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สารประกอบอินทรี ย์ซงึ่ อะตอมคาร์ บอนไม่เป็ นชนิดวงหรื อเชื่อมต่อกับอะตอมคาร์ บอนหรื อไฮโดรเจน
(Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds
containing a carbon atom not being member of a ring and having no bond to
a carbon or hydrogen atom, e.g. derivatives of carbonic acid)
จานวน 107 เรื่ อง
ปราโมทย์ ธรรมรัตน์และนิศากร วรวุฒยิ านันท์
หน่วยสร้ างสานึกและพัฒนาประโยชน์จาก
เอกสารสิทธิบตั รเพื่อการวิจยั และพัฒนา (สสวพ.) สกว.
สถาบันค้ นคว้ าและพัฒนาผลิตภัณฑ์อาหาร มหาวิทยาลัยเกษตรศาสตร์ 0-2942-8629 ต่อ 626, 908
1/2194
1. BE771683 - 12/31/1971
USE OF DINITROPHENYL AZIDES AS HERBICIDES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=BE771683
Inventor(s):
ORLETT M J (--)
Applicant(s):
LILLY CO ELI (--)
IP Class 4 Digits: A01N
IP Class:A01N
E Class: A01N33/26; A01N35/04; A01N37/22; A01N37/48; A01N41/06; A01N41/10; A01N47/48;
C07C117/00D
Application Number:
BE19710771683 (19710824)
Priority Number: BE19710771683 (19710824)
Family: BE771683
Abstract:
Abstract of BE771683
The dinitrophenylazides are of formula: (in which R is H, 1-4 C alkyl, 3-8 C cycloalkyl, 1-3 C
alkyloxy, NO2, halogen, 1-3 C alkylsulphonyl, 1-3 C haloalkyl, -NR1R11, -SO2NR1R11, CONR1R11, CN, SCN, -NHCOR1 or -COR1, where R1 and R11 are H or 1-3 C alkyl, and any
halogen atoms present have an atomic wt. 130). They are esp. suitable for use as selective herbicides in
rice crops. (I) may also be converted to dinitroanilines of formula (II), which are herbicides and
fungicides - (in which R111 and R1111 are H, 1-7 C alkyl, 3-5 C alkenyl, 3-5 C alkynyl, or 1-5 C alkyl
or 3-5 C alkenyl or alkynyl substd. by halogen of atomic wt. 85, 1-5 C alkyl substd. by 1 or 2 1-3 C
alkoxy gps., 3-8 C cycloalkyl or 5-8 C cycloalkenyl, with the proviso that only one of R111 and R1111
may be H, or NR111R1111 may form a pyrrolidyl, piperidyl, hexamethyleneiminyl,
heptamethyleneiminyl or morpholinyl ring) by reaction with an amine of formula HNR111R1111.
2/2194
2. CA1230119
- 12/8/1987
N-2-CARBOXYLPHENYLSULFONYL-N'-PYRIMIDIN-2-YL OR TRIAZIN-2YL-UREA COMPOUNDS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CA1230119
Inventor(s):
HILLEMANN CRAIG L (--)
Applicant(s):
DU PONT (--)
IP Class 4 Digits: A01N; C07D
IP Class:A01N47/36; C07D239/28; C07D251/12
E Class: A01N47/36; C07D521/00S
Application Number:
CA19860522875 (19861113)
Priority Number: US19850801120 (19851122); US19850801165 (19851122); US19860826682
(19860210)
Family: CA1230119
Equivalent:
EP0235449
Abstract:
Abstract of CA1230119
TITLE The invention relates to certain herbicidal sulfonamides, agriculturally suitable compositions
thereof and a method for their use as a general or selective preemergent or postemergent herbicide or as
a plant growth regulant. Especially preferred for usage in paddy rice crop because of its selectivity to
rice, especially Japonica rice or paddy rice, and activity against undesired plant growth is the
compound of Formula I where R1 is ethyl, R2 is difluoromethoxy, X and Y are methoxy and Z is CH
as shown below: >;IMG; or >;IMG; I II wherein R is H or CH3: R1 is C1-C3 alkyl, C3-C4
alkoxyalkyl, C2-C4 halo alkyl, C3-C4 alkenyl or C3-C4 alkynyl: R2 is C2-C6 alkoxy, C3-C6
cycloalkoxy. C4-C6 cycloalkylalkoxy, C1-C6 haloalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy,
C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C2-C4 alkoxyalkoxyC2-C4 haloalkoxyalkoxy, C2-C4
alkylthioalkoxy, C2-C4 haloalkylthioalkoxy, C2-C4 alkylsulfinylalkoxy, C2-C4
haloalkylsulfinylalkoxy, C2-C4 alkylsulfonylalkoxy, C2-C4 haloalkylsulfonylalkoxy, C2-C4
cyanoalkoxy, OCH2C(O)CH3, OCH2CH2C(O)CH3, C2-C4 aminoalkoxy, C1-C8 alkylthio, C3-C6
cycloalkylthio, C4-C6 cycloalkylalkylthio, C1-C8 haloalkylthio, C2-C6 alkenylthio, C2-C6
haloalkenylthio, C3-C6 alkynylthio, C3-C6 haloalkynylthio, C2-C4 alkoxyalkylthio, C2-C4
haloalkoxyalkylthio, C2-C4 alkylthioalkylthio, C2-C4 haloalkylthioalkylthio, C2-C4 cyanoalkylthio,
SCH2C(O)CH3, SCH2CH2C(O)CH3, C2-C4 aminoalkylthio, SC6H5, SCH2C6H5, C1-C8
alkylsulfinyl, C3-C6 cycloalkylsulfinyl, C4-C6 cycloalkylalkylsulfinyl, C1-C8 haloalkylsulfinyl, C2C6 alkenylsulfinyl, C2-C6 haloalkenylsulfinyl, C3-C6 alkynylsulfinyl, C3-C6 haloalkynylsulfinyl, C2C4 alkoxyalkylsulfinyl, C2-C4 haloalkoxyalkylsulfinyl, C2-C4 cyanoalkylsulfinyl, S(O)CH2C(O)CH3,
S(O)CH2CH2C(O)CH3, C2-C4 aminoalkylsulfinyl, C2-C8 alkylsulfonyl, C3-C6 cycloalkylsulfonyl,
C4-C6 cycloalkylalkylsulfonyl, C1-C8 haloalkylsulfonyl, C2-C6 alkenylsulfonyl, C2-C6
haloalkenylsulfonyl, C3-C6 alkynylsulfonyl, C3-C6 haloalkynylsulfonyl, C2-C4 alkoxyalkylsulfonyl,
C2-C4 haloalkoxyalkylsulfonyl, C2-C4 cyanoalkylsulfonyl. SO2CH2C(O)CH3,
SO2CH2CH2C(O)CH3, C2-C4 aminoalkylsulfonyl, CH2F, CHF2, CH2Cl, CHCl2, CH2Br, CHBr2,
C2-C6 alkyl substituted with 1-3 atoms of F, Cl or Br, C2-C6 alkenyl. C2-C6 haloalkenyl, C?CH, C2C6 haloalkynyl, OC(O)C1-C4 alkyl, CH2C(O)NRaRb, NHCH3, NRbRc or C1-C4 alkyl substituted
with C1-C4, alkoxy, C3-C4 cycloalkoxy, cyclopropylmethoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy,
3/2194
C2-C4 haloalkenyloxy, C3-C4 alkynyloxy, C3-C4 haloalkynyloxy, C2-C4 alkoxyalkoxy, C2-C4
aminoalkoxy, C1-C4 alkylcarbonyloxy, C1-C4 haloalkylcarbonyloxy, C1-C4 carbamoyloxy, Cl-C4
alkoxycarbonyloxy, OH, OP(O)(OC1-C2 alkyl)2, C1-C4 alkylsulfonyloxy, C1-C2
haloalkylsulfonyloxy. OSi(CH3)3, OSi(CH3)2C(CH3)3, C1-C4 alkylthio, C3-C4 cycloalkylthio,
cyclopropylmethylthio, C1-C4 haloalkylthio, C2-C4 alkenylthio, C2-C4 haloalkenylthio, C3-C4
alkynylthio, C3-C4 haloalkynylthio, C2-C4 alkoxyalkylthio, C2-C4 aminoalkylthio, SH, SP(O)(OC1C2 alkyl)2, C1-C4 alkylsulfinyl, C3-C4 cycloalkylsulfonyl, cyclopropylmethylsulfinyl. C1-C4
haloalkylsulfinyl, C2-C4 alkenylsulfinyl, C2-C4 haloalkenylsulfinyl, C3-C4 alkynylsulfinyl. C3-C4
haloalkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl, C2-C4 aminoalkylsulfinyl, C1-C4 alkylsulfonyl, C3C4 cycloalkylsulfonyl, cyclopropylmethylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkenylsulfonyl.
C2-C4 haloalkenylsulfonyl, C3-C4 alkynylsulfonyl, C3-C4 haloalkynylsulfonyl. C2-C4
alkoxyalkylsulfonyl or C2-C4 aminoalkylsulfonyl: R? is C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkyl sulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl,
propargyloxy, propargylthio, propargylsulfinyl, propargylsulfonyl, C1-C3 haloalkoxy, C1-C3 alkyl
substituted with 1-3 atoms of F or Cl, C1-C2 alkyl substituted with C1-C2 alkoxy, C1-C2 haloalkoxy.
C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1-C2
alkylsulfonyl, C1-C2 haloalkysulfonyl, OH or OC(O)C1-C2 alkyl, C1-C2 alkoxy substituted with ClC2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthlo, C1-C2 haloalkylthio, C1-C2 alkylsulfinyl, C1-C2
haloalkylsulfinyl C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl or CN, OCH2CH2NH2,
OCH2CH2NHCH3, OCH2CH2N(CH3)2. C1-C2 alkylthio substituted by C1-C2 alkoxy, C1-C2
haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio or CN, C1-C3 haloalkylthio, C1-C3
haloalkylsulfinyl, C1-C3 haloalkylsulfonyl, C2-C3 alkenyl, C?CH, NR?R? or OC(O)C1-C2 alkyl: Ra
and Rb are independently H or C1-C3 alkyl: Rc is C2-C4 alkyl, cyclopropylmethyl, C2-C4 cyano
alkyl, CH2C(O)CH3, CH2CH2C(O)CH3, C1-C4 haloalkyl, C3-C4 alkenyl, C3-C4 haloalkenyl, C3-C4
alkynl, C3-C4 haloalkynyl, C1-C4 alkyl substituted with C1-C4 alkoxy, C1-C4 alkylthio, C1-C4
alkylsulfinyl, C1-C4 alkylsulfonyl, OH, NH2, NHCH3 or N(CH3)2: R? is H or C1-C2 aDescription:
Description of corresponding document: EP0235449
HERBICIDAL SULFONAMIDES
Background of the Invention
This invention relates to certain herbicidal sulfonamides, agriculturally suitable compositions thereof
and a method for their use as a general or selective preemergent or postemergent herbicide or as a plant
growth regulant.
New compounds effective for controlling the growth of undesired vegetation are in constant demand.
In the most common situation, such compounds are sought to selectively control the growth of weeds
in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed growth
in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the
consumer. In other situations, herbicides are desired which will control all plant growth. Examples of
areas in which complete control of all vegetation is desired are areas around fuel storage tanks,
ammunition depots and industrial storage areas. There are many products commercially available for
these purposes, but the search continues for products which are more effective, less costly and
environmentally safe.
The "sulfonylurea" herbicides are an extremely potent class of herbicides discovered within the last few
years which generally consist of a sulfonylurea bridge, -SO2NHCONH-, linking two aromatic or
heteroaromatic rings.
U.S. 4,394,506 discloses herbicidal ortho-alkoxycarbonylbenzenesulfonamides such as EMI2.1
wherein
R2 is H, F, Cl, Br, C1-C3 alkyl, NO2, SO2CH3, OCH3, SCH3, CF3, N(CH3)2, NH2 or CN;
X is H, Cl, CH3, OCH3, OCH2CH3 or OCH2CH2OCH3;
and
Y is H, halogen, C1-C4 alkyl, C1-C4 substituted alkyl, C1-C4 alkoxy, etc.
4/2194
South African Patent Application 81/4874 discloses herbicidal sulfonamides of formula EMI2.2
wherein
A is a C1-C6 alkyl radical which is substituted by halogen or various other organic substituents or a
C2-C6 alkenyl radical which is substituted or unsubstituted;
X is O, S, SO or SO2;
R1 is H, halogen, C1-C5 alkyl, C2-C5 alkenyl or YR5;
R2 is H, halogen, C1-C5 alkyl, C2-C5 alkenyl, C1-C4 haloalkyl, CO2R6, YR5, NO2 or CONR7R8;
and
R3 and R4, each independently of the other, are hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4
alkylthio, C1-C4 haloalkyl, halogen or alkoxyalkyl of at most 4 carbon atoms.
South African Patent Application 82/5042 discloses herbicidal sulfonamides of formula EMI3.1
wherein
A is C3-C6 alkynyl;
X is O, S, SO or SO2;
R1 is H, halogen, C1-C5 alkyl, C2-C5 alkenyl or YR5;
R2 is H, halogen, C1-C5 alkyl, C2-C5 alkenyl, C1-C4 haloalkyl, CO2R6, YR5, NO2 or CONR7R8;
and
R3 and R4, independently of one another, are hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio,
C1-C4 haloalkyl, C1-C4 haloalkoxy, halogen or alkoxyalkyl of at most 4 carbon atoms.
South African Patent Application 82/5671 discloses herbicidal sulfonamides of formula EMI3.2
wherein
A is a C1-C6 alkyl radical or a C2-C6 alkenyl radical which is substituted by halogen or various other
organic substituents;
X is O, S, SO or SO2;
R1 is H, halogen, C1-C5 alkyl, C2-C5 alkenyl or YR5;
R2 is H, halogen, C1-C5 alkyl, C2-C5 alkenyl, C1-C4 haloalkyl, CO2R6, YR5, NO2 or CONR7R8;
R3 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 haloalkyl, C1-C4 haloalkoxy,
halogen or alkoxyalkyl of at most 4 carbon atoms; and
R4 is C1-C4 haloalkoxy or C1-C4 haloalkylthio.
South African Patent Application 83/0127 discloses herbicidal sulfonamides of formula EMI4.1
wherein
R1 is hydrogen, halogen, cyano, nitro, C1-C4 haloalkyl, C1-C4 alkyl, C1-C4 alkoxy, COR6, NR7R8,
S(O)m-C1-C4 alkyl or SO2R9;
R2 is H, F, Cl, Br, NO2, CF3, NR20R21, C1-C2 alkyl, C1-C2 alkoxy or S(O)m-C1-C4 alkyl;
R3 is H, F, Cl, Br, NH2, NO2 or OCH3;
R6 is hydrogen, C1-C4 alkyl, C3-C5 alkenyloxy, C3-C5 alkynyloxy, C1-C4 haloalkyl, C1-C5
alkylthio, phenoxy, benzyloxy, NR10R11 or C1-C5 alkoxy which is unsubstituted or substituted by 1-3
halogen atoms or C1-C3 alkoxy;
R18 is hydrogen, C1-C3 alkyl or C1-C3 alkoxy; m is 0, 1 or 2; and
Y is C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkoxyalkyl, C1-C3
alkylthio, halogen or NR16R17.
South African Patent Application 84/2245 discloses herbicidal sulfonamides of formula EMI5.1
wherein
A is C1-C6 haloalkyl;
R1 is hydrogen, halogen, nitro, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 alkylthio,
C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, COR6, NR7R8, CONR9R10 or SO2NR11R12;
R2 is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl or C1-C4
alkylsulfonyl; and
R3 and R4, independently of one another, are each hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl,
C2-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C2-C4 alkoxyalkyl, C1-C4 alkoxy or
NR12R13.
South African Patent Application 84/2722 discloses herbicidal benzenesulfonamides of formula
EMI5.2 wherein
5/2194
A is a radical of the formula CR6R7XR8, CR9R10R11 or CHR7SCQR21;
R1 is hydrogen, halogen, nitro, cyano, C1-C4 alkyl, C1-C4 haloalkyl, YR14, CONR12R13, NR12R13,
SONR15R16, OSO2R17 or COR18;
R2 is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl or C1-C4
alkylsulfonyl;
R3 and R4, independently of one another, are each hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl,
C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C2-C5 alkoxyalkyl or
NR19R20;
R9 is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl or C1-C4
alkylsulfonyl;
R10 is hydrogen, halogen or methyl;
R11 is a radical COR24 or a C1-C4 alkyl group that is mono- or polysubstituted by substituents
selected from the group: cyano, nitro, hydroxyl, C1-C4 alkoxy, C1-C4 alkylthio, etc.
R18 is H, C1-C4 alkoxy and various other organic radicals.
South African Patent Application 83/0441 discloses herbicidal benzenesulfonamides of formula
EMI6.1 wherein
R1 is H, halogen, NO2, C1-C4 haloalkyl, C1-C4 alkyl, C1-C4 alkoxy, C2-C5 alkenyl or C1-C4
alkoxycarbonyl;
R2 is C1-C3 alkyl or C1-C3 alkoxy, each unsubstituted or substituted by 1 to 3 halogen atoms;
R3 is halogen, H, NR4R5, C1-C3 alkyl, unsubstitued or substituted by 1 to 3 halogen atoms or C1-C4
alkoxy, or is C1-C3 alkoxy, unsubstituted or substituted by methoxy, ethoxy, or 1 to 3 halogen atoms;
A is C1-C4 alkylene or C2-C4 alkenylene, each unsubstituted or substituted by C1-C4 alkyl;
m is 0 or 1;
E is N or CH;
X is oxygen, sulfur, SO or SO2; and
Q is, in part, OH, CN, NR6R7, SO2R8, cycloalkyl or COC1-C6 alkyl.
South African Patent Application 83/3779 discloses herbicidal benzenesulfonamides of formula
EMI7.1 wherein
A is C IDENTICAL CR;
m is 1 or 2;
E is CH or N;
Z is oxygen or sulfur,
R is, in part, H, C1-C9 alkyl or C1-C9 haloalkyl;
R1 is H, halogen, C1-C5 alkyl, C2-C5 alkenyl or YR5;
R2 is H, halogen, C1-C5 alkyl, C2-C5 alkenyl, C1-C4 haloalkyl, YR5, CO2R6, NO2 or CONR7R8;
R3 and R4, each independently of the other, are H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 haloalkylthio, halogen, C2-C5 alkoxyalkyl, NR9R10 or
OCH2CH2NR9R10.
South African Patent Application 82/7439 discloses herbicidal sulfonamides of formula EMI8.1
wherein
A is a C3-C6 alkynyl group, a C1-C6 alkyl group which is substituted by halogen, C1-C4 alkoxy, C1C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkoxy, C1-C4 haloalkylthio, C1C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl, or it is a C2-C6 alkenyl group substituted by one of
the above substituents;
X is O, S, SO or SO2;
R1 is hydrogen, halogen, C1-C5 alkyl, C2-C5 alkenyl or a YR6 group;
R2 is hydrogen, halogen, C1-C5 alkyl, C2-C5 alkenyl, C1-C4 haloalkyl, YR6, CO2R7, NO2 or
CONR8R9;
R3 is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 haloalkyl, C1-C4 haloalkoxy,
halogen or alkoxyalkyl having at most 4 carbon atoms;
R4 is hydrogen, methyl or ethyl;
R5 is hydrogen, C1-C4 alkyl, C1-C3 alkoxy, methoxymethyl, cyanomethyl or cyanoethyl;;
R6 and R7 are each C1-C5 alkyl, C2-C5 alkenyl or C2-C6 alkynyl.
South African Patent Application 83/6449 (Swiss priority 01.09.82) discloses herbicidal
benzenesulfonamides of formula EMI9.1 wherein
6/2194
R1 is H, halogen, NO2, amino, C1-C5 alkyl, C1-C4 haloalkyl or a QR7, CO2R8 or (CO)nNR9R10
radical;
R2 is H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 haloalkyl, C1-C4 haloalkoxy, halogen
or alkoxyalkyl containing not more than 4 carbon atoms;
R3 is C2-C10 alkenyl which is substituted by one or more fluorine or bromine atoms or by one or
more hydroxyl, cyano, nitro, (Y)mCO(Z)nR8, SO2NR11R12, S(O)pC1-C3 haloalkyl or S(O)nC1-C3
alkyl groups and which may additionally be substituted by one or more chlorine atoms;
R4 is C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy;
R5 is H, halogen, NR13R14, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C2 haloalkoxy; and
E is CH or N.
There is however a continuing need to find herbicides that are more effective and more selective
toward agricultural products.
Summary of the Invention
This invention relates to certain compounds of the structural formulae: EMI10.1 wherein
R is H or CH3;
R1 is C1-C3 alkyl, C3-C4 alkoxyalkyl, C2-C4 haloalkyl, C3-C4 alkenyl or C3-C4 alkynyl;
R2 is C2-C6 alkoxy, C3-C6 cycloalkoxy, C4-C6 cycloalkylalkoxy, C1-C6 haloalkoxy, C2-C6
alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C2-C4 alkoxyalkoxy,
C2-C4 haloalkoxyalkoxy, C2-C4 alkylthioalkoxy, C2-C4 haloalkylthioalkoxy, C2-C4
alkylsulfinylalkoxy, C2-C4 haloalkylsulfinylalkoxy, C2-C4 alkylsulfonylalkoxy, C2-C4
haloalkylsulfonylalkoxy, C2-C4 cyanoalkoxy, OCH2C(O)CH3, OCH2CH2C(O)CH3, C2-C4
aminoalkoxy, C1-C8 alkylthio, C3-C6 cycloalkylthio, C4-C6 cycloalkylalkylthio, C1-C8 haloalkylthio,
C2-C6 alkenylthio, C2-C6 haloalkenylthio, C3-C6 alkynylthio, C3-C6 haloalkynylthio, C2-C4
alkoxyalkylthio, C2-C4 haloalkoxyalkylthio, C2-C4 alkylthioalkylthio, C2-C4 haloalkylthioalkylthio,
C2-C4 cyanoalkylthio, SCH2C(O)CH3, SCH2CH2C(O)CH3, C2-C4 aminoalkylthio, SC6H5,
SCH2C6H5, C1-C8 alkylsulfinyl, C3-C6 cycloalkylsulfinyl, C4-C6 cycloalkylalkylsulfinyl, C1-C8
haloalkylsulfinyl, C2-C6 alkenylsulfinyl, C2-C6 haloalkenylsulfinyl, C3-C6 alkynylsulfinyl, C3-C6
haloalkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl, C2-C4 haloalkoxyalkylsulfinyl, C2-C4
cyanoalkylsulfinyl, S(O)CH2C(O)CH3, S(O)CH2CH2C(O)CH3, C2-C4 aminoalkylsulfinyl, C2-C8
alkylsulfonyl, C3-C6 aminoalkylsulfonyl, C4-C6 cycloalkylalkylsulfonyl, C1-C8 haloalkylsulfonyl,
C2-C6 alkenylsulfonyl, C2-C6 haloalkenylsulfonyl, C3-C6 alkynylsulfonyl, C3-C6
haloalkynylsulfonyl, C2-C4 alkoxyalkylsulfonyl, C2-C4 haloalkoxyalkylsulfonyl, C2-C4
cyanoalkylsulfonyl, SO2CH2C(O)CH3, SO2CH2CH2C(O)CH3, C2-C4 aminoalkylsulfonyl, CH2F,
CHF2, CH2Cl, CHCl2, CH2Br, CHBr2, C2-C6 alkyl substituted with 1-3 atoms of F, Cl or Br, C2-C6
alkenyl, C2-C6 haloalkenyl, C IDENTICAL CH, C2-C6 haloalkynyl, OC(O)C1-C4 alkyl,
CH2C(O)NRaRb, NHCH3, NRbRc or C1-C4 alkyl substituted with C1-C4 alkoxy, C3-C4
cycloalkoxy, cyclopropylmethoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C3C4 alkynyloxy, C3-C4 haloalkynyloxy, C2-C4 alkoxyalkoxy, C2-C4 aminoalkoxy, C1-C4
alkylacarbonyloxy, C1-C4 haloalkylcarbonyloxy, C1-C4 carbamoyloxy, C1-C4 alkoxycarbonyloxy,
OH, OP(O)(OC1-C2 alkyl)2, C1-C4 alkylsulfonyloxy, C1-C2 haloalkylsulfonyloxy, OSi(CH3)3,
OSi(CH3)2C(CH3)3, C1-C4 alkylthio, C3-C4 cycloalkylthio, cyclopropylmethylthio, C1-C4
haloalkylthio, C2-C4 alkenylthio, C2-C4 haloalkenylthio, C3-C4 alkynylthio, C3-C4 haloalkynylthio,
C2-C4 alkoxyalkylthio, C2-C4 aminoalkylthio, SH, SP(O)(OC1-C2 alkyl)2, C1-C4 alkylsulfinyl, C3C4 cycloalkylsulfonyl, cyclopropylmethylsulfinyl, C1-C4 haloalkylsulfinyl, C2-C4 alkenylsulfinyl,
C2-C4 haloalkenylsulfinyl, C3-C4 alkynylsulfinyl, C3-C4 haloalkynylsulfinyl, C2-C4
alkoxyalkylsulfinyl, C2-C4 aminoalkylsulfinyl, C1-C4 alkylsulfonyl, C3-C4 cycloalkylsulfonyl,
cyclopropylmethylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkenylsulfonyl, C2-C4
haloalkenylsulfonyl, C3-C4 alkynylsulfonyl, C3-C4 haloalkynylsulfonyl, C2-C4 alkoxyalkylsulfonyl
or C2-C4 aminoalkylsulfonyl;;
R@ is C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3
alkylsulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl, propargyloxy, propargylthio,
propargylsulfinyl, propargylsulfonyl, C1-C3 haloalkoxy, C1-C3 alkyl substituted with 1-3 atoms of F
or Cl, C1-C2 alkyl substituted with C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2
haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2
7/2194
haloalkylsulfonyl, OH or OC(O)C1-C2 alkyl, C1-C2 alkoxy substituted with C1-C2 alkoxy, C1-C2
haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkysulfinyl, C1C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl or CN, OCH2CH2NH2, OCH2CH2NHCH3,
OCH2CH2N(CH3)2, C1-C2 alkylthio substituted by C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2
alkylthio, C1-C2 haloalkylthio or CN, C1-C3 haloalkylthio, C1-C3 haloalkylsulfinyl, C1-C3
haloalkylsulfonyl, C2-C3 alkenyl, C IDENTICAL CH, NR@R@ or OC(O)C1-C2 alkyl;
Ra and Rb are independently H or C1-C3 alkyl;
Rc is C2-C4 alkyl, cyclopropylmethyl, C2-C4 cyanoalkyl, CH2C(O)CH3, CH2CH2C(O)CH3, C1-C4
haloalkyl, C3-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C4 haloalkynyl, C1-C4 alkyl substi
tuted with C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, OH, NH2,
NHCH3 or N(CH3)2;
R@ is H or C1-C2 alkyl;
R@ is H, C1-C2 alkyl or C1-C2 haloalkyl;
Y' is CH3, OCH3 or OCF2H;
X is CH3, OCH3, OC2H5, Cl or Br;
Y is C1-C2 alkyl, C1-C2 alkoxy, OCH2CH2F, OCH2CHF2, OCH2CF3, NHCH3 or N(CH3)2; and
Z is CH or N; and
their agriculturally suitable salts;
provided that
1) when X is Cl or Br, then Z is CH and Y is C1-C2 alkoxy, NHCH3 or N(CH3)2; and
2) when R2 is SCH3, then R is H, R1 is CH3, and X is OCH3, Y is OCH3 and Z is CH.
