb;125
>;tb;
>;tb;126
>;tb;
>;tb;
>;tb;127
>;tb;
>;tb;
>;tb;
>;tb;128
>;tb;
>;tb;
>;tb;
>;tb;129
>;tb;
>;tb;130
>;tb;
>;tb;
>;tb;
>;tb;131
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;132
>;tb;
>;tb;
>;tb;
>;tb;133
q(4)4.2; m(9)6.8-7.5
COCH2 Cl
CF3 s(3)3.9; s(2)4.1;
m(9)6.8-7.8
COCF2 CF3
OCH(CH3)2
d(6)1.2; s(3)3.9;
m(1)4.9; m(9)6.9-7.8
COCF2 Cl
OCH(CH3)2
d(6)1.2; s(3)3.8;
m(1)4.9; m(9)6.9-7.8
CONHCH3
OCH(CH3)2
d(6)1.2; d(3)2.8;
s(3)3.8; m(1)4.9;
m(1)5.3; m(9)6.9-7.8
COCCl3 CF3 s(3)3.9; m(9)6.8-7.7
CON(CH3)2
OCH(CH3)2
d(6)1.4; s(6)2.7;
s(3)3.9; m(1)5.0;
m(9)6.8-7.8
COCF2 CF3
CF2 Cl
d(3)3.8; m(8)6.8-7.8;
bs(1)8.5
COCF2 CF3
CF3 d(3)3.8; m(8)6.8-7.7;
bs(1)8.6
SO2 CF3
CF3 d(3)3.8; m(9)6.8-7.8
CO2 CH3
CF3 s(3)3.8; s(3)3.9;
m(9)6.8-7.8
COCF2 CF3
OCH2 C6 H5
s(3)3.8; s(2)5.0;
m(14)6.8-7.8
CONHCH3
CF3 bs(3)2.7; s(3)3.8;
bs(1)5.5; m(8)6.8-7.8;
s(1)9.2
COCH3 OCH3 s(3)3.7; s(3)3.8;
m(9)6.8-7.8
CONHC2 H5
CF3 t(3)1.1; m(2)3.1;
s(3)3.8; bs(1)5.8;
m(9)6.8-7.8
CONHC2 H5
OCH(CH3)2
m(9)1.2; m(2)3.2;
s(3)3.8; m(1)4.9;
m(9)6.8-7.8
COCH3 OCHCH2
s(3)2.0; s(3)3.8;
m(2)4.4-4.9; m(1)6.5;
m(9)6.8-7.8
PO(OCH2 H5)2
337/612
>;tb;
OCH(CH3)2
>;tb;
m(12)1.3; s(3)3.9;
>;tb;
m(4)4.1; m(1)5.0;
>;tb;
m(9)6.8-7.7
>;tb;134 PO(OC2 H5)2
>;tb;
OCH2 CH3
>;tb;
m(9)1.2; s(3)3.8;
>;tb;
q(6)4.1; m(9)6.8-7.7
>;tb;______________________________________
>;tb; NOTES FOR TABLES 1-4B
>;tb; (1) S = Singlet, d = doublet, t = triplet q = quartet, m = multiplet bs >;tb; broad singlet
>;tb; (2) the number in parenthesis represents the number of protons
>;tb; (3) CD CL3 is deuterated chloroform
>;tb;
TABLE 4
>;tb;______________________________________
>;tb; ##STR9##
>;tb;COMNMR DATA FOR
>;tb;POUND X
R
TABLE 4 (CDCL,3)
>;tb;______________________________________
>;tb;135 2-CH3O, OCH(CH3)2
>;tb;
d(6)1.5; s(3)4.0; m(1)5.2;
>;tb;
5-C6H5
m(8)7.0-7.9
>;tb;156 3-OC6 H5
>;tb;
OC(CH3)3
>;tb;
s(9)1.6; m(9)7.0-7.5
>;tb;158 3-OCH2 C6 H5
>;tb;
OC2 H5
>;tb;
t(3)1.4; q(2)4.4; s(2)5.0;
>;tb;
m(9)7.1-7.5
>;tb;159 2-CH3,
>;tb;
OCH(CH3)2
>;tb;
d(6)1.5; s(3)2.7; m(1)5.2;
>;tb;
5-C6 H5 m(8)7.2-7.8
>;tb;160 2-OCH3,
>;tb;
OCH(CH3)2
>;tb;
d(6)1.4; s(3)4.0; m(1)5.2;
>;tb;
5-OC6 H5 m(8)6.9-7.4
>;tb;161 2-Br,
OCH(CH3)2
>;tb;
d(6)1.5; m(1)5.3;
>;tb;
5-C6 H5 m(8)7.0-7.7
>;tb;______________________________________
>;tb;
TABLE 4A
>;tb;______________________________________
>;tb; ##STR10##
>;tb;
NMR DATA FOR
>;tb;COMPOUND R
TABLE 4A (CDCL3)
>;tb;______________________________________
>;tb;141
CH(CH3)2
>;tb;
d(6)1.2; s(3)3.9; m(1)5.0;
>;tb;
bs(2)6.5; m(6)7.0-7.6
>;tb;142
C(CH3)3 s(9)1.5; s(3)4.0; bs(2)6.5;
>;tb;
m(6)7.1-7.6
>;tb;151
CH2 CHCH2
>;tb;
s(3)4.0; d(2)4.7; m(3)5.1-5.8;
>;tb;
bs(2)6.5; m(6)7.1-7.6
>;tb;152
CH3 s(3)3.8; s(3)4.0; bs(2)6.5;
>;tb;
m(6)7.0-7.6
>;tb;153
C3 H7
338/612
>;tb;
t(3)1.0; m(2)1.6; s(3)4.0;
>;tb;
m(2)4.2; bs(2)6.6; m(6)7.1-7.6
>;tb;______________________________________
>;tb;
TABLE 4B
>;tb;______________________________________
>;tb; ##STR11##
>;tb;
NMR DATA FOR
>;tb;COMPOUND R
TABLE 4B (CDCL3)
>;tb;______________________________________
>;tb;157
CH(CH3)2
>;tb;
d(6)1.4; s(3)4.1; m(6)7.1-7.7
>;tb;______________________________________
EXAMPLE 10
Preparation of Formulations
The remaining examples relate to the pesticidal use of the compounds of this invention. In all these
examples a stock solution for the compounds were prepared at 3000 ppm by dissolving 0.3 gram of the
compound to be tested in 10 ml of acetone and adding 90 ml of distilled water plus for drops of
ethoxylated sorbitan monolaurate, or a similar suitable wetting agent. For each example that follows,
this stock solution was used and the specificied dilutions made. All the tests discussed below, which
involved treatment with compounds of this invention, were always repeated with controls, in which the
active compound was not provided, to permit a comparison upon which the percent control was
calculated.
EXAMPLE 11
Mite Adulticide and Mite Ovicide/Larvicide Tests
One day before treatment, a "FIG. 8" configuration of tree tanglefoot was applied to each of two
cowpea primary leaves, one from each of two plants in a pot. In each figure, the circle nearer the stem
was designated for the mite ovicide/larvicide test and the circle further from the stem was designated
for the mite adulticide test.
Groups of adult mites (Tetranychus urticae Koch) were transferred into ovicide circles one day before
treatment and the females were allowed to deposit eggs until one hour before treatment when they were
removed. Plants were sprayed to run off with a 1000 ppm solution diluted from the 3000 ppm stock
solution.
One day following treatment, groups of approximately 25 adult mites were transferred into the
adulticide rings. Five days later these rings were examined for live mites remaining on the leaves. The
percent control was estimated based on the number of mites surviving on the check plants.
Nine days following treatment the ovicide/larvicide rings were examined for hatched eggs and living
immature mites. The percent control was estimated based on the number of eggs hatching and
immature mites surviving on the check plants. When the treatment effect was to eggs, control was
designated as ovicidal (O); when the treatment effect was to immatures, control was designated as
larvicidal (L).
Results of the mite adulticide (MI) and ovicide/larvicide (MIOLV) tests are presented in Table 5.
>;tb;
TABLE 5
>;tb;______________________________________
>;tb;COMPOUND
>;tb;NO.
MI
MIOVL
>;tb;______________________________________
>;tb; 1
50
80
(L)
>;tb; 2
100
100
>;tb; 3
100
100 (L)
339/612
>;tb; 4
>;tb; 5
>;tb; 6
>;tb; 7
>;tb; 8
>;tb; 9
>;tb;10
>;tb;11
>;tb;12
>;tb;13
>;tb;14
>;tb;15
>;tb;16
>;tb;17
>;tb;18
>;tb;19
>;tb;20
>;tb;21
>;tb;22
>;tb;23
>;tb;24
>;tb;25
>;tb;26
>;tb;27
>;tb;28
>;tb;29
>;tb;30
>;tb;39
>;tb;40
>;tb;41
>;tb;42
>;tb;43
>;tb;44
>;tb;45
>;tb;46
>;tb;47
>;tb;49
>;tb;50
>;tb;51
>;tb;52
>;tb;53
>;tb;54
>;tb;55
>;tb;56
>;tb;57
>;tb;58
>;tb;59
>;tb;60
>;tb;62
>;tb;63
>;tb;64
>;tb;65
>;tb;66
>;tb;67
>;tb;68
>;tb;69
>;tb;70
>;tb;72
>;tb;73
100
30
100
100
70
70
100
100
95
70
100
100
100
70
98
100
100
100
100
70
100
100
100
99
100
80
50
100
50
80
100
100
50
70
100
100
100
100
100
100
100
100
100
70
90
100
100
100
98
100
100
100
70
90
100
100
100
0
100
100
80
100
100
0
0
100
100
90
70
100
100
100
0
100
100
100
100
20
0
70
100
100
50
100
80
50
100
0
50
100
100
30
50
30
100
100
100
100
100
100
100
100
0
95
30
0
100
50
70
100
100
50
95
100
100
100
50
100
(L)
(L)
(L)
(O)
(O/L)
(O/L)
(L)
(L)
(L)
(L)
(L)
(L)
(O)
(O)
(O)
(L)
(L)
(O)
(O)
(L)
(L)
(L)
(L)
(L)
(L)
(O)
(O)
(L)
(L)
(L)
(L)
(O)
(O)
(O)
(O)
(L)
(O)
(O)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
340/612
>;tb;74
>;tb;75
>;tb;76
>;tb;77
>;tb;78
>;tb;79
>;tb;80
>;tb;81
>;tb;82
>;tb;83
>;tb;84
>;tb;85
>;tb;86
>;tb;93
>;tb;94
>;tb;95
>;tb;96
>;tb;97
>;tb;98
>;tb;99
>;tb;101
>;tb;102
>;tb;105
>;tb;107
>;tb;108
>;tb;109
>;tb;112
>;tb;114
>;tb;115
>;tb;116
>;tb;117
>;tb;118
>;tb;119
>;tb;120
>;tb;121
>;tb;122
>;tb;124
>;tb;125
>;tb;126
>;tb;128
>;tb;130
>;tb;131
>;tb;133
>;tb;135
>;tb;136
>;tb;137
>;tb;138
>;tb;139
>;tb;140
>;tb;141
>;tb;142
>;tb;143
>;tb;144
>;tb;145
>;tb;146
>;tb;147
>;tb;148
>;tb;149
>;tb;150
99
100
100
100
100
70
100
99
95
100
100
100
100
100
100
100
100
70
100
100
70
70
95
100
100
100
60
100
100
100
100
100
100
100
100
100
100
80
100
100
100
100
100
100
98
100
100
100
100
70
50
70
30
100
70
100
70
30
80
30
100
100
100
100
70
70
90
30
100
100
100
100
80
100
100
100
30
100
100
80
0
0
50
100
100
0
100
100
100
100
100
100
100
100
100
100
30
100
100
50
100
100
100
100
100
98
100
100
100
80
30
0
90
50
100
30
0
0
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(1)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(O)
(O)
(O)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(O)
(L)
(L)
(L)
(L)
(L)
(L)
(O)
(O)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(O)
(L)
(L)
(L)
(L)
341/612
>;tb;151
0
0
>;tb;152
0
0
>;tb;153
100
90
(L)
>;tb;154
100
100 (L)
>;tb;155
0
0
>;tb;156
98
0
>;tb;157
30
80
(L)
>;tb;158
100
98
(O)
>;tb;159
100
100 (O)
>;tb;160
100
20
(O)
>;tb;161
100
100 (O)
>;tb;______________________________________
>;tb; NOTES:
>;tb; MI = MITE ADULTICIDE
>;tb; MIOVL = MITE OVICIDE/LARVICIDE
EXAMPLE 12
European Red Mite Test
Orchard apple trees with infestations of European red mite (Panonychus ulmi) were sprayed with
aqueous solutions of emulsifiable concentrates of individual compounds. Greater than 75 percent
control with an application rate of 150 ppm ai was achieved by compound numbers 103, 10, 11, 19, 20,
25, 26, and 82.
EXAMPLE 13
Nematode Test
The stock solution of 3000 ppm was diluted to 1000 ppm. For each compound, 25 ml was drenched
onto 500 grams of soil infested with root knot nematode (Meloidogyne incognita) eggs in a pot, for a
soil concentration of 50 ppm sc.
One day after treatment, two tomato seedlings were planted in each pot. Nineteen days after planting,
the roots were evaluated for the presence of knots or galls, and the percent control was estimated based
on the infestation levels in check plants.
The results of the testing of nematodes (NE) are given in Table 6.