In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio"
or "haloalkyl", denotes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the
different butyl, pentyl, hexyl, heptyl and octyl isomers.
Alkoxy denotes methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy, pentoxy or hexoxy
isomers.
Alkenyl denotes straight chain or branched alkenes, e.g., vinyl, 1-propenyl, 2-propenyl, 3-propenyl and
the different butenyl, pentenyl and hexenyl isomers.
Alkynyl denotes straight chain or branched alkynes, e.g., ethynyl, 1-propynyl, 2-propynyl and the
different butynyl, pentynyl and hexynyl isomers.
Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
C4-C6 cycloalkylalkyl means cyclopropylmethyl through cyclopropylpropyl or cyclopentylmethyl.
The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine,
bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be
partially or fully substituted with halogen atoms, which may be the same or different. Examples of
haloalkyl include CH2CH2F, CF2CF3 and CH2CHFCl.
The total number of carbon atoms in a substituent group is indicated by the Ci-Cj prefix where i and j
are numbers from 1 to 8. For example, C1-C3 alkylsulfonyl would designate methylsulfonyl through
propylsulfonyl, C2 alkoxyalkoxy would designate OCH2OCH3; C4 alkoxyalkoxy would designate the
various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4
carbon atoms, examples including OCH2OCH2CH2CH3 and OCH2CH2OCH2CH3; C2 cyanoalkyl
would designate CH2CN and C3 cyanoalkyl would designate CH2CH2CN and CH(CN)CH3;C4
aminoalkoxy would designate the various isomers of an alkoxy group substituted by an amino,
alkylamino or dialkylamino group containing a total of 4 carbon atoms, examples including
OCH2CH2CH2CH2NH2 and OCH2CH2N(CH3)2; as further example, CH(H, C1-C3 alkyl)OC1-C2
alkyl would designate the various isomers of a methyl group substituted by a C1-C2 alkoxy group and
optionally substituted by a C1-C3 alkyl group, examples including CH2OCH3 and
CH(CH2CH2CH3)OCH2CH3.
Compounds of the invention which are preferred for their higher herbicidal activity, greater plant
growth regulant activity and/or more favorable ease of synthesis are:
8/2194
1) Compounds of Formula I wherein
R2 is C2-C6 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfinyl, C2-C8 alkylsulfonyl, C3-C6 alkenyloxy,
C3-C6 alkynyloxy, C3-C6 alkenyl thio, C3-C6 alkenylsulfinyl, C3-C6 alkenylsulfonyl, C3-C6
alkynylthio, C3-C6 alkynylsulfinyl, C3-C6 alkynylsulfonyl, OCH2CH2OCH3, OCH2CH2SCH3,
OCH2CH2S(O)CH3, OCH2CH2SO2CH3, C2-C6 alkyl substituted with 1-3 atoms of F, Cl or Br,
CH2F, CHF2, C1-C4 alkyl substituted with C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 alkylsulfinyl or
C1-C2 alkylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl, S-cyclohexyl,
SC6H5 or SCH2C6H5;
2) Compounds of Preferred (1) where
R2 is CH3S, C3-C6 alkenyloxy alkynyloxy, C3-C6 alkenylthio, C3-C6 alkenylsulfinyl, C3-C6
alkenylsulfonyl, C3-C6 alkynylthio, C3-C6 alkynylsulfinyl, C3-C6 alkynylsulfonyl, C2-C6 alkyl
substituted with 1-3 atoms of F, Cl or Br, CH2F, CHF2, C1-C4 alkyl substituted in a nonbenzylic
position with C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 alkyl sulfinyl or C1-C2 alkylsulfonyl,
OCH2CH2OCH3, OCH2CH2SCH3, OCH2CH2S(O)CH3, OCH2CH2SO2CH3, OCF2H,
OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl, S-cyclohexyl, SC6H5 or SCH2C6H5.
3) Compounds of Preferred (2) wherein R is H;
4) Compounds of Preferred (3) wherein
R2 is CH3S, C3-C4 alkenyloxy, C3-C4 alkenylthio, C3-C4 alkenylsulfinyl, C3-C4 alkenylsulfonyl,
C2-C3 alkyl substituted with 1-3 atoms of F or Cl, CH2F, CHF2, OCHF2, OCH2CH2F, OCH2CF3 or
OCH2CH2Cl.
5) Compounds of Preferred (4) wherein
R1 is CH3 or CH2CH3;
X is CH3, OCH3 or Cl; and
Y is CH3, OCH3, C2H5 or OC2H5.
6) Compounds of Preferred (5) wherein
R2 is allyloxy, allylthio, propargyloxy, propargylthio, CH2F, OCHF2, OCH2CH2F or CH3S.
7) Compounds of Preferred (1) wherein
R2 is C2-C6 alkoxy, C2-C8 alkylthio, C2-C8 alkylsulfonyl, C1-C8 alkylsulfinyl, CH(H, C1-C3
alkyl)OC1-C2 alkyl, CH(H, C1-C3 alkyl)-SC1-C2 alkyl, CH(H, C1-C3 alkyl)S(O)C1-C2 alkyl or
CH(H, C1-C3 alkyl)SO2C1-C2 alkyl.
8) Compounds of Preferred (7) wherein R is H.
9) Compounds of Preferred (8) wherein
R2 is C2-C4 alkoxy, C2-C4 alkylthio, C2-C4 alkylsulfonyl, C1-C4 alkylsulfinyl, CH2OC1-C2 alkyl,
CH2SC1-C2 alkyl, CH2S(O)C1-C2 alkyl or CH2SO2C1-C2 alkyl.
10) Compounds of Preferred (9) wherein
R1 is CH3 or C2H5
X is CH3, OCH3 or Cl; and
Y is CH3, OCH3, C2H5 or OC2H5.
11) Compounds of Preferred (10) wherein
R2 is C2-C3 alkoxy, C2-C3 alkylthio, C1-C3 alkylsulfinyl, CH2OCH3, CH2SCH3, CH2S(O)CH3 or
CH2SO2CH3.
12) Compounds of Formula I wherein
R2 is C3-C6 cycloalkoxy, C4-C6 cycloalkylalkoxy, OCF2Cl, OCF2Br, OCF3, OCF2CF2H,
OCF2CHFCl, OCF2CHFBr, OCF2CF3, OCH2CH2Br, OCH2CCl3, C3-C6 haloalkoxy, vinyloxy, C2C6 haloalkenyloxy, C3-C6 haloalkynyloxy, OCH2OCH3, OCH2OCH2CH3, OCH(CH3)OCH3, C4
alkoxyalkoxy, C2-C4 haloalkoxyalkoxy, OCH2SCH3, OCH2SCH2CH3, OCH(CH3)SCH3, C4
alkylthioalkoxy, C2-C4 haloalkylthioalkoxy, OCH2S(O)CH3, OCH2S(O)CH2CH3,
OCH(CH3)S(O)CH3, C4 alkylsulfinylalkoxy, C2-C4 haloalkylsul finylalkoxy, OCH2SO2CH3,
OCH2SO2CH2CH3, OCH(CH3)SO2CH3, C4 alkylsulfonylalkoxy, C2-C4 haloalkylsulfonylalkoxy,
C2-C4 cyanoalkoxy, OCH2C(O)CH3, OCH2CH2C(O)CH3, C2-C4 aminoalkoxy, C3-C5
cycloalkylthio, C4-C6 cycloalkylalkylthio, SCF2H, SCF2Cl, SCF2Br, SCF3, C2-C8 haloalkylthio,
vinylthio, C2-C6 haloalkenylthio, C3-C6 haloalkynylthio, C2-C4 alkoxyalkylthio, C2-C4
haloalkoxyalkylthio, C2-C4 alkylthioalkylthio, C2-C4 haloalkylthioalkylthio, C2-C4 cyanoalkylthio,
SCF2C(O)CH3, SCH2CH2C(O)CH3, C2-C4 aminoalkylthio, C3-C6 cycloalkylsulfinyl, C4-C6
cycloalkylalkylsulfinyl, C1-C8 haloalkylsulfinyl, vinylsulfinyl, C2-C6 haloalkenylsulfinyl, C3-C6
haloalkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl, C2-C4 haloalkoxyalkylsulfinyl, C2-C4
cyanoalkylsulfinyl, S(O)CH2C(O)CH3, S(O)CH2CH2C(O)CH3, C2-C4 aminoalkylsulfinyl, C3-C6
cycloalkylsulfonyl, C4-C6 cycloalkylalkylsulfonyl, C1-C8 haloalkylsulfonyl, vinylsulfonyl, C2-C6
haloalkenylsulfonyl, C3-C6 haloalkynylsulfonyl, C2-C4 alkoxyalkylsulfonyl, C2-C4
9/2194
haloalkoxysulfonyl, C2-C4 cyanoalkylsulfonyl, SO2CH2C(O)CH3, SO2CH2CH2C(O)CH3, C2-C4
aminoalkylsulfonyl, CH2Cl, CHCl2, CH2Br, CHBr, C2-C6 alkenyl, C2-C6 haloalkenyl, C
IDENTICAL CH, C2-C6, haloalkynyl, OC(O)C1-C4 alkyl, CH2C(O)NRaRb, NHCH3, NRbRc or C1C4 alkyl substituted with C3-C4 alkoxy, C3-C4 cycloalkoxy, cyclopropylmethoxy, C1-C4 haloalkoxy,
C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C3-C4 alkynyloxy, C3-C4 haloalkynyloxy, C2-C4
alkoxyalkoxy, C2-C4 aminoalkoxy, C1-C4 alkyl carbonyloxy, C1-C4 haloalkylcarbonyloxy, C1-C4
carbamoyloxy, C1-C4 alkoxycarbonyloxy, OH, OP(O)(OC1-C2 alkyl)2, C1-C4 alkylsulfonyloxy, C1C2 haloalkylsulfonyloxy, OSi(CH3)3, OSi(CH3)2C(CH3)3, C3-C4 alkylthio, C3-C4 cycloalkylthio,
cyclopropylmethylthio, C1-C4 haloalkylthio, C2-C4 alkenylthio, C2-C4 haloalkenylthio, C3-C4
alkynylthio, C3-C4 haloalkynylthio, C2-C4 alkoxyalkylthio, C2-C4 aminoalkylthio, SH, SP(O)(OC1C2 alkyl)2, C3-C4 alkylsulfinyl, C3-C4 cycloalkylsulfinyl, cyclopropylmethylsulfinyl, C1-C4
haloalkylsulfinyl, C2-C4 alkenylsulfinyl, C2-C4 haloalkenylsulfinyl, C3-C4 alkynylsulfinyl, C3-C4
haloalkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl, C2-C4 aminoalkylsulfinyl, C3-C4 alkylsulfonyl, C3C4 cycloalkylsulfonyl, cyclopropylmethylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkenylsulfonyl,
C2-C4 haloalkenylsulfonyl, C3-C4 alkynylsulfonyl, C3-C4 haloalkynylsulfonyl, C2-C4
alkoxyalkylsulfonyl or C2-C4 aminoalkylsulfonyl.
13) Compounds of Preferred (12) wherein
R2 is C3-C6 cycloalkoxy, C4-C6 cycloalkylalkoxy, OCF2Cl, OCF2Br, OCF3, OCF2CF2H,
OCF2CHFC, OCF2CHFBr, OCF2CF3, OCH2CH2Br, OCH2CCl3, C3-C6 haloalkoxy, vinyloxy, C2C6 haloalkenyloxy, OCH2OCH3, OCH2OCH2CH3, OCH(CH3)OCH3, C4 alkoxyalkoxy, C2-C4
haloalkoxyalkoxy, OCH2SCH3, OCH2SCH2CH3, OCH(CH3)SCH3, C4 alkylthioalkoxy, C2-C4
haloalkylthioalkoxy, OCH2S(O)CH3, OCH2S(O)CH2CH3, OCH(CH3)S(O)CH3, C4
alkylsulfinylalkoxy, C2-C4 haloalkylsulfinylalkoxy, OCH2SO2CH3, OCH2SO2CH2CH3,
OCH(CH3)SO2CH3, C4 alkylsul fonylalkoxy, C2-C4 haloalkylsulfonylalkoxy, C2-C4 cyanoalkoxy,
OCH2C(O)CH3, OCH2CH2C(O)CH3, C2-C4 aminoalkoxy, C3-C5 cycloalkylthio, SCF3 SCF2Cl,
SCF2Br, C4-C6 cycloalkylalkylthio, SCF2H, C2-C6 haloalkylthio, vinylthio, C2-C6 haloalkenylthio,
C2-C4 alkoxyalkylthio, C2-C4 haloalkoxyalkylthio, C2-C4 alkylthioalkylthio, C2-C4
haloalkylthioalkylthio, C2-C4 cyanoalkylthio, SCH2C(O)CH3, SCH2CH2C(O)CH3, C2-C4
aminoalkylthio, C3-C6 cycloalkylsulfinyl, C4-C6 cycloalkylalkylsulfinyl, C1-C6 haloalkylsulfinyl,
vinylsulfinyl, C2-C6 haloalkenylsulfinyl, C2-C4 alkoxyalkylsulfinyl, C2-C4 haloalkoxyalkylsulfinyl,
C2-C4 cyanoalkylsulfinyl, S(O)CH2C(O)CH3, S(O)CH2CH2C(O)CH3, C2-C4 aminoalkylsulfinyl,
C3-C6 cycloalkylsulfonyl, C4-C6 cycloalkylalkylsulfonyl, C1-C6 haloalkylsulfonyl, vinylsulfonyl, C2C6 haloalkenylsulfonyl, C2-C4 alkoxyalkylsulfonyl, C2-C4 haloalkoxysulfonyl, C2-C4
cyanoalkylsulfonyl, SO2CH2C(O)CH3, SO2CH2CH2(O)CH3, C2-C4 aminoalkylsulfonyl, CHBr2,
C2-C6 alkenyl substituted by one or more fluorine or bromine atoms, C IDENTICAL CH, C3-C6
haloalkynyl, NRbRc, CH(H, C1-C3 alkyl)OC1-C4 haloalkyl having 1 or 2 halogen atoms, CH(H, C1C3 alkyl)OC2-C4 haloalkenyl, CH(H, C1-C3 alkyl)OC3-C5 alkynyl, CH(H, C1-C3 alkyl)OC2-C4
alkoxyalkyl, CH(H, C1-C3 alkyl)SC1-C4 haloalkyl having 1 or 2 halogen atoms, CH(H, C1-C3
alkyl)SC2-C4 haloalkenyl, CH(H, C1-C3 alkyl)SC3-C4 alkynyl, CH(H, C1-C3 alkyl)SC2-C4
alkoxyalkyl, CH(H, C1-C3 alkyl)S(O)C1-C4 haloalkyl having 1 or 2 halogen atoms, CH(H, C1-C3
alkyl)S(O)C2-C4 haloalkenyl, CH(H, C1-C3 alkyl)S(O)C3-C4 alkynyl, CH(H, C1-C3 alkyl)-S(O)C2C4 alkoxyalkyl, CH(H, C1-C3 alkyl)-SO2C1-C4 haloalkyl having 1 or 2 halogen atoms, CH(H, C1-C3
alkyl)SO2C2-C4 haloalkenyl, CH(H, C1-C3 alkyl)SO2C3-C4 alkynyl, CH(H, C1-C3 alkyl)SO2C2-C4
alkoxyalkyl, or C1-C4 alkyl substituted in a nonbenzylic position with C3-C4 alkoxy, C1-C4
haloalkoxy, C1-C4 alkylcarbonyloxy, C1-C4 haloalkylcarbonyloxy, C1-C4 carbamoyloxy,
alkoxycarbonyloxy, C1-C4 alkylsulfonyloxy, C1-C2 haloalkylsulfonyloxy, C3-C4 alkylthio, C1-C4
haloalkylthio, C3-C4 alkylsulfinyl or C3-C4 alkylsulfonyl; and
Rc is C2-C4, CH2C(O)CH3, CH2CH2C(O)CH3, C1-C4 haloalkyl, C3-C4 alkenyl, C3-C4
haloalkenyl, C3-C4 alkynyl or C3-C4 haloalkynyl;
14) Compounds of Preferred (13) wherein R is H.
15) Compounds of Preferred (14) wherein
R2 is OCF3, OCF2CF3, OCH2CH2Br, C3 haloalkoxy, OCH2CH2OCH2CH3, SCF2H, SCF3, C2
haloalkylthio, C2-C3 alkoxyalkylthio, C1-C2 haloalkylsulfinyl, C1-C2 haloalkylsulfonyl, C
IDENTICAL CH, CH2OC1-C2 haloalkyl having 1 or 2 halogen atoms, CH2SC1-C2 haloalkyl having
1 or 2 halogen atoms, CH2S(O)C1-C2 haloalkyl having 1 or 2 halogen atoms, or CH2SO2C1-C2
haloalkyl having 1 or 2 halogen atoms.
16) Compounds of Preferred (15) wherein
R1 is CH3 or CH2CH3;
X is CH3, OCH3 or Cl; and
10/2194
Y is CH3, OCH3, C2H5 or OC2H5.
17) Compounds of Preferred (16) wherein
R2 is OCF2CF3, SCF2H, SCH2CH2OCH3, S(O)CF2H, SO2CF2H, C IDENTICAL CH,
CH2OCH2CH2F or CH2OCH2CHF2.
18) Compounds of Preferred (12) wherein
R2 is C3-C6 haloalkynyloxy, C7-C8 haloalkylthio, C3-C6 haloalkynylthio, C7-C8 haloalkylsulfinyl,
C3-C6 haloalkynylsulfinyl, C7-C8 haloalkylsulfonyl, C3-C6 haloalkynylsulfonyl, CH2Cl, CHCl2,
CH2Br, C2-C6 alkenyl, C2-C6 alkenyl substituted with one or more chlorine atoms, C2 haloalkynyl,
OC(O)C1-C4 alkyl, CH2C(O)NRaRb, NHCH3, NRbRc, CH(H, C1-C3 alkyl)OC3-C4 alkyl, CH(H,
C1-C3 alkyl)OC1-C4 haloalkyl having 3 or more halogen atoms, CH(H, C1-C3 alkyl)OC(O)C1-C3
alkyl, CH(H, C1-C3 alkyl)OC(O)C1-C3 haloalkyl, CH(H, C1-C3 alkyl)OC1-C4 carbamoyl, CH(H,
C1-C3 alkyl)-OC(O)OC1-C3 alkyl, CH(H, C1-C3 alkyl)OSO2C1-C4 alkyl, CH(H, C1-C3
alkyl)OSO2C1-C2 haloalkyl, CH(H, C1-C3 alkyl)SC3-C4 alkyl, CH(H, C1-C3 alkyl)SC1-C4 haloalkyl
having 3 or more halogen atoms, CH(H, C1-C3 alkyl)S(O)C3-C4 alkyl, CH(H, C1-C3 alkyl)S(O)C1C4 haloalkyl having 3 or more halogen atoms, CH(H, C1-C3 alkyl)-SO2C3-C4 alkyl, CH(H, C1-C3
alkyl)SO2C1-C4 haloalkyl having 3 or more halogen atoms, C1-C4 alkyl substituted in a nonbenzylic
position by C2-C4 haloalkenyloxy, C3-C4 alkynyloxy, C2-C4 alkoxyalkoxy, C2-C4 haloalkenylthio,
C3-C4 alkynylthio, C2-C4 alkoxyalkylthio, C1-C4 haloalkylsulfinyl, C2-C4 haloalkenylsulfinyl, C3C4 alkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl, C1-C4 haloalkylsulfonyl, C2-C4 haloalkenylsulfonyl,
C3-C4 alkynylsulfonyl, or C2-C4 alkoxyalkylsulfonyl, or C1-C4 alkyl substituted by C3-C4
cycloalkoxy, cyclopropylmethoxy, C2-C4 alkenyloxy, C3-C4 haloalkynyloxy, C2-C4 aminoalkoxy,
OH, OP(O)(OC1-C2 alkyl)2, OSi(CH3)3, OSi(CH3)2C(CH3)3, cycloalkylthio, cyclopropylmethylthio,
C2-C4 alkenylthio, C3-C4 haloalkynylthio, C2-C4 aminoalkylthio, SH, SP(O)(OC1-C2 alkyl)2, C3-C4
cycloalkylsulfinyl, cyclopropylmethylsulfinyl, C2-C4 alkenylsulfinyl, C3-C4 haloalkynylsulfinyl, C2C4 aminoalkylsulfinyl, C3-C4 cycloalkylsulfonyl, cyclopropylmethylsulfonyl, C2-C4 alkenylsulfonyl,
C3-C4 haloalkynylsulfonyl, or C2-C4 aminoalkylsulfonyl; and
Rc is C2-C4 alkyl, cyclopropylmethyl, or C1-C4 alkyl substituted with C1-C4 alkoxy, C1-C4
alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkyl sulfonyl, OH, NH2, NHCH3 or N(CH3)2.
19) Compounds of Preferred (18) wherein R is H.
20) Compounds of Preferred (19) wherein
R2 is OCF2CF2H, C2-C3 cyanoalkoxy, C2-C3 aminoalkoxy, C2-C4 cyanoalkylthio, C2-C3 alkenyl,
CH2C(O)NRaRb, NHCH3, NRbRc, CH2OC1-C2 haloalkyl having 3 or more halogen atoms,
CH2OC(O)C1-C2 alkyl, CH2OSO2C1-C2 alkyl, CH2SC1-C2 haloalkyl having 3 or more halogen
atoms, CH2S(O)C1-C2 haloalkyl having 3 or more halogen atoms or CH2SO2C1-C2 haloalkyl having
3 or more halogen atoms.
21) Compounds of Preferred (20) wherein
R1 is CH3 or C2H5;
X is CH3, OCH3 or Cl; and
Y is CH3, OCH3, C2H5 or OC2H5.
22) Compounds of Preferred (21) wherein
R2 is OCF2CF2H, OCH2CH2CN, SCH2CH2CN, CH=CH2, CH2C(O)NH2, NHCH3,
CH2OCH2CF3, CH2OC(O)CH3 or CH2OSO2CH3.
23) Compounds of Formula II wherein
R@ is C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3
alkylsulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl, propargyloxy, propargylthio,
propargylsulfinyl, propargylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl or
C1-C3 alkyl substituted with 1-3 atoms of F or Cl, C1-C2 alkyl substituted with OCH3 or SCH3.
24) Compounds of Preferred (23) wherein
R@ is C1-C2 alkyl, C1-C2 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, CF3,
propargyloxy, propargylthio, propargylsulfinyl, propargylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2,
OCH2CF3, OCH2CH2Cl, CH2CH2OCH3 or CH2CH2SCH3.
25) Compounds of Preferred (24) wherein
R is H;
R1 is C1-C2 alkyl;
R@ is C1-C2 alkyl, C1-C2 alkoxy, C1-C3 alkylthio, CF3 or OCF2H; and
Y' is CH3 or OCH3.
26) Compounds of Preferred (25) wherein
R@ is CH3, OCH3 OCH2CH3 or CF3.
27) Compounds of Preferred (26) wherein
11/2194
R@ is propyl, isopropyl, cyclopropyl, propoxy, isopropoxy, allyloxy, allylthio, allylsulfinyl,
allylsulfonyl, CH2OCH3, CH(CH3)OCH3, CH2SCH3, CH(CH3)SCH3, CH2F, CHF2, C2-C3 alkyl
substituted with 103 atoms of F or C1-C3 alkyl substituted with 1-3 atoms of Cl.
28) Compounds of Preferred (27) wherein
R is H;
R1 is C1-C2 alkyl;
R@ is CH2F or CH2CH2F; and
Y' is CH3 or OCH3.
29) Compounds of Formula II wherein
R@ is C1-C2 alkyl substituted with OC2H5, C1-C2 haloalkoxy, SC2H5, C1-C2 haloalkylthio, C1-C2
alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, OH or
OC(O)C1-C2 alkyl, C1-C2 alkoxy substituted with C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio,
C1-C2 haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2
haloalkylsulfonyl or CN, OCH2CH2NH2, OCH2CH2NHCH3, OCH2 CH2N(CH3)2, C1-C2 alkylthio
substituted by C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio or CN, C1-C3
haloalkylthio, C1-C3 haloalkylsulfinyl, C1-C3 haloalkylsulfonyl, C2-C3 alkenyl, C IDENTICAL CH,
NR@R@, OCF2Cl, OCF2Br, OCF3, C3 haloalkoxy or OC(O)C1-C2 alkyl.
30) Compounds of Preferred (29) wherein
R@ is CH2CH2OCH2CH3, CH2OC1-C2 haloalkyl having 1 or 2 halogen atoms, CH(CH3)OC1-C2
haloalkyl having 1 or 2 halogen atoms, CH2CH2 OC1-C2 haloalkyl, CH2CH2SCH2CH3, CH2SC1-C2
haloalkyl having 1 or 2 halogen atoms, CH(CH3)SC1-C2 haloalkyl having 1 or 2 halogen atoms,
CH2CH2SC1-C2 haloalkyl, CH2CH2S(O)C1-C2 alkyl, CH2S(O)C1-C2 haloalkyl having 1 or 2
halogen atoms, CH(CH3)S(O)C1-C2 haloalkyl having 1 or 2 halogen atoms, CH2CH2SO2C1-C2
alkyl, CH2SO2C1-C2 haloalkyl having 1 or 2 halogen atoms, CH(CH3)SO2C1-C2 haloalkyl having 1
or 2 halogen atoms, CH2CH2OH, CH2CH2OC(O)C1-C2 alkyl, C1-C2 alkoxy substituted with C1-C2
alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkyl thio, C1-C2 alkylsulfinyl, C1-C2
haloalkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl or CN, OCH2CH2NH2,
OCH2CH2NHCH3, OCH2CH2N(CH3)2, C1-C2 alkylthio substituted by C1-C2 alkoxy, C1-C2
haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio or CN, C1-C3 haloalkylthio, C1-C3
haloalkylsulfinyl, C1-C3 haloalkylsulfonyl, C IDENTICAL CH, Nr@R@, OCF2Cl, OCF2Br, OCF3 or
C3 haloalkoxy; and
R@ is C1-C2 haloalkyl.
31) Compounds of Preferred (30) wherein
R is H;
R1 is C1-C2 alkyl;
R@ is CH2OC1-C2 haloalkyl having 1 or 2 halogen atoms, CH2SC1-C2 haloalkyl having 1 or 2
halogen atoms, C1-C2 haloalkylthio, C IDENTICAL CH, NR@R@ or OCF3; and
Y' is CH3 or OCH3.
32) Compounds of Preferred (31) wherein
R@ is CH2OCH2CH2F, CH2OCH2CHF2, NH2 NHCH3 or N(CH3)2.
33) Compounds of Preferred (29) wherein
R@ is CH2OCH2CH3, CH(CH3)OCH2CH3, CH2OC1-C2 haloalkyl having 3 to 5 halogen atoms,
CH(CH3)-OC1-C2 haloalkyl having 3 to 5 halogen atoms, CH2SCH2CH3, CH(CH3)SCH2CH3,
CH2SC1-C2 haloalkyl having 3 to 5 halogen atoms, CH2(CH3)-SC1-C2 haloalkyl having 3 to 5
halogen atoms, CH2S(O)C1-C2 alkyl, CH(CH3)S(O)C1-C2 alkyl, CH2CH2S(O)C1-C2 haloalkyl,
CH2S(O)C1-C2 haloalkyl having 3 to 5 halogen atoms, CH(CH3)- S(O)C1-C2 haloalkyl having 3 to 5
halogen atoms, CH2SO2C1-C2 alkyl, CH(CH3)SO2C1-C2 alkyl, CH2CH2SO2C1-C2 haloalkyl,
CH2SO2C1-C2 haloalkyl having 3 to 5 halogen atoms, CH(CH3)SO2C1-C2 haloalkyl having 3 to 5
halogen atoms, CH2OH, CH(CH3)OH, CH2C(O)C1-C2 alkyl, CH(CH3)OC(O)C1-C2 alkyl, C2-C3
alkenyl, NR@R@ or OC(O)C1-C2 alkyl; and
R@ is H or C1-C2 alkyl.
34) Compounds of Preferred (33) wherein
R is H;
R1 is C1-C2 alkyl;
R@ is CH2OCH2CH3, CH2OCH2CF3, CH2SCH2CH3, OCH2CN, OCH2CH2CN, SCH2CN,
SCH2CH2CN, C2-C3 alkenyl or NR@R@; and
Y' is CH3 or OCH3.
35) Compounds of Preferred (34) wherein
R@ is CH2OCH2CH3, CH2OCH2CF3, CH=CH2, NH2, NHCH3 or N(CH3)2.
12/2194
Other groups of compounds within the scope of our invention are those disclosed in our copending US
Patent Applications Serial Nos. 801,120; 801,165 and 826,682, copies of which are available for
inspection on the file of the present Application.
This invention further relates to the method of use of the compound EMI26.1 for weed control on a
rice crop because of its selectivity to rice, especially Japonica rice or paddy rice, and activity against
undesired plant growth and also the method of use for blackgrass control on wheat and barley with
safety to the crop.
DETAILED DESCRIPTION OF THE INVENTION
Synthesis
The compounds of Formula I can be prepared by one or more of the following methods described in
Equations 1 to 3 and 14. Reagents and reaction conditions are given by way of illustration.
As shown in Equation 1, compounds of Formula I can be prepared by reacting an appropriately
substituted sulfonyl isocyanate of Formula (1) with an appropriate amino or methylamino heterocycle
of Formula (2).
A is EMI27.1 and R, R1, R2, X, Y and Z are as previously defined.
Equation 1
EMI27.2
The reaction is best carried out in inert aprotic organic solvents such as dichloromethane, 1,2dichloroethane, tetrahydrofuran, or acetonitrile, at a temperature between 20 DEG and 85 DEG C. The
order of addition is not critical; however, it is often convenient to add the sulfonyl isocyanate or a
solution of it in the reaction solvent to a stirred suspension of the amine.
In some cases, the desired product is insoluble in the reaction solvent at ambient temperature and
crystallizes from it in pure form. Products soluble in the reaction solvent are isolated by evaporation of
the solvent. Compounds of Formula I then may be purified by trituration of the evaporation residue
with solvents such as 1-chlorobutane or ethyl ether and filtration, by recrystallization from mixtures of
solvents such as 1,2-dichloroethane, 1-chlorobutane, and heptane, or by chromatography on silica gel.
Many of the compounds of Formula I can be prepared by the procedure shown in Equation 2, where A,
R, R1, and R2 are as previously defined.
Equation 2
EMI28.1
The reaction shown in Equation 2 is carried out by contacting phenyl carbamates of Formula (3) with
aminoheterocycles of Formula (2) in an inert organic solvent such as dioxane or tetrahydrofuran at
temperatures of about 20-100 DEG C for a period of about one-half to twenty-four hours. The product
can be isolated by evaporation of the reaction solvent and purified by methods previously described.
Phenyl carbamates of Formula (3) can be prepared by the methods described, or modifications thereof
known to those skilled in the art, in European Patent Application 81810282.4 (Publication No. 44,808),
published January 27, 1982; or South African Patent Application 825042.
Alternatively, many of the compounds of Formula I can be prepared by the method described in
Equation 3, where A, R1, and R2 are as previously defined and R is H.
Equation 3
13/2194
EMI29.1
The reaction of Equation 3 can be carried out by contacting equimolar amounts of a sulfonamide of
Formula (4) with a heterocyclic phenyl carbamate of Formula (5) in the presence of an equimolar
amount of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU), by methods analogous to those described in
South African Patent Application 830441. The phenyl carbamate of Formula (5) can be prepared by
methods, or modifications thereof known to those skilled in the art, described in South African Patent
Application 825671 and South African Patent Application 825045.
Some of the compounds of Formula I may be prepared from compounds of Formula I where R2 is OH,
NRbH or SH. See Equation 14 for a discussion of this method.
The compounds of Formula II can be prepared by one or more of the following methods described in
Equations 1A to 3A and 14A.
As shown in Equation 1A, compounds of Formula II can be prepared by reacting an appropriately
substituted sulfonyl isocyanate of Formula (1A) with an appropriate amino or methylamino heterocycle
of Formula (2A). Y', R, R1, and R@ are as previously defined.
Equation 1A
EMI30.1
The reaction is best carried out in inert aprotic organic solvents such as dichloromethane, 1,2dichloroethane, tetrahydrofuran, or acetonitrile, at a temperature between 20 DEG and 85 DEG C. The
order of addition is not critical; however, it is often convenient to add the sulfonyl isocyanate or a
solution of it in the reaction solvent to a stirred suspension of the amine.
In some cases, the desired product is insoluble in the reaction solvent at ambient temperature and
crystallizes from it in pure form. Products soluble in the reaction solvent are isolated by evaporation of
the solvent. Compounds of Formula II then may be purified by trituration of the evaporation residue
with solvents such as 1-chlorobutane or ethyl ether and filtration, by recrystallization from mixtures of
solvents such as 1,2-dichloroethane, 1-chlorobutane, and heptane, or by chromatography on silica gel.
Many of the compounds of Formula II can be prepared by the procedure shown in Equation 2A, where
Y', R, R1, and R@ are as previously defined.
Equation 2A
EMI31.1
The reaction shown in Equation 2A is carried out by contacting phenyl carbamates of Formula (3A)
with aminoheterocycles of Formula (2A) in an inert organic solvent such as dioxane or tetrahydrofuran
at temperatures of about 20-100 DEG C for a period of about one-half to twenty-four hours. The
product can be isolated by evaporation of the reaction solvent and purified by methods previously
described.
Phenyl carbamates of Formula (3A) can be prepared by the methods described, or modifications
thereof known to those skilled in the art, in European Patent Application 44,808, published January 27,
1982; or South African Patent Application 82/5042.
Alternatively, many of the compounds of Formula II can be prepared by the method described in
Equation 3A, where Y', R1, and R@ are as previously defined and R is H.
Equation 3A
EMI31.2
The reaction of Equation 3A can be carried out by contacting equimolar amounts of a sulfonamide of
Formula (4A) with a heterocyclic phenyl carbamate of Formula (5A) in the presence of an equimolar
amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), by methods analogous to those described in
South African Patent Application 83/0441. The phenyl carbamate of Formula (5A) can be prepared by
14/2194
methods, or modifications thereof known to those skilled in the art, described in South African Patent
Application 82/5671 and South African Patent Application 82/5045.
For both compounds of Formulae I and II, the unsubstituted and substituted alkoxy, allyloxy and
propargyloxy benzenesulfonamide intermediates of Formula (4a) can be prepared by one or more of
the following general methods.
As shown in Equation 4, one highly useful general route starts from the phenol (6). EMI32.1 EMI33.1
where R1 is as previously defined, and R3 is C2-C6 alkyl, C3-C6 cycloalkyl, C4-C6 cycloalkylalkyl,
C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 haloalkynyl, C3-C6 alkynyl, C2-C4
alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkylthioalkyl, C2-C4 haloalkylthioalkyl, CH2C(O)CH3,
CH2CH2C(O)CH3, or benzyl. M1 is EMI34.1
A solution or suspension of 4-hydroxy-2-nitrobenzoic acid (6) in a suitable polar aprotic solvent, such
as dichloromethane or N,N-dimethylformamide (DMF), is treated with at least two equivalents of
R3X1 (7) in the presence of at least two equivalents of a suitable base such as N,Ndiisopropylethylamine or potassium carbonate and at a temperature between 20 and 155 DEG C for
four to sixteen hours (Equation 4a). If the solvent is miscible with water, it is then evaporated, and the
residue is taken up in dichloromethane. The product solution is washed with aqueous sodium or
potassium carbonate solution and aqueous hydrochloric acid, and then is dried over a suitable desiccant
such as magnesium sulfate. Filtration and evaporation of the solvent leaves (8) in semipurified form. It
may be further purified through recrystallization or chromatography on a column of silica gel.The
requisite alkylating, alkenylating, and alkynylating agents R3X1 (7) are either known or may be made
by a wide variety of methods known in the art.
In cases where R3 is not the same as R1, the ester (8) is treated with at least one equivalent of sodium
or potassium hydroxide in a mixture of water and a suitable organic cosolvent such as ethanol or pdioxane at a temperature between 20 and 100 DEG C for four to sixteen hours (Equation 4b). The
reaction mixture is then acidified with concentrated hydrochloric acid. If the product separates out in
crystalline form, it is collected. Otherwise the aqueous solution is extracted with ether. The ether
solution is dried over sodium sulfate and filtered, and the solvent is evaporated to afford the carboxylic
acid (10).
To convert carboxylic acid (10) to ester (12), a solution of it in pyridine is treated sequentially with ptoluenesulfonyl chloride and R1OH (11) according to the general procedure of J. H. Brewster and C. J.
Ciotti, Jr., J. Am. Chem. Soc. 1955, 77, 6214.
Alternatively, the carboxylic acid (10) may be converted to ester (12) through the use of excess R1OH
(11) and a strong acid catalyst such as hydrogen chloride as reviewed by C. A. Buehler and D. E.
Pearson, Survey of Organic Syntheses, Wiley-Interscience, New York, 1970, pp 802-807 (Equation
4c).
The nitrobenzene (12) is reduced to the aniline (13) either by use of iron in acetic acid as reviewed by
C. A. Buehler and D. E. Pearson (ibid, pp 413-414) or by hydrogenation using platinum sulfide as
catalyst and the conditions of F. S. Dovel and H. Greenfield, J. Am. Chem. Soc., 87, 2767 (1965)
(Equation 4d). When the other substitutents present are not potentially susceptible to hydrogenation or
hydrogenolysis, palladium may replace platinum sulfide as catalyst.
The aniline (13) is converted to the sulfonyl chloride (14) using the general procedures of H.
Meerwein, G. Dittmar, R. Gollner, K. Hafner, F. Mensch, O. Steinfort, Chem. Ber., 90, 841 (1957)
(Equation 4e). To limit the hydrolysis of the product during the coupling step, the use of
dichloromethane as a cosolvent is advantageous.
Finally, the sulfonyl chloride (14) is aminated to give (4a) using two equivalents of ammonia in
dichloromethane solution at a temperature between -30 and -10 DEG C (Equation 4f).
Alternatively, many of the sulfonamides of Formulae (4a) or (4c') can be prepared via the route shown
in Equation 5. EMI36.1 EMI37.1 where M1, R1, Ra, Rb, and X1 are as previously defined; R5 is C1-
15/2194
C6 alkyl, C1-C6 haloalkyl or CH2C(O)NRaRb; and R3 is as previously defined or C2-C4 aminoalkyl
but not C2-C6 alkenyl, C2-C6 haloalkenyl, C3-C6 alkynyl or C3-C6 haloalkynyl.
Phenol (15) is added to a solution of two equivalents of sodium in anhydrous methanol, ethanol, or
amyl alcohol. A little more than one equivalent of R3X1 (7) is added and the mixture is heated at reflux
for 4 to 24 hours. The solvent is removed in vacuo and the residue is partitioned between 1N
hydrochloric acid and ether. The ether phase is dried over sodium sulfate, and filtered. Evaporation of
the ether leaves the phenol (16) (Equation 5a).
In Equations 5b, c, d, e and f compounds 17a, 18a, 19a, 21a and 14a have the same structure as 17, 18,
19, 21, and 14 respectively except that the OR3 substituent is replaced by R5.
The carboxylic acid (16/16a) is converted to ester (17/17a) through the use of excess R1OH and a
strong acid catalyst such as hydrogen chloride as reviewed by C. A. Buehler and D. E. Pearson (op.cit.,
pp 802-807) (Equation 5b).
The phenol (17/17a) is converted to the thiocarbamate (18/18a) through the use of
dimethylthiocarbamoyl chloride and 1,4-diazabicyclo[2.2.2]octane (DABCO) in N,Ndimethylformamide according to the general procedure of M. S. Newman and H. A. Karnes, J. Org.
Chem. 1966, 31, 3890 (Equation 5c). Alternatively a mixture of the phenol (17/17a), at least one
equivalent of dimethylthiocarbamoyl chloride, at least one equivalent of triethylamine (Et3N), and a
catalytic amount of 4-dimethylaminopyridine (DMAP) in dichloromethane is heated at reflux for one to
seven days. The reaction mixture is washed with 1N hydrochloric acid and 10% aqueous sodium
hydroxide solution, then dried over magnesium sulfate and filtered. Evaporation of the solvent leaves
crude (18/18a) which may be purified by chromatography on silica gel or by recrystallization if it is
crystalline.
The thiocarbamate (18/18a) is converted to its isomer (19/19a) by heating according to the general
procedure of M. S. Newman and H. A. Karnes (op. cit.) (Equation 5d).
The solution of (19/19a) in anhydrous R1OH (11) is added little more than one equivalent of NaOR1
(20). The mixture is heated at 60-70 DEG C for 0.5-1 hour. The solvent is removed in vacuo, and the
residue is partitioned between dichloromethane and water. The aqueous phase is washed with
dichloromethane, acidified with 12N hydrochloric acid, and extracted with dichloromethane. The
dichloromethane extracts are dried over sodium sulfate and filtered. Evaporation of the solvent leaves
thiol (21/21a) (Equation 5e).
To a mixture of the thiol (21/21a) and at least one equivalent of sodium formate in formic acid is added
at least three equivalents of hydrogen peroxide at such a rate as to keep the temperature between 40 and
50 DEG C. The reaction mixture is then heated at 45-55 DEG C for 1 to 5 hours. The excess peroxide
is destroyed within sodium sulfite, and the solvent is evaporated. The residue is added to excess thionyl
chloride, and a catalytic amount of N,N-dimethylformamide (DMF) is added. The mixture is heated at
reflux for 8 to 24 hours, and then the solvent is evaporated. The residue is partitioned between water
and ether. The ether solution is washed with aqueous sodium bicarbonate solution, dried over
magnesium sulfate and filtered. Evaporation of the solvent leaves the sulfonyl chloride (14/14a)
(Equation 5f).
Finally the sulfonyl chloride (14) is aminated giving the sulfonamide (4a) and likewise (14a) gives (4c')
as already described for Equation 4f (Equation 5g).
Most of the sulfonamides (4a) can be prepared via the route shown in Equation 6 starting from 6hydroxysaccharin (22). EMI40.1 where R1 and X1 are as previously defined and R3 is as defined for
Equation 4 or C2-C4 cyanoalkyl.
6-Hydroxysaccharin (22) can be prepared as described by C. Finzi and M. Colonna, Atti. accad. Lincei,
Classe, sci. fis., mat. mat., 1937, 26, 19 (Chem. Abst. 1938, 32, 3762). Alternatively, (4a), where R1 =
CH3, R3 = C6H5CH2 may be prepared via the route described by Equation 5. A solution of this
sulfonamide in dichloromethane is treated with one equivalent of 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU). The solvent is evaporated, and the residue is dissolved in minimal water and acidified with
16/2194
concentrated hydrochloric acid to precipitate 6-benzyloxysaccharin. This is dissolved in ethanol
containing palladium catalyst. The mixture is hydrogenated at 20-40 DEG C and 1-10 psi until
hydrogen uptake ceases. Filtration and evaporation of the solvent affords 6-hydroxysaccharin (22).
In the method described by Equation 6a, 6-hydroxysaccharin (22) is added to a solution of two
equivalents sodium in anhydrous methanol, ethanol, or amyl alcohol. A little more than one equivalent
of R3X1 (7) is added and the mixture is heated at reflux for 4 to 24 hours. The solvent is removed in
vacuo and the residue is dissolved in minimal water. It is acidified with concentrated hydrochloric acid.
If the product crystallizes, it is collected, washed with dilute hydrochloric acid, and dried. If it does not
crystallize, the aqueous mixture is extracted with dichloromethane. The dichloromethane phase is dried
over sodium sulfate and filtered. Evaporation of the solvent leaves the saccharin (23) (Equation 6a).
A solution or suspension of the saccharin (23) in R1OH (11) is saturated with hydrogen chloride. The
mixture is heated at 65-80 DEG C for 1-6 hours. The solvent and hydrogen chloride are evaporated.
The residue is dissolved in dichloromethane, washed with aqueous sodium bicarbonate solution, dried
over sodium sulfate, and filtered. Evaporation of the solvent affords the sulfonamide (4a) (Equation
6b).
Alternatively, saccharin (22) may be opened to the sulfonamide (24) using the conditions already
described for the conversion of (23) to (4a) in Equation 6b (Equation 6c). To a solution of the
sulfonamide (24) in anhydrous methanol, ethanol, amyl alcohol, or a suitable aprotic solvent such as
N,N-dimethylformamide is added one equivalent of sodium or potassium methoxide, ethoxide, or tertbutoxide followed by the alkylating agent R3X1 (7). The mixture is held at 20-80 DEG C for 1-8
hours. The solvent is removed in vacuo, and the residue is dissolved in dichloromethane, washed with
aqueous sodium bicarbonate solution, dried over Na2SO4, and filtered. Evaporation of the solvent
affords the sulfonamide (4a) (Equation 6d).
Many sulfonamides of Formulae (4a), (4b) and (4e) can be prepared by the methods shown in Equation
7. EMI42.1 EMI43.1 EMI44.1 where M1, R1 and X1 are as previously defined, X2 is F, Cl, Br or I,
W is O, S, or NRb; Rb is as previously defined; and R4 is R3 as defined for Equation 6 or H, CH3,
cyclohexyl, or phenyl.
The hydroxysaccharin (22) is converted to the thiocarbamate (25) through the use of
dimethylthiocarbamoyl chloride and 1,4-diazabicyclo[2.2.2]octane (DABCO) in N,Ndimethylformamide according to the general procedure, or modifications thereof known to those skilled
in the art, of M. S. Newman and H. A. Karnes (op.cit.) (Equation 7a).
The thiocarbamate (25) is converted to its isomer (26) by heating according to the general procedure, or
modifications thereof known to those skilled in the art, of M. S. Newman and H. A. Karnes (ibid.)
(Equation 7b).
To a solution of (26) in anhydrous methanol is added a little more than two equivalents of sodium
methoxide. The mixture is heated at 60-70 DEG C for 0.5-1 hour. The solvent is removed in vacuo, and
the residue is partitioned between dichloromethane and water. The aqueous phase is washed with
dichloromethane and acidified with concentrated hydrochloric acid. If the saccharin (27) crystallizes, it
is collected, rinsed with dilute cold hydrochloric acid, and dried. If it does not crystallize, the aqueous
phase is extracted with dichloromethane. The dichloromethane extracts are dried over sodium sulfate
and filtered. Evaporation of the solvent leaves saccharin (27) (Equation 7c).
The mercaptan (27) is added to a solution of two equivalents sodium in anhydrous methanol, ethanol,
or amyl alcohol. A little more than one equivalent of R4X1 (28) is added, and the mixture is heated at
reflux for 1 to 8 hours. The requisite alkylating, alkenylating, and alkynylating agents R4X1 (28) are
either known in the art or may be made by a wide variety of methods known in the art.
The solvent is removed in vacuo, and the residue is dissolved in minimal water. It is acidified with
concentrated hydrochloric acid. If the saccharin (29) crystallizes, it is collected, washed with cold
dilute hydrochloric acid, and dried. If it does not crystallize, the aqueous mixture is extracted with
dichloromethane. The dichloromethane phase is dried over sodium sulfate and filtered. Evaporation of
the solvent leaves the saccharin (29) (Equation 7d).
17/2194
Alternatively, in many cases, the saccharins of Formula (29) or (29b) may be prepared by treating a
halosaccharin (30) in a polar aprotic solvent such as N-N-dimethylformamide at 20-100 DEG C with at
least two equivalents of the corresponding thiolate or alkoxide of Formula (31) for 4-24 hours. The
reaction is worked up by evaporation of the solvent. The residue is dissolved in minimal water and
acidified with concentrated hydrochloric acid. If the saccharin (29/29b) crystallizes, it is filtered.
Otherwise the aqueous solution is extracted with dichloromethane, and evaporation of the solvent
leaves the saccharin (29/29b) (Equation 7e).
Many 5-aminosaccharins (29a) can be prepared by heating the halosaccharin (30) in N,Ndimethylformamide under pressure at 125-190 DEG C in the presence of amines for 8-16 hours. The
reaction is worked up as described in the preceding paragraph.
In addition, aminosaccharins (29a) wherein R4 is H can be alkylated in the same fashion as described
previously for alkoxy and mercapto saccharins in Equations (6a) and (7d). The conversion of
aminosaccharins (29a) into aminosulfonamides (4e) or (32a) can be effected using conditions described
previously in Equations (6b and c) (Equation 7f).
The requisite precursor halosaccharins of Formula (30) may be prepared by conversion of the
corresponding 4-halo-2-nitrobenzoic acids to esters of 2-(aminosulfonyl)-4-halobenzoic acids by use of
methods analogous to those described for Equation 4. These esters are closed to the corresponding
saccharins of Formula (30) by treatment with DBU according to the general method already described
for the preparation of 6-benzyloxysaccharin.
Saccharins (29/29b) are similarly opened to the corresponding sulfonamides (4b/4a) using the
conditions already described for the conversion of (23) to (4a) in Equation 6b (Equation 7f).
Alternatively, saccharin (27/29a) may be opened to the sulfonamide (32/32a) using the conditions
already described for the conversion of (23) to (4a) in Equation 6b (Equation 7g). The thiol (32) or
aniline (32a) is then converted to (4b/4e) using the method already described for the conversion of (24)
to (4a) in Equation 6d (Equation 7h).
Most sulfonamides of Formula (4b) (R1 and R4 as previously defined) can also be prepared by
synthetic routes analogous to that described for R1=R4=CH3 in Examples 9 through 16.
Sulfonamides of Formula (4c) can be prepared by the method shown in Equation 8. EMI47.1
EMI48.1 EMI49.1 where R1 is as previously defined; R5 is alkyl, haloalkyl, alkenyl, haloalkenyl,
alkynyl, haloalkynyl or CH2C(O)NRaRb; Ra and Rb are as previously defined ; W1 is O or S; M2 is
Na or K; R6 is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, cyclopropylmethyl, C3-C4
alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C4 haloalkynyl, C2-C4 alkoxyalkyl, or C2-C4
aminoalkyl; and R7 is C1-C4 alkyl substituted with W1R6.
The starting nitrobenzenes (33) are either known in the art or may be made by a wide variety of
methods known in the art. Some of these methods include the nitration (for review, see G. Lehmann, H.
Eichmann "Formation of Carbon-Nitrogen Bonds" in Preparative Organic Chemistry, G. Hilgetag, A.
Martini ed., Wiley-Interscience, New York, 1972) of the coupling product obtained from reaction of
the appropriate halide with diphenylcuprate (for review, see G. H. Posner "Substitution Reactions
Using Organo-copper Reagents" in Organic Reactions, Vol. 22, W. G. Dauben ed., Wiley, New York,
1975).
Another method is the Friedel-Crafts acylation of benzene with the appropriate acid halide or
anhydride (for a review, see G. A. Olah, Friedel-Crafts and Related Reactions, Volumes I-IV, WileyInterscience, New York, 1963-1965), followed by reductive removal of the carbonyl oxidation (for a
review, see C. Bischoff, P. -G. Dietrich, E. Höft, D. Murowski, "Formation of Carbon-Hydrogen
Bonds" in Preparative Organic Chemistry, G. Hilgetag, A. Martini ed., Wiley-Interscience, New York,
1972) and then nitration.