EXAMPLE 14
Rice Planthopper Foliar Test
The stock solution of 3000 ppm was diluted to 1000 ppm. One pot containing approximately 20 Mars
variety rice seedlings was treated with each formulation by spraying with a spray atomizer. One day
after treatment plants were covered with a tubular cage and twenty adult rice delphacids, Sogatodes
oryzicola, were transferred into each cage. Five days after transferring, counts were made of the
surviving planthoppers in each pot and percent control was estimated.
The results of the testing of rice planthoppers (RPH) are given in Table 6.
EXAMPLE 15
Tobacco Budworm Test
The stock solution of 3000 ppm was used for this test. For each compound, 0.2 ml was pipetted onto
the surface of each of 5 diet cells, allowed to spread over the surfaces and air dried for two hours. Then
a second istar Heliothis virescens larva was introduced into each cell. After 14 days, the number of
342/612
living larvae was determined for each treatment and percent control, corrected by Abbott's formula,
was calculated.
The results of the testing of tobacco budworms (TB) are given in Table 6.
EXAMPLE 16
Southern Corn Rootworm Test
The stock solution of 3000 ppm was diluted to 100 ppm. For each compound, 2.5 ml was pipetted onto
a filter paper (Whatman #3) at the bottom of a 100 mm petri dish. Two corn seedlings were soaked in
the 100 ppm solution for 1 hour and transferred to the petri dish. After 24 hours, each dish was loaded
with 5 second instar larvae of Diabrotica undecimpunctata. After five days, the number of live larvae
were noted and the percent control, corrected by Abbott's formula (see J. Economic Entomology, 18,
265-267 (1925)) was calculated.
The results appear in Table 6.
>;tb;
TABLE 6
>;tb;______________________________________
>;tb;COMPOUND
PERCENT CONTROL
>;tb;NO.
NE RPH
TB SCR
>;tb;______________________________________
>;tb; 1
0 30
100 0
>;tb; 2
30 100
79 75
>;tb; 3
0 100
58 50
>;tb; 4
70 100
100 100
>;tb; 5
0
0
100 0
>;tb; 6
0 100
100 0
>;tb; 7
0 100
100 100
>;tb; 8
50 PT
0 0
>;tb; 9
85
0
0 0
>;tb;10
0 50
20 0
>;tb;11
0 10
100 0
>;tb;12
50
0
20 0
>;tb;13
0
5
100 0
>;tb;14
70
0
0 0
>;tb;17
70
0
0 0
>;tb;18
0
0
80 0
>;tb;19
70 60
0 14
>;tb;20
0
0
80 0
>;tb;23
95
0
75 0
>;tb;24
0 80
0 0
>;tb;25
30
0
56 0
>;tb;26
20
0
100 0
>;tb;27
0
0
56 0
>;tb;28
70
0
40 6
>;tb;31
50 55
100 15
>;tb;33
0 20
100 0
>;tb;34
50 15
0 0
>;tb;35
100 20
0 0
>;tb;36
50
0
0 20
>;tb;37
PT 25
80 17
>;tb;38
0
0
80 0
>;tb;42
0 100
100 100
>;tb;43
0 100
100 80
>;tb;45
0
0
100 0
>;tb;47
80 50
0 20
>;tb;48
50 25
0 0
>;tb;49
0 80
0 0
343/612
>;tb;50
>;tb;51
>;tb;53
>;tb;54
>;tb;55
>;tb;57
>;tb;58
>;tb;59
>;tb;60
>;tb;62
>;tb;64
>;tb;65
>;tb;67
>;tb;74
>;tb;78
>;tb;80
>;tb;81
>;tb;83
>;tb;84
>;tb;87
>;tb;88
>;tb;89
>;tb;90
>;tb;91
>;tb;92
>;tb;95
>;tb;96
>;tb;99
>;tb;100
>;tb;102
>;tb;103
>;tb;103
>;tb;105
>;tb;106
>;tb;108
>;tb;110
>;tb;111
>;tb;112
>;tb;113
>;tb;115
>;tb;116
>;tb;117
>;tb;119
>;tb;121
>;tb;125
>;tb;127
>;tb;128
>;tb;129
>;tb;130
>;tb;131
>;tb;132
>;tb;133
>;tb;134
>;tb;135
>;tb;136
>;tb;137
>;tb;138
>;tb;139
>;tb;140
30 100
30 100
0 100
0 95
0 70
0 35
0 25
50 20
0 40
0
0
70 25
60
0
0 10
0
0
95
0
0
0
0 50
30 50
0 50
50
0
50
0
0
0
0
0
0 70
0
0
0 25
30
0
0 80
70 60
70 0
0
0
0
0
0
0
30 55
70 0
0 30
0
0
50 0
0
0
70 50
60 0
50 0
0 40
50 40
98 25
50 50
70 30
50 25
70 15
70 25
70 50
0 55
70 60
-- 55
100 30
100 25
0 90
0 98
0
0
0 100
100 0
100 0
80 0
40 0
100 37
100 0
100 75
60 -100 0
0 21
0 0
100 0
80 0
0 14
78 0
78 0
73 16
20 6
0 0
100 0
60 33
100 0
80 0
75 0
100 100
50 20
0 100
0 0
0 0
100 0
100 0
100 0
0 0
0 0
100 0
100 20
0 0
100 6
16 0
0 60
55 33
78 0
0 0
0 0
0 0
0 0
0 0
0 16
0 16
0 0
60 0
0 0
-- -20 0
0 100
0 0
0 40
0 0
344/612
>;tb;141
100 0
60 0
>;tb;142
0 0
60 0
>;tb;143
PT
0
20 20
>;tb;144
0
0
0 80
>;tb;145
0
0
0 80
>;tb;146
0 PT
0 20
>;tb;147
0
0
0 100
>;tb;148
0
0
0 100
>;tb;149
50 0
0 60
>;tb;150
0
0
36 0
>;tb;151
0
0
60 20
>;tb;152
0
0
60 0
>;tb;153
50 0
37 0
>;tb;154
0 80
58 0
>;tb;155
-0
75 0
>;tb;156
0
0
0 0
>;tb;157
100 0
40 0
>;tb;158
-- --- ->;tb;159
0 100
58 0
>;tb;160
-0
0 0
>;tb;161
-- 100
100 60
>;tb;______________________________________
>;tb; NOTES:
>;tb; NE = NEMATODE
>;tb; RPH = RICE PLANT HOPPER
>;tb; TB = TOBACCO BUDWORM
>;tb; SCR = SOUTHERN CORN ROOTWORM
>;tb; PT = PHYTOTOXIC PLANT DIED, NO SCORE APPLICABLEData supplied from the
esp@cenet database - Worldwide
Claims:
Claims of corresponding document: US5367093
What is claimed is:
1. A compound having the structural formula: ##STR12## wherein X is a) phenyl; phenoxy; or benzyl;
the phenyl ring of each substituent being optionally substituted with one or more of halogen, nitro,
lower alkyl, lower alkoxy, lower haloalkyl or diaklylamino; or b) one substituent from group a) and
one or more substituents selected from C1 -C4 alkoxy; halogen; lower alkyl; and lower alkylthio; Y is
H, C1 -C4 alkanoyl, C1 -C4 haloalkanoyl, dialkoxyphosphoryl, alkylaminocarbonyl, haloalkylsulfonyl,
or C1 -C4 alkoxy carbonyl; R is H, C1 -C6 alkoxy, C3 -C6 cycloalkoxy, haloalkyl, alkoxyalkyl,
arylalkoxy, alkenyl, alkylthio, alkoxycarbonyl, alkylamino, thiophenyl, furyl, arylalkyl, haloalkoxy,
aryloxy, or C3 -C6 cycloalkyl; and Z is O or S;
with the proviso that when X is phenyl, then R is not alkylamino or alkoxycarbonyl.
2. A compound in accordance with claim 1 wherein X is phenyl or phenyl and C1 -C4 alkoxy; Y is H
or COCF3 ; R is CF3, C1 -C4 alkyl, C1 -C4 alkoxy, or C3 -C6 cycloalkyl; and Z is O.
3. The compound of claim 1 wherein R is 2-thiophenyl or 2-furyl.
4. The compound of claim 1 wherein Y is H, Z is O and when X is 2--C6 H5, R is OCH(CH3)2 or OC3
H7, when X is 3--C6 H5, R is OCH(CH3)2, when X is 2Br, 5--C6 H5, R is CH(CH3)2, when X is 2-CH3, 5--C6 H5, R is CH(CH3)2 , and when X is 2--OCH3, 5--OC6 H5, R is CH(CH3)2.
5. The compound of claim 1 wherein Y is H, Z is O, X is 2CH3 O, 5--C6 H5 and R is one of OCH3,
OCH2 CH3, O(CH2)3 CH3, OCH2 CH2 CH3, OCH2 CH(CH3)2, OCH2 CH.dbd.CH2 or
OCH(CH3)2.
6. The compound of claim 5 wherein R is OCH(CH3)2.
345/612
7. A compound having the structural formula: ##STR13## wherein X is a) phenyl; lower
phenylalkoxy; phenoxy; or benzyl; the phenyl ring of each substituent being optionally substituted with
one or more of halogen, nitro, lower alkyl, lower alkoxy, lower haloalkyl or diaklylamino; or b) one
substituent from group a) and one or more substituents selected from C1 -C4 alkoxy; halogen; lower
alkyl; and lower alkylthio; Y is H, C1 -C4 alkanoyl, C1 -C4 haloalkanoyl, dialkoxyphosphoryl,
alkylaminocarbonyl, haloalkylsulfonyl, or C1 -C4 alkoxy carbonyl; R is H, C1 -C6 alkyl, C1 -C6
alkoxy, C3 -C6 cycloalkoxy, haloalkyl, alkoxyalkyl, arylalkoxy, alkenyl, alkylthio, alkoxycarbonyl,
alkylamino, thiophenyl, furyl, arylalkyl, haloalkoxy, aryloxy, or C3 -C6 cycloalkyl; and Z is O or S;
with the proviso that when X is phenyl, then R is not alkylamino or alkoxycarbonyl, and with the
further proviso that when X is lower phenylalkoxy, Y is H and Z is O, then R is not hydrogen, methyl
or trifluoromethyl.
8. A pesticidal composition comprising A) a pesticidally effective amount of a compound having the
structural formula: ##STR14## wherein X is a) phenyl; lower phenylalkoxy; phenoxy; or benzyl; the
phenyl ring of each substituent being optionally substituted with one or more of halogen, nitro, lower
alkyl, lower alkoxy, lower haloalkyl or diaklylamino; or b) one substituent from group a) and one or
more substituents selected from C1 -C4 alkoxy; halogen; lower alkyl; and lower alkylthio; Y is H, C1 C4 alkanoyl, C1 -C4 haloalkanoyl, dialkoxyphosphoryl, alkylaminocarbonyl, haloalkylsulfonyl, or C1 C4 alkoxy carbonyl; R is H, C1 -C6 alkyl, C1 -C6 alkoxy, C3 -C6 cycloalkoxy, haloalkyl, alkoxyalkyl,
arylalkoxy, alkenyl, alkylthio, alkoxycarbonyl, alkylamino, thiophenyl, furyl, arylalkyl, haloalkoxy,
aryloxy, or C3 -C6 cycloalkyl; and Z is O or S; and B) an acceptable carrier.
9. The composition of claim 8 wherein R is 2-thiophenyl or 2-furyl.
10. The composition of claim 8 wherein Y is H, Z is O and when X is 2--C6 H5, R is OCH(CH3)2 or
OC3 H7, when X is 3--C6 H5, R is OCH(CH3)2, when X is 2Br, 5--C6 H5, R is CH(CH3)2, when X is
2--CH3, 5--C6 H5, R is CH(CH3)2 , and when X is 2--OCH3, 5--OC6 H5, R is CH(CH3)2.
11. The compound of claim 8 wherein Y is H, Z is O, X is 2CH3 O, 5--C6 H5 and R is one of OCH3,
OCH2 CH3, O(CH2)3 CH3, OCH2 CH2 CH3, OCH2 CH(CH3)2, OCH2 CH.dbd.CH2 or
OCH(CH3)2.
12. The compound of claim 11 wherein R is OCH(CH3)2.
13. A process for controlling undesirable pests which comprises applying to a locus to be protected a
pesticidally effective amount of a compound having the structural formula: ##STR15## wherein X is a)
phenyl; lower phenylalkoxy; phenoxy; or benzyl; the phenyl ring of each substituent being optionally
substituted with one or more of halogen, nitro, lower alkyl, lower alkoxy, lower haloalkyl or
diaklylamino; or b) one substituent from group a) and one or more substituents selected from C1 -C4
alkoxy; halogen; lower alkyl; and lower alkylthio; Y is H, C1 -C4 alkanoyl, C1 -C4 haloalkanoyl,
dialkoxyphosphoryl, alkylaminocarbonyl, haloalkylsulfonyl, or C1 -C4 alkoxy carbonyl; R is H, C1 C6 alkyl, C1 -C6 alkoxy, C3 -C6 cycloalkoxy, haloalkyl, alkoxyalkyl, arylalkoxy, alkenyl, alkylthio,
alkoxycarbonyl, alkylamino, thiophenyl, furyl, arylalkyl, haloalkoxy, aryloxy, or C3 -C6 cycloalkyl;
and Z is O or S.
14. The composition of claim 7 wherein R is 2-thiophenyl or 2-furyl.
15. The composition of claim 13 wherein Y is H, Z is O and when X is 2--C6 H5, R is OCH(CH3)2 or
OC3 H7, when X is 3--C6 H5, R is OCH(CH3)2, when X is 2Br, 5--C6 H5, R is CH(CH3)2, when X is
2--CH3, 5--C6 H5, R is CH(CH3)2 , and when X is 2--OCH3, 5--OC6 H5, R is CH(CH3)2.