Still another method involves conversion of the appropriate 4-nitrobenzyl alcohols, aldehydes, or
ketones to their mono or difluoro alkyl homologues using the conditions reviewed by G. A. Boswell,
18/2194
Jr., W. C. Ripka, R. M. Scribner, C. W. Tullock, "Fluorination by Sulfur Tetrafluoride" and C. M.
Sharts, W. A. Sheppard "Modern Methods to Prepare Monofluoroaliphatic Compounds" in Organic
Reactions, Vol. 21, W. G. Dauben ed., Wiley, New York, 1974).
The nitrobenzene (33) is reduced to the aniline (34) using the conditions already described for the
conversion of (12) to (13) in Equation 4d (Equation (8a).
The aniline (34) in a suitable solvent such as benzene is treated with at least one equivalent of acetic
anhydride and heated at reflux for 8-24 hours. The reaction mixture is cooled, and if the acetanilide
(35) crystallizes, it is collected and dried. If it does not crystallize, the benzene solution is washed with
1N hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate, and
filtered. Evaporation of the solvent leaves the acetanilide (35) (Equation 8b).
The acetanilide (35) is then nitrated using the general conditions reviewed by G. Lehmann and H.
Teichmann (op.cit.) to give nitroacetanilide (36) (Equation 8c).
A slurry of acetanilide (36) in 1N hydrochloric acid is heated at reflux until all of the solid dissolves.
The solution is then made slightly basic with sodium bicarbonate and is extracted with
dichloromethane. The dichloromethane extracts are dried over sodium sulfate and filtered. Evaporation
of the solvent leaves the aniline (37) (Equation 8d).
Many of the substituents described within R7 are prepared from aniline (37) having an R5 substituent
containing a displaceable halogen atom at the position where the substituent W1R6 is to be placed.
Thus the halide (37) in a suitable solvent such as N,N-dimethylformamide is treated with a little more
than one equivalent of the appropriate sodium or potassium salt (38).
The mixture is held at 20-100 DEG C for 1-8 hours. The solvent is then evaporated, and the residue is
partitioned between water and dichloromethane. The dichloromethane solution is dried over sodium
sulfate and filtered. Evaporation leaves the desired compound (39) (Equation 8e).
The aniline (39/37) is then diazotized and subjected to the Sandmeyer reaction according to the general
experimental procedure of G. T. Morgan and E. A. Coulson, J. Chem. Soc. 1929, 2551 to give nitrile
(40/40a) (Equation 8f).
A suspension of the nitrile (40/40a) in 75-80% aqueous sulfuric acid is heated at 95-100 DEG C for 2-5
hours. Then over 1-2 hours and at a temperature of 80-100 DEG C 1.5-2.5 equivalents of sodium nitrite
is added in small portions. The heating is continued 0.5-1 hour longer, then the mixture is cooled and
poured onto excess ice. If the carboxylic acid (41/41a) crystallizes, it is collected, rinsed with ice water
and dried. If it does not crystallize, the aqueous mixture is extracted with dichloromethane. The
dichloromethane solution is extracted with aqueous 10% sodium carbonate solution. The aqueous
extract is made acidic with concentrated hydrochloric acid. If the carboxylic acid (41/41a) then
crystallizes, it is collected, rinsed with ice water and dried. If it does not crystallize, the aqueous
solution is extracted with ether.The ether extracts are dried over magnesium sulfate and filtered.
Evaporation of the solvent leaves carboxylic acid (41/41a) (Equation 8g).
By use of the methods previously described, carboxylic acid (41) can be converted to sulfonamide (4c)
and likewise (41a) give (4c') (Equation 8h).
In the case where R7 substituents of sulfonamide (4c) are incompatible with the strongly acidic
conditions described in Equation 8g, an alternative scheme is used.
Sulfonamide of Formula (4c') wherein R5 is C1-C4 alkyl substituted with Cl, Br, or I in a suitable
solvent such as acetonitrile is treated with one equivalent of tert-butyldimethylsilyl chloride in the
presence of a mild base such as pyridine at 15-25 DEG C for 1-8 hours. when the reaction is judged
complete by thin layer chromatography the mixture is poured onto ice water. If the silylsulfonamide
crystallizes, it is collected, rinsed with water and dried. If not, the aqueous solution is extracted with
ether. The ether extracts are dried and concentrated to furnish the silylsulfonamide of (4c') (Equation
8i).
19/2194
A stirred solution of the silylsulfonamide of (4c') in a solvent such as DMF is treated at 0 DEG -80
DEG C with at least one equivalent of (38) for 1-8 hours. When the reaction is judged complete by thin
layer chromatography the mixture is poured onto ice water and the reaction is worked up as described
in the previous paragraph (Equation 8j).
The silylsulfonamide of (4c) can then be converted directly into sulfonylurea (I) using the same
conditions described in Equation 3, with the exception that tetra-n-butyl ammonium fluoride is used as
base in lieu of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
Sulfonamides of Formula (4) where R2 contains sulfinyl or sulfonyl groups can be prepared by peracid
oxidation of the corresponding mercapto sulfonamides using methods analogous to those described for
the preparation of sulfinyl sulfonamides of Formula (4d,n=1) and sulfonyl sulfonamides of Formula
(4d,n=2) in Equation 9 (vide infra).
For example, the sulfinyl sulfonamides of Formula (4d,n=1) and sulfonyl sulfonamides of Formula
(4d,n=2) can be prepared from the corresponding thio sulfonamides of Formula (4b) as shown in
Equation 9. EMI53.1 where R1 and R4 are as previously defined, except that R4 cannot be
alkylthioalkyl or haloalkylthioalkyl, and n is 1 or 2.
To prepare the sulfinyl sulfonamides of Formula (4d,n=1) a solution of one equivalent of a peracid,
such as 3-chloroperoxybenzoic acid, in an inert solvent, such as dichloromethane, is added to a stirred
solution of the appropriate thio sulfonamide (4b) in an inert solvent, such as a mixture of
dichloromethane and tetrahydrofuran, at 0-5 DEG C. The mixture is then warmed to 20-40 DEG C.
When thin layer chromatography has revealed the sulfonamide (4b) to have been oxidized, the mixture
is washed in turn with 5% aqueous sodium sulfite solution, saturated aqueous sodium bicarbonate
solution, water, and brine, and then dried (MgSO4). Evaporation of the solvent then leaves the sulfinyl
sulfonamide of formula (4d, n=1).
To prepare sulfonyl sulfonamides of Formula (4d, n=2) a solution of more than two equivalents (only
two equivalents when R4 is alkenyl or alkynyl) of a peracid, such as 3-chloroperoxybenzoic acid, in an
inert solvent, such as 1,2-dichloroethane, is added to a stirred mixture of the appropriate thio
sulfonamide (4b) in an inert solvent, such as 1,2-dichloroethane, containing 1-5 mol % of a free radical
inhibitor, such as 4,4-thiobis(6-tert-butyl-m-cresol). The mixture is heated to 50-80 DEG C. When thin
layer chromatography shows the thio sulfonamide (4b) and intermediate sulfinyl sulfonamide (4d, n=1)
to have been consumed, the mixture is cooled and diluted with tetrahydrofuran to maintain sulfonamide
solubility. Using the same work up method as already described for the preparation of sulfinyl
sulfonamides (4d, n=1), one obtains the sulfonyl sulfonamides of formula (4d, n=2).
Sulfonamides of Formula (4d) where R4 is alkylthioalkyl or haloalkylthioalkyl and n is 1 or 2 can be
prepared from the homologous sulfonamides of Formula (4d) having a R4 monohaloalkyl substituent
with a displaceable halogen atom at the position where the alkylthioalkyl or haloalkylthioalkyl group is
to be placed. These monohaloalkyl sulfonamides are first closed to the corresponding saccharins by use
of DBU as previously described for the preparation of 6-benzyloxysaccharin. The halogen atom is then
replaced with the appropriate alkylthio or haloalkylthio group using the displacement conditions
previously described for the conversion of halide (37) to thioether (39) in Equation 8. When the
appropriate haloalkylthiolate reagent is unstable to self-condensation, the corresponding hydroxy-,
carbonyl-, and/or carboxy-containing alkylthiolate can be used. After formation of the thioether bridge,
these oxygen-containing groups can be converted to the desired halogen substitution pattern by use of a
wide variety of methods known in the art. Finally, the saccharins are opened to the desired
sulfonamides of Formula (4d) where R4 is alkylthioalkyl or haloalkylthioalkyl and n is 1 or 2 by the
method already described for the conversion of (23) to (4a) in Equation 6b.
The amino sulfonamides of Formula (4e) are prepared as shown in Equation 9.1 and discussed below.
EMI55.1 EMI56.1 where R1 and X2 are as previously defined, Rb' is H or alkyl, and Rc' is H, alkyl, or
haloalkyl.
In most cases the amino saccharins of Formula (41.2) are prepared by treating halo saccharins of
Formula (30) with one or more equivalents of the corresponding amine derivatives of Formula (41.1)
using one or more of a wide variety of experimental conditions known in the art. In some cases the
20/2194
reaction can be run using an excess of the amine derivative (41.1) as the only solvent and heating the
mixture to 30-200 DEG C at atmospheric pressure or, if the boiling point of the amine derivative makes
necessary, at above atmospheric pressure. In other cases the use of a polar inert solvent such as N, Ndimethylformamide is advantageous.When the amine derivative is itself difficult or expensive to
prepare, the amount of it used can be reduced to little more than one equivalent if at least one
equivalent of another base such as triethylamine, N, N-diisopropyl-N-ethylamine,
diazabicyclo[5.4.0]undec-7-ene, sodium hydride, or n-butyllithium is added to the reaction mixture.
Besides reducing the amount of amine derivative needed, the use of at least two equivalents of very
strong bases, such as n-butyllithium or sodium hydride, capable of deprotonating the amine derivative
can accelerate the rate of the displacement reaction and allow it to proceed at lower temperatures as is
well known in the art. The requisite amine derivatives (41.1) are either known or can be made by
methods known in the art.
After the displacement reaction is complete the solvent and excess of any volatile amine derivative
(41.1) is evaporated and the residue is dissolved in 5% aqueous sodium hydroxide solution.
Concentrated hydrochloric acid is added until the pH is 7. If the saccharin (41.2) crystallizes, it is
filtered. Otherwise the aqueous solution is saturated with salt and then extracted with dichloromethane,
and in most cases evaporation of the dichloromethane leaves the saccharin (41.2). If it does not, the
aqueous solution is evaporated to dryness and the residue is continuously extracted with
tetrahydrofuran. Evaporation of the solvent then leaves the saccharin (41.2) (Equation 9.1a).
In some cases saccharins of formula (41.2) may be prepared from saccharins of Formula (41.2) having
fewer substituents on the amino group. A variety of methods are well-known in the art for the
alkylation of aniline amino groups and their derivatives.
To prepare the sulfonamide of Formula (4e) a solution or suspension of the saccharin (41.2) in the
appropriate alcohol R1OH (11) is saturated with hydrogen chloride. The mixture is heated at 65-80
DEG C for 1-12 hours. The solvent and hydrogen chloride are evaporated. The residue is dissolved in a
mixture of brine and 5:1 (vol.) dichloromethane-tetrahydrofuran. Sodium carbonate is added to the
vigorously stirred mixture until it is made basic. The dichloromethane-tetrahydrofuran phase is then
separated, and evaporation of the solvent leaves the sulfonamide of Formula (4e) (Equation 9.1b).
Sulfonyl isocyanates (1) or (1A) are prepared from the corresponding sulfonamides (4) or (4A) with
compatible R2 (R@) substituents by one of the following two general methods. EMI58.1 where R1
and R2 (R@) are as previously defined.
The sulfonamide (4) or (4A) and an alkyl isocyanate (e.g., n-butyl isocyanate) in xylene or other
solvent boiling above 135 DEG C are mixed in the presence or absence of a catalytic amount of 1,4diaza[2.2.2]bicyclooctane (DABCO) and heated to 135-140 DEG C. After 5-60 minutes phosgene is
slowly added to the heated mixture at such a rate that the temperature remains between 133-135 DEG
C. When the consumption of phosgene has ceased, the mixture is cooled and filtered to removed
insoluble material. Finally, the solvent, alkyl isocyanate, and excess phosgene are evaporated, leaving
the sulfonyl isocyanate (1) or (1A).
If desired, the alkyl isocyanate-sulfonamide adduct can be made and isolated before reaction with the
phosgene. In this case, the sulfonamide (4) or (4A), alkyl isocyanate, and anhydrous base (e.g.,
K2CO3) in a polar, aprotic solvent (e.g. acetone, butanone, or acetonitrile) are mixed and heated under
reflux for 1 to 6 hours. The reaction mixture is then diluted with water, and the pH is adjusted to about
3 with acid (e.g. HCl, H2SO4). The adduct is filtered out and dried, and then reacted with phosgene as
described above. This procedure modification is especially useful when sulfonamide (4) or (4A) is high
melting and has low solubility in the phosgenation solvent.
Sulfonyl isocyanates (1) or (1A) can also be prepared by the following method. EMI59.1 where R1
and R2 (R@) are as previously defined.
The sulfonamide (4) or (4A) is heated at reflux in an excess of thionyl chloride. The reaction is
continued until the sulfonamide protons are no longer detectable in the proton magnetic resonance
spectrum. From 16 hours to 5 days is typically sufficient for complete conversion to the thionylamide
(42) (Equation 11a).
21/2194
The thionyl chloride is evaporated and the residue is treated with an inert solvent (e.g. toluene)
containing at least one equivalent (typically 2-3 equivalents) of phosgene. A catalytic amount of
pryridine (typically 0.1 equivalent) is added, and the mixture is heated to about 60-140 DEG C. with
80-100 DEG preferred. Conversion to the isocyanate (1) or (1A) is usually substantially complete
within 15 minutes to 3 hours (Equation 11b). The mixture is then cooled and filtered, and the solvent is
evaporated, leaving the sulfonyl isocyanate (1) or (1A).
The heterocyclic amines of Formula (2) below are either known, disclosed in this application, or can
be prepared by obvious methods by one skilled in the art. EMI60.1
For a review of the synthesis and reactions of 2-amino and 2-methylaminopyrimidines (2, Z=CH) see
The Chemistry of Heterocyclic Compounds, Vol. 16, Wiley-Interscience, New York (1962). For a
review of the synthesis and reactions 2-amino- and 2-methylamino-s-triazines (2, Z=N) see The
Chemistry of Heterocyclic Compounds, Vol, 13, Wiley-Interscience, New York (1959), F. C. Schaefer,
U.S. Patent 3,154,537 and F. C. Schaefer and K. R. Huffman J. Org. Chem., 28, 1812 (1963).
In some cases, heterocycles of Formula (2) may be more easily prepared with R being H than with R
being CH3. Many heterocycles (2, R=CH3) can be prepared from the corresponding heterocycles (2,
R=H) by one or more of the following two methods. EMI61.1 where A is as previously defined.
In this method, a solution or slurry of the appropriate heterocycle (2, R=H) in a suitable aprotic solvent
(e.g., tetrahydrofuran, dioxane, glyme) at 0-30 DEG C is treated with two equivalents of sodium
hydride. After gas evolution ceases, the reaction mixture is treated with one equivalent of dimethyl
carbonate and stirred at 20-30 DEG C for 8 to 24 hours to provide a suspension of the sodium salt (43)
(Equation 12a).
The reaction mixture containing (43) is treated with at least two equivalents of iodomethane and then
heated at 60-80 DEG C for 8 to 24 hours. The mixture is cooled and filtered, and the solvent is
evaporated. The residue is taken up in dichloromethane, washed with water, and the solvent is
evaporated, leaving the N-methyl carbamate (44, R=CH3) (Equation 12b).
The carbamate (44, R=CH3) is dissolved in anhydrous, alcohol-free chloroform saturated with
propylene gas. Slightly more than one equivalent (typically 1.1-1.2 equivalents) of iodotrimethylsilane)
is added and the stirred solution is heated at 50-60 DEG C for 2 to 4 hours. The mixture is cooled and
two equivalents of methanol is added. The solvent is evaporated and the residue is taken up in
methanol. The mixture is carefully neutralized with 10% sodium methoxide in methanol, and then the
solvent is evaporated. The residue is triturated with ice water. If a precipitate forms, it is filtered out,
rinsed with ice water and dried to provide (2, R=CH3). If no precipitate forms, the solution is saturated
with sodium chloride and extracted with ethyl acetate. Evaporation of the solvent leaves heterocycle (2,
R=CH3)(Equation 12c).
Alternatively, the following two-step procedure is useful in many cases. EMI62.1 where A is as
previously defined.
A solution of the amine (2, R=H) in concentrated hydrochloric acid is treated with sodium nitrite
solution and the chloro compound (45) is isolated in the usual manner by filtration of the acidic
solution (Equation 13a). A representative procedure is described by Bee and Rose in J. Chem. C. 1966,
2031, for the case in which Z=CH, and X=Y=OCH3.
The heterocycle (45) is then treated with at least two equivalents of methylamine in a suitable inert
solvent (e.g. tetrahydrofuran, glyme, or diglyme) at a temperature between 20 DEG and 80 DEG C for
1-18 hours (Equation 13b). The reaction mixture is then cooled and filtered. Evaporation of the solvent
leaves (2, R=CH3) contaminated with a little CH3NH@Cl>;-; salt. The product may be purified by
trituration with ice water or by dissolution in dichloromethane, followed by washing with a small
amount of water, drying, and evaporation of solvent. Further purification may be accomplished by
recrystallization or column chromatography on silica gel.
The heterocyclic amines of Formula (2a) to (2c) below are taught in U.S. Patent 4,478,635. EMI63.1
22/2194
In some cases, heterocycles of Formula (2) may be more easily prepared with R being H than with R
being CH3. Many heterocycles (2A, R=CH3) can be prepared from the corresponding heterocycles
(2A, R=H) by one or more of the following two methods. EMI64.1 where A is EMI64.2 and Y is as
previously defined.
In this method, a solution or slurry of the appropriate heterocycle (2, R=H) in a suitable aprotic solvent
(e.g., tetrahydrofuran, dioxane, glyme) at 0-30 DEG C is treated with two equivalents of sodium
hydride. After gas evolution ceases, the reaction mixture is treated with one equivalent of dimethyl
carbonate and stirred at 20-30 DEG C for 8 to 24 hours to provide a suspension of the sodium salt (43)
(Equation 12Aa).
The reaction mixture containing (43) is treated with at least two equivalents of iodomethane and then
heated at 60-80 DEG C for 8 to 24 hours. The mixture is cooled and filtered, and the solvent is
evaporated. The residue is taken up in dichloromethane, washed with water, and the solvent is
evaporated, leaving the N-methyl carbamate (44, R=CH3) (Equation 12Ab).
the carbamate (44, R=CH3) is dissolved in anhydrous, alcohol-free chloroform saturated with
propylene gas. Slightly more than one equivalent (typically 1.1-1.2 equivalents) of iodotrimethylsilane)
is added and the stirred solution is heated at 50-60 DEG C for 2 to 4 hours. The mixture is cooled and
two equivalents of methanol is added. The solvent is evaporated and the residue is taken up in
methanol. The mixture is carefully neutralized with 10% sodium methoxide in methanol, and then the
solvent is evaporated. The residue is triturated with ice water. If a precipitate forms, it is filtered out,
rinsed with ice water and dried to provide (2A, R=CH3). If no precipitate forms, the solution is
saturated with sodium chloride and extracted with ethyl acetate. Evaporation of the solvent leaves
heterocycle (2A, R=CH3)(Equation 12Ac).
Alternatively, the following two-step procedure is useful in many cases. EMI65.1 EMI66.1 where A
is as previously defined.
A solution of the amine (2A, R=H) in concentrated hydrochloric acid is treated with sodium nitrite
solution and the chloro compound (45) is isolated in the usual manner by filtration of the acidic
solution (Equation 13Aa). A representative procedure is described by Bee and Rose in J. Chem. Soc. C.
1966, 2031.
The heterocycle (45) is then treated with at least two equivalents of methylamine in a suitable inert
solvent (e.g. tetrahydrofuran, glyme, or diglyme) at a temperature between 20 DEG and 80 DEG C for
1-18 hours (Equation 13b). The reaction mixture is then cooled and filtered. Evaporation of the solvent
leaves (2A, R=CH3) contaminated with a little CH3NH@Cl>;-; salt. The product may be purified by
trituration with ice water or by dissolution in dichloromethane, followed by washing with a small
amount of water, drying, and evaporation of solvent. Further purification may be accomplished by
recrystallization or column chromatography on silica gel.
As an alternative to the methods already described in which the sulfonamides of Formulae (4a), (4b),
(4d), and (4e) are fully elaborated prior to construction of the urea bridge of compounds of Formulae I
or II, many compounds of Formulae Ia or IIa may be prepared by the method described in Equations 14
or 14A. EMI67.1 where R1, X, X1, Y and Z are as previously defined; W is S, O or NRb; Rb is as
previously defined; R8 is C4-C6 cycloalkylalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C3-C6 alkynyl,
C3-C6 haloalkynyl, C2-C8 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C8 alkylthioalkyl, C2-C4
haloalkylthioalkyl, C2-C4 cyanoalkyl, CH2C(O)CH3, CH2CH2C(O)CH3 or C1-C6 alkyl.
In this method a solution of the appropriate compound of Formula (46) in a polar solvent such as a
mixture of acetonitrile and N, N-dimethylformamide is treated with two equivalents of a strong base
such as sodium methoxide or sodium hydride with catalytic methanol followed by a little more than
one equivalent of the appropriate alkylating, alkenylating, or alkynylating agent (47). The mixture is
held at 20-60 DEG C for 2-24 hours. Then the mixture is poured into excess hydrochloric acid. If the
compound of formula Ia crystallizes, it is filtered.Otherwise the aqueous mixture is extracted with
dichloromethane, and evaporation of the solvent leaves the compound of Formula Ia, The compounds
of Formula (46) are in turn prepared by coupling the appropriate sulfonamides of Formulae (4a, 4b or
23/2194
4e) with the appropriate heterocyclic phenyl carbamates of Formula (5,R=H) according to the general
method described for Equation 3.
Many of the compounds of Formula Ia where R8 is alkyl, cycloalkyl, cycloalkylalkyl, haloalkyl,
alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxyalkyl, haloalkoxyalkyl, cyanoalkyl, -CH2C(O)CH3,
or -CH2CH2C(O)CH3 and W is S(O) or S(O)2 can be made by oxidation of the corresponding
compounds of Formula Ia where W is S using methods similar to those already described for the
conversion of (4b) to (4d) in Equation 9.
Compounds of Formula I where R2 contains a carbonyloxy, carbamoyloxy, phosphoryloxy,
sulfonyloxy, silyloxy, or phosphorylthio group are prepared from the corresponding compounds of
Formula I where R2 contains a hydroxyl or thiol group by use of a wide variety of methods known in
the art. EMI68.1 where R1, X1 and Y' are as previously defined, W is O, NR@ or S, and R8 is alkyl,
haloalkyl, alkenyl, alkynyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl,
alkylsulfinylalkyl, haloalkylsulfinylalkyl, alkylsulfonylalkyl, haloalkylsulfonylalkyl, or cyanoalkyl
when W is O; R8 is alkyl, haloalkyl, alkenyl, alkynyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl,
haloalkylthioalkyl, or cyanoalkyl when W is S; and R8 is alkyl or haloalkyl when W is NRb' (Rb' is as
previously defined).
In this method a solution of the appropriate compound of Formula (46a) in a polar solvent such as a
mixture of acetonitrile and N,N-dimethylformamide is treated with two equivalents of a strong base
such as sodium methoxide or sodium hydride with catalytic methanol followed by a little more than
one equivalent of the appropriate alkylating, alkenylating, or alkynylating agent (47). The mixture is
held at 20-60 DEG C for 2-24 hours. Then the mixture is poured into excess hydrochloric acid. If the
compound of Formula IIa crystallizes, it is filtered. Otherwise the aqueous mixture is extracted with
dichloromethane, and evaporation of the solvent leaves the compound of Formula IIa.The compounds
of Formula (46a) are in turn prepared by coupling the appropriate sulfonamides of Formulae
(24)(W=O), (32)(W=S), or (4e)(Rc'=H) (W=NR@) with the appropriate heterocyclic phenyl
carbamates of Formula (5A,R=H) according to the general method described for Equation 3A.
Many of the compounds of Formula IIa where R8 is alkyl, haloalkyl, alkenyl, alkynyl, alkoxyalkyl,
haloalkoxyalkyl, or cyanoalkyl, and W is S(O) or S(O)2 can be made by oxidation of the corresponding
compounds of Formula Ia where W is S using methods similar to those already described for the
conversion of (4b) to (4d) in Equation 9.
The following examples further illustrate the synthesis of this invention.
Example 1
6-Hydroxy-1,2-benzisothiazol-3(2H)-one, 1,1-dioxide
To methyl 2- (aminosulfonyl)-4-(methoxy)benzoate (34 g, 0.139 mol) in dry N,N-dimethylformamide
(DMF) (500 mL) was added potassium tert-butoxide (46.6 g, 0.42 mol) portionwise. The mixture was
stirred 15 minutes at room temperature then 2-propanethiol (25 mL, 0.28 mol) was added dropwise.
The reaction exothermed to 37 DEG and became homogeneous. The mixture was heated at reflux for 4
hours and then was cooled to room temperature. The mixture was diluted with water and acidified with
concentrated HCl until the pH was approximately 2. The homogeneous solution was extracted with
ethyl acetate. The organic layer was washed with water and brine and dried with magnesium sulfate.
Concentration furnished 28 g of the subject compound as a white solid, m.p. 148-150 DEG C.NMR (90
MHz) D6-acetone; delta 9.8 (bs. 2H + water), 8.0 (d, 1H) and 7.5 (m, 2H).
Example 2
6-(Difluoromethoxy)-1,2-benzisothiazol-3(2H)-one, 1,1-dioxide
24/2194
To a solution of 6-hydroxysaccharin (1.0 g, 5.0 mmol) in aqueous KOH (0.85 g, 15 mmol in water
(10mL)) was added methylene chloride (25 mL) and tetrabutyl ammonium bromide (0.2 g, catalytic).