16. The compound of claim 13 wherein Y is H, Z is O, X is 2CH3 O, 5--C6 H5 and R is one of OCH3,
OCH2 CH3, O(CH2)3 CH3, OCH2 CH2 CH3, OCH2 CH(CH3)2, OCH2 CH.dbd.CH2 or
OCH(CH3)2.
17. The compound of claim 16 wherein R is OCH(CH3)2.Data supplied from the esp@cenet database Worldwide
346/612
26. US3553323
- 1/5/1971
METHOD OF CONTROLLING RICE BLAST WITH THIOLPHOSPHATES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US3553323
Inventor(s):
KADO MASARU (--); MAEDA TAIZO (--); YOSHINAGA EIICHI (--)
Applicant(s):
KUMIAI CHEMICAL INDUSTRY CO (--)
IP Class 4 Digits: A01N
IP Class:A01N9/36
E Class: A01N57/14; C07F9/165A7
Application Number:
USD3553323 (19650706)
Priority Number: JP19650018285 (19650331)
Family: US3553323
Equivalent:
DE1252961
Abstract:
Abstract not available for US3553323
347/612
27. US3705241
- 12/5/1972
FUNGICIDAL PROCESS EMPLOYING ORGANIC PHOSPHOROUS ACID
ESTERS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US3705241
Inventor(s):
SCHRADER GERHARD (JP); SCHEINPFLUG HANS (JP); JUNG HERBERT F
(JP); KUYAMA SHIMPEI (JP); KISHINO SHIGEO (JP); YAMADA YASUO (JP)
Applicant(s):
NIHON TOKUSHU NOYAKU SEIZO KK (JP)
IP Class 4 Digits: A01N
IP Class:A01N9/36
E Class: A01N57/14; C07F9/205
Application Number:
USD3705241 (19701020)
Priority Number: JP19670002399 (19670112); JP19670012231 (19670225); JP19660078594
(19661201); JP19660078595 (19661201); US19700082528 (19701020)
Family: US3705241
Equivalent:
NL6716404; GB1210924; FR1583740; DE1643482; CH493202; BE707271
Abstract:
Abstract of US3705241
Agricultural and horticultural fungicides of the formula wherein R is selected from the group consisting
of C1-4 alkyl and chloroethyl, X is selected from the group consisting of chlorine and methyl and n is
zero or one are especially useful for the control of the blast and sheath blight, which have been
regarded from the past as serious diseases of rice, processes for the preparation of active ingredients
thereof and method of the utilization thereof. These fungicides have good control effects and their
active ingredients contain no heavy metals harmful to men and cattle, in contrast to the conventional
fungicides heretofore applied for the same purpose which give such bad influence as direct and indirect
toxicity to men and cattle owing to the presence of heavy metals such as mercury and
arsenic.Description:
Description of US3705241
The present invention relates to agricultural and horticultural fungicides whose active ingredients are
organic phosphorous acid esters not containing heavy metals harmful to men and cattle, processes for
the preparation of active ingredients thereof and method of the utilization thereof.
More particularly, the present invention relates to agricultural and horticultural fungicides containing a
fungicidal amount of at least one compound selected from the group consisting of organic phosphorous
acid esters represented by the following formula (1) ##SPC2##
(wherein R stands for a member selected from the group consisting of alkyl groups and haloalkyl
groups, X stands for a member selected from the group consisting of halogen atoms and alkyl groups
and n is a number selected from the group consisting of zero and 1), especially preferably organic
phosphorous acid esters of said formula (1) wherein R stands for an alkyl group having one to four
carbon atoms, X stands for a member selected from the group consisting of chlorine and methyl, and n
is a number selected from the group consisting of zero and 1 and organic phosphorous acid esters of
348/612
said formula (1) wherein R stands for Cl--CH2 CH2 -, X stands for methyl and n is a number selected
from the group consisting of zero and 1 as active ingredients, processes for the preparation of said
active ingredients and method of the utilization thereof.
For the control of blast (Piricuralia oryzae ) and sheath blight (Hypochnus sasakii), important diseases
of rice from the past, such compounds as phenyl mercuric acetate and methyl arsonic acid metal salts,
etc. have been applied extensively due to their superior fungicidal efficacy and for economical reasons.
Of late, however, the application of organic mercury compounds to rice plant in its growing stage has
been brought to light in view of giving bad influence to public health by their direct toxicity and
indirect residual toxicity to the human body. Therefore, the development of agricultural chemicals not
containing these heavy metals harmful to men and cattle and effective against the aforementioned rice
diseases and cheap-priced has been earnestly desired.
We, the inventors, after testing biological activity of various organic phosphorous acid esters in order
to solve the aforementioned problem, have discovered that novel organic phosphorous acid esters
shown by the aforementioned general formula (1) were useful as agricultural and horticultural
fungicides, though inferior in their insecticidal actions, and especially they had excellent efficacy
against important rice diseases such as blast, Brown spot (ti Cochliobolus miyabeanus) and sheath
blight and thus we have completed this invention.
The following Table 1 shows the compounds exemplified to be used in this invention. ##SPC3##
The aforementioned compounds may be easily prepared by reacting an alkyl dihalogeno phosphorous
acid ester represented by the following formula (2)
(wherein R stands for a member selected from the group consisting of alkyl groups and haloalkyl
groups and Hal. stands for halogen atoms) with a compound represented by the following formula (3).
(wherein M stands for a member selected from the group consisting of hydrogen atom and alkali metal
atoms, X stands for a member selected from the group consisting of halogen atoms and alkyl groups
and n is a number selected from the group consisting of zero and 1) in accordance with the following
reaction scheme: ##SPC4##
Said reaction suffices to react a compound of said formula (2) with a compound of said formula (3) in
the optional presence of an organic solvent, however, it is preferable to carry out the reaction with
heating.
Of the material dihalogeno phosphorous acid esters of said general formula (2), a compound wherein R
is alkyl is easily synthesized by the known method using the corresponding alcohol and phosphorous
trichloride. The following are its representative compounds and properties.
>;tb;
Properties (melting point
>;tb; Chemical name
or boiling point)
>;tb;__________________________________________________________________________
>;tb;O-methyl dichlorophosphorous acid ester
>;tb;
m.p. 95 DEG - 96 DEGC.
>;tb;O-ethyl dichlorophosphorous acid ester
>;tb;
b.p. 54 DEG - 60 DEG C/100 mm Hg
>;tb;O-propyl dichlorophosphorous acid ester
>;tb;
m.p. 143 DEG - 145 DEGC
>;tb;O-butyl dichlorophosphorous acid ester
>;tb;
b.p. 49 DEG - 50 DEG C/11 mm Hg
>;tb;__________________________________________________________________________
Of the material compounds of said general formula (2), a compound wherein R is haloalkyl may be
obtained similarly except using a halo-substituted alcohol instead of said alcohol.
The representative compound is shown below
>;tb; Chemical name
Properties (boiling point.)
349/612
>;tb;O-(2-chloroethyl) dichlorophosphorous acid ester
>;tb;
b.p. 70 DEG - 75 DEG C/5 - 10 mm Hg
ester
The reaction shown by said reaction scheme may employ a usually utilized acid-binding agent such as
an organic base, for instance, triethylamine, benzyldimethylamine and pyridine or an inorganic base,
for instance, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
As a compound of said formula (3), when substituted or unsubstituted thiophenol wherein M is a
hydrogen atom is used, utilization of an acid binding-agent is recommended.
As the reaction temperature, normally a temperature within the range of 0 DEGC. to 80 DEGC. may be
adopted, however, it is possible to carry out the reaction at a temperature higher or lower than said
range if desired.
When as a reaction medium an organic solvent is utilized, a solvent, for instance, hydrocarbon
(benzene, xylene, hexane), chlorinated hydrocarbon, ether and ketone may be utilized.
The reaction time is properly changed depending upon the reaction temperature, reaction components
and other reaction conditions, however, normally a period of 1 - 10 hours is sufficient.
Further, as occasion demands it is possible to carry out the reaction in a nitrogen gas stream.
After completion of the reaction, the product may be obtained by filtering the produced salts, further
washing the filtrate with water or an aqueous solution of carbonic acid and drying with sulfuric soda
anhydride and then removing the solvent, thereafter purifying the product as occasion demands.
The compounds of said formula (1) obtained by said process are oily or solid substances generally
insoluble in water, but soluble in an organic solvent, for instance, alcohol, benzene, xylene, hexane,
ether, ketone, chlorinated hydrocarbon and hydrocarbon. When they are used, they may be utilized by
various methods known in the agricultural and horticultural fields.
Namely, when the compounds of this invention are used as agricultural andhorticultural fungicides,
they are used diluted with water directly or in admixture with carriers and formulated into wettable
powders, emulsifiable concentrates, dusts, granules or pastes by methods generally used in ordinary
agricultural chemicals. As solid carriers are exemplified inactive materials such as talc, clay, kaolin,
montmorillonite, diatomaceous earth, calcium carbonate, etc. As liquid carriers either solvents or even
non-solvents which can disperse or dissolve the active ingredient by adjuvant can be used, e.g., alcohol,
benzene, xylene, dimethyl naphthalene, aromatic naphtha, dimethyl formamide, surface active agent,
etc.
They can be applied, for assuring their efficacy, in admixture with such adjuvants used for agricultural
chemicals in general as spreader, emulsifier, wetting agent, adhesive agent, etc. Further, they can be
applied in admixture with such insecticides, acaricides and nematocides as organo-phosphorus
compounds, carbonate compounds, chlorinated compounds, dinitro compounds, such fungicides as
organophosphorus compounds, organic sulfur, copper compounds, dithiocarbamates, dinitro
compounds, antibiotics, such herbicides as substituted phenoxy compounds, carbamates, urea
compounds, triazine compounds, chlorophenol, substituted diphenyl ether, anilide compounds and
other agricultural chemicals and fertilizers.
In using the fungicides of the invention, in case of powder material, it can be directly dusted on the
leaves or stems of plants or treated on the seed, and in case of emulsifier concentrate, it can be diluted
with water etc. to a suitable concentration and may be applied on leaves and stems of plants by
spraying it with a sprayer and in case of wettable powders they can be applied by spraying as a
suspension of a suitable concentration with water and in case of granular formulation they can be
sprinkled upon soil as such.
The fungicides of this invention are ordinarily used at a ratio of 25g - 24 100g, preferably 40g - 100g,
especially 60g - 80g of the active ingredients per 10 ares, however, if desired they may be used in
350/612
smaller or larger amounts. The used amounts are properly variable depending upon kind of the active
ingredients, applying method, applying period, object of application or formulation of fungicides.
As aforementioned in contrast to the conventional fungicides heretofore applied for controlling the
most important diseases of rice plant which have serious deficiency in that they are directly and
indirectly toxic to men and cattle due to containing heavy metals such as mercury and arsenic, the
fungicides of this invention completely overcome such deficiency due to harmful heavy metals,
moreover, they have excellent fungicidal effects to rice diseases, above all, blast, Brown spot and
sheath spot. As the active ingredient of this invention, a compound wherein R = alkyl and n = o is
preferable. In case n is 1, a compound wherein X is alkyl is more effective than a compound wherein X
is halogen.
The following Examples illustrate the process for the preparation of active ingredients of our invention,
but supplements and specific compounds of the Examples are alterable and will not restrict our
invention.
[ I ] Examples of preparing the active ingredients:
Example 1
148 G of p-methyl thiophenol are dissolved in 600 ml of benzene. After having added 124g of
triethylamine there are further added at 0 DEG to 5 DEGC. 90g of O-ethyldichlorophosphorous acid
ester with stirring while passing nitrogen therethrough. The reaction mixture is stirred for 1 hour, then
washed with water until it reacts neutrally. Then the benzene solution is dried over sodium sulfate and
the solvent is distilled off. In this way, there are obtained 70g (38 percent of the theoretical) of a novel
O-ethyl-S,S-di(p-methylphenyl)-dithiophosphite in the form of a pale yellow water-insoluble oily
matter.
>;tb;Analysis:
P
S
>;tb;Calculated for a molecular weight of 322:
9.6 % 19.9 %
>;tb;Found:
9.1 % 20.2 %
Example 2
172 G of p-chlorothiophenol are dissolved in 600 ml of benzene. The solution is treated with 124g of
triethylamine. Subsequently at 0 DEG to5 DEGC there are added 90g of 0-ethyldichlorophosphorous
acid ester while stirring and passing nitrogen through the solution. The reaction mixture is further
stirred for 1 hour and then treated as described in Example 1. There are obtained 160g (73 percent of
the theoretical) of O-ethyl-S,S-di(p-chlorophenyl)-dithiophosphite in the form of a pale yellow waterinsoluble oily matter.
Example 3
124 G of triethylamine are added to a solution of 172g of p-chlorothiophenol in 600 ml of benzene.
Then 97g of O-n-propyldichlorophosphorous acid ester are added to the solution at 0 DEG to 5 DEGC.
with stirring and passing through nitrogen. The reaction mixture is further stirred for 1 hour and then
treated as described in Example 1. A novel O-n-propyl-S,S-di(p-chlorophenyl)-dithiophosphite is
obtained as a pale yellow water-insoluble oily matter. The yield amounts to 148g (65 percent of the
theoretical).
>;tb;Analysis:
P
S
Cl
>;tb;Calculated for a molecular weight of 377:
>;tb;
8.2% 17.0% 18.8%
>;tb;Found:
8.4% 17.2% 18.3%
Example 4
172 G of p-chlorothiophenol are dissolved in 600 ml of benzene. 124 g of triethylamine are added.
Then 97g of O-isopropyldichlorophosphorous acid ester are added to the solution at 0 DEG to 5 DEGC
with stirring and passing through nitrogen. The reaction mixture is further stirred for 1 hour and then
351/612
treated as described in Example 1. In this way there are obtained 145g (77 percent of the theoretical) of
the novel O-isopropyl-S,S-di(p-chlorophenyl)-dithiophosphite in the form of colorless needles.
>;tb;Analysis:
P
S
Cl
>;tb;Calculated for a molecular weight of 377:
>;tb;
8.2% 17.0% 18.8%
>;tb;Found:
8.4% 17.3% 18.6%
Example 5
The mixed solution of 22g of thiophenol, 20g of triethylamine and 100 ml of benzene is added
dropwise into a solution wherein 14.7g of O-ethyldichloro phosphorous acid ester are dissolved in 200
ml of benzene at 10 DEG - 15 DEGC. After the completion of dropping, stirring is further continued
for 3 hours at 10 DEGC and the formed amine salt is filtered. The filtrate is washed with water and 1
percent sodium carbonate aqueous solution twice and dried with sulfuric soda anhydride. When the
benzene is distilled off and dried under a reduced pressure (0.05 mm Hg) at 100 DEGC. 26.5g of light
yellow and oily O-ethyl-S,S-diphenyl dithiophosphite are obtained.
Example 6
205 G of triethylamine are added into a solution wherein 220g of thiophenol are dissolved in 1,000 ml
of benzene. Into this solution the solution of 100 ml of benzene in which 150g of O-ethyldichloro
phosphorous acid ester are dissolved is added dropwise at 0 DEG - 5 DEGC. gradually with stirring.
After the reaction mixture is stirred for 2 hours more at the room temperature, it is washed with ice
water and the benzene solution is separated. After the organic layer is dried over sulfuric soda
anhydride and the solvent is distilled off under a reduced pressure, 265g (90 percent of theoretical
value) of light yellow, water-insoluble and oily O-ethyl-S,S-diphenyl dithiophosphite are obtained,
boiling at 134 DEGC. (0.01 mm Hg)
Example 7
13.2 G of sodium salt of thiophenol are added into 200 ml of methyl ethyl ketone. Into this solution,
7.3g of O-ethyl dichloro phosphorous acid ester are added dropwise with stirring. After continuing the
stirring for eight hours at 60 DEGC, the formed inorganic salt is filtered. Methyl ethyl ketone is
distilled off and the residue is dissolved in ether. After being washed with a 1 percent sodium carbonate
aqueous solution and water, ether solution is dried over sodium sulfate anhydride and ether is distilled
off. Then 11.5g of O-ethyl-S,S-diphenyl dithiophosphite are obtained.
Example 8
8 G of O-n-propyl dichloro phosphorous acid ester are added dropwise into a solution wherein 11g of
thiophenol and 10g of triethyl amine are dissolved in 200 ml of benzene at room temperature.
After having stirred for an hour, the mixture is refluxed for 2 hours. After cooling, amine salt is filtered
and further treated as described in Example 1. Under the reduced pressure (0.05 mm Hg) at 100 DEGC.
13.5g of undistillable oily O-n-propyl-S,S-diphenyl dithiophosphite are obtained.
Example 9
124 G of triethyl amine are added into a solution wherein 132g of thiophenol are dissolved in 600 ml of
benzene. To this solution 7g of O-n-propyl dichloro phosphorous acid esters are added at 0 DEG - 5
DEGC with stirring and passing through nitrogen gas. After the reaction mixture is stirred for an hour,
it is washed with water until it reacts neutrality. Then the benzene solution is dried over sulfuric soda
anhydride and the solvent is distilled off. Then 147g (80 percent of theoretical value) of light yellow,
water-insoluble and oily O-n-propyl-S,S-diphenyl dithiophosphite are obtained.
>;tb;Analysis:
P
S
>;tb;Calculated for a molecular weight of 322:
10.1% 20.8%
>;tb;Found:
9.6%
21.0%
Example 10
352/612
124 G of triethyl amine are added into a solution wherein 132g of thiophenol are dissolved in 600 ml of
benzene. Into this solution 97 g of O-isopropyl phosphorous acid ester are added dropwise at 0 DEG - 5
DEGC with stirring. Further having stirred for an hour, the reaction mixture is treated in the manner as
described in Example 1 and then 150g (81 percent of theoretical value) of yellow, water-insoluble and
oily O-iso-propyl-S,S-diphenyl dithiophosphite boiling at 118 DEGC/0.01 mm Hg are obtained.
Example 11
A mixed solution of 22g of thiophenol, 20g of triethyl amine and 100 ml ofbenzene is added dropwise
into solution wherein 18.1g of O-(2-chloroethyl)dichloro dichloro phosphorous acid ester are dissolved
in 200 ml of benzene at 10 DEG - 15 DEGC.
After the completion of dropping, stirring is further continued for 3 hours at 20 DEGC and the formed
amine salt is filtered. The filtrate is treated in the manner as described in Example 1 and then 24.7g of
light yellow and oily O-(2-chloroethyl)-S,S-diphenyl dithiophosphite are obtained.
The following Examples illustrate the preparation of fungicides and also the method of using the same
will be explained in the following examples.
It should be noted that the additives and active ingredients may be changed over a wide range.
[ II ] Preparation of fungicides (compositions) :
Example 1
50 Parts of O-ethyl-S,S-di(p-methylphenyl) dithiophosphite, 48 parts of clay and 2 parts of emulsifier
Sorpol W-150 (active ingredient polyoxyethylene alkylarylether, Toho Kagaku Kogyo K.K., Japan) are
formulated into a wettable powder by crushing and mixing and applied diluted with water. In case of
using, the wettable powder was suspended in water and sprayed on the leaves and stems of paddy field
rice plant infected by rice blast (Piricularia oryzae) to destroy the disease.
Example 2
3 Parts of O-ethyl-S,S-di(p-chlorophenyl) dithiophosphite and 97 parts of mixture of talc and clay are
formulated into a dust by crushing and mixing and applied as it is.
Example 3
25 Parts of O-ethyl-S,S-diphenyl dithiophosphite, 25 parts of O-ethyl O-cyclohexyl S-(p-chlorophenyl)
thiophosphate, 30 parts of xylene and 20 parts of emulsifier Sorpol 2020 (active ingredient
polyoxyethylene alkylarylether, Toho Kagaku Kogyo K.K., Japan) are formulated into an emulsifiable
concentrate by mixing and stirring and applied diluted with water.
Example 4
50 Parts of O-propyl-S,S-diphenyl dithiophosphite, 48 parts of clay, 2 parts of emulsifier Sorpol W-150
(trade name of the product of Toho Kagaku Kogyo K.K., Japan) are formulated into a wettable powder
by crushing and mixing and applied diluted with water.
Example 5
30 Parts of O-ethyl-S,S-diphenyl dithiophosphite, 50 parts of xylene and 20 parts of emulsifier Sorpol
2020 (trade name of the product of Toho Kagaku Kogyo K.K., Japan) are formulated into an
emulsifiable concentrate by mixing and stirring and applied diluted with water.
Example 6
353/612
2 Parts of O-ethyl-S,S-diphenyl dithiophosphite, 2 parts of O,O-dimethyl O-(4-methylthio-m-tolyl)
phosphorothioate and 96 parts of mixture of talc and clay are formulated into dust by crushing and
mixing and applied as it is. The powder may be directly dusted by means of a duster on the spots where
rice blast (Piricularia oryzae), sheath blight (Pellicularia sasakii) or rice stem borer have been infected
to destroy the disease.
Example 7
50 Parts of O-(2-chloroethyl)-S,S-di(p-methylphenyl) dithiophosphite, 30 parts of xylene and 20 parts
of emulsifier Sorpol 2020 (trade name of the product of Toho Kagaku Kogyo K.K., Japan) are
formulated into an emulsifiable concentrate by mixing and stirring, and applied after diluted with
water.
Example 8
2 Parts of O-(2-chloroethyl)-S,S-diphenyldithiophosphite and 98 parts of mixture of talc and clay are
formulated into a dust by crushing and mixing, and applied as it is.
Example 9
A solution of 5 parts of O-ethyl-S,S-diphenyldithiophosphite in a solvent is sprayed over 95 parts of
vermiculite to form a granular preparation, and is sprinkled over soil as such.
[ III ] Applying Example:
Some experimental results of fungicidal effect of the compounds of the present invention are shown in
the following Tables II, III.
Testing methods:
a. Tests against blast (Pot test)
Paddy rice (Jukkoku variety) was cultivated in pots with the diameters of 12 cm and the suspensions of
test chemicals were sprayed on rice plants at their young ear forming period. From the next day the
treated rice plants were kept in a green house at a temperature of 25 DEGC for 48 hours. During that
time the suspensions of spores of rice blast pathogen were sprayed for inoculation twice. After the
inoculated rice plants were kept in the green house for 7 days, the disease attack rates per pot were
classified in the degrees from 0 (no attack) to 5 (heavy attack) and valued. The controlling values of the
testing chemicals were calculated out by the index numbers obtained from the disease attack rates to
paddy rice in the treated plots against those in the control plots.
b. Tests against sheath blight (Pot test)
The suspensions of test chemicals were applied to paddy rice seedlings (Kinmaze variety) cultivated in
pots with the diameters of 12 cm for 14 days after their sowing, and then the suspension of spores of
sheath blight germs cultured on the barley medium for 10 days was sprayed for inoculation at the part
close to the earth. They were kept at high temperature and humidity for 5 days for accelerating disease
attack. As in the case of blast, the disease attack rate per pot was classified in degrees from 0 (no
attack) to 5 (heavy attack) and valued. Then the controlling values of test compounds were calculated
and compared.
c. Test against plant pathogen (agar dilution method)
The compounds of this invention were mixed in the agar culture medium of potato making the
concentration as prescribed. After the agar was poured into schales with the diameters of 9 cm and
hardened, pathogen was inoculated. After having been cultured at 27 DEGC for 4 days, the growth
condition of pathogen was investigated and the lowest concentration of growth inhibition was sought.
##SPC5## ##SPC6##Data supplied from the esp@cenet database - Worldwide
Claims:
354/612
Claims of US3705241
1.
1. A process for controlling blast (Piricuralia oryzae), brown spot (Cochliobolus miyabeanus) and
sheath blight (Hypochnus sasakii) of rice plants which comprises applying to a rice plant, rice seed or
soil an effective amount of an agricultural and horticultural fungicide composition consisting
essentially of an agriculturally and horticulturally acceptable carrier and an organic phosphorous acid
ester of the formula: ##SPC7##
wherein R represents a member selected from the group consisting of alkyl of from one to four carbon
atoms and a chloroethyl group, X represents a member selected from the group consisting of chlorine
and methyl, and n is zero or 1, said phosphorous acid ester being applied in an amount of
2. The process of claim 1 wherein the ester is
3. The process of claim 1 wherein the ester is
4. The process of claim 1 wherein the ester is O-ethyl
5. The process of claim 1 wherein the ester is O-methyl-S,S-diphenyl
6. The process of claim 1 wherein the ester is O-ethyl-S,S-diphenyl
7. The process of claim 1 wherein the ester is
8. The process of claim 1 wherein the ester is
9. The process of claim 1 wherein the ester is
10. The process of claim 1 wherein the ester is
11. The process of claim 1 wherein the ester is O-n-propyl-S,S-diphenyl
12. The process of claim 1 wherein the ester is O-n-butyl-S,S-diphenyl
13. The process of claim 1 wherein the ester is
14. The process of claim 1 wherein the ester is
15. The process of claim 1 wherein the ester is O-i-propyl-S,S-diphenyl
16. The process of claim 1 wherein the ester is O-sec.-butyl-S,S-diphenyl dithiophosphite.Data
supplied from the esp@cenet database - Worldwide
355/612
28. US3832394
- 8/27/1974
METHANEPHOSPHINYLETHANE SUBSTITUTED AMID TRIMER OF
ALANINE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US3832394
Inventor(s):
NIIDA T (--); INOUE S (--); TSURUOKA T (--); OGAWA Y (--); WATANABE H
(--); SHOMURA T (--); KONDO Y (--); IGARASHI H (--); SEKIZAWA Y (--); WATANABE T (--)
Applicant(s):
MEIJI SEIKA KAISHA (--)
IP Class 4 Digits: C07F; A01N; A61K
IP Class:A01N9/36; A61K27/00; C07F9/46
E Class: C07F9/30A1; A01N57/20
Application Number:
US19720272676 (19720717)
Priority Number: US19720272676 (19720717)
Family: US3832394
Abstract:
Abstract of US3832394
New antibiotic SF-1293 substance and a microbiological process for the production thereof. SF-1293
substance can be produced by cultivation of Streptomyces hygroscopicus SF-1293 (ATCC 21705) SF1293 substance can be used to control various fungal infections of plants, for example, sheath blight
and rice blast of rice plant, and to treat trichophytosis, as SF-1293 substance exhibits the growth of
various fungi such as Pellicularia sasakii, Piricularia oryzae and Trichophyton asteroides.Description:
Description of US3832394
This invention relates to a new and useful antibiotic substance designated as SF-1,293 substance, and
this invention further relates to the fermentative production of this antibiotic SF-1,293 substance as
well as to its uses as pesticide and fungicide.
Most of pesticides which have been utilised in agriculture are such synthetic compounds which have
been synthesized by chemical processes, and large quantities of synthetic chlorine-containing
356/612
compounds, synthetic mercury-containing compounds and synthetic arseniccontaining compounds etc.,
have been applied as the pesticides to various plants and soil. As a rule, however, these synthetic
pesticides are entirely or relatively difficult to be degraded or decomposed after they are applied to the
plants or soil, and therefore they continue to exist on or in the body of the plants and also in the soil.