An excess of Freon >;( TM ); was added and the reaction was heated to reflux using a dry-ice/acetone
condenser. After 3 hours the reaction was filtered and the filtrate was acidified with concentrated HCl
to pH 2. The solids were collected by filtration, washed with water and dried to give 0.32 g of the
desired compound as a white solid, m.p. 183-185 DEG C. A second crop of 0.16 g was obtained from
the filtrate and was combined with the first. NMR (90 MHz) D6-acetone: delta 8.2 (d, 1H), 7.9 (d,
1H), 7.7 (dd, 1H) and 7.3 (t, 1H, J=72 Hz).
Example 3
2-(Aminosulfonyl)-4-(difluoromethoxy)benzoic acid, 2-methoxyethyl ester
A solution of 6-difluoromethoxysaccharin (1.5 g) in 2-methoxyethanol (25 mL) was cooled to 0 DEG
and HCl gas was bubbled into the reaction for 30 minutes. The mixture was heated at reflux for 20
minutes and cooled to 25 DEG . After 3 hours, there was no change as judged by thin layer
chromatography (TLC) so the reaction was heated an additional 12 hours. The reaction was judged
complete and was cooled to room temperature and concentrated. The resultant mixture was taken up in
ethyl acetate and washed with 5% sodium bicarbonate followed by brine and then dried with
magnesium sulfate.Concentration furnished 0.8 g of the desired compound as a white solid, m.p. 80-81
DEG C NMR (200 MHz) D6-acetone: delta 7.9 (d, 1H), 7.8 (d, 1H), 7.5 (dd, 1H), 7.2 (t, 1H, J=72
Hz), 4.4 (t, 2H), 3.8 (t, 2H) and 3.4 (s, 3H).
Example 4
4-(Difluoromethoxy)-2-[[(4,6-dimethoxypyrimidin-2-yl)-aminocarbonyl]aminosulfonyl]benzoic acid,
(2-methoxyethyl)ester
To 2-methoxyethyl 2-(aminosulfonyl)-4-difluoromethoxy)benzoate (0.1 g, 0.31 mmol) and
dimethoxypyrimidine phenylcarbamate (0.09 g, 0.31 mmol) in dry acetonitrile (5 mL) was added 1,8diazabicyclo[5.4.0]-undec-7-ene (DBU) (0.5 mL). The mixture was allowed to stir for 1 hour, then
water and 1N HCl (to pH 3) was added. The resultant solid was collected, washed with water and dried
to furnish 0.08 g of the desired compound as a white solid, m.p. 121-125 DEG C. NMR (200 MHz)
D6-acetone: delta 13.2 (bs. 1H), 9.2 (bs, 1H), 8.1 (d, 1H), 7.9 (d, 1H), 7.6 (dd, 1H), 7.2 (t, 1H), 5.8 (s,
1H), 4.5 (t, 2H), 4.0 (s, 6H), 3.7 (t, 2H) and 3.3 (s, 3H).
Example 5
6-(4-Methoxybenzylthio)-1,2-benzisothiazol-3(2H)-one, 1,1-dioxide
To 6-chlorosaccharin (10 g, 46 mmol) and 4-methoxybenzyl mercaptan (7.8 g, 50 mmol) in N,Ndimethylformamide (DMF) (50 mL) was added potassium tert-butoxide (14 g, 125 mmol) portionwise.
The reaction was allowed to exotherm to 60 DEG and slowly cool to room temperature. After stirring
for 14 hours, the mixture was poured onto ice-water (100 g) and acidified with concentrated HCl to pH
2. The desired compound was collected by filtration, washed with water and dried to furnish 13 g of a
white solid, m.p. 162-165 DEG C. NMR (90 MHz) D6-acetone: delta 8.2 (s, 1H), 8.0 (s, 2H), 7.7 (d,
2H), 7.2 (d, 2H), 4.6 (s, 2H) and 3,8 (s, 3H).
Example 6
6-(Thio)-1,2-benzisothiazol-3(2H)-one,1,1-dioxide
25/2194
A solution of 6-(4-methoxybenzyl)thiosaccharin in trifluoroacetic acid (50 mL) was heated at reflux for
14 hours. the heterogeneous reaction mixture was cooled and the solids were collected by filtration.
The solids were washed with butyl chloride and air dried and 6.3 g of the desired compound was
obtained as a greenish solid, m.p. 216-218 DEG C. NMR (90 MHz) D6-acetone: delta 8.2 (s, 1H),
7.95 (s, 2H), 5.3 (bs, 1H) and 5.1 (bs, 1H).
Example 7
6-(2,2,2-Trifluoroethylthio)-1,2-benzisothiazol-3)2H)-one, 1,1-dioxide
To 6-thiosaccharin (5.0 g, 27.3 mmol) in N,N-dimethylformamide (50 mL) was added potassium tertbutoxide (6.7 g, 60 mol) portionwise. Then 2,2,2-trifluoroethanol toluene sulfonate (7.2 g, 28 mmol)
was added in one portion. The mixture stirred for 14 hours at room temperature and was poured onto
ice-water. The solution was acidified to pH 2 with concentrated HCl and the solid was collected by
filtration, washed with water and air-dried. The desired compound was obtained as a white solid, m.p.
170-173 DEG C. NMR (90 MHz) D6-acetone: delta 8.3 (s, 1H), 8.1 (s, 2H), 7.5 (bs, 1H) and 4.2 (q,
2H).
Example 8
2-(Aminosulfonyl)-4-(2,2,2-trifluoroethylthio)benzoic acid, methyl ester
Into 6-trifluoroethoxy-thiosaccharin (1.5 g) in methanol (50 mL) at 0 DEG was bubbled HCl gas for
0.5 hours. The reaction was allowed to warm to room temperature and stirred for 14 hours. The solvent
was removed on the rotary evaporator and the solids were taken up in ethyl acetate and washed with
5% sodium bicarbonate, brine and dried with magnesium sulfate. After filtration, the filtrate was
concentrated and the desired compound was obtained as a white solid, m.p. 117-120 DEG C. NMR
(200 MHz) D6-acetone: delta 8.1 (s, 1H), 7.95 (s, 2H), 6.7 (bs, 2H), 4.1 (q, 2H) and 3.95 (s, 3H).
Example 9
4-(2,2,2-Trifluoroethylthio)-2-[[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester
To methyl 2-(aminosulfonyl)-4-(2,2,2-trifluoroethylthio)benzoate (0.1 g, 0.3 mmol) and
dimethoxypyrimidine phenylcarbamate (0.08 g, 0.31 mmol) in dry acetonitrile (5 mL) was added 1,8diazabicyclo[5.4.0]-undec-7-ene (DBU) (0.5 mL). The mixture was allowed to stir for 1 hour, then
water and 1N HCl (to pH 3) was added. The resultant solid was collected, washed with water and dried
to furnish 0.1 g of the desired subject as a white solid, m.p. 171-173 DEG C. NMR (200 MHz) D6acetone: delta 12.3 (bs, 1H), 9.8 (bs, 1H), 8.3 (d, 1H), 8.0 (dd, 1H), 7.8 (d, 1H), 5.9 (s, 1H), 4.1 (q,
2H), 4.0 (s, 6H) and 3.9 (s, 3H).
Using the procedures and examples shown above, the following compounds can be prepared.
It will be understood that the substituents X and Y are indistinguishable in the final product, and the
compounds below wherein X is OCH3 and Y is Cl should be regarded as compounds wherein X is Cl
and Y is OCH3, and are thus within the scope of our invention. EMI75.1 EMI76.1 EMI77.1
EMI78.1 EMI79.1 EMI80.1 EMI81.1 EMI82.1 EMI83.1 EMI84.1 EMI85.1 EMI86.1 EMI87.1
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Formulations
Useful formulations of the compounds of Formula I can be prepared in conventional ways. They
include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable
concentrates and the like. Many of these may be applied directly. Sprayable formulations can be
extended in suitable media and used at spray volumes of from a few liters to several hundred liters per
hectare. High strength compositions are primarily used as intermediates for further formulation. The
formulations, broadly contain about 0.1% to 99% by weight of active ingredient(s) and at least one of
(a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More
specifically, they will contain these ingredients in the following approximate proportions: EMI243.1
Lower or higher levels of active ingredient can, of course, be present depending on the intended use
and the physical properties of the compound. Higher ratios of surfactant to active ingredient are
sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and
Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or
manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the
denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide,"
2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates;
solution concentrates are preferably stable against phase separation at 0 DEG C. "McCutcheon's
Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely
and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964,
list surfactants and recommended uses.All formulations can contain minor amounts of additives to
reduce foaming, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing
the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or
fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent
3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular
carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering,
December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill,
New York, 1973, pp. 8-57ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and
Examples 10 through 41;
R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14, 1967, Col. 5, line 43 through Col. 7, line 62
and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17
and Examples 1-4;
G. C. Klingman, "Weed Control as a Science". John Wiley and Sons, Inc., New York, 1961, pp. 8196; and
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J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications,
Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
Example 10
Wettable Powder
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypryrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 80%
sodium alkylnaphthalenesulfonate 2%
sodium ligninsulfonate 2%
synthetic amorphous silica 3%
kaolinite 13%
The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
Example 11
Wettable Powder
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 50%
sodium alkylnaphthalenesulfonate 2%
low viscosity methyl cellulose 2%
diatomaceous earth 46%
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles
essentially all below 10 microns in diameter. The product is reblended before packaging.
Example 12
Granule
Wettable Powder of Example II 5%
attapulgite granules 95%
(U.S.S. 20-40 mesh; 0.84-0.42 mm)
A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules
while tumbling in a double-cone blender. The granules are dried and packaged.
Example 13
Extruded Pellet
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 25%
anhydrous sodium sulfate 10%
28/2194
crude calcium ligninsulfonate 5%
sodium alkylnaphthalenesulfonate 1%
calcium/magnesium bentonite 59%
The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is
extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These
may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve
(0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged
for use and the fines recycled.
Example 14
Oil Suspension
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 25%
polyoxyethylene sorbitol hexaoleate 5%
highly aliphatic hydrocarbon oil 70%
The ingredients are ground together in a sand mill until the solid particles have been reduced to under
about 5 microns. The resulting thick suspension may be applied directly, but preferably after being
extended with oils or emulsified in water.
Example 15
Wettable Powder
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid methyl ester 20%
sodium alkylnaphthalenesulfonate 4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose 3%
attapulgite 69%
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles
essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve
(0.3 mm opening) and packaged.
Example 16
Low Strength Granule
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 1%
N,N-dimethylformamide 9%
attapulgite granules 90%
(U.S.S. 20-40 sieve)
The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a
double cone blender. After spraying of the solution has been completed, the blender is allowed to run
for a short period and then the granules are packaged.
Example 17
29/2194
Aqueous Suspension
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 40%
polyacrylic acid thickener 0.3%
dodecylphenol polyethylene glycol ether 0.5%
disodium phosphate 1%
monosodium phosphate 0.5%
polyvinyl alcohol 1.0%
water 56.7%
The ingredients are blended and ground together in a sand mill to produce particles essentially all under
5 microns in size.
Example 18
Solution
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 5%
water 95%
The salt is added directly to the water with stirring to produce the solution, which may then be
packaged for use.
Example 19
Low Strength Granule
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid methyl ester 0.1%
attapulgite granules 99.9%
(U.S.S. 20-40 mesh)
The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a
double-cone blender. After spraying of the solution has been completed, the material is warmed to
evaporate the solvent. The material is allowed to cool and then packaged.
Example 20
Granule
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 80%
wetting agent 1%
crude ligninsulfonate salt (containing 5-20% of the natural sugars) 10%
attapulgite clay 9%
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added
to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of
30/2194
water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules
of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally
with heat, until the water content is reduced to the desired level, generally less than 1%. The material is
then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and
packaged for use.
Example 21
High Strength Concentrate
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 99%
silica aerogel 0.5%
synthetic amorphous silica 0.5%
The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a
U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.
Example 22
Wettable Powder
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 90%
dioctyl sodium sulfosuccinate 0.1%
synthetic fine silica 9.9%
The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100
microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.
Example 23
Wettable Powder
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 40%
sodium ligninsulfonate 20%
montmorillonite clay 40%
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce
particles essentially all below 10 microns in size. The material is reblended and then packaged.
Example 24
Oil Suspension
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 35%
blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6%
xylene 59%
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The ingredients are combined and ground together in a sand mill to produce particles essentially all
below 5 microns. The product can be used directly, extended with oils, or emulsified in water.
Example 25
Dust
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 10%
attapulgite 10%
pyrophyllite 80%
The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce
particles substantially all below 200 microns. The ground concentrate is then blended with powdered
pyrophyllite until homogeneous.
Example 26
Emulsifiable Concentrate
4-(2,2,2-trifluoroethylthio)-2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]benzoic
acid, methyl ester 20%
chlorobenzene 74%
sorbitan monostearate and polyoxyethylene condensates thereof 6%
The ingredients are combined and stirred to produce a solution which can be emulsified in water for
application.
Utility
Test results indicate that the compounds of the present invention are highly active preemergent or
postemergent herbicides or plant growth regulants. Many of them have utility for broad-spectrum preand/or postemergence weed control in areas where complete control of all vegetation is desired, such as
around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drive-in theaters,
around billboards, highway and railroad structures. Some of the compounds have utility for selective
weed control in crops such as wheat, barley, corn, cotton, soybean, sugar beets, and rice. With regard to
usage in rice, this includes especially Japonica rice or paddy rice. The compound identified herein as
Compound 88 is especially effective in control of undesired vegetation in paddy rice and the control of
blackgrass in wheat and barley. Alternatively, the subject compounds are useful to modify plant
growth.
The rates of application for the compounds of the invention are determined by a number of factors,
including their use as plant growth modifiers or as herbicides, the crop species involved, the types of
weeds to be controlled, weather and climate, formulations selected, mode of application, amount of
foliage present, etc. In general terms, the subject compounds should be applied at levels of around
0.004 to 10 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low
organic matter content, for plant growth modification or for situations where only short-term
persistence is required.
The compounds of the invention may be used in combination with any other commercial herbicides.
They are particularly useful in combination with the following herbicides. EMI253.1 EMI254.1
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The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests.
The test procedures and results follow.
Test A
Seeds of crabgrass (Digitaria sp.). barnyard-grass (Echinochloa crusgalli), wild oats (Avena fatua),
sicklepod (Cassia obtusifolia), morningglory (Ipomoea spp.). cocklebur (Xanthium pensylvanicum),
sorghum, corn, soybean, sugar beet, cotton, rice, wheat and purple nutsedge (Cyperus rotundus) tubers
were planted and treated preemergence with the test chemicals dissolved in a non-phytotoxic solvent.
At the same time, these crop and weed species were treated with a soil/foliage application. At the time
of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained
in a greenhouse for sixteen days, after which all species were compared to controls and visually rated
for response to treatment. The ratings are based on a numerical scale extending from O = no injury, to
10 = complete kill.The accompanying descriptive symbols have the following meanings:
B = burn;
C = chlorosis/necrosis;
D = defoliation;
E = emergence inhibition;
G = growth retardation;
H = formative effects;
S = albinism;
U = unusual pigmentation;
X = axillary stimulation; and
6Y = abscised buds or flowers.
- = no test EMI267.1 EMI268.1 EMI269.1 EMI270.1 EMI271.1 EMI272.1 EMI273.1 EMI274.1
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Test B
Two ten-inch in diameter plastic pans lined with polyethylene liners were filled with prepared
Fallsington silt loam soil. One pan was planted with seeds of wheat (Triticum aestivum), barley
(Hordeum vulgare), wild oats (Avena fatua), cheatgrass (Bromus secalinus), blackgrass (Alopecurus
myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), rapeseed (Brassica napus)
and Italian ryegrass (Lolium multiflorum). The other pan was planted with seeds of Russian thistle
(Salsola kali), kochia (Kochia scoparia), speedwell (Veronica persica), shepherd's purse (Capsella
bursa-pastoris), Matricaria inodora, black nightshade (Solanum nigrum), wild buckwheat (Polygonum
convolvulus), Galium aparine and sugar beets. The above two pans were treated preemergence. At the
same time two pans in which the above plant species were growing were treated postemergence.Plant
height at the time of treatment ranged from 1-15 cm depending on plant species.
The compounds applied were diluted with a non-phytotoxic solvent and sprayed over-the-top of the
pans. An untreated control and a solvent alone control were included for comparison. All treatments
were maintained in the greenhouse for 20 days at which time the treatments were compared to the
controls and the effects visually rated.
Test C
Sixteen-cm diameter Wagner pots, equipped with a stoppered drain opening near the bottom of the side
wall, were filled with Woodstown sandy loam. About 1500 ml of water were added to each pot to bring
the water level to a point 3 cm above the soil surface. Japonica and Indica rice seedlings were
transplanted. Also, a number of barnyardgrass (Echinochloa crusgalli) seeds were added to each pot. At
the same time, seedlings or tubers of the following species were transplanted into the muddy soil: water
plaintain (Alisma trivale), Scirpus (Scirpus mucranatus) and Cyperus (Cyperus difformis). The weed
species selected for this test are of economic importance in major rice-growing areas. The chemical
treatments were applied within hours after transplanting two additional species selected from: water
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chestnut (Eleocharis spp.), arrowhead (Sagittaria latifolia) and pond plant (Potamogeton Americanus).
Shortly after treatment, the drain hold was opened to drop the water level by two cm. Water was then
added to restore the water level to its original height. The following day the draining and refilling
process was repeated. The pots were then maintained in the greenhouse. Rates of application and plant
response ratings were made 21 days after treatment.
These test results demonstrate the utility of compound 88 for weed control in rice. The results also
show utility for Japonica rice and Indica rice. Useful rates of application range from 4-2000 g/ha with
4-32 g being preferred and 8-16 g being most preferred. EMI292.1Data supplied from the esp@cenet
database - Worldwide
Claims:
Claims of corresponding document: EP0235449
1. A compound of the formulae EMI293.1 wherein
R is H or CH3;
R1 is C1-C3 alkyl, C3-C4 alkoxyalkyl, C2-C4 haloalkyl, C3-C4 alkenyl or C3-C4 alkynyl;
R2 is C2-C6 alkoxy, C3-C6 cycloalkoxy, C4-C6 cycloalkylalkoxy, C1-C6 haloalkoxy, C2-C6
alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C2-C4 alkoxyalkoxy,
C2-C4 haloalkoxyalkoxy, C2-C4 alkylthioalkoxy, C2-C4 haloalkylthioalkoxy, C2-C4
alkylsulfinylalkoxy, C2-C4 haloalkylsulfinylalkoxy, C2-C4 alkylsulfonylalkoxy, C2-C4
haloalkylsulfonylalkoxy, C2-C4 cyanoalkoxy, OCH2C(O)CH3, OCH2CH2C(O)CH3, C2-C4
aminoalkoxy, C1-C8 alkylthio, C3-C6 cycloalkylthio, C4-C6 cycloalkylalkylthio, C1-C8 haloalkylthio,
C2-C6 alkenylthio, C2-C6 haloalkenylthio, C3-C6 alkynylthio, C3-C6 haloalkynylthio, C2-C4
alkoxyalkylthio, C2-C4 haloalkoxyalkylthio, C2-C4 alkylthioalkylthio, C2-C4 haloalkylthioalkylthio,
C2-C4 cyanoalkylthio, SCH2C(O)CH3, SCH2CH2C(O)CH3, C2-C4 aminoalkylthio, SC6H5,
SCH2C6H5, C1-C8 alkylsulfinyl, C3-C6 cycloalkylsulfinyl, C4-C6 cycloalkylalkylsulfinyl, C1-C8
haloalkylsulfinyl, C2-C6 alkenylsulfinyl, C2-C6 haloalkenylsulfinyl, C3-C6 alkynylsulfinyl, C3-C6
haloalkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl, C2-C4 haloalkoxyalkylsulfinyl, C2-C4
cyanoalkylsulfinyl, S(O)CH2C(O)CH3, S(O)CH2CH2C(O)CH3, C2-C4 aminoalkylsulfinyl, C2-C8
alkylsulfonyl, C3-C6 cycloalkylsulfonyl, C4-C6 cycloalkylalkylsulfonyl, C1-C8 haloalkylsulfonyl, C2C6 alkenylsulfonyl, C2-C6 haloalkenylsulfonyl, C3-C6 alkynylsulfonyl, C3-C6 haloalkynylsulfonyl,
C2-C4 alkoxyalkylsulfonyl, C2-C4 haloalkoxyalkylsulfonyl, C2-C4 cyanoalkylsulfonyl,
SO2CH2C(O)CH3, SO2CH2CH2C(O)CH3, C2-C4 aminoalkylsulfonyl, CH2F, CHF2, CH2Cl,
CHCl2, CH2Br, CHBr2, C2-C6 alkyl substituted with 1-3 atoms of F, Cl or Br, C2-C6 alkenyl, C2-C6
haloalkenyl, C IDENTICAL CH, C2-C6 haloalkynyl, OC(O)C1-C4 alkyl, CH2C(O)NRaRb, NHCH3,
NRbRc or C1-C4 alkyl substituted with C1-C4 alkoxy, C3-C4 cycloalkoxy, cyclopropylmethoxy, C1C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C3-C4 alkynyloxy, C3-C4 haloalkynyloxy,
C2-C4 alkoxyalkoxy, C2-C4 aminoalkoxy, C1-C4 alkylcarbonyloxy, C1-C4 haloalkylcarbonyloxy,
C1-C4 carbamoyloxy, C1-C4 alkoxycarbonyloxy, OH, OP(O)(OC1-C2 alkyl)2, C1-C4
alkylsulfonyloxy, C1-C2 haloalkylsulfonyloxy, OSi(CH3)3, OSi(CH3)2C(CH3)3, C1-C4 alkylthio,
C3-C4 cycloalkylthio, cyclopropylmethylthio, C1-C4 haloalkylthio, C2-C4 alkenylthio, C2-C4
haloalkenylthio, C3-C4 alkynylthio, C3-C4 haloalkynylthio, C2-C4 alkoxyalkylthio, C2-C4
aminoalkylthio, SH, SP(O) (OC1-C2 alkyl)2, C1-C4 alkylsulfinyl, C3-C4 cycloalkylsulfonyl,
cyclopropylmethylsulfinyl, C1-C4 haloalkylsulfinyl, C2-C4 alkenylsulfinyl, C2-C4
haloalkenylsulfinyl, C3-C4 alkynylsulfinyl, C3-C4 haloalkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl,
C2-C4 aminoalkylsulfinyl, C1-C4 alkylsulfonyl, C3-C4 cycloalkylsulfonyl,
cyclopropylmethylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkenylsulfonyl, C2-C4
haloalkenylsulfonyl, C3-C4 alkynylsulfonyl, C3-C4 haloalkynylsulfonyl, C2-C4 alkoxyalkylsulfonyl
or C2-C4 aminoalkylsulfonyl;;
R@ is C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3
alkylsulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl, propargyloxy, propargylthio,
propargylsulfinyl, propargylsulfonyl, C1-C3 haloalkoxy, C1-C3 alkyl substituted with 1-3 atoms of F
or Cl, C1-C2 alkyl substituted with C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2
haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2
haloalkylsulfonyl, OH or OC(O)C1-C2 alkyl, C1-C2 alkoxy substituted with C1-C2 alkoxy, C1-C2
haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl or CN, OCH2CH2NH2, OCH2CH2NHCH3,
OCH2CH2N(CH3)2, C1-C2 alkylthio substituted by C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2
34/2194
alkylthio, C1-C2 haloalkylthio or CN, C1-C3 haloalkylthio, C1-C3 haloalkylsulfinyl, C1-C3
haloalkylsulfonyl, C2-C3 alkenyl, C IDENTICAL CH, NR@R@ or OC(O)C1-C2 alkyl;
Ra and Rb are independently H or C1-C3 alkyl;
Rc is C2-C4 alkyl, cyclopropylmethyl, C2-C4 cyanoalkyl, CH2C(O)CH3, CH2CH2C(O)CH3, C1-C4
haloalkyl, C3-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C4 haloalkynyl, C1-C4 alkyl substi
tuted with C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, OH, NH2,
NHCH3 or N(CH3)2;
R@ is H or C1-C2 alkyl;
R@ is H, C1-C2 alkyl or C1-C2 haloalkyl;
Y' is CH3, OCH3 or OCF2H;
X is CH3, OCH3, OC2H5, Cl or Br;
Y is C1-C2 alkyl, C1-C2 alkoxy, OCH2CH2F, OCH2CHF2, OCH2CF3, NHCH3 or N(CH3)2; and
Z is CH or N; and
their agriculturally suitable salts;
provided that
1) when X is Cl or Br, then Z is CH and Y is C1-C2 alkoxy, NHCH3 or N(CH3)2;
2) when R2 is SCH3, then R is H, R1 is CH3, X is OCH3, Y is OCH3 and Z is CH;
3) when R1 is C1-C3 alkyl then R2 is other than C2-C6 alkoxy, C1-C8 alkylthio, C1-C8
alkylsulfinyl, C2-C8 alkylsulfonyl, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C3-C6 alkenylthio, C3-C6
alkenylsulfinyl, C3-C6 alkenylsulfonyl, C3-C6 alkynylthio, C3-C6 alkynylsulfinyl, C3-C6
alkynylsulfonyl, OCH2CH2OCH3, OCH2CH2SCH3, OCH2CH2S(O)CH3, OCH2CH2SO2CH3, C2C6 alkyl substituted with 1-3 atoms of F, Cl or Br, CH2F, CHF2, C1-C4 alkyl substituted with C1-C2
alkoxy, C1-C2 alkylthio, C1-C2 alkylsulfinyl or C1-C2 alkylsulfonyl, OCF2H, OCH2CH2F,
OCH2CHF2, OCH2CF3, OCH2CH2Cl, S-cyclohexyl, S-C6H5 or SCH2C6H5;
4) when R1 is C1-C3 alkyl then R2 is other than C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3
alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl,
propargyloxy, propargylthio, propargylsulfinyl, propargylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2,
OCH2CF3, OCH2CH2Cl, or C1-C3 alkyl substituted with 1-3 atoms of F or Cl, or C1-C2 alkyl
substituted with OCH3 or SCH3.