The continued existence of these pesticides applied can lead to the problem of pollution of the natural
environment and environmental destruction. Accordingly, a demand is increasing in recent years to
exploit such pesticides which are capable of being degraded and dissipating soon when they have
exerted their pesticidal actions as intended after the application of them. As the pesticides of antibiotics
type are generally more degradable than the synthetic pesticides, it is more reasonable and desirable to
use antibiotic substances as the pesticide in order to avoid the problem of pollution of the natural
environment.
An object of the present invention is to provide a new antibiotic substance which is useful as a
pesticide to control various kinds of phyto-pathogenic microorganisms and particularly phytopathogenic fungi. A further object of the present invention is to provide a process for the production of
such a new antibiotic substance. Another objects of the present invention will be clear from the
following description.
We have made our extensive researches to examine metabolic products of many strains of the genus
Streptomyces for the purpose to seek for a new antibiotic substance which is active in inhibiting the
growth of micro-organisms pathogenic to various plant diseases. We have now found that an antibiotic
substance which is unknown but exhibits a high activity of inhibiting the growth of various pathogenic
fungi, including pathogenic fungi of rice sheath blight and rice blast, is produced and accumulated in
the culture of a strain of the genus Streptomyces, and that this active substance can be isolated from the
culture. We have succeeded in isolating this active substance in a pure form, and we have designated
this active substance as SF-1,293 substance.
According to a first aspect of the present invention, therefore, there is provided a new antibiotic SF1,293 substance effective in inhibiting the growth of fungi, which forms a white colored amorphous
powder melting at 159 DEG - 161 DEGC., is soluble in water and methanol but sparingly soluble in
ethanol, butanol, acetone, ethyl acetate, chloroform, benzene, hexane and ethyl ether, which is
amphoteric and positive in the reactions with ninhydrin reagent, biuret reagent and Lemieux reagent
but is negative in the reactions with ferric chloride, Fehling reagent, Molisch reagent and Folin reagent,
which shows an optical rotation of [.alpha.]D@25 = minus 34 DEG in its 1 percent aqueous solution,
which gives an elementary analysis C 40.28 percent, H 6.82 percent, N 11.89 percent, P 8.90 percent
and O 32.11 percent (the balance), which shows a molecular weight of 355 as determined from the
titration curve and hence has an empirical formula C11 H22 O6 N3 P, and which exhibits characteristic
absorption bands in the infra-red region of spectrum when pelleted in potassium bromide at the
following wave numbers in cm@@-1 : 1,650 and 1,540 attributable to the amide linkages.
This SF-1293 substance is now identified as a compound represented by the following formula:
##SPC1##
Further properties of the SF-1,293 substance are described below.
In filter paper electrophoresis, the SF-1293 substance migrates over a distance of 4 cm towards the
cathode in 20 minutes at a pH of 1.9 and at a voltage of 3,500 volts, while it migrates over a distance of
5.5 cm towards the anode in 2 hours at a pH of 9.5 and at a voltage of 250 volts. This fact indicates that
the SF-1,293 substance is an amphoteric substance.
In paper chromatography, the SF-1,293 substance shows the following RF-values for different solvent
systems: 0.02 for water-saturated n-butanol; 0.98 for 3 percent aqueous ammonium chloride; 0.50 for
75 percent aqueous phenol; 0.92 for 50 percent aqueous acetone, 0.11 for n-butanol-methanol-water
(4:1:2) 0.01 for benzene-methanol (3:1) and 0.93 for distilled water.
In silica gel and cellulose thin layer chromatography, the SF-1,293 substance exhibits different Rfvalues for different solvent systems as shown in the following table. With different solvent systems, the
SF-1293 substance gives a single spot having different Rf-values, and therefore it is confirmed that the
SF-1,293 substance is pure and homogeneous.
357/612
>;tb;
Table 1
>;tb;______________________________________
>;tb;
Rf-Values
>;tb;
Silica gel Cellulose
>;tb;
thin layer thin layer
>;tb;Developing solvent systems
>;tb;
chromatography
>;tb;
chromatography
>;tb;______________________________________
>;tb;n-Butanol-acetic acid>;tb;water (2:1:1) 0.42
0.65
>;tb;n-Butanol-methanol-water
>;tb;(4:1:2)
0.21
0.41
>;tb;Ethanol-ammonia-water
>;tb;(8:1:1)
0.65
0.43
>;tb;Ethanol-water (4:1)
>;tb;
0.25
0.66
>;tb;n-Propanol-pyridine-acetic
>;tb;acid-water (15:10:3:10)
>;tb;
0.45
0.40
>;tb;______________________________________
The SF-1293 substance was hydrolysed by treating with 6N hydrochloric acid at 110 DEGC. for 20
hours. When the reaction mixture from this hydrolysis reaction was examined by paper
chromatography, it was observed that there were given two spots which were positive in the reaction
with ninhydrin reagent, and that one of these two spots showed a Rf-value corresponding to that of
alanine.
The SF-1,293 substance shows only the terminal absorption in the ultra-violet region of spectrum.
Referring to the attached drawings:
FIG. 1 shows a curve of the infra-red absorption spectrum of the SF-1,293 substance pelleted in
potassium bromide.
FIG. 2 shows a curve of the nuclear magnetic resonance spectrum of the SF-1,293 substance dissolved
in deutero-water.
Referring to the infra-red absorption spectrum curve of the SF-1,293 substance, it is seen that the
absorption band of the amide I exists at 1,650 cm@@-1 and the absorption band of the amide II exists
at 1,540 cm@-@1. From this, it is clear that the SF-1293 substance is one of the peptide-type
antibiotics.
The SF-1,293 substance mainly exhibits an activity of inhibiting the growth of fungal microorganisms.
The minimum inhibitory concentrations of the SF-1,293 substance against various fungi were
determined using the known broth dilution method and are shown in Table 2 below.
>;tb;
Table 2
>;tb;______________________________________
>;tb;
Minimum inhibitory
>;tb;Test micro-organisms
>;tb;
concentrations (mcg/ml)
>;tb;______________________________________
>;tb;Alternaria kikuchiana
>;tb;
3.1
>;tb;Alternaria mali 3.1
>;tb;Botrytis cinerae 3.1
>;tb;Glomerella cingulata
358/612
>;tb;
6.2
>;tb;Pellicularia sasakii
>;tb;
0.09
>;tb;Muccor angulisporus
>;tb;
100
>;tb;Leptosphaeria salvinii
>;tb;
0.75
>;tb;Sclerotinia screlotiorum
>;tb;
0.37
>;tb;Trichophyton asteroides
>;tb;
0.18
>;tb;Piricularia oryzae
>;tb;
25
>;tb;______________________________________
The culture medium used for the determination of the minimum inhibitory concentrations was Czapek's
agar medium.
As will be seen from the results of Table 2, the SF-1,293 substance exhibits a high antimicrobial
activity of inhibiting the growth of a wide range of phyto-pathogenic micro-organisms. Furthermore,
the SF-1,293 substance was confirmed to be highly effective in controlling sheath blight (Pellicularia
sasakii) of rice plants when a series of tests were carried out in a green house and paddy field.
Polyoxins (see the "Agricultural biological chemistry" Vol. 29, pages 848 - 854 (1965) and Vol. 31,
pages 190 - 199 (1967)) and validamycins A and B (see the "Journal of Antibiotics" Vol. 24, pages 119
- 123 (1971)) are known as such antibiotics which are effective to inhibit the growth of various phytopathogenic microorganisms and particularly of Pellicularia sasakii. The SF-1,293 substance can be
differentiated from polyoxins which show clear absorption band in the ultra-violet region of spectrum,
and also from validamycins which are glycoside-type antibiotic.
As mentioned in the above, the SF-1,293 substance of the present invention has antimicrobial activity
and particularly fungicidal activity against phyto-pathogenic fungi. The SF-1,293 substance is useful
for the protection of plants from attack by phyto-pathogenic fungi as well as for the therapeutic
treatment of infections of plants which have been caused by phyto-pathogenic fungi.
According to a second aspect of the present invention, therefore, there is provided a method of
controlling fungal infections of plants, which comprises applying an effective amount of the SF-1,293
substance to plants. In particular, according to an embodiment of the second aspect of the present
invention, there is provided a method of controlling the sheath blight and rice blast diseases of rice
plant, which comprises applying an effective amount of the SF-1,293 substance to rice plants.
For use in the control of fungal infections of plants, the SF-1,293 substance of the present invention
may be applied to plants, either directly or in admixture with an inert carrier or diluent which may be
solid or liquid. The SF-1,293 substance of the present invention may be formulated in the form of dust,
wettable powder, granules, solution, suspension or emulsion, as desired. For the preparation of dust,
wettable powder and granules, solid carrier or vehicle such as diatomaceous earth, talc, kaolin, clay,
silica, calcium carbonate and the like may be used. For the preparation of solution, suspension and
emulsion, liquid carrier or vehicle such as water and organic solvents, for example, xylene, toluene,
benzene, methanol, ethanol, acetone, cyclohexanone, dimethyl-formamide and the like may be used. In
these formulations as prepared, there may be incorporated a variety of surface-active agents as
spreading agent, dispersing agent, wetting agent and/or emulsifying agent.
The SF-1,293 substance of the present invention also exhibits a high inhibitory activity to Trichophyton
asteroides which causes the trichophytosis. Therefore, the SF-1,293 substance of the present invention
is useful for the therapeutic treatment of trichophytosis. For use in the therapeutic treatment of
trichophytosis, the SF-1,293 substance may be formulated into a solution in an appropriate organic
solvent such as cetanol or into an ointment, and these formulations may externally be applied to the
locus of skin where the trichophytosis has ocurred. The SF-1,293 substance is of a low toxicity. Acute
toxicity, of the SF-1,293 substance was tested by intravenously injecting an aqueous solution of the SF-
359/612
1,293 substance into groups of mice, each group consisting of 5 mice. None of mice was dead in each
group treated at dosages of 25 mg/kg. and 50 mg/kg. of the SF-1,293 substance but all of mice were
dead in a group treated at a dosage of 100 mg/kg. of the SF-1,293 substance.
The SF-1,293 substance of the present invention may be produced by cultivating a strain of
Streptomyces hygroscopicus under aerobic conditions. According to a further aspect of the present
invention, therefore, there is provided a process for the production of the SF-1,293 substance, which
comprises cultivating a SF-1,293 substance-producing strain of Streptomyces hygroscopicus under
aerobic conditions in a culture medium containing assimilable nitrogen and carbon sources to produce
and accumulate the SF-1,293 substance in the culture, and then recovering this antibiotic substance
from the culture.
As an example of the SF-1,293 substance-producing strain of Streptomyces hygroscopicus is such a
strain which we firstly isolated from a soil sample and we have designated as Streptomyces
hygroscopicus SF-1,293. This SF-1,293 strain has been deposited in the American Type Culture
Collection, Washington D.C. under ATCC number 21,705 (a culture of this strain was received by the
ATCC on 16th July, 1971) as well as in a Japanese public depository "Fermentation Research
Institute," Chiba, Japan, under a deposition number FERM-P No. 996.
Streptomyces hygroscopicus SF-1,293 has the following microbiological characteristics:
I. morphological observation
Aerial mycelium are well produced and spores are abundantly formed on starch-agar, oat meal-agar,
yeast-malt-agar and tyrosin-agar media. Aerial mycelium branches simply but does not branch in the
form of whorl. Closed, compact spirals or open, short spirals are formed at the tip of the aerial
mycelium. No formation of sclerotium is observed. Electron-microscopic observation shows that the
surface structure of the spore is smooth. Spores are of elliptical shape to oval shape, and 10 or more
spores normally link with each other. The size of the spore is measuring 0.6 - 0.8 microns by 0.8 - 1.1
microns.
Ii. characteristics on different culture media are tabulated in Table 3 below.
>;tb;
Table 3
>;tb;__________________________________________________________________________
>;tb;
Soluble
>;tb;Culture medium
>;tb;
Growth Aerial mycelium
>;tb;
pigment
>;tb;__________________________________________________________________________
>;tb;Sucrose nitrate
>;tb;
Colorless to
>;tb;
Scant, white to
>;tb;
None
>;tb;agar
light brown,
>;tb;
whity grey in
>;tb;
with slight
>;tb;
color
>;tb;
greenish
>;tb;
tinge
>;tb;Glucose aspara>;tb;
Cream to faint
>;tb;
White, later
>;tb;
None
>;tb;gine agar green turning into
>;tb;
light greenish
>;tb;
brown
>;tb;Glycerine aspara>;tb;
Cream to light
>;tb;
Scant, white in
>;tb;
None
>;tb;gine agar yellow color
360/612
>;tb;Starch agar
>;tb;
good growth,
>;tb;
Abundant, greyish
>;tb;
None
>;tb;
cream with
>;tb;
brown, gradually
>;tb;
faint green>;tb;
becoming
>;tb;
ish tinge,
>;tb;
hygroscopicus
>;tb;
gradually turn>;tb;
ing into light
>;tb;
brown
>;tb;Tyrosine agar
>;tb;
Good growth,
>;tb;
Abundant, greyish
>;tb;
None
>;tb;
yellowish cream
>;tb;
brown, gradually
>;tb;
to light becoming
>;tb;
yellowish
>;tb;
hygroscopicus
>;tb;
brown
>;tb;Nutrient agar
>;tb;
Thin growth,
>;tb;
Scant, white in
>;tb;
None
>;tb;
light yellow
>;tb;
color
>;tb;Yeast malt agar
>;tb;
Good growth,
>;tb;
Abundant, brown>;tb;
None
>;tb;
yellowish
>;tb;
ish grey, gradua>;tb;
brown lly becoming
>;tb;
hygroscopicus
>;tb;Oat meal agar
>;tb;
Good growth,
>;tb;
Abundant, greyish
>;tb;
None
>;tb;
light greyish
>;tb;
brown, gradually
>;tb;
green becoming
>;tb;
hygroscopicus
>;tb;Yeast starch
>;tb;
Good Growth,
>;tb;
Abundant, brown>;tb;
None
>;tb;agar
yellowish
>;tb;
ish grey, gradu>;tb;
brown ally becoming
>;tb;
hygroscopicus
>;tb;Potato plug
>;tb;
Raised growth,
>;tb;
Not observed
>;tb;
None
>;tb;
highly wrinkl>;tb;
ed, light brown
361/612
>;tb;__________________________________________________________________________
>;tb; Note: The incubation temperature was 28 DEGC. on all the culture
>;tb; media.