2.A compound of Claim 1 wherein
R2 is C2-C6 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfinyl, C2-C8 alkylsulfonyl, C3-C6 alkenyloxy,
C3-C6 alkynyloxy, C3-C6 alkenylthio, C3-C6 alkenylsulfinyl, C3-C6 alkenylsulfonyl, C3-C6
alkynylthio, C3-C6 alkynylsulfinyl, C3-C6 alkynylsulfonyl, OCH2CH2OCH3, OCH2CH2SCH3,
OCH2CH2S(O)CH3, OCH2CH2SO2CH3, C2-C6 alkyl substituted with 1-3 atoms of F, Cl or Br,
CH2F, CHF2, C1-C4 alkyl substituted with C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 alkylsulfinyl or
C1-C2 alkylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl, S-cyclohexyl,
SC6H5 or SCH2C6H5;
3. A compound of Claim 2 wherein
R2 is CH3S, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C3-C6 alkenylthio, C3-C6 alkenylsulfinyl, C3-C6
alkenylsulfonyl, C3-C6 alkynylthio, C3-C6 alkynylsulfinyl, C3-C6 alkynyl sulfonyl, C2-C6 alkyl
substituted with 1-3 atoms of F, Cl or Br, CH2F, CHF2, C1-C4 alkyl substituted in a nonbenzylic
position with C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 alkylsulfinyl or C1-C2 alkylsulfonyl,
OCH2CH2OCH3, OCH2CH2SCH3, OCH2CH2S(O)CH3, OCH2CH2SO2CH3, OCF2H,
OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl, S-cyclohexyl, SC6H5 or SCH2C6H5.
4. A compound of Claim 3 wherein R is H.
5. A compound of Claim 4 wherein
R2 is CH3S, C3-C4 alkenyloxy, C3-C4 alkenylthio, C3-C4 alkenylsulfinyl, C3-C4 alkenylsulfonyl,
C2-C3 alkyl substituted with 1-3 atoms of F or Cl, CH2F, CHF2, OCHF2, OCH2CH2F, OCH2CF3 or
OCH2CH2Cl.
6.A compound of Claim 5 wherein
R1 is CH3 or CH2CH3;
X is CH3, OCH3 or Cl; and
Y is CH3, OCH3, C2H5 or OC2H5.
35/2194
7. A compound of Claim 1 wherein
R@ is C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3
alkylsulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl, propargyloxy, propargylthio,
propargylsulfinyl, propargylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl or
C1-C3 alkyl substituted with 1-3 atoms of F or Cl, C1-C2 alkyl substituted with OCH3 or SCH3.
8. A compound of Claim 7 wherein
R@ is C1-C2 alkyl, C1-C2 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, CF3,
propargyloxy, propargylthio, propargylsulfinyl, propargylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2,
OCH2CF3, OCH2CH2Cl, CH2CH2OCH3 or CH2CH2SCH3.
9.A compound of Claim 8 wherein
R is H;
R1 is C1-C2 alkyl;
R@ is C1-C2 alkyl, C1-C2 alkoxy, C1-C3 alkylthio, CF3, or OCF2H; and
Y' is CH3 or OCH3.
10. An agriculturally suitable composition for controlling the growth of undesired vegetation or for use
as a plant growth regulant comprising an effective amount of a compound of any of Claims 1 to 9 and
at least one of the following: surfactant, solid or liquid diluent.
11. A method for controlling the growth of undesired vegetation which comprises applying to the locus
to be protected an effective amount of a compound of any of Claims 1 to 9.
12. A method for controlling the growth of undesired vegetation which comprises applying to the locus
of the rice paddy rice crop to be protected an effective amount of the compound EMI299.1
13.A method for controlling the growth of blackgrass in whet and barley which comprises applying to
the locus to be protected an effective amount of the compound EMI299.2
14. A method for regulating the growth of plants which comprises applying to the locus of such plants
an effective but substantially non-phytotoxic amount of plant growth regulant compound of any of
claims 1 to 9.
15.A process for the preparation of a compound of claim 1 which comprises:
(a) reacting a sulfonyl isocyanate of formula EMI300.1 with an amino or methylamino heterocycle
of formula
H@-A (2);
(b) reacting a phenyl carbamate of formula EMI300.2 with said amino or methylamino heterocycle;
(c) reacting a sulfonamide of formula EMI300.3 with a heterocyclic phenyl carbamate of formula
C6H5O@NHA (5);
wherein A, R, R1 and R2 are as defined in claim 1; or
(d) reacting a compound of formula EMI301.1 wherein R1, X, Y and Z are as defined in claim 1; W
is S, O or NRb;Rb is as defined in claim 1;
with an appropriate alkylating, alkenylating or alkylylating agent of formula
R8X1
wherein R8 is C4-C6 cycloalkylalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C3-C6 alkynyl, C3-C6
haloalkynyl, C2-C8 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C8 alkylthioalkyl, C2-C4
haloalkylthioalkyl, C2-C4 cyanoalkyl, CH2C(O)CH3, CH2CH2C(O)CH3 or C1-C6 alkyl;;
EMI301.2
(e) oxidising a compound of formula (I) wherein R8 is alkyl, cycloalkyl, cycloalkylalkyl, haloalkyl,
alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxyalkyl, haloalkoxyalkyl, cyanoalkyl, -CH2C(O)CH3,
or -CH2CH2(O)CH3 and W is S to obtain a corresponding product wherein W is S(O) or SO2, or
(f) reacting a compound of formula EMI302.1 wherein R1 and Y' are as defined in claim 1 and W is
O, NR@ or S, where R@ is as defined in claim 1,
with an appropriate reagent of formula
R8X1
36/2194
wherein R8 is alkyl, haloalkyl, alkenyl, alkynyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl,
haloalkylthioalkyl, alkylsulfinylalkyl, haloalkylsulfinylalkyl, alkylsulfonylalkyl,
haloalkylsulfonylalkyl, or cyanoalkyl when W is O;R8 is alkyl, haloalkyl, alkenyl, alkynyl,
alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, or cyanoalkyl when W is S; and R8 is
alkyl or haloalkyl when W is NRb', and X1 is as defined above.
16. Intermediates suitable for the preparation of a compound of claim 1, having the formula EMI302.2
wherein R1 and R2 are as defined in claim 1 and R9 is NCO, NH2 or NHCOC6H5
17. Intermediates suitable for the preparation of a compound claim 1, having the formula (46) or (46a)
as defined in claim 15. >;/SL;
Claims for the following contracting States: AT ES
1.A process for the preparation of a compound of the formulae EMI304.1 wherein
R is H or CH3;
R1 is C1-C3 alkyl, C3-C4 alkoxyalkyl, C2-C4 haloalkyl, C3-C4 alkenyl or C3-C4 alkynyl;
R2 is C2-C6 alkoxy, C3-C6 cycloalkoxy, C4-C6 cycloalkylalkoxy, C1-C6 haloalkoxy, C2-C6
alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C2-C4 alkoxyalkoxy,
C2-C4 haloalkoxyalkoxy, C2-C4 alkylthioalkoxy, C2-C4 haloalkylthioalkoxy, C2-C4
alkylsulfinylalkoxy, C2-C4 haloalkylsulfinylalkoxy, C2-C4 alkylsulfonylalkoxy, C2-C4
haloalkylsulfonylalkoxy, C2-C4 cyanoalkoxy, OCH2C(O)CH3, OCH2CH2C(O)CH3, C2-C4
aminoalkoxy, C1-C8 alkylthio, C3-C6 cycloalkylthio, C4-C6 cycloalkylalkylthio, C1-C8 haloalkylthio,
C2-C6 alkenylthio, C2-C6 haloalkenylthio, C3-C6 alkynylthio, C3-C6 haloalkynylthio, C2-C4
alkoxyalkylthio, C2-C4 haloalkoxyalkylthio, C2-C4 alkylthioalkylthio, C2-C4 haloalkylthioalkylthio,
C2-C4 cyanoalkylthio, SCH2C(O)CH3, SCH2CH2C(O)CH3, C2-C4 aminoalkylthio, SC6H5,
SCH2C6H5, C1-C8 alkylsulfinyl, C3-C6 cycloalkylsulfinyl, C4-C6 cycloalkylalkylsulfinyl, C1-C8
haloalkylsulfinyl, C2-C6 alkenylsulfinyl, C2-C6 haloalkenylsulfinyl, C3-C6 alkynylsulfinyl, C3-C6
haloalkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl, C2-C4 haloalkoxyalkylsulfinyl, C2-C4
cyanoalkylsulfinyl, S(O)CH2C(O)CH3, S(O)CH2CH2C(O)CH3, C2-C4 aminoalkylsulfinyl, C2-C8
alkylsulfonyl, C3-C6 cycloalkylsulfonyl, C4-C6 cycloalkylalkylsulfonyl, C1-C8 haloalkylsulfonyl, C2C6 alkenylsulfonyl, C2-C6 haloalkenylsulfonyl, C3-C6 alkynylsulfonyl, C3-C6 haloalkynylsulfonyl,
C2-C4 alkoxyalkylsulfonyl, C2-C4 haloalkoxyalkylsulfonyl, C2-C4 cyanoalkylsulfonyl,
SO2CH2C(O)CH3, SO2CH2CH2C(O)CH3, C2-C4 aminoalkylsulfonyl, CH2F, CHF2, CH2Cl,
CHCl2, CH2Br, CHBr2, C2-C6 alkyl substituted with 1-3 atoms of F, Cl or Br, C2-C6 alkenyl, C2-C6
haloalkenyl, C IDENTICAL CH, C2-C6 haloalkynyl, OC(O)C1-C4 alkyl, CH2C(O)NRaRb, NHCH3,
NRbRc or C1-C4 alkyl substituted with C1-C4 alkoxy, C3-C4 cycloalkoxy, cyclopropylmethoxy, C1C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C3-C4 alkynyloxy, C3-C4 haloalkynyloxy,
C2-C4 alkoxyalkoxy, C2-C4 aminoalkoxy, C1-C4 alkylcarbonyloxy, C1-C4 haloalkylcarbonyloxy,
C1-C4 carbamoyloxy, C1-C4, alkoxycarbonyloxy, OH, OP(O)(OC1-C2 alkyl)2 C1-C4
alkylsulfonyloxy, C1-C2 haloalkylsulfonyloxy, OSi(CH3)3, OSi(CH3)2C(CH3)3, C1-C4 alkylthio,
C3-C4 cycloalkylthio, cyclopropylmethylthio, C1-C4 haloalkylthio, C2-C4 alkenylthio, C2-C4
haloalkenylthio, C3-C4 alkynylthio, C3-C4 haloalkynylthio, C2-C4 alkoxyalkylthio, C2-C4
aminoalkylthio, SH, SP(O) (OC1-C2 alkyl)2, C1-C4 alkylsulfinyl, C3-C4 cycloalkylsulfonyl,
cyclopropylmethylsulfinyl, C1-C4 haloalkylsulfinyl, C2-C4 alkenylsulfinyl, C2-C4
haloalkenylsulfinyl, C3-C4 alkynylsulfinyl, C3-C4 haloalkynylsulfinyl, C2-C4 alkoxyalkylsulfinyl,
C2-C4 aminoalkylsulfinyl, C1-C4 alkylsulfonyl, C3-C4 cycloalkylsulfonyl,
cyclopropylmethylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkenylsulfonyl, C2-C4
haloalkenylsulfonyl, C3-C4 alkynylsulfonyl, C3-C4 haloalkynylsulfonyl, C2-C4 alkoxyalkylsulfonyl
or C2-C4 aminoalkylsulfonyl;;
R@ is C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3
alkylsulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl, propargyloxy, propargylthio,
propargylsulfinyl, propargylsulfonyl, C1-C3 haloalkoxy, C1-C3 alkyl substituted with 1-3 atoms of F
or Cl, C1-C2 alkyl substituted with C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2
haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2
haloalkylsulfonyl, OH or OC(O)C1-C2 alkyl, C1-C2 alkoxy substituted with C1-C2 alkoxy, C1-C2
haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl or CN, OCH2CH2NH2, OCH2CH2NHCH3,
OCH2CH2N(CH3)2, C1-C2 alkylthio substituted by C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2
37/2194
alkylthio, C1-C2 haloalkylthio or CN, C1-C3 haloalkylthio, C1-C3 haloalkylsulfinyl, C1-C3
haloalkylsulfonyl, C2-C3 alkenyl, C IDENTICAL CH, NR@R@ or OC(O)C1-C2 alkyl;
Ra and Rb are independently H or C1-C3 alkyl;
Rc is C2-C4 alkyl, cyclopropylmethyl, C2-C4 cyanoalkyl, CH2C(O)CH3, CH2CH2C(O)CH3, C1-C4
haloalkyl, C3-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C4 haloalkynyl, C1-C4 alkyl substi
tuted with C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, OH, NH2,
NHCH3 or N(CH3)2;
R@ is H or C1-C2 alkyl;
R@ is H, C1-C2 alkyl or C1-C2 haloalkyl;
Y' is CH3, OCH3 or OCF2H;
X is CH3, OCH3, OC2H5, Cl or Br;
Y is C1-C2 alkyl, C1-C2 alkoxy, OCH2CH2F, OCH2CHF2, OCH2CF3, NHCH3 or N(CH3)2; and
Z is CH or N; and
of an agriculturally suitable salt thereof;
provided that
1) when X is Cl or Br, then Z is CH and Y is C1-C2 alkoxy, NHCH3 or N(CH3)2;
2) when R2 is SCH3, then R is H, R1 is CH3, X is OCH3, Y is OCH3 and Z is CH;
3) when R1 is C1-C3 alkyl then R2 is other than C2-C6 alkoxy, C1-C8 alkylthio, C1-C8
alkylsulfinyl, C2-C8 alkylsulfonyl, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C3-C6 alkenylthio, C3-C6
alkenylsulfinyl, C3-C6 alkenylsulfonyl, C3-C6 alkynylthio, C3-C6 alkynylsulfinyl, C3-C6
alkynylsulfonyl, OCH2CH2OCH3, OCH2CH2SCH3, OCH2CH2S(O)CH3, OCH2CH2SO2CH3, C2C6 alkyl substituted with 1-3 atoms of F, Cl or Br, CH2F, CHF2, C1-C4 alkyl substituted with C1-C2
alkoxy, C1-C2 alkylthio, C1-C2 alkylsulfinyl or C1-C2 alkylsulfonyl, OCF2H, OCH2CH2F,
OCH2CHF2, OCH2CF3, OCH2CH2Cl, S-cyclohexyl, S-C6H5 or SCH2C6H5;
4) when R1 is C1-C3 alkyl then R2 is other than C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3
alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl,
propargyloxy, propargylthio, propargylsulfinyl, propargylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2,
OCH2CF3, OCH2CH2Cl, or C1-C3 alkyl substituted with 1-3 atoms of F or Cl, or C1-C2 alkyl
substituted with OCH3 or SCH3;
which comprises
(a) reacting a sulfonyl isocyanate of formula EMI308.1 with an amino or methylamino heterocycle of
formula
H@-A (2);
(b) reacting a phenyl carbamate of formula EMI308.2 with said amino or methylamino heterocycle;
(c) reacting a sulfonamide of formula EMI308.3 with a heterocyclic phenyl carbamate of formula
C6H5O@NHA (5);
wherein A, R, R1 and R2 are as defined above;;
or
(d) reacting a compound of formula EMI309.1 wherein R1, X, Y and Z are as defined above;
W is S, O or NRb; Rb is as defined above;
with an appropriate alkylating, alkenylating or alkylylating agent of formula
R8X1
wherein R8 is C4-C6 cycloalkylalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C3-C6 alkynyl, C3-C6
haloalkynyl, C2-C8 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C8 alkylthioalkyl, C2-C4
haloalkylthioalkyl, C2-C4 cyanoalkyl, CH2C(O)CH3, CH2CH2C(O)CH3 or C1-C6 alkyl;;
EMI309.2 (e) oxidising a compound of formula (I) wherein R8 is alkyl, cycloalkyl, cycloalkylalkyl,
haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxyalkyl, haloalkoxyalkyl, cyanoalkyl, CH2C(O)CH3, or -CH2CH2(O)CH3 and W is S to obtain a corresponding product wherein W is S(O)
or SO2, or
(f) reacting a compound of formula EMI310.1 wherein R1 and Y' are as defined above and W is O,
NR@ or S, where R@ is as defined in above,
with an appropriate reagent of formula
R8X1
wherein R8 is alkyl, haloalkyl, alkenyl, alkynyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl,
haloalkylthioalkyl, alkylsulfinylalkyl, haloalkylsulfinylalkyl, alkylsulfonylalkyl,
haloalkylsulfonylalkyl, or cyanoalkyl when W is O;R8 is alkyl, haloalkyl, alkenyl, alkynyl,
alkoxylalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, or cyanoalkyl when W is S; and R8 is
alkyl or haloalkyl when W is NRb', and X1 is as defined above.
38/2194
2. A process of Claim 1 wherein
R2 is C2-C6 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfinyl, C2-C8 alkylsulfonyl, C3-C6 alkenyloxy,
C3-C6 alkynyloxy, C3-C6 alkenylthio, C3-C6 alkenylsulfinyl, C3-C6 alkenylsulfonyl, C3-C6
alkynylthio, C3-C6 alkynylsulfinyl, C3-C6 alkynylsulfonyl, OCH2CH2OCH3, OCH2CH2SCH3,
OCH2CH2S(O)CH3, OCH2CH2SO2CH3, C2-C6 alkyl substituted with 1-3 atoms of F, Cl or Br,
CH2F, CHF2, C1-C4 alkyl substituted with C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 alkylsulfinyl or
C1-C2 alkylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl, S-cyclohexyl,
SC6H5 or SCH2C6H5;
3.A process of Claim 2 wherein
R2 is CH3S, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C3-C6 alkenylthio, C3-C6 alkenylsulfinyl, C3-C6
alkenylsulfonyl, C3-C6 alkynylthio, C3-C6 alkynylsulfinyl, C3-C6 alkynylsulfonyl, C2-C6 alkyl
substituted with 1-3 atoms of F, Cl or Br, CH2F, CHF2, C1-C4 alkyl substituted in a nonbenzylic
position with C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 alkylsulfinyl or C1-C2 alkylsulfonyl,
OCH2CH2OCH3, OCH2CH2SCH3, OCH2CH2S(O)CH3, OCH2CH2SO2CH3, OCF2H,
OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl, S-cyclohexyl, SC6H5 or SCH2C6H5.
4. A process of Claim 3 wherein R is H.
5. A process of Claim 4 wherein
R2 is CH3S, C3-C4 alkenyloxy, C3-C4 alkenylthio, C3-C4 alkenylsulfinyl, C3-C4 alkenylsulfonyl,
C2-C3 alkyl substituted with 1-3 atoms of F or Cl, CH2F, CHF2, OCHF2, OCH2CH2F, OCH2CF3 or
OCH2CH2Cl.
6. A process of Claim 5 wherein
R1 is CH3 or CH2CH3;
X is CH3, OCH3 or Cl; and
Y is CH3, OCH3, C2H5 or OC2H5.
7. A process of Claim 1 wherein
R@ is C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3
alkylsulfonyl, allyloxy, allylthio, allylsulfinyl, allylsulfonyl, propargyloxy, propargylthio,
propargylsulfinyl, propargylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2, OCH2CF3, OCH2CH2Cl or
C1-C3 alkyl substituted with 1-3 atoms of F or Cl, C1-C2 alkyl substituted with OCH3 or SCH3.
8. A compound of Claim 7 wherein
R@ is C1-C2 alkyl, C1-C2 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, CF3,
propargyloxy, propargylthio, propargylsulfinyl, propargylsulfonyl, OCF2H, OCH2CH2F, OCH2CHF2,
OCH2CF3, OCH2CH2Cl, CH2CH2OCH3 or CH2CH2SCH3.
9.A process of Claim 8 wherein
R is H;
R1 is C1-C2 alkyl;
R@ is C1-C2 alkyl, C1-C2 alkoxy, C1-C3 alkylthio, CF3, or OCF2H; and
Y' is CH3 or OCH3.
10. An agriculturally suitable composition for controlling the growth of undesired vegetation or for
use as a plant growth regulant comprising an effective amount of a compound of formulae (I) or (II) as
defined in any of Claims 1 to 9 and at least one of the following: surfactant, solid or liquid diluent.
11. A method for controlling the growth of undesired vegetation which comprises applying to the
locus to be protected an effective amount of a compound of formulae (I) or (II) as defined in any of
Claims 1 to 9.
12. A method for controlling the growth of undesired vegetation which comprises applying to the
locus of the rice paddy rice crop to be protected an effective amount of the compound EMI312.1
13. A method for controlling the growth of blackgrass in wheat and barley which comprises applying
to the locus to be protected an effective amount of the compound EMI312.2
14. A method for regulating the growth of plants which comprises applying to the locus of such
plants an effective but substantially non-phytotoxic amount of a plant growth regulant compound of
formulae (I) or (II) as defined in any of claims 1 to 9.Data supplied from the esp@cenet database Worldwide
39/2194
3. CH651446
- 9/30/1985
SYNERGISTIC AGENT FOR SELECTIVE CONTROL OF WEEDS IN RICE
CROPS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CH651446
Inventor(s):
BELLUCCI SERGIO (--); QUADRANTI MARCO (--)
Applicant(s):
CIBA GEIGY AG (CH)
IP Class 4 Digits: A01N
IP Class:A01N37/22; A01N43/46
E Class: A01N47/16
Application Number:
CH19820004622 (19820730)
Priority Number: CH19820004622 (19820730)
Family: CH651446
Equivalent:
BR8304085
Abstract:
Abstract of CH651446
A synergistic agent for the selective control of weeds in dry rice cultures or in paddy fields contains- as
active ingredient, a mixt. of the herbicide 2-chloro-6-ethyl-N-(2'' methody-1''-methylethyl)-acet-o toluidide of formula (I) and the herbicide S-ethylhexahydroazepin-1- carbothioate of formula (II) and
inert additivesDescription:
Description of CH651446
**WARNUNG** Anfang DESC Feld konnte Ende CLMS uberlappen **.
PATENTANSPRÜCHE
1. Synergistisch wirkendes Mittel zur selektiven Bekämpfung von Unkräutern in trocken oder in
Wasser wachsenden Reiskulturen, dadurch gekennzeichnet, dass es neben inerten Zusatzstoffen als
Wirkstoff eine Mischung bestehend aus dem Herbizid2-Chlor-6-äthyl-N-(2"-methoxy- 1 -methyläthyl)- acet-o-toluidid der Formel I
EMI1.1
und dem Herbizid S-Äthyl-hexahydro-azepin-l-carbothioat der Formel II
EMI1.2
enthält.
2. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es neben inerten Zusatzstoffen als
Wirkstoff eine Mischung bestehend aus den Herbiziden der Formeln I und II sowie, zur Erhöhung der
Toleranz des Reises gegen diese Herbizide, das Gegenmittel2-Phenyl-4,6-dichlor-pyrimidin der
Formel III
EMI1.3
enthält.
40/2194
3. Mittel gemäss Patentanspruch 1 und 2, dadurch gekennzeichnet, dass das Mengenverhältnis der
Komponenten I und II, bezogen auf das Gewicht,1:1 bis1 : 30 beträgt.
4. Mittel gemäss Patentanspruch 1 bis 3, dadurch gekennzeichnet, dass das Mengenverhältnis der
KomponentenI und II, bezogen auf das Gewicht, 1:5 bis1 : 20 beträgt.
5. Verfahren zur selektiven Unkrautbekämpfung in trokken oder in Wasser wachsenden Reiskulturen,
dadurch gekennzeichnet, dass man die Kulturen pre- oder post-emergent mit einer wirksamen Menge
eines Mittels gemäss einem der Patentansprüche 1 bis 4 behandelt.
6. Verfahren zur selektiven Unkrautbekämpfung, dadurch gekennzeichnet, dass man Reissamen oder
die Anbaufläche des Reises vor der Saat mit einer wirksamen Menge eines Mittels gemäss einem der
Patentansprüche 1 bis 4 behandelt.
7. Reissamen, behandelt nach dem Verfahren gemäss Anspruch 6.
Die vorliegende Erfindung betrifft ein synergistisch wirkendes Mittel, welches eine herbizide
Wirkstoffkombination enthält, die sich hervorragend zur selektiven Bekämpfung von Unkräutern in
trocken oder in Wasser wachsenden
Reiskulturen eignet, sowie ein Verfahren zur selektiven Un krautbekämpfung mit dieser Kombination.
Sowohl in trocken als auch in überfluteten Reisfeldern tritt bereits kurz nach der Saat ein starker Befall
durch Unkräuter auf. Der günstigste Zeitpunkt zur Bekämpfung dieser Unkräuter ist kurz nach der Saat
des Reises. Man hat versucht, die Unkräuter durch eine Frühbehandlung des Feldes mit herbiziden
Mitteln zu bekämpfen. Mit den bisher für diesen Zweck verwendeten Herbiziden konnte das Problem
jedoch nicht zufriedenstellend gelöst werden. Da die jungen Reispflanzen gegen phytotoxische
Einflüsse ausserordentlich empfindlich sind, besteht bei Verwendung von Herbiziden mit starker
Wirkung gegen Unkräuter stets die Gefahr einer Schädigung der Reispflanze. Bei Verwendung
schwächerer Herbizide, bei denen die Gefahr einer Schädigung der Reispflanze nicht mehr besteht,
gelingt es nicht, die Unkräuter vollständig zu beseitigen. Auch sind die bisher verwendeten Herbizide
bezüglich Wirkungsspektrum, Wirkungsdauer und Aktivität nicht genügend an die speziellen
Gegebenheiten bei der Unkrautbekämpfung in Reis angepasst. Eine derartige Anpassung ist u.a. auch
deshalb schwierig, weil der Wildreis (engl. Red Rice , Oryza sativa L.), der in Nordund Südamerika zu
einem der wichtigsten Problemunkräuter geworden ist, botanisch mit dem Kulturreis (Oryza sativa L.)
praktisch identisch ist. Die biologischen und physiologischen Eigenschaften von Wildreis und
Kulturreis sind daher sehr ähnlich und es ist schwierig, Herbizide zu finden, mit denen die selektive
Bekämpfung des Wildreises möglich ist.