>;tb;______________________________________
>;tb;III. Physiological properties:
>;tb;1.
Growth temperature range:
>;tb;
Good growth is made at a temperature in a range
>;tb;
of 20 DEG to 40 DEGC on yeast malt agar
>;tb;
slant medium.
>;tb;2.
Liquefaction of gelatine:
>;tb;
No liquefaction is observed during the
>;tb;
incubation at 20 DEGC for 30 days.
>;tb;3.
Hydrolysis of starch:
>;tb;
Postive (strong)
>;tb;4.
Coagulation of skimmed
>;tb;
Negative (at 28 DEGC
>;tb;
milk:
and at 37 DEGC)
>;tb;5.
Peptonization of skimmed
>;tb;
Positive (at 28 DEGC
>;tb;
milk:
and at 37 DEGC)
>;tb;6.
Formation of melanin>;tb;
Negative
>;tb;
like pigment:
>;tb;IV. Utilization of carbon sources: (estimated in
>;tb;
Pridham-Gottlieb's agar medium)
>;tb;1.
Utilize: D-glucose, D-fructose, D-mannitol,
>;tb;
sucrose and raffinose.
>;tb;2.
Doubtful: D-xylose and L-arabinose.
>;tb;3.
Not utilize:
>;tb;
I-inositol and rhamnose.
>;tb;______________________________________
The above-mentioned microbiological characteristics of Streptomyces hygroscopicus SF-1,293
(hereinafter, merely called the SF-1,293 strain) may be summarised as follows: the aerial mycelium
produces spirals and the surface structure of the spore is smooth. The color of the growth is cream to
light green to yellowish brown. The aerial mycellium is greyish brown in color and gradually becomes
hygroscopicus. Formation of soluble pigment is observed neither on synthetic culture media nor on
organic culture media, and hence the SF-1,293 strain is non-chromogenic.
The above-mentioned properties of the SF-1,293 strain well coincide with those of the known species
Streptomyces hygroscopicus. Thus, the SF-1,293 strain exhibits the following three properties:
a. The aerial mycelium produces spirals,
b. the aerial mycelium produced is greyish brown in color, and
c. the aerial mycelium becomes hygroscopicus:
Whose properties are characteristic of the known species Streptomyces hygroscopicus.
Comparison of the SF-1,293 strain is made with the known strain Streptomyces hygroscopicus
according to the Waksman's description (Waksman's "The Actinomycetes" Vol. 2, pages 230 - 231
(1961)). It is recognized that the SF-1,293 strain is differentiated from the known species Streptomyces
hygroscopicus with respect to the colors of the growth on the sucrose-nitrate agar and glucoseasparagine agar media as well as with respect to the formation of soluble pigment, but that the SF1,293 strain well coincides with the known species Streptomyces hygroscopicus with respect to their
other conditions of the growth and physiological properties.
In consequence, the SF-1,293 strain well coincides with the known strain of Streptomyces
hygroscopicus mentioned in the Waksman's description in respect to the above-mentioned basic three
characteristics, though they may be differentiated from each other with respect to some minute
properties of them. Therefore, it is reasonable to consider that the SF-1,293 strain belongs to the
362/612
species Streptomyces hygroscopicus. Accordingly, we have designated the SF-1,293 strain as
Streptomyces hygroscopicus SF-1,293 in order to make the SF-1,293 strain distinguishable from the
known strain of Streptomyces hygroscopicus.
The SF-1,293 strain has properties which are liable to vary as may usually be observed with the other
Streptomyces. Thus, for example, the SF-1,293 strain may produce a variant or mutant when it is
treated with various mutagens such as ultra-violet radiations, X-rays, radio-active rays, high-frequency
electromagnetic waves and chemicals. Any natural or artificial variant or mutant of the SF-1,293 strain
may be used for the production of the SF-1,293 substance according to the present invention, as long as
the variant or mutant has the ability to produce the SF-1,293 substance of the present invention.
According to an embodiment of the present invention, therefore, there is provided a process for the
production of the SF-1,293 substance, which comprises cultivating a strain of Streptomyces
hygroscopicus identified as ATCC 21,705 under aerobic conditions in a culture medium containing
assimilable nitrogen and carbon sources to produce and accumulate the SF-1,293 substance in the
culture, and then recovering this antibiotic substance from the culture.
In the process according to the present invention, a SF-1,293 substance-producing strain of
Streptomyces hygroscopicus and particularly the SF-1,293 strain (ATCC 21,705) may be cultivated in
a known manner under aerobic conditions in a culture medium containing such nutrients which may be
utilised by usual micro-organisms. As the nutrient sources may be employed any of the known nutrient
substances which have commonly been used in the cultivation of the known strains of Streptomyces.
For instance, glucose, starch, glycerine, sucrose, starch syrup, molasses and the like are useful as the
carbon source. Further, soybean meal, wheat-embryo, meat extract, peptone, dried yeast, corn steep
liquor, soluble vegetable protein, ammonium sulfate, sodium nitrate and the like may be used as the
nitrogen source. If required, inorganic salts such as calcium carbonate, sodium chloride, potassium
chloride, iron sulfate, nickel chloride, phosphates and the like may be added to the culture medium. In
addition, to the culture medium may be added such organic and inorganic materials which aid the
growth of the SF-1,293 strain and promote the production of the SF-1,293 substance.
As the method of cultivating the SF-1,293 strain, liquid cultivation methods and particularly liquid
cultivation method under submerged aerobic conditions are most preferred similar to the general
processes of the production of the known antibiotics. The cultivation may suitably be effected under
aerobic conditions and the suitable incubation temperature is in a range of 25 DEGC to 35 DEGC. For
the commercial or laboratory production of the SF-1,293 substance, however, it is often preferred to
carry out the cultivation at a temperature in the vicinity of 28 DEGC. In these circumstances, the
concentration of the SF-1,293 substance in the culture broth reaches a maximum at the end of 3 to 5
days of fermentation, either in shake-cultivation method or in tank-cultivation method.
For assay of the SF-1,293 substance, the following method may be used: the assaying culture medium
comprising 2.5 percent glucose, 0.2 percent sodium nitrate, 0.1 percent mono-potassium phosphate,
0.05 percent magnesium sulfate, 0.05 percent potassium chloride, 0.01 percent ferrous sulfate, 1.5
percent agar, pH 6.0 may be used. As the assaying micro-organism may be used Pellicularia sasakii. In
this assaying method, at a concentration of 1 mcg/ml. to 32 mcg/ml. of the SF-1,293 substance, the
relation between the logarithm of the concentrations and the diameter of the inhibition zone can be
plotted linearly, giving the inhibition zone of 24 to 50 mm in diameter (as determined by the cupplate
method).
For the control of fungal disease of plants, the culture broth containing the SF-1,293 substance which
has been obtained from the cultivation of the SF-1,293 strain may directly be applied to plants without
isolation of the SF-1,293 substance. However, the SF-1293 substance may be receovered from the
culture by isolation and then purified by using any of the known methods which have commonly
utilised for the recovery and purification of known antibiotics.
The SF-1,293 substance as producted by the cultivation of the SF-1,293 strain is mainly present
dissolved in the liquid phase of the culture broth. As the SF-1,293 substance is a water-soluble and
amphoteric substance as mentioned hereinbefore, it may be recovered from the culture by adsorbing
either onto a cation-exchange resin such as sulfonated polystyrene resin (for example, a product
commercially available under a trade name "Amberlite IR 120") and sulfonated copolymer of styrene
363/612
and divinylbenzene (for example, a product commercially available under a trade name "Dowex
50W"), or onto an anion-exchange resin such as quarternary ammonium hydroxide derivative of
polystyrene containing groups --N-(CH3)3 OH as the functional group (for example, a product
commercially available under a trade name "Amberlite IRA-400"), polyaminated polystyrene (for
example, a product commercially available under a trade name "Amberlite IR-45") and polyaminated
phenol-formaldehyde copolymer (for example, a product commercially available under a trade name
"Amberlite IR-4B"), and then eluting from the resin with an aqueous solution of a suitable acid, alkali
or salt.
For the recovery of the SF-1,293 substance from the culture broth of the SF-1,293 strain, it is effective
to filter the culture broth, separate the filter cake (that is, the solid phase of the broth containing
mycellium cake) from the filtrate (that is, the liquid phase of the culture broth), pass the filtrate through
a column of a strongly acidic cation-exchange resin such as sulfonated copolymer of styrene and
divinylbenzene (for example, a product commercially available under a trade name "Dowex 50W" of H
cycle) and then pass a stream of aqueous ammonia through the resin column for elution. The eluate
may be evaporated in vacuo to give a crude powder of the SF-1,293 substance.
For the purification of a crude powder of the SF-1,293 substance so obtained, it may be
chromatographed on cellulose, silica gel, alumina or dextran gel which has been cross-linked with
epichlorohydrin. In this way, the SF-1,293 substance may be obtained in the form of a pure white
colored amorphous powder of a melting point of 159 DEG - 161 DEGC.
The present invention is now illustrated but in no way limited by the following Examples.
Example 1
A stock culture of Streptomyces hygroscopicus SF-1,293 (identifiled as ATCC No. 21,705) was
inoculated to 15 litres of a liquid culture medium comprising 2.0 percent starch, 1.0 percent peptone,
0.3 percent meat extract, 0.05 percent di-potassium phosphate, pH 7.0, and then stirr-cultured at 28
DEGC for 24 hours under aeration of prepare a seed culture.
This seed culture was inoculated to 200 l. of a liquid culture medium comprising 3.0 percent glucose,
1.0 percent starch syrup, 2.5 percent wheat-embryo, 0.5 percent soluble vegetable protein, 0.1 percent
soybean oil, 0.1 percent yeast extract, 0.001 percent ferrous sulfate, 0.0001 percent nickel chloride,
0.0001 percent cobalt chloride, pH 7.0, and then stirr-cultured at 28 DEGC for 96 hours under aeration.
The resulting culture broth was adjusted to pH 3 by addition of 6N hydrochloric acid and then filtered
to give 150 l. of the broth filtrate (potency, 110 mcg/ml.).
The broth filtrate was passed through a column of active carbon (of a volume of 7.5 l.), and
subsequently 30 l. of water was passed through said column for the washing purpose. The solution
which passed out of the column and the washings were combined together (to a total volume of 180 l.),
and the combined solution was passed through a column of 9 l. of a cation-exchange resin comprising a
polysulfonated copolymer of styrenedivinylbenzene of the H-cycle (commercially available under a
trade name "Dowex 50W-X2") in the form of beads of 50 - 100 meshes in order to make the active
substance adsorbed by the cation-exchange resin. The resin column was washed with water and then
subjected to elution using 0.05N aqueous ammonia. The active fractions of the eluate were combined
together (to a total volume of 45 l.), and the solution was concentrated by evaporation under reduced
pressure to give 50 g. of a crude power of light yellowish brown color (potency, 200 mcg/mg).
20 g. of the crude powder so obtained was dissolved in 2 l. of distilled water, and the resulting solution
was passed through a column of 1.7 l. of cation-exchange resin comprising a sulfonated copolymer of
styrenedivinylbenzene of the H-cycle (commercially available under a trade name "Dowex 50W-X2")
in the form of beads of 200 - 400 meshes, so that the active substance was adsorbed by the cationexchange resin. The resin column was washed with water and then eluted with 0.01N aqueous
ammonia while the eluate was collected in fractions of each 2.5 l. The fractions No. 37 to No. 42 which
showed the antifungal activity were combined together and then concentrated by evaportion under
reduced pressure to give 3.1 g. of a white colored powder containing the SF-1,293 substance (potency,
680 mcg/mg). 500 mg. of this powder was dissolved in 4 ml. of distilled water, and the resulting
solution was passed through a column of 800 ml. of a dextran gel cross-linked with epichlorohydrin (a
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product commercially available under a trade name "Sephadex G-10") for the chromatographic
purpose. The adsorbed active substance was chromatographically developed by passing distilled water
through the column of the dextran gel, and the eluate was collected in fractions of each 6 ml. volume.
Such fractions No. 55 to No. 58 which showed a single spot of the SF-1,293 substance on cellulose thin
layer chromatography (using a solvent mixture of n-butanol-acetic acid-water (2:1:1) as the developing
solvent) were combined together and then concentrated by evaporation under reduced pressure to yield
210 mg. of a pure, white-colored powder of the SF-1,293 substance (potency, 1,000 mcg/mg).
Example 2
5 g. of the crude powder of light yellowish brown color obtained in Example 1 was dissolved in 1 litre
of distilled water, and the resulting solution was passed through a column of 300 ml. of an anionexchange resin comprising a quarternary ammonium hydroxide derivative of polystyrene containing
the functional groups --N-(CH3)3 OH (commercially available under a trade name "Amberlite IRA400"), so that the active substance was adsorbed by the anion-exchange resin. The resin column was
washed with water and then eluted with 0.2N sulfuric acid. Active fractions of the eluate were
combined together (to a total volume of 800 ml), and to the eluted solution was added an amount of
barium carbonate. Barium sulfate which was formed was filtered off and the filtrate separated was
immediately evaporated to dryness under reduced pressure to give 2.1 g. of a powder of a light yellow
color.
This powder was dissolved in 300 ml. of distilled water and the solution was passed through a column
of 100 ml. of an anion-exchange dextran gel containing diethylaminoethyl as the functional group
(commercially available under a trade name "DEAE-Sephadex A-25") in the form of chloride. The
column was washed with water and developed chromatographically using a 0.02 M aqueous solution of
sodium chloride. Active fractions of the eluate were combined to a total volume of 450 ml. and then
concentrated to dryness. The residue was extracted with methanol, and the methanolic solution was
separated by filtration from the sodium chloride which remained un-dissolved. The methanolic extract
was evaporated under reduced pressure to give 520 mg. of a white colored powder (potency 650
mcg/mg).
This powder was dissolved in a small amount of water, and the aqueous solution obtained was mixed
with a small amount of cellulose powder. The mixture was dried up and placed on the top of a cellulose
column (400 g.) and the column was developed using a solvent mixture of n-butanol-acetic acid-water
(2:1:1). The eluate was collected in fractions of each 15 ml. volume. Such active fractions No. 71 to
No. 80 were combined together and evaporated to dryness under reduced pressure. The residue
obtained was dissolved in 10 ml. of distilled water and the aqueous solution was freeze-dried to yield
240 mg. of the SF-1,293 substance in the form of a pure, white colored powder (potency, 1,000
mcg/ml.).
Example 3
A stock culture of Streptomyces hygroscopicus SF-1,293 (identified as ATCC No. 21,705) was
inoculated to 800 ml. of a liquid culture medium comprising 2.0 percent glucose, 2.0 percent dried
bouillon, pH 7, and then stirr-cultured at 28 DEGC. for 30 hours under aeration to give a seed culture.
This seed culture was inoculated to 35 l. of a liquid culture medium comprising 2.5 percent molasses,
1.0 percent glucose, 2.5 percent defatted cotton seed meal, 0.1 percent yeast extract, 0.5 percent wheatembryo, pH 7, and then incubated at 28 DEGC. for 72 hours under aeration and agitation. The culture
broth obtained was adjusted to pH 3 by addition of 6N hydrochloric acid and then filtered to give 30 l.
of the broth filtrate (potency, 180 mcg/ml.).
This broth filtrate was then treated in the same manner as in Example 1 for the recovery and
purification of the SF-1,293 substance. 820 mg. of the SF-1,293 substance was yielded in the form of a
pure, white colored powder (potency, 1,000 mcg/ml.).
Example 4
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This example demonstrates that the SF-1,293 substance is highly effective to control the sheath blight
disease of rice plants.
An inoculum of sheath blight-causing microorganism (Pellicularia sasakii) was inoculated by spraying
onto aquatic rice plants in a paddy field. At an initial phase of infection when all the rice plants
appeared to be infected evenly, a test solution containing an active substance at a concentration as
indicated in Table 4 below was sprayed onto the infected rice plants. 5 Days after this first application
of the test solution, a second application of the test solution was made, if required. The test was carried
out in two replications. The test solution was applied at a rate of 150 l. per 10 ares. 14 Days after the
first application of the test solution, length of such a lesion which developed to the highest extent
among many lesions ocurring in each rice plant was measured for 40 rice plants per one plot, either
treated or untreated. Rate of controlling effect was calculated according to the following equation:
##SPC2##
The test results obtained are shown in Table 4 below.
>;tb;
Table 4
>;tb;__________________________________________________________________________
>;tb;Active substance Average length
>;tb;
Rate of
>;tb;tested (con>;tb;
Times of
>;tb;
of the most de>;tb;
controlling
>;tb;centration
>;tb;
application
>;tb;
veloped lesion
>;tb;
effect
>;tb;__________________________________________________________________________
>;tb;The SF-1293 sub>;tb;
1
12.1 mm 70.6%
>;tb;stance (40 ppm.)
>;tb;The SF-1293 sub>;tb;
2
10.7 mm 74,0%
>;tb;stance (20 ppm.)
>;tb;Polyoxins (40
>;tb;ppm.) (compara>;tb;
2
20.7 mm 49.4%
>;tb;tive)
>;tb;Untreated -- 41.1 mm 0
>;tb;__________________________________________________________________________
From the results of the above Table, it is clear that the SF-1,293 substance exhibits a remarkably higher
effect to control the sheath blight of rice plants in paddy field than the polyoxins which are known and
have been utilized as one of antibiotics effective against the sheath blight.
In another tests, an aqueous solution of 30 ppm. of the SF-1,293 substance was sprayed onto rice plants
which were planted in pots. After the sprayed solution was dried, an inoculum of Pellicuraria sasakii
was sprayed onto the treated rice plants. The inoculated rice plants were then incubated at 30 DEGC.
for 5 days in a green house under a high humidity. Thereafter, the incubated rice plants were visually
examined, and it was observed that the treated rice plants were prevented perfectly from the infection
of sheath blight.
Example 5
A test solution containing an active substance at a concentration as indicated in Table 5 below was
sprayed by means of a spray-gun evenly onto aquatic rice plants of 4 true leave age which were planted
in pots of 9 cm in diameter. The test solution was sprayed at a rate of 35 ml. per two pots. After the
sprayed solution was dried in air, the treated rice plants were placed in a green house at 25 DEGC. and
under a high humidity. In this green house, an aqueous suspension of spores of the rice blast-causing
366/612
micro-organism (Piricularia oryzae) was sprayed onto the treated rice plants for inoculation. 5 days
after the inoculation, the number of lesions per leaf of the infected rice plants was counted. Rate of
controlling effect was calculated according to the following equation: ##SPC3##
The test results obtained are shown in Table 5 below.
>;tb;______________________________________
>;tb;
Concentration
>;tb;
(ppm.) of the
>;tb;
Average num>;tb;
Rate of
>;tb;
active substance
>;tb;
ber of control>;tb;Active substance
>;tb;
in the test lesions per
>;tb;
ling ef>;tb;tested
solution sprayed
>;tb;
leaf
fect(%)
>;tb;______________________________________
>;tb;The SF-1293 sub>;tb;
25
0.5
96
>;tb;stance
>;tb;do.
50
0.1
99
>;tb;do.
100
0
100
>;tb;Kasugamycin
>;tb;(comparative)
>;tb;
25
1.9
84
>;tb;do.
50
1.1
91
>;tb;do.
100
0.5
96
>;tb;Phenylmercuric
>;tb;acetate
15
1.1
91
>;tb;(comparative)
>;tb;
(as Hg)
>;tb;Untreated -11.8
0
>;tb;______________________________________
From the results of the above table, it is seen that the SF-1,293 substance is much more effective to
control the rice blast than kasugamycin and phenyl-mercuric acetate which have frequently been
utilized for that purpose.
Example 6
The SF-1,293 substance was formulated into a hydrophilic ointment containing 3 percent of the SF1,293 substance well mixed with a mixture of cetanol-polyethylene glycol (commercially available
under trade namr of "Emulgen 408") -white vaseline-water (18:5:38:39) as the ointment base.
Groups of male, white guinea pigs (10 guinea pigs in each group) of an average body weight of 240 g.
were used as the test animal.
Hairs were removed from four separate sections, each of a size of about 4 .times. 4 cm., on the back
portion of guinea pig, and the skin in these sections was lightly rubbed with a pumice stone. A
suspension of Trichophyton asteroides which is one of the trichophytosis --causing micro-organisms
was then applied onto the skin in these sections for inoculation. 2 Days after the inoculation, the abovementioned ointment was applied to the skin situating in the aforesaid sections at a rate of about 0.2 g.
per section. The application of the ointment was made for 10 days once a day. One of the four sections
was used as the control (untreated) and was left free from the application of the ointment after the
inoculation. 12 Days after the inoculation, the guinea pigs were killed, and three pieces of the skin
(each piece was of a size of 3 mm .times. 3 mm) were cut out of the skin in each section. Each of these
skin pieces was incubated at 27 DEGC. for 7 days on Sabourand's agar medium to examine the
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presence of the inoculated microorganism. Rate of inhibition to the infection of Trichophyton asteroids
was expressed by the following equation: ##SPC4##
It was found that the rate of inhibition of the SF-1,293 substance-treated sections was 73.3 percent and
0 percent for the control section (untreated). This indicates that the SF-1,293 substance is effective for
the therapeutic treatment of the infection of Trichophyton asteroides.Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of US3832394
1.
1. ##SPC5##Data supplied from the esp@cenet database - Worldwide
368/612
29. US4056617
- 11/1/1977
ORGANIC PYRIDAZYL PHOSPHOROTHIOATES AND THEIR USE AS
INSECTICIDES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=US4056617
Inventor(s):
JOJIMA TERUOMI (--); TSUJI HIDEAKIRA (--); YAMAMOTO SHINJIRO (--);
OMINO TEIJI (--)
Applicant(s):
SANKYO CO (--)
IP Class 4 Digits: A01N
IP Class:A01N9/36
E Class: C07F9/6509B2K2
Application Number:
US19750620227 (19751006)
Priority Number: US19750620227 (19751006); JP19690069218 (19690901); JP19690073788
(19690917); US19750540234 (19750110)
Family: US4056617
Abstract:
Abstract of US4056617
New organic phosphorus compounds having the formula wherein R1 represents an alkyl group of 1-4
carbon atoms, R2 represents an alkoxy group of 1-4 carbon atoms or phenyl group and R3 represents
hydrogen atom, an alkyl group of 1-4 carbon atoms, phenyl group or the group of the formula -X-R4 in
which R4 represents an alkyl group of 1-6 carbon atoms or a benzyl group which may be substituted
with a halogen atom in the phenyl moiety and X represents oxygen atom or sulfur atom. The present
compounds are prepared by reacting a phosphoric or phosphonic acid halide having the formula
wherein R1 and R2 are as defined above and Y represents a halogen atom with a pyridazinone
derivative having the formula wherein R3 is as defined above. The present compounds show a superior
insecticidal activity against various harmful insects, e.g., rice stem borers, planthoppers, mites, aphids,
flies, mosquitoes and the like and thus they are useful as an insecticide or acaricide.Description:
Description of US4056617
This invention relates to a new class of organic phosphorus compounds, process for the preparation
thereof and their use as an insecticide or acaricide.
More particularly, it is concerned with an organic phosphorus compound having the formula
##STR4## wherein R1 represents an alkyl group of 1-4 carbon atoms, R2 represents an alkoxy group
of 1-4 carbon atoms or phenyl group and R3 represents hydrogen atom, an alkyl group of 1-4 carbon
atoms, phenyl group or the group of the formula
--X--R4
in which R4 represents an alkyl group of 1-6 carbon atoms or a benzyl group which may be substituted
with a halogen atom in the phenyl moiety and X represents oxygen atom or sulfur atom, with a process
for the preparation thereof as well as with an insecticidal and acaricidal composition containing the
same as an active ingredient and a method for controlling harmful insects by utilizing the same.
369/612
In the above formula (I), the group R1 may be illustrated by methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl or tert.butyl; the group R2 may be illustrated by methoxy, ethoxy, isopropoxy, n-butoxy,
isobutoxy, tert.butoxy or phenyl; the group R3 may be illustrated by hydrogen, methyl, ethyl, n-propyl,
tert.butyl, phenyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.butoxy, isobutoxy,
tert.butoxy, pentyloxy, hexyloxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec.
butylthio, isobutylthio, tert.butylthio, pentylthio, hexylthio, benzyloxy, benzylthio, o-, m- or pfluorobenzyloxy, o-, m- or p-chlorobenzylthio, o-, m- or p-bromobenzylthio or o-, m- or pfluorobenzylthio.
Heretofore, a number of organic phosphorus compounds of various types have been synthesized and
evaluated for insecticidal activities and many organic phosphorus compounds are now commercially
available as an insecticide, including, for example, parathion, methyl parathion, E.P.N. (Registered
Trade Mark, O-Ethyl O-p-nitrophenylphenylphosphonothioate), malathion, diazinon and the like.
Such prio insecticidal phosphorus compounds have still, however, some shortcomings to be improved,
for example, in that they are not equally effective against all kinds of harmful insects. For instance,
some prior phosphorus compounds are known effective against certain kinds of harmful insects, e.g.,
rice stem borers, planthoppers and the like, but not so effective against many mites and aphids.
Thus, many attempts have been made in the art to discover and develop universally effective
insecticidal phosphorus compounds.
As a result of our extensive investigations on the preparation of various roganic phosphorus
compounds and the insecticidal activity thereof, it has been found that a new type of the organic
phosphorus compounds of the above formula (I) is successfully synthesized and they exhibit high
insecticidal and acaricidal activity against various harmful insects as compared with prior analogous
phosphorus compounds.
It is, accordingly, an object of this invention to provide new organic phosphorus compounds of the
above formula (I) which are highly effective for controlling harmful insects.
It is another object of this invention to provide a process for the preparation of the valuable organic
phosphorus compounds of the above formula (I).
It is another object of this invention to provide a new method for controlling harmful insects which
comprises applying the new phosphorus compound of the above formula (I) to harmful insects.