Die vorliegende Erfindung betrifft ein synergistisch wirkendes Mittel, welches eine herbizide
Wirkstoffkombination bestehend aus2-Chlor-6'-äthyl-N-(2"-methoxy-l"-methyl- äthyl)-acet-O-toluidid
Metolachlor und S-Äthyl-hexahdro-l-H-azepin-l carbothioat Molinate neben inerten Zusatzstoffen
enthält und der man zwecks Erhöhung der Verträglichkeit gegenüber dem Reis als Gegenmittel 2Phenyl4,6- dichlorpyrimidin zugeben kann.
Es wurde gefunden, dass der Red-Rice gegenüber dem Molinate empfindlicher ist als der Kulturreis
bei nicht immer befriedigender Herbizidwirkung. Metolachlor weist eine hervorragende Wirkung
gegen die im Reis vorkommenden Gräser und Cyperaceen, z. B. gegen Echinochloa crus galli,
Bracharia plantaginea, Cyperus esculentus.
Metolachlor hat zugleich den Vorteil, dass es über dem Boden wirkt, d. h. es weist eine
Dauerwirkung auf. Dadurch werden Unkräuter, die erst nach der Applikation auflaufen, ebenfalls
bekämpft. Sowohl mit Metolachlor wie mit Molinate sind beim Reis Toleranzprobleme beobachtet
worden, wenn sie allein angewendet werden.
Es hat sich gezeigt, dass durch die Erniedrigung der Dosen der Wirkstoffe ein synergistischer Effekt
der Herbizidwirkung gegen wichtige Reisunkräuter erreicht werden konnte.
Erstaunlich dabei war die Feststellung, dass bei den eingesetzten Dosierungen der Herbizide, eine
echte synergistische Wirkungsverstärkung erreicht wurde. Ferner gelingt es durch Beimischen oder
41/2194
Zugeben von 2-Phenyl-4,6-dichlorpyrimidin als Gegenmittel (Antidote oder Safener) die Toleranz des
Reises gegen dieses Herbizidgemisch merklich zu erhöhen, ohne dass dadurch die Herbizidwirkung
oder der synergistische Effekt herabgesetzt worden wäre. Der Red Rice wird dabei erfolgreich
bekämpft.
Das erfindungsgemässe synergistisch wirkende Mittel enthält demnach neben inerten Zusatzstoffen als
Wirkstoff eine Mischung bestehend aus dem Herbizid 2-Chlor-6äthyl-N-(2"-methoxy- 1 -methyläthyl)acet-O-toluidid, Metolachlor der Formel I
EMI2.1
und dem Herbizid S-Äthyl-hexahydro-azepin-l-carbothioat, Molinate der Formel II
EMI2.2
und gegebenenfalls als Gegenmittel 2-Phenyl-4,6-dichlorpyrimidin der Formel III
EMI2.3
Der Wirkstoff der Formel I 2-Chlor-6'-äthyl-N-(2methoxy-l"-methyl-äthyl)-acet-O-toluidid ist
bekannt, z. B. aus der DOS 2 328 340, dem britischen Patent No. 1 438 312 oder dem USP 4 168 965.
Er eignet sich als selektives Herbizid in Getreide, aber auch in Reis. Es handelt sich um ein vom
Wirkungsspektrum her gesehen interessantes Herbizid, das jedoch bisher noch nicht optimal eingesetzt
werden konnte.
Der Wirkstoff der Formel I kann als Racemat oder als optisch aktive R- und S-Form vorliegen.
Der Wirkstoff der Formel II S-Äthyl-hexahydro-azepinl-carbothioat ist ebenfalls bekannt, z. B. aus
dem US Patent No. 3 189 786. Er wird als Herbizid im Reis gegen breitblättrige und grasartige
Unkräuter in Aufwandmengen von 2-4 kg pro Hektar eingesetzt sowohl im Vor- wie im
Nacauflaufverfahren, möglichst zu einem Zeitpunkt wo die Reiskultur noch nicht oder nicht mehr
überflutet ist. Siehe dazu The Pesticide Manual S. 369, British Crop Protection Council, 5th Ed. 1977.
Der Wirkstoff der Formel III schliesslich2-Phenyl-4,6- dichlorpyrimidin wirkt als Gegenmittel oder
Antidote zum Chloracetanilid der Formel I und vermag spezifisch die Toleranz von Reis und anderen
getreideartigen Kulturpflanzen gegenüber der phytotoxischen Wirkung dieses Herbizides zu
verringern, ohne dass dabei die Herbizidwirkung allgemein verringert würde. Man kann so einerseits
höhere Herbizidmengen einsetzen, um auch widerstandsfähige Unkräuter zu bekämpfen, anderseits ist
es möglich, durch den Zusatz des Gegenmittels den Schaden, den eine zufällige Uberdosierung des
Herbizidgemisches verursachen könnte, zu verhindern oder aber zu vermindern.
Das Gegenmittel der Formel III kann der Mischung der Herbizide der Formeln I und II beigemengt
werden. Es kann für sich allein vor oder nach dem Herbizidgemisch appliziert werden. Am
vorteilhaftesten ist es jedoch, wenn man eine wirksame Menge des Gegenmittels durch Behandeln der
Reissamen auf diese aufbringt (Samenbeizung). Schliesslich ist es auch möglich, dass man die
Reissamen z. B. während des Vorkeimens im Wasser mit einer wirksamen Menge Gegenmittel
versieht, welcher Vorgang als Samenquellung bekannt ist.
Durch die Kombination der Wirkstoffe wird eine höhere Phytotoxizität gegen Unkräuter erreicht, als
die blosse Addition der Einzelwirkungen erwarten lässt. Die Schadwirkung gegen die Reiskulturen
hingegen wird nicht synergistisch erhöht, so dass eine breitere Sicherheitsmarge gegenüber der Kultur
bei der Anwendung gegeben ist als bei der Verwendung der Einzelwirkstoffe zur Erzielung der
gleichen Wirkung gegen die Unkräuter. Andererseits genügen zur Erreichung des gleichen herbiziden
Effektes gegen Unkräuter kleinere Aufwandmengen an Wirkstoff, was wiederum zu Verringerung der
Phytotoxität auf die Kultur führt.
Das Gemisch kann als solches in die Kultur appliziert werden oder es kann jede Komponente einzeln
abgegeben werden. Das Gegenmittel wird vorzugsweise als Samenbeizung angewendet. Schliesslich ist
es auch möglich, das gesamte Herbizid- respektive Herbizid-Gegenmittel-Gemisch auf die Reiskörner
zu bringen in einem Samenbeiz-Verfahren und das Wirkstoffgemisch so zur Applikation zu bringen.
Mit der erfindungsgemässen Mischung werden vor allem folgende wichtige Reisunkräuter nachhaltig
bekämpft: Alternathera phyloxeroides Lindernia pyxidaria Ammannia spp. Limnocharis flava Bidens
sp. Lobelia sp.
42/2194
Boerhaavia erecta Ludwigia angustifolia Callitriche sp. Ludwigia prostrata Cyperus compactus
Ludwigia repens Cyperus difformis Marsilea crenata Cyperus diffusus Marsilea minuta Cyperus iria
Melampodium sp.
Cyperus microiria Monochoria vaginalis Cyperus serotinus Nymphaea stellata Digitaria sanguinalis
Oenanthe javanica Dopatrium junceum Paspalum dilatatum Echinochloa colonum Palpalum distichum
Echinochloa crus-galli Paspalum escrobiculatum Eclipta alba Polygonum spp.
Elatine orientalis Polytrias amaura Elatine triandra Portulaca oleracea Eleocharis acicularis
Potamogeton spp.
Eleocharis atropurpureus Rotala indica Eriocaulon cinereum Sagittaria pygmaea Eriocaulon
sieboldianum Scirpus lateriflorus Fimbristylis miliacea Scirpus maritimus Ixophorus unisetus
Sphenoclea zeylanica Leptochloa chinensis Trianthema portulacastrum Leptochloa filiformis Vandellia
sp.
Das Mengenverhältnis (Gewicht) der Komponenten I und II kann in weiten Grenzen variiert werden,
und liegt in der Regel im Bereich von 1:1 bis 1:30. Vorzugsweise beträgt das Mengenverhältnis der
Komponenten I undIn 1:5 bis1 : 20. Die Gesamtaufwandmenge beider Wirkstoffe zusammen beträgt
in der Regel 3 bis 8 kg/ha. Das Gegenmittel der Formel III wird bei der Samenbeizung im allgemeinen
in Mengen von 0,1-10 g pro kg Samen benötigt. Die bevorzugte Menge liegt zwischen 1 und 2 Gramm.
Falls das Gegenmittel kurz vor der Aussaat durch Samenquellung appliziert werden soll, werden
Gegenmittel-Lösungen, welche den Wirkstoff in einer Konzentration von 1-10 000 ppm, verwendet.
In einem solchen Konzentrationsbereich der Anwendung des erfindungsgemässen Mittels lässt sich
praktisch keine oder nur geringe Schadwirkung auf die Reiskulturen feststellen, während Ungräser und
Unkräuter schon bei niedrigen Konzentrationen praktisch total absterben.
Vorliegende Erfindung betrifft auch die Verwendung des erfindungsgemässen Mittels, also ein
Verfahren zur selekti ven Unkrautbekämpfung in Reiskulturen unter Anwendung des Mittels, wobei
das erfindungsgemässe Mittel pre- und postemergent angewendet wird. Vorzugsweise wird das
erfindungsgemässe Mittel preemergent angewendet.
Das erfindungsgemässe Mittel mit der neuen Wirkstoffkombination enthält neben den genannten
Wirkstoffen noch geeignete Träger- und/oder andere Zuschlagstoffe. Diese können fest oder flüssig
sein und entsprechen den in der Formulierungstechnik üblichen Stoffen wie z. B. natürlichen oder
regenerierten mineralischen Stoffen, Lösungs-, Dispergier-, Netz-, Haft-, Verdickungs-, Bindemittel
oder Düngemitteln. Geeignete Anwendungsformen sind daher z. B.
Emulsionskonzentrate, direkt versprühbare oder verdünnbare Lösungen, verdünnte Emulsionen,
Spritzpulver, lösliche Pulver, Stäubemittel, Granulate, auch Verkapselungen in z. B. polymeren
Stoffen. Die Anwendungsverfahren wie Versprühen, Vernebeln, Verstäuben, Verstreuen oder Giessen
werden gleich wie die Art der Mittel den angestrebten Zielen und den gegebenen Verhältnissen
entsprechend gewählt.
Die Formulierungen, d.h. die das erfindungsgemässe Wirkstoffgemisch und gegebenenfalls einen
festen oder flüssigen Zusatzstoff enthaltenden Mittel, Zubereitungen oder Zusammensetzungen werden
in bekannter Weise hergestellt, z. B. durch inniges Vermischen und/oder Vermahlen der Wirkstoffe mit
Streckmitteln, wie z. B. mit Lösungsmitteln, festen Trägerstoffen, und gegebenenfalls
oberflächenaktiven Verbindungen (Tensiden).
Als Lösungsmittel können in Frage kommen: Aromatische Kohlenwasserstoffe, bevorzugt die
Fraktionen C8 bisCd 2, wie z. B. Xylolgemische oder substituierte Naphthaline, Phthalsäureester wie
Dibutyl- oder Dioctylphthalat, aliphatische Kohlenwasserstoffe wie Cyclohexan oder Paraffine,
Alkohole und Glykole sowie deren Äther und Ester, wie Äthanol,
Äthylenglykol,Äthylenglykolmonomethyl- oder -äthyläther, Ketone wie Cyclohexanon, stark polare
Lösungsmittel wie N-Methyl-2-pyrrolidon, Dimethylsulfoxid oder Dimethylformamid, sowie
gegebenenfalls epoxierte Pflanzenöle wie epoxiertes Kokosnussöl oder Sojaöl; oder Wasser.
43/2194
Als feste Trägerstoffe,z. B. für Stäubemittel und dispergierbare Pulver, werden in der Regel natürliche
Gesteinsmehle verwendet, wie Calcit, Talkum, Kaolin, Montmorillonit oder Attapulgit. Zur
Verbesserung der physikalischen Eigenschaften können auch hochdisperse Kieselsäure oder
hochdisperse saugfähige Polymerisate zugesetzt werden. Als gekörnte, adsorptive Granulatträger
kommen poröse Typen, wie z. B. Bimsstein, Ziegelbruch, Sepiolit oder Bentonit, als nicht sorptive
Trägermaterialien z. B. Calcit oder Sand in Frage. Darüberhinaus kann eine Vielzahl von
vorgranulierten Materialien anorganischer Natur wie insbesondere Dolomit oder zerkleinerte
Pflanzenrückstände verwendet werden.
Als oberflächenaktive Verbindungen kommen nichtionogene, kation- und/oder anionaktive Tenside
mit guten Emulgier-, Dispergier- und Netzeigenschaften in Betracht. Unter Tensiden sind auch
Tensidgemische zu verstehen.
Geeignete anionische Tenside können sowohl sog. wasserlösliche Seifen als auch wasserlösliche
synthetische oberflächenaktive Verbindungen sein.
Als Seifen seien die Alkali-, Erdalkali- oder gegebenenfalls substituierte Ammoniumsalze von höheren
Fettsäuren(C10-C22), wie z. B. die Na- oder K-Salze derÖ1- oder Stearinsäure, oder von natürlichen
Fettsäuregemischen, die z. B. aus Kokosnuss- oder Talgöl gewonnen werden können, genannt. Ferner
sind auch die Fettsäuremethyl-taurinsalze zu erwähnen.
Häufiger werden jedoch sogenannte synthetische Tenside verwendet, insbesondere Fettsulfonate,
Fettsulfate, sulfonierte Benzimidazolderivate oder Alkylarylsulfonate.
Die Fettsulfonate oder -sulfate liegen in der Regel als Alkali-, Erdalkali- oder gegebenenfalls
substituierte Ammoniumsalze vor und weisen einen Alkylrest mit 8 bis 22 C Atomen auf, wobei Alkyl
auch den Alkylteil von Acylresten einschliesst, z. B. das Na- oder Ca-Salz der Ligninsulfonsäure, des
Dodecylschwefelsäureesters oder eines aus natürlichen Fettsäuren hergestellten
Fettalkoholsulfatgemisches.
Hierher gehören auch die Salze der Schwefelsäureester und Sulfonsäuren vonFettalkohol-ÄthylenoxidAddukten. Die sulfonierten Benzimidazolderivate enthalten vorzugsweise 2 Sulfonsäuregruppen und
einen Fettsäurerest mit 8-22 C Atomen. Alkylarylsulfonate sind z. B. die Na-, Ca- oder Tri
äthanolaminsalze der Dodecylbenzolsulfonsäure, der Dibutylnaphthalinsulfonsäure, oder eines
Naphthalinsulfonsäre-Formaldehydkondensationsproduktes.
Ferner kommen auch entsprechende Phosphate wie z. B.
Salze des Phosphorsäureesters eines p-Nonylphenol-(4-14) Äthylenoxid-Adduktes in Frage. Als
nichtionische Tenside kommen in erster Linie Polyglykolätherderivate von aliphatischen oder
cycloaliphatischen Alkoholen, gesättigten oder ungesättigten Fettsäuren und Alkylphenolen in Frage,
die 3 bis 30 Glykoläthergruppen und 8 bis 20 Kohlenstoffatome im (aliphatischen)
Kohlenwasserstoffrest und 6 bis 18 Kohlenstoffatome im Alkylrest der Alkylphenole enthalten können.
Weitere geeignete nichtionische Tenside sind die wasserlöslichen, 20 bis 250
Äthylenglykoläthergruppen und 10 bis 100 Propylenglykoläthergruppen enthaltenden
Polyäthylenoxidaddukte an Polypropylenglykol, Äthylendiaminopolypropylenglykol und
Alkylpolypropylenglykol mit 1 bis 10 Kohlenstoffatomen in der Alkylkette. Die genannten
Verbindungen enthalten üblicherweise pro Propylenglykol Einheit 1 bis 5 Äthylenglykoleinheiten.
Als Beispiele nichtionischer Tenside seien Nonylphenolpolyäthoxyäthanole, Ricinusölpolyglykoläther,
Polypropylen-Polyäthylenoxidaddukte, Tributylphenoxypolyäthoxy äthanol, Polyäthylenglykol und
Octylphenoxypolyäthoxy äthanol erwähnt. ferner kommen auch Fettsäureester von
Polyoxyäthylensorbitan wie das Polyoxyäthylensorbitan-trioleat in Betracht.
Bei den kationischen Tensiden handelt es sich vor allem um quartäre Ammoniumsalze, welche als NSubstituenten mindestens einen Alkylrest mit 8 bis 22 C-Atomen enthalten und als weitere
Substituenten niedrige, gegebenenfalls halogenierte Alkyl-, Benzyl- oder niedrige Hydroxyalkylreste
44/2194
aufweisen. Die Salze liegen vorzugsweise als Halogenide, Methylsulfate oder Äthylsulfate vor, z. B.
das Stearyltrimethylammoniumchlorid oder dasBenzyldi(2-chloräthyl)- äthylammoniumbromid.
Die in der Formulierungstechnik gebräuchlichen Tenside sind u. a. in folgenden Publikationen
beschrieben: Mc Cutcheon's Detergents and Emulsifiers Annual MC Publishing Corp., Ridgewood,
New Jersey, 1979.
Sisley and Wood, Encyclopedia of Surface Active Agents, Chemical Publishing Co., Inc. New York,
1964.
Der Wirkstoffgehalt in handelsfähigen Mitteln liegt zwischen 0,1 und 95 Gewichtsprozent,
vorzugsweise 1 bis 80 Gewichtsprozent.
Insbesondere setzen sich bevorzugte Formulierungen folgendermassen zusammen: (% =
Gewichtsprozent) Lösungen Aktiver Wirkstoff: 9 bis 95%, vorzugsweise 10 bis 80% Lösungsmittel: 95
bis5%, vorzugsweise 90 bis 0% oberflächenaktives Mittel: 1 bis 30%, vorzugsweise 2 bis 20%.
Emulgierbare Konzentrate Aktiver Wirkstoff: 10 bis 50%, bevorzugt 10 bis 40% oberflächenaktives
Mittel: 5 bis 40%, bevorzugt 10 bis 20% flüssiges Trägermittel: 20 bis 93%, vorzugsweise 40 bis 80%.
Stäube Aktiver Wirkstoff: 0,5 bis 10%, vorzugsweise 2 bis 8% festes Trägermaterial: 99,5 bis 90%,
vorzugsweise 98 bis 92%.
Suspensionskonzentrate Aktiver Wirkstoff: 5 bis 75%, vorzugsweise 10 bis 50% Wasser: 94 bis 25%,
vorzugsweise 90 bis 30% oberflächenaktives Mittel: 1 bis 40%, vorzugsweise 2 bis 30%.
Benetzbare Pulver Aktiver Wirkstoff: 5 bis 90%, vorzugsweise 10 bis 80% und insbesondere 20 bis
60% oberflächenaktives Mittel: 0,5 bis 20%, vorzugsweise 1 bis 15% festes Trägermaterial: 5 bis 90%,
vorzugsweise 30 bis 70%.
Granulate aktiver Wirkstoff: 0,5 bis 30%, vorzugsweise 3 bis 15% festes Trägermaterial: 99,5 bis 70%,
vorzugsweise 97 bis 85%.
Während als Handelsware eher konzentrierte Mittel bevorzugt werden, verwendet der Endverbraucher
in der Regel verdünnte Mittel. Die Anwendungsformen können bis hinab zu0,001% an Wirkstoff
verdünnt werden.
Den beschriebenen erfindungsgemässen Mitteln lassen sich andere biozide Wirkstoffe oder Mittel
beimischen. So können die neuen Mittel ausser den genannten Verbindungen der allgemeinen Formel I
und der Formel II z. B. Insektizide, Fungizide, Bakterizide, Fungistatika, Bakteriostatika oder
Nematizide zur Verbreiterung des Wirkungsspektrums enthalten.
Ein synergistischer Effekt liegt bei Herbiziden immer dann vor, wenn die herbizide Wirkung
derWirkstoftkombi- nationI+ II grösser ist als die Summe aus der Wirkung der einzeln applizierten
Wirkstoffe.
Das zu erwartende Pflanzenwachstum E für eine gegebene Kombination zweier Herbizide kann (vgl.
COLBY, S.R., Calculating synergistic and antagonistic response of herbicide combinations , Weeds
15, Seiten20-22,1967) wie folgt berechnet werden: Y - (10O-x)
E = X + 100 Dabei bedeuten:
X = Prozent Wachstumshemmung bei Behandlung mit einem Herbizid I mit p kg Aufwandmenge pro
Hektar im Vergleich zur unbehandelten Kontrolle.
Y = Prozent Wachstumshemmung bei Behandlung mit einem Herbizid II mit q kg Aufwandmenge pro
Hektar im Vergleich zur unbehandelten Kontrolle.
E = erwartete herbizide Wirkung (Prozent Wachstumshemmung im Vergleich zur unbehandelten
Kontrolle) nach Behandlung mit Herbizidgemisch1 + II bei einer Aufwandmenge von p + q kg
Wirkstoffmenge pro Hektar.
45/2194
Ist der tatsächlich beobachtete Wert grösser als der zu erwartende Wert E, so liegt Synergismus vor.
Der synergistische Effekt der Kombinationen der Wirkstoffe I und II wird in den folgenden Beispielen
demonstriert.
Um die synergistische Wirkung der Wirkstoffkombinationen hervorzuheben, sind nachfolgend die
biologischen Resultate gegen die ausgesuchte Testpflanze Red-Rice unter Gewächshausbedingungen
aufgeführt.
Beispiel 1
Versuch in trocken gesätem Reis, dessen Anbaufläche nachher überflutet wird. Applikation des
Herbizidgemisches durchTankmischung auf dem noch trockenen Boden, Applikation des Gegenmittels
durch Saatbeizung.
Reissamen der Sorte Labelle werden mit dem Gegenmittel2-Phenyl-4,6-dichlor-pyridin in einen
Glasbehälter gemischt. Samen und Produkt werden durch Schütteln und Rotation gut
zusammengemischt. Dann werden Container (47 cm lang, 29 cm breit und 24 cm hoch) mit sandiger
Lehmerde gefüllt und die gebeizten Samen sowie Red Rice und Echinochloa crus galli werden
eingesät. Nach dem Bedecken des Samens werden die Gemische von Metolachlor und Molinate in
einer verdünnten Lösung auf die Bodenoberfläche versprüht. Etwa 20 Tage nach der Saat (3Blattstadium der Reispflanzen) wird die Bodenoberfläche mit 4 cm Wasser-Höhe beschichtet. 14 Tage
nach der Herbizidapplikation wird die relative Schutzwirkung des Antidots in Prozent bonitiert. Als
Referenzen dienen dabei die mit den Herbiziden allein behandelten Pflanzen (keine Schutzwirkung)
sowie die vollständig unbehandelte Kontrolle (100% Wachstum).
Die Ergebnisse sind in der untenstehenden Tabelle zusammengefasst.
Wirkstoffgemisch Aufwandmenge relative Schutzwirkung
Reis Red Echinochloa Labelle Rice crus galli I Metolachlor 0,125 kg/ha II Molinate 6 kg/ha 25%
0% 0% III2-Phenyl-4,6-dichlorpyrimidin 2 g/kg Samen1 0,25 kg/ha II 6 kg/ha 63% 0% 0% III 2 g/kg
Samen1 0,5kg/ha II 6 kg/ha 13% 0% 0% III 2 g/kg Samen
Tabelle (Fortsetzung) Wirkstoffgemisch Aufwandmenge relative Schutzwirkung
Reis Red Echinochloa Labelle Rice crus galli 10,125kg/ha II 8 kg/ha 25% 0% 0% III 2 g/kg Samen
10,25kg II 8kg/ha 50% 0% 0% III 2 g/kg Samen I0,5kg/ha II 8 kg/ha 13% 0% 0% III 2 g/kg Samen
Gleichartige Ergebnisse wurden erzielt, wenn das Herbizidgemisch1 + II vor der Saat in den Boden
eingearbeitet wurde (3-4 cm) was in der Praxis einer pre-plant-incorporated (ppi) ApplikationsMethode entspricht.
Beispiel 2
Versuch zur Ermittlung der synergistischen Herbizidwirkung vom Gemisch Metolachlor und
Molinate in wässriger Anbaufläche in trocken gesätem und später überflutetem Reis.
Samen von Red Rice und von Echinochloa crus galli werden in mit sandiger Lehmerde gefüllte
Container (47 cm lang, 29 cm breit und 24 cm hoch) gesät. Nach Bedecken des Samens werden die
Herbizide Metolachlor oder Molinate oder Gemische davon in einer verdünnten Lösung auf die
Bodenfläche versprüht. Etwa 20 Tage nach der Saat, wenn die Pflänzchen das 3-Blattstadium erreicht
haben, wird die Bodenoberfläche mit 4 cm Wassser-Höhe beschichtet. 14 Tage nach der
Herbizidapplikation wird der Zustand der Versuche ausgewertet und das Wachstum der Pflanzen in %
angegeben. Normaler Wuchs von Kontrollpflanzen = 100% Wachstum oder 0% Herbizidwirkung.
Abgestorbene Pflanzen = 100% Herbizidwirkung oder 0 oder 1% Wachstum.
Die Ergebnisse sind in der untenstehenden Tabelle zusammengefasst.
Wirkstoff oder Aufwandmenge Herbizidwirkung Wirkstoffgemisch Red Rice I Metolachlor 0,125
kg/ha 50% I Metolachlor 0,5 kg/ha 75% II Molinate 6 kg/ha 75% II Molinate 8 kg/ha 75%
I+II0,125+8kg/ha 88%I+ll 0,5+6kg/ha 100%
46/2194
Gleichartige Ergebnisse wurden erzielt, wenn das HerbizidgemischI+II vor der Saat in den Boden
eingearbeitet wurde (3-4 cm), was in der Praxis einer pre-plant-incorporated (ppi)
Applikationsmethode entspricht.
Zur Demonstration des synergistischen Effektes werden die gemessenen und die nach Colby
berechneten Wachstumswerte verglichen. Da die beobachteten Wachstumswerte für Red Rice grösser
sind als die nach Colby berechneten, liegt Synergismus vor.
Pflanze Herbizidgemisch herbizide Wirkung erwarteter gemessener
Wert Wert Red Rice I Metolachlor 0,125kg/ha 78 88
II Molinate 8 kg/ha Red Rice I 0,5kg/ha 94 100
II 6 kg/ha
Beispiel 3
Versuch mit Trockenreis. Der Reis wird trocken gesät und bleibt ausser bei natürlichen Regenfällen im
trockenen Boden. Das Herbizidgemisch wird als Tankmischung auf den trockenen Boden appliziert.