Still another object of this invention is to provide an insecticidal and acaricidal composition which
comprises as an active ingredient the new phosphorus compound of the above formula (I) and an
agriculturally-acceptable carrier.
These and other objects of this invention will become apparent to those skilled in the art from the
following description.
The new organic phosphorus compound (I) of this invention can be easily prepared by reacting a
phosphoric or phosphonic acid halide having the formula ##STR5## wherein R1 and R2 are as defined
above and Y represents a halogen atom with a pyridazinone derivative having the formula ##STR6##
wherein R3 is as defined above.
In carrying out the process of this invention, the reaction can be usually and preferably effected by
admixing the starting halide of the above formula (II) with the pyridazinone derivative of the above
formula (III) in the presence or absence of a solvent and then either maintaining the resulting mixture at
room temperature or heating said mixture up to about 70 DEG C. Examples of a suitable solvent which
may be employed in the process of this invention include inert organic solvents, e.g., ether, acetone,
methyl ethyl ketone, benzene, toluene, xylene, acetonitrile and the like and water. The reagent, the
pyridazinone derivative of the above formula (III), may be employed in the reaction as a free base, but
it is preferable for the better proceeding of the reaction that, where the free base is employed in the
reaction, the reaction be effected in the presence of an acid-binding agent. Examples of a suitable acid-
370/612
binding agent include inorganic bases such as alkali metal hydroxides or carbonates, e.g., sodium
hydroxide or potassium carbonate; organic bases such as alkali metal alcoholates, e.g., sodium
methylate or ethylate, cyclic amines, e.g., pyridine, or alkylamines, e.g., triethylamine or diethylamine;
and the like. It is also preferable for the better proceeding of the reaction that the reagent be employed
in the reaction as the previously-formed alkali metal salt thereof.
After completion of the reaction, the reaction product (I) can be readily recovered and purified from the
reaction mixture by a conventional method. For instance, the reaction mixture is filtered to remove
inorganic salts and the filtrate is concentrated. To the residue (crude end product) is added an aqueous
alkali solution, e.g., aqueous sodium hydroxide or aqueous sodium carbonate and the resulting mixture
is extracted with a suitable water-immiscible organic solvent, e.g., benzene, toluene or chloroform. The
organic layer is separated and washed thoroughly with water and then the solvent is distilled off and, if
necessary, column-chromatographed to give the pure end product (I).
Illustrative of the preferred group of the organic phosphorus compounds (I) of this invention are as
follows:
1. O,O-Diethyl O-3-pyridazylphosphorothioate;
2. O,O-diethyl O-(6-methyl-3-pyridazyl)phosphoro thioate;
3. O,O-diethyl O-(6-phenyl-3-pyridazyl)phosphoro thioate;
4. O,O-diethyl O-(6-methylthio-3-pyridazyl)phosphorothioate;
5. O,O-diethyl O-(6-ethylthio-3-pyridazyl)phosphorothioate;
6. O,O-diethyl O-(6-isopropylthio-3-pyridazyl)phosphorothioate;
7. O,O-diethyl O-(6-benzylthio-3-pyridazyl)phosphorothioate;
8. O,O-diethyl O-(6-p-chlorobenzylthio-3-pyridazyl)phosphorothioate;
9. O,O-diethyl O-(6-methoxy-3-pyridazyl)phosphorothioate;
10. O,O-diisopropyl O-(6-methylthio-3-pyridazyl)phosphorothioate;
11. O,O-diisobutyl O-(6-methylthio-3-pyridazyl)phosphorothioate;
12. O-ethyl O-(6-methylthio-3-pyridazyl)phenylphosphonothioate;
13. O-ethyl O-(6-n-butylthio-3-pyridazyl)phenylphosphonothioate;
14. O,O-di-n-butyl O-(6-methylthio-3-pyridazyl)phosphorothioate;
15. O,O-diisopropyl O-(6-ethylthio-3-pyridazyl)phosphorothioate;
16. O,O-diethyl O-(6-n-butylthio-3-pyridazyl)phosphorothioate;
17. O,O-di-n-butyl O-(6-n-butylthio-3-pyridazyl)phosphorothioate;
18. O,O-diisopropyl O-(6-n-butylthio-3-pyridazyl)phosphorothioate;
19. O-ethyl O-(6-methoxy-3-pyridazyl)phenylphosphonothioate;
20. O,O-diisopropyl O-(6-methoxy-3-pyridazyl)phosphorothioate;
21. O,O-di-n-butyl O-(6-methoxy-3-pyridazyl)phosphorothioate;
22. O,O-diethyl O-(6-ethoxy-3-pyridazyl)phosphorothioate;
23. O,O-diisopropyl O-(6-ethoxy-3-pyridazyl)phosphorothioate;
24. O,O-diethyl O-(6-isopropoxy-3-pyridazyl)phosphorothioate;
25. O,O-diethyl O-(6-n-propoxy-3-pyridazyl)phosphorothioate;
26. O,O-diethyl O-(6-n-butoxy-3-pyridazyl)phosphorothioate;
27. O,O-diisopropyl O-(6-n-butoxy-3-pyridazyl)phosphorothioate;
28. O,O-di-n-butyl O-(6-n-butoxy-3-pyridazyl)phosphorothioate;
29. O-ethyl O-(6-n-butoxy-3-pyridazyl)phenylphosphonothioate;
30. O,O-diethyl O-(6-isobutoxy-3-pyridazyl)phosphorothioate;
31. O,O-diethyl O-(6-n-pentoxy-3-pyridazyl)phosphorothioate;
32. O,O-diethyl O-[6-(3-methyl-n-butoxy)-3-pyridazyl]phosphorothioate;
33. O,O-diethyl O-(6-n-hexyloxy-3-pyridazyl)phosphorothioate;
34. O,O-dimethyl O-(6-n-butylthio-3-pyridazyl)phosphorothioate;
35. O,O-diemethyl O-(6-isobutoxy-3-pyridazyl)phosphorothioate;
36. O,O-diethyl O-(6-sec.butoxy-3-pyridazyl)phosphorothioate;
37. O,O-diethyl O-(6-tert.butoxy-3-pyridazyl)phosphorothioate;
38. O,O-diethyl O-(6-benzyloxy-3-pyridazyl)phosphorothioate; and
39. O,O-dimethyl O-(6-isopropoxy-3-pyridazyl)phosphorothioate.
The pyridazinone derivatives of the above formula (III) which may be employed as a reagent in the
process of this invention are new substances except for those derivatives of the above formula (III)
wherein R3 represents hydrogen, methyl, phenyl, methoxy or methylthio. Such new substances can be
371/612
readily prepared, for example, by heating the corresponding 3-halo-6-alkoxy (or benzyloxy)pyridazine
together with anhydrous potassium acetate and acetic acid at about 120 DEG-150 DEG C in a sealed
tube, by heating a 6-halo-pyridazinone together with the corresponding alkyl(or benzyl)mercaptan in an
alcohol in the presence of a base at about 100 DEG-150 DEG C in a sealed tube, or by reacting the
corresponding .omega.-acyl propionic acid with hydrazine hydrate to form the corresponding 6-alkyl4,5-dihydro-3(2H)-pyridazinone and then oxidizing the resulting product with selenium dioxide.
In another aspect of this invention, there is provided a method for controlling harmful insects which
comprises contacting said insects with an insecticidally effective amount of the organic phosphorus
compound of the above formula (I) and also an insecticidal and acaricidal composition which
comprises as an active ingredient the organic phosphorus compound of the above formula (I) and an
agriculturally-acceptable carrier.
The active compound (I) used according to this invention may be conveniently formulated by a known
procedure and employed in various forms including liquids, dusts, granules and wettable powders etc.
Liquids may be prepared by dissolving the active compound in an agriculturally-acceptable liquid
carrier, i.e. a suitable solvent with or without one or more of known adjuvants commonly employed in
the art such as emulsifying agents, wetting agents, or dispersing agents. Suitable solvents include
water, alcohols such as methanol or ethanol, acetone, benzene, toluene, xylene, solvent naphtha,
petroleum ether, the mixture thereof and the like. Suitable adjuvants may be any of those which is
ordinarily employed in the art, and include, for example, the condensation products of alkylene oxides
with phenols or organic acids, alkylarylsulfonates, dialkyl sulfosuccinate, polyoxyethylene ether or
ester derivatives of alcohols or acids and the like.
Dusts and granules may be prepared by mixing said active compound in aninert agriculturally
acceptable solid carrier by a conventional procedure. Suitable solid carriers for use in this invention
include, for example, talc, pyrophylite, kieselguhr, clay, bentonite, diatomaceous earth, kaolin,
precipitated chalk and the like.
Wettable powders may be prepared by mixing said active compound with one or more of the
aforementioned solid carriers and suitable dispersing agents. Suitable dispersing agents include, for
example, those aforementioned adjuvants such as alkylbenzenesulfonates, lignosulfontes or
polyoxyalkylene glycol ethers or esters.
The concentration of the active compound in the composition of this invention may normally be from
about 0.1 to about 95% by weight, and preferably from about 0.5 to about 70% by weight, based upon
the total weight of the composition, although the amount of the active ingredient employed will largely
depend upon such factors as the degree of insect damage, the form of a composition or the particular
active compound, toxicity of the active compound and the like. It should be, however, understood that
the amount of an active compound employed is not critical feature of this invention. Two or more of
said active ingredients may be conveniently incorporated into the agricultural insecticidal composition
of this invention.
The agricultural insecticidal and acaricidal composition of this invention may also include other known
insecticidal agents, e.g., benzenehexachloride, 1,1,1-trichloro-2,2-bis (p-chlorophenyl)ethane, 0,0dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate, 0,0-diethyl S-2-(ethylthio)ethyl
phosphorodithioate and the like; fungicidal agents e.g., phenylmercurychloride, kasugamycin, zinc
ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, ferric methylarsonate, Ntrichloromethylthio-4-cyclohexane-1,2-dicarboxyimide, and the like; fertilizers, and the like.
The method for controlling harmful insects of this invention comprises contacting said insects with an
insecticidally effective amount of the active compound (I). The active compound is, of course, to be
applied in such an amount sufficient to exert the desired insecticidal effect, usually in a concentration
of about 5 ppm or higher for liquid preparations, e.g. liquids and diluted wettable powders and in a
dose rate of about 7-50 g. of the active compound per 10 ares for solid preparations, e.g., dusts and
granules.
372/612
The active compound (I) of this invention has been found to be highly effective for controlling various
harmful insects, e.g. mosquitoes, flies, rice borers, rice leafhoppers, rice maggots, planthoppers, aphids,
mites, cutworms, spider mites and the like.
In order to demonstrate the excellent insecticidal and acaricidal activity of the organic phosphorus
compound (I) according to this invention, the insecticidal and acaricidal tests and the results therefrom
are shown hereinbelow.
All parts and percentages in the Experiments and herein are by weight unless otherwise stated.
EXPERIMENT 1
Test for Acaricidal Activity of the Organic Phosphorus Compounds of this Invention Against TwoSpotted Spider Mite (Tetranychus Urticae)
A wettable powder was prepared by homogeneously admixing and pulverizing 20 parts of each of the
indicated test compounds, 3 parts of sodium dodecylbenzenesulfonate, 2 parts of polyvinyl alcohol and
75 parts of clay. The wettable powder thus prepared was diluted with water to the indicated
concentration and then 0.01% of a spreader ["Gramin", Trade name of a spreader available from Nihon
Nyukazai K.K., Japan, containing polyoxyethylene dodecyl ether, polyoxyethylene aryl ether sulfonic
acid and abietic acid polyalcohol ester] was added thereto.
Into the diluted wettable powder thus prepared was dipped for 10 seconds leaves of cowpea (Vigna
sinensis) upon which adult two-spotted spider mites lived. After air-drying, the leaves were left in a
room maintained at 25 DEG C. After 24 hours, mortality of mite (%) was investigated. An average
number of the mites which were employed in this test was 50 mites for each test.
The results are summarized in the following Table I.
>;tb;
Table I
>;tb;______________________________________
>;tb;
Mortality of mite (%)
>;tb;Test compound No.*
>;tb;
100 ppm 10 ppm
>;tb;______________________________________
>;tb;1
80.3
15.5
>;tb;2
100
100
>;tb;3
100
100
>;tb;4
100
100
>;tb;5
100
100
>;tb;6
100
86.0
>;tb;7
85.2
35.0
>;tb;8
100
68.0
>;tb;9
100
92.0
>;tb;10
92.4
41.1
>;tb;11
81.3
47.5
>;tb;12
100
100
>;tb;13
100
100
>;tb;14
100
100
>;tb;15
100
100
>;tb;16
100
100
>;tb;17
80.0
16.0
>;tb;18
100
100
>;tb;______________________________________
>;tb; *The number of the test compound is the same as specified hereinabove.
EXPERIMENT 2
Test for Insecticidal Activity of the Organic Phosphorus Compounds of this Invention Against Turnip
Aphid (Rhopalosiphum Pseudobrassicae)
373/612
The test compound indicated below was formulated and diluted as set forth in the above Experiment 1.
Into the diluted wettable powder thus prepared were dipped for 30 seconds leaves of radish (Raphanus
sativus) upon which turnip aphids lived. After air-drying, the leaves, which were put into a small bottle
filled with water together with a cotton stopper, were placed into a glass cylinder. Then, the leaves
were left while maintaining at 25 DEG C. After 24 hours, mortality of aphid (%) was investigated.
The test aphids were employed at a rate of 50 insects for each test.
The results are summarized in the following Table II.
>;tb;
Table II
>;tb;______________________________________
>;tb;
Mortality of aphid (%)
>;tb;Te