Das Gegenmittel wird durch Samenbeizung aufgetragen.
Reissamen der Sorte Labelle werden mit dem Gegenmittel2-Phenyl-4,6-dichlor-pyrimidin in einen
Glasbehälter gemischt. Samen und Produkt werden durch Schütteln und Rotation gut
zusammengemischt. Anschliessend werden Plastikcontainer (47 cm lang, 29 cm breit und 24 cm hoch)
mit sandiger Lehmerde gefüllt und diegebeizten Samen werden eingesät. Nach dem Bedecken des
Samens wird das Gemisch der Herbizide Metolachlor und Molinate auf die Bodenoberfläche
versprüht. 14 Tage nach der Saat wird die relative Schutzwirkung des Antidots in Prozent bonitiert.
Als Referenz dienen dabei die mit den Herbiziden allein behandelten Pflanzen (keine Schutzwirkung)
sowie die vollständig unbehandelte Kontrolle (100% Schutzwirkung).
Die Ergebnisse sind in der nachstehenden Tabelle zusam mengefasst.
Wirkstoffgemisch Aufwandmenge relative Schutzwirkung
Reis Red Echinochloa Labelle Rice crus galli 1 Metolachlor 0,125 kg/ha
II Molinate 6 kg/ha 25% 0% 0% III 2-Phenyl-4,6-dichlorpyrimidin 2 g/kg Samen 1 0,25kg/ha
II6kg/ha 63% 0% 0%
III 2 g/kg Samen
I 0,5 kg/ha
II6kg/ha 13% 0% 0%
III 2 g/kg Samen 1 0,125 kg/ha
II8kg/ha 25% 0% 0%
III 2 g/kg Samen 1 0,25 kg
II 8 kg/ha 50% 0% 0%
III 2 g/kg Samen
10,5kg/ha
II8kg/ha 13% 0% 0%
III 2 g/kg Samen
Gleichartige Ergebnisse wurden erzielt, wenn das Herbizidgemisch1 + II vor der Saat in den Boden
eingearbeitet wurde (3-4 cm) was in der Praxis einer pre-plant-incorporated (ppi) ApplikationsMethode entspricht. die gemessenen und die nach Colby berechneten Wachstumswerte verglichen. Da
die beobachteten Wachstumswerte für Red Rice grösser sind als die nach Colby berechneten, liegt
Synergismus vor.
Beispiel 4
Versuch zur Ermittlung der synergistischen Wirkung von Metolachlor und Molinate auf trockener
Anbaufläche.
Samen von Red Rice und von Echinochloa crus galli werden in mit sandiger Lehmerde gefüllte
Plastikcontainer (47 cm lang, 29 cm breit und 24 cm hoch) gesät. Nach dem Bedecken des Samens
werden die Herbizide Metolachlor und Molinate je einzeln und als Mischungen auf die Bo denfläche
versprüht. 14 Tage nach der Saat wird der Versuch ausgewertet und der Zustand der Pflanzen in %
angegeben.
47/2194
Normaler Wuchs von Kontrollpflanzen =0% Herbizid wirkung oder 100% Wachstum. Abgestorbene
Pflanzen = 0 oder 1% Wachstum oder 100% Herbizidwirkung. Die Er gebnisse sind in der
untenstehenden Tabelle zusammenge fasst.
Pflanze Herbizidgemisch Pflanzenwuchs erwarteter gemessener
Wert Wert Red Rice I Metolachlor
0,25 kg/ha 78 88
II Molinate 6 kg/ha Red Rice I 0,5 kg/ha 94 100 118 kg/ha
Formulierungsbeispiele Wirkstoff oder Aufwandmenge Herbizidwirkung Wirkstoffgemisch Red Rice
1 Metolachlor 0,125 kg/ha 50%
I Metolachlor 0,5 kg/ha 75%
II Molinate 6 kg/ha 75% II Molinate 8 kg/ha 75% 1+11 0,125+8kg/ha 88%
I+II 0,5+6kg/ha 100%
Gleichartige Ergebnisse wurden erhalten, wenn das Her bizidgemisch1 + II vor der Saat in den Boden
eingearbeitet wurde (3-4 cm), was in der Praxis einer pre-plant-incorpo rated (ppi)
Applikationsmethode entspricht.
Zur Demonstration des synergistischen Effektes werden
Beispiel 5 Formulierungsbeispiele für synergistische Wirkstoffgemische der Formeln I undII ( /O =
Gewichtsprozent) a) Spritzpulver a) b) c) d) Wirkstoff I und II 10% 20% 5% 30%
Wirkstoff II (und III) 10% 40% 15% 30%
Na-Ligninsulfonat 5% 5% 5%5%
Na-Laurylsulfat3%-3%
Na-Diisobutylnaphthali sulfonat 6% 6%
Octylphenolpolyäthylengly koläther 7-8 MolAeO - 2% - 2%
Hochdisperse Kieselsäure 5% 27% 5% 27%
Kaolin67%-67%
Das Wirkstoffgemisch 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-Konzentrat a) b) c)
Wirkstoff I 5% 5% 12%
Wirkstoff II (und III) 5% 20% 13%
Octylphenolpolyäthylengly koläther (4-5 Mol AeO) 3% 3% 3%
Ca-Dodecylbenzolsulfonat 3% 3% 2%
Ricinusölpolyglykoläther (36 Mol Aeo) 4% 4% 4%
Cyclohexanon 30% 30% 31%
Xylolgemisch 50% 35% 35%
Aus diesen Konzentraten können durch Verdünnen mit Wasser Emulsionen jeder gewünschten
Konzentration hergestellt werden. c) Stäubemittel a) b) c) d)
Wirkstoff I 2% 4% 2%4 S
Wirkstoff II (und III) 3% 4% 4%8of
Talkum 95%- 94% Kaolin 92% 880/;
Man erhält anwendungsfertige Stäubemittel, indem das Wirkstoffgemisch mit dem Träger vermischt
und auf einer geeigneten Mühle vermahlen wird. d) Extruder Granulat a) b) c)
Wirkstoff I 5% 3% 5%
Wirkstoff II (und III) 5% 7% 15%
Na-Ligninsulfonat 2% 2% 2%
Carboxymethylcellulose >;RTI 1% 1% 1%
Kaolin 87% 87% 77%
Das Wirkstoffgemisch wird mit den Zusatzstoffen vermischt, vermahlen und mit Wasser angefeuchtet.
Dieses Gemisch wird extrudiert und anschliessend im Luftstrom getrocknet. e) Umhüllungs-Granulat
a) b)
Wirkstoff I -1,5% 3%
Wirkstoff II (und III)1,5% 5%
Polyäthylenglykol (MG 2000) 3% 3%
Kaolin 94% 89%
48/2194
Das fein gemahlene Wirkstoffgemisch wird in einem Mischer auf das mit Polyäthylenglykol
angefeuchtete Kaolin gleichmässig aufgetragen. Auf diese Weise erhält man staubfreie UmhüllungsGranulate. f) Suspensions-Konzentrat a) b)
Wirkstoff I 20% 20%
Wirkstoff II (und III) 20% 40% Äthylenglykol 10% 10%
Nonylphenolpolyäthylen glykoläther (15 Mol AeO) 6% 6%
Na-Ligninsulfonat 10% 10%
Carboxymethylcellulose1% 1% 37 /Oige Wässrige Formalde hyd-Lösung0,2% 0,2%
Silikonöl in Form einer 75%igen wässrigen Emul sion0,8% 0,8%
Wasser 32% 12%
Das fein gemahlene Wirkstoffgemisch wird mit den Zusatzstoffen innig vermischt. Man erhält so ein
Suspensions Konzentrat, aus welchem durch Verdünnen mit Wasser Suspensionen jeder gewünschten
Konzentration hergestellt werden können.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of CH651446
PATENTANSPRÜCHE
1. Synergistisch wirkendes Mittel zur selektiven Bekämpfung von Unkräutern in trocken oder in
Wasser wachsenden Reiskulturen, dadurch gekennzeichnet, dass es neben inerten Zusatzstoffen als
Wirkstoff eine Mischung bestehend aus dem Herbizid2-Chlor-6-äthyl-N-(2"-methoxy- 1 -methyläthyl)- acet-o-toluidid der Formel I
EMI1.1
und dem Herbizid S-Äthyl-hexahydro-azepin-l-carbothioat der Formel II
EMI1.2
enthält.
2. Mittel gemäss Anspruch 1, dadurch gekennzeichnet, dass es neben inerten Zusatzstoffen als
Wirkstoff eine Mischung bestehend aus den Herbiziden der Formeln I und II sowie, zur Erhöhung der
Toleranz des Reises gegen diese Herbizide, das Gegenmittel2-Phenyl-4,6-dichlor-pyrimidin der
Formel III
EMI1.3
enthält.
3. Mittel gemäss Patentanspruch 1 und 2, dadurch gekennzeichnet, dass das Mengenverhältnis der
Komponenten I und II, bezogen auf das Gewicht,1:1 bis1 : 30 beträgt.
4. Mittel gemäss Patentanspruch 1 bis 3, dadurch gekennzeichnet, dass das Mengenverhältnis der
KomponentenI und II, bezogen auf das Gewicht, 1:5 bis1 : 20 beträgt.
5. Verfahren zur selektiven Unkrautbekämpfung in trokken oder in Wasser wachsenden Reiskulturen,
dadurch gekennzeichnet, dass man die Kulturen pre- oder post-emergent mit einer wirksamen Menge
eines Mittels gemäss einem der Patentansprüche 1 bis 4 behandelt.
6. Verfahren zur selektiven Unkrautbekämpfung, dadurch gekennzeichnet, dass man Reissamen oder
die Anbaufläche des Reises vor der Saat mit einer wirksamen Menge eines Mittels gemäss einem der
Patentansprüche 1 bis 4 behandelt.
7. Reissamen, behandelt nach dem Verfahren gemäss Anspruch 6.
Die vorliegende Erfindung betrifft ein synergistisch wirkendes Mittel, welches eine herbizide
Wirkstoffkombination enthält, die sich hervorragend zur selektiven Bekämpfung von Unkräutern in
trocken oder in Wasser wachsenden
Reiskulturen eignet, sowie ein Verfahren zur selektiven Un krautbekämpfung mit dieser Kombination.
Sowohl in trocken als auch in überfluteten Reisfeldern tritt bereits kurz nach der Saat ein starker Befall
durch Unkräuter auf. Der günstigste Zeitpunkt zur Bekämpfung dieser Unkräuter ist kurz nach der Saat
des Reises. Man hat versucht, die Unkräuter durch eine Frühbehandlung des Feldes mit herbiziden
Mitteln zu bekämpfen. Mit den bisher für diesen Zweck verwendeten Herbiziden konnte das Problem
49/2194
jedoch nicht zufriedenstellend gelöst werden. Da die jungen Reispflanzen gegen phytotoxische
Einflüsse ausserordentlich empfindlich sind, besteht bei Verwendung von Herbiziden mit starker
Wirkung gegen Unkräuter stets die Gefahr einer Schädigung der Reispflanze. Bei Verwendung
schwächerer Herbizide, bei denen die Gefahr einer Schädigung der Reispflanze nicht mehr besteht,
gelingt es nicht, die Unkräuter vollständig zu beseitigen. Auch sind die bisher verwendeten Herbizide
bezüglich Wirkungsspektrum, Wirkungsdauer und Aktivität nicht genügend an die speziellen
Gegebenheiten bei der Unkrautbekämpfung in Reis angepasst. Eine derartige Anpassung ist u.a. auch
deshalb schwierig, weil der Wildreis (engl. Red Rice , Oryza sativa L.), der in Nordund Südamerika zu
einem der wichtigsten Problemunkräuter geworden ist, botanisch mit dem Kulturreis (Oryza sativa L.)
praktisch identisch ist. Die biologischen und physiologischen Eigenschaften von Wildreis und
Kulturreis sind daher sehr ähnlich und es ist schwierig, Herbizide zu finden, mit denen die selektive
Bekämpfung des Wildreises möglich ist.
Die vorliegende Erfindung betrifft ein synergistisch wirkendes Mittel, welches eine herbizide
Wirkstoffkombination bestehend aus2-Chlor-6'-äthyl-N-(2"-methoxy-l"-methyl- äthyl)-acet-O-toluidid
Metolachlor und S-Äthyl-hexahdro-l-H-azepin-l carbothioat Molinate neben inerten Zusatzstoffen
enthält und der man zwecks Erhöhung der Verträglichkeit gegenüber dem Reis als Gegenmittel 2Phenyl4,6- dichlorpyrimidin zugeben kann.
Es wurde gefunden, dass der Red-Rice gegenüber dem Molinate empfindlicher ist als der Kulturreis
bei nicht immer befriedigender Herbizidwirkung. Metolachlor weist eine hervorragende Wirkung
gegen die im Reis vorkommenden Gräser und Cyperaceen, z. B. gegen Echinochloa crus galli,
Bracharia plantaginea, Cyperus esculentus.
Metolachlor hat zugleich den Vorteil, dass es über dem Boden wirkt, d. h. es weist eine
Dauerwirkung auf. Dadurch werden Unkräuter, die erst nach der Applikation auflaufen, ebenfalls
bekämpft. Sowohl mit Metolachlor wie mit Molinate sind beim Reis Toleranzprobleme beobachtet
worden, wenn sie allein angewendet werden.
Es hat sich gezeigt, dass durch die Erniedrigung der Dosen der Wirkstoffe ein synergistischer Effekt
der Herbizidwirkung gegen wichtige Reisunkräuter erreicht werden konnte.
Erstaunlich dabei war die Feststellung, dass bei den eingesetzten Dosierungen der Herbizide, eine
echte synergistische Wirkungsverstärkung erreicht wurde. Ferner gelingt es durch Beimischen oder
Zugeben von 2-Phenyl-4,6-dichlorpyrimidin als Gegenmittel (Antidote oder Safener) die Toleranz des
Reises gegen dieses Herbizidgemisch merklich zu erhöhen, ohne dass dadurch die Herbizidwirkung
oder der synergistische Effekt herabgesetzt worden wäre. Der Red Rice wird dabei erfolgreich
bekämpft.
Das erfindungsgemässe synergistisch wirkende Mittel enthält demnach neben inerten Zusatzstoffen als
Wirkstoff eine Mischung bestehend aus dem Herbizid 2-Chlor-6äthyl-N-(2"-methoxy- 1 -methyläthyl)acet-O-toluidid, Metolachlor der Formel I
**WARNUNG** Ende CLMS Feld konnte Anfang DESC uberlappen**.Data supplied from the
esp@cenet database - Worldwide
50/2194
4. CN1444562
- 9/24/2003
RICE BLAST CONTROL AGENTS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=CN1444562
Inventor(s):
(JP)
KAZUMI YAMAMOTO (JP); TAKESHI TERAOKA (JP); HIROSHI KURIHARA
Applicant(s):
MEIJI SEIKA KAISHA (JP)
IP Class 4 Digits: A01N; C07D
IP Class:C07D215/233; A01N43/42
E Class: A01N43/42; A01N47/06; C07D215/22C
Application Number:
CN20010813588 (20010529)
Priority Number: JP20000160316 (20000530)
Family: AU782532
Equivalent:
EP1291344; WO0192231; US6787557; CN1193017C; AU782532
Abstract:
Abstract not available for CN1444562
Abstract of corresponding document: EP1291344
Disclosed is a compound of formula (1) or an acid addition salt thereof which has excellent rice blast
control effect: >;CHEM; wherein R represents a hydrogen atom, -COR>;1;, -COOR>;1;, in which
R>;1; represents alkyl having 1 to 4 carbon atoms,-COCH2OCH3, or -COCH2OCOCH3.Description:
Description of corresponding document: EP1291344
BACKGROUND OF THE INVENTION
Field of the Invention
[0001] The present invention relates to a controlling agent for rice blast.
Background Art
[0002] Up to now, a large number of active compounds having control effect against various plant
diseases have been found, and various controlling agents for plant diseases, comprising them as active
ingredients have been developed. For example, from the viewpoint of appearance of resistant strains,
however, there is room for improvement in control effect of the controlling agents.
[0003] Blast may be mentioned as one of plant diseases, and is induced by infection of fungi of the
genus Pyricularia which are a kind of mold fungi and belong to deuteromycotina. In particular, an
outbreak of rice blast sometimes takes place in abnormal weather such as low temperature or much rain
in the summer period, and, thus, rice blast is one of the most serious diseases of rice.
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[0004] For this reason, the development of controlling agents having excellent control effect against
rice blast has been desired.
[0005] International Publication WO 98/55460 discloses 4-quinolinol derivatives and fungicides for
agricultural and horticultural applications, comprising these derivatives as active ingredients. In this
publication, however, there is no description on usefulness of 2,3-dimethyl-6-t-butyl-8-fluoro-4quinolinol derivatives.
SUMMARY OF THE INVENTION
[0006] The present inventors have now found that, among 4-quinolinol derivatives, those having tbutyl (tertiary butyl) at the 6-position and fluorine at the 8-position, that is, 2,3-dimethyl-6-t-butyl-8fluoro-4-quinolinol derivatives, have significantly high control effect against rice blast. This control
effect is significantly superior to that attained by other 4-quinolinol derivatives disclosed, for example,
in International Publication WO 98/55460. The present invention has been made based on such finding.
[0007] Accordingly, it is an object of the present invention to provide a compound and a controlling
agent which have excellent control effect against rice blast.
[0008] According to one aspect of the present invention, there is provided a compound of formula (1)
or an acid addition salt thereof:
EMI2.1
wherein
R represents a hydrogen atom, -COR>;1;, -COOR>;1;, in which R>;1; represents alkyl having 1 to 4
carbon atoms,-COCH2OCH3, or -COCH2OCOCH3.
[0009] According to another aspect of the present invention, there is provided a controlling agent for
rice blast, comprising as active ingredients at least one compound selected from the group consisting of
the compounds of formula (1) or acid addition salts thereof.
DETAILED DESCRIPTION OF THE INVENTION
Compounds of formula (1)
[0010] The present invention relates to the compounds of formula (1) (2,3-dimethyl-6-t-butyl-8fluoro-4-quinolinol derivatives) or acid addition salts thereof. The compounds of formula (1) or acid
addition salts thereof have excellent control effect against rice blast (Pyricularia oryzae) and can be
advantageously used as controlling agents for rice blast.
[0011] In the compounds of formula (1), R represents a hydrogen atom, -COR>;1;, -COOR>;1;, COCH2OCH3, or -COCH2OCOCH3, wherein R>;1; represents alkyl having 1 to 4 carbon atoms, for
example, methyl, ethyl, propyl, or butyl.
[0012] In formula (1), when R represents a hydrogen atom, the compounds of formula (1) may take a
structure of formula (2) which is a tautomer of the compounds of formula (1). It would be apparent to a
person having ordinary skill in the art that the compounds of formula (1) embrace the compounds of
formula (2).
EMI3.1
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[0013] In the present invention, the term "acid addition salt" refers to salts, which are generally
usable in the fields of agriculture and horticulture, for example, hydrochlorides, nitrates, sulfates,
phosphates, and acetates.
[0014] It should be noted that the compounds of formula (1) may take the form of hydrates or
solvates. In the present invention, such hydrates and solvates are also embraced in the compounds of
formula (1).
[0015]
Specific examples of compounds of formula (1) include:
2,3-dimethyl-6-t-butyl-8-fluoro-4-hydroxyquinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-acetylquinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-propionyl-quinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-butyrylquinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-valerylquinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-methoxycarbonyl-quinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-ethoxycarbonyl-quinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-n-propoxy-carbonylquinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-n-butoxycarbonyl-quinoline;
2,3-dimethyl-6-t-butyl-8-fluoro-4-methoxyacetyl-quinoline; and
2,3-dimethyl-6-t-butyl-8-fluoro-4-acetoxyacetyl-quinoline.
Production process of compounds of formula (1)
[0016] The compounds of formula (1) according to the present invention may be synthesized by any
appropriate process regarding the formation of a bond or the introduction of a substituent.
[0017] For example, a compound of formula (1) can be produced from 4-t-butyl-2-fluoroaniline,
which can be synthesized by a conventional method, according to the following scheme.
EMI4.1
EMI5.1
wherein
R represents a hydrogen atom, -COR>;1;, -COOR>;1;, in which R>;1; represents alkyl having 1 to 4
carbon atoms,-COCH2OCH3, or -COCH2OCOCH3.
[0018] According to this scheme, a compound of formula (2) is first provided (step (a)), and the
compound of formula (2) is then reacted with the compound of formula (3) or (4) in the presence or
absence of a base (step (b)) to give the compound of formula (1).
[0019]
The above scheme will be described in more detail.
Step (a)
[0020] At the outset, a compound of formula (2) is prepared from 4-t-butyl-2-fluoroaniline and ethyl
2-methyl-acetoacetate, for example, according to J. Am. Chem. Soc. 70, 2402 (1948), Tetrahedron
Lett. 27, 5323 (1986). The compound of formula (2) corresponds to the compound of formula (1)
wherein R represents a hydrogen atom. 4-t-Butyl-2-fluoroaniline used herein may be prepared by a
conventional method described, for example, in Chem. Abs. 42, 2239 or J. Chem. Soc., Chem.
Commun., 1992, 595.
Step (b)
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[0021] Next, when a compound of formula (1), wherein R represents a group other than a hydrogen
atom, is desired, this compound can be produced by reacting the compound of formula (2) with the
compound of formula (3) or (4) in the presence or absence of a base.
[0022] Bases usable herein include, for example, organic amines, such as triethylamine and pyridine,
and inorganic bases, such as sodium carbonate, potassium carbonate, and sodium hydride. The
compound of formula (3) or (4) is preferably used in an amount of 1 to 50 equivalents, more preferably
1 to 10 equivalents, based on the compound of formula (2). The reaction in step (b) may be carried out
in the absence of a solvent or in the presence of an organic solvent inert to the reaction, for example,
dimethylformamide or tetrahydrofuran, for example, in the temperature range of 0 to 140 DEG C.
Controlling agent for rice blast
[0023] The controlling agent for rice blast according to the present invention comprises as an active
ingredient at least one compound selected from the group consisting of the compounds of formula (1)
or acid addition salts thereof.
[0024] The expression "comprising as an active ingredient" as used herein means that a carrier
according to the formulation may of course be incorporated and, in addition, other chemical agents
usable in combination with the compound of the present invention may be incorporated.
[0025] Accordingly, when the compound of formula (1) is used as a controlling agent for rice blast,
the compound of formula (1) as such may be used. In general, however, the compound of formula (1)
may be mixed, for example, with suitable solid carriers, liquid carriers, gaseous carriers, surfactants,
dispersants and/or other adjuvants for formulations, to prepare any suitable formulation, such as
emulsifiable concentrates, liquid formulations, wettable powder, dust formulation, granules, oil
solutions, aerosols, or flowables.
[0026] Solid carriers usable herein include, for example, talc, bentonite, clay, kaolin, diatomaceous
earth, vermiculite, white carbon, and calcium carbonate.
[0027] Examples of liquid carriers include: alcohols, such as methanol, n-hexanol, and ethylene
glycol; ketones, such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons, such
as n-hexane, kerosine, and kerosene; aromatic hydrocarbons, such as toluene, xylene, and
methylnaphthalene; ethers, such as diethyl ether, dioxane, and tetrahydrofuran; esters, such as ethyl
acetate; nitriles, such as acetonitrile and isobutyronitrile; acid amides, such as dimethylformamide and
dimethylacetamide; vegetable oils, such as soy bean oil and cotton seed oil; dimethylsulfoxide; and
water.
[0028]
Gaseous carriers include, for example, LPG, air, nitrogen, carbon dioxide, and dimethyl ether.
[0029] Surfactants or dispersants usable, for example, for emulsifying, dispersing, or wetting the
compound of formula (1) include, for example, alkylsulfonic esters, alkylsulfonic acid salts,
alkylarylsulfonic acid salts, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylaryl ethers, polyhydric
alcohol esters, and lignin sulfonic acid salts.
[0030] Adjuvants usable for improving the properties of formulations include, for example,
carboxymethylcellulose, gum arabic, polyethylene glycol, and calcium stearate.
[0031] At least two members may be selected from the above group of carriers, group of surfactants,
group of dispersants, and group of adjuvants (the selected members may belong to the same group or
different groups) and used in combination.
[0032] The content of the compound of formula (1) or acid addition salt thereof in the controlling
agent for rice blast may be properly varied by taking into consideration formulations, application
methods and application environment of the controlling agent and other conditions. The content of the
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compound of formula (1) is generally 1 to 75% by weight, preferably 5 to 30% by weight, when the
controlling agent is an emulsifiable concentrate; generally 0.3 to 25% by weight, preferably 1 to 3% by
weight, when the controlling agent is dust; generally 1 to 90% by weight, preferably 5 to 50% by
weight, when the controlling agent is wettable powder; and generally 0.5 to 50% by weight, preferably
2 to 30% by weight, when the controlling agent is granules.
[0033] The controlling agent for rice blast according to the present invention is generally used as
such or after dilution.
[0034] Methods of application of the controlling agent for rice blast according to the present
invention include, for example, application to rice plant per se (application to stems and leaves),
application to nursery boxes, application to soil (admixing with soil or side dressing(i.e. what is called
"sokujou" in Japanese), application to field water (application to water surface or application to regular
paddy field), and application to seeds (seed treatment).
[0035] According to a further aspect of the present invention, there is provided a method for
controlling rice blast, comprising the step of applying the compound of formula (1) or acid addition salt
thereof to a rice plant per se, soil, or field water.
[0036] The controlling agent for rice blast according to the present invention may be applied in an
amount which is properly determined by taking into consideration, for example, application
environment and state of growth and development of rice plant. For example, however, when the
controlling agent is applied to soil or field water for the growth and development of rice plants, the
amount of the controlling agent in terms of the amount of the active ingredient is preferably 9 to 500 g,
more preferably 30 to 300 g, per 10 ares.
[0037] Further, the controlling agent for rice blast according to the present invention may be used as
a mixture, for example, with other fungicides, bactericides, insecticides, miticides, herbicides, plant
growth-regulating agents, or fertilizers.
EXAMPLES
[0038] The following examples further illustrate the present invention, but are not intended to limit it.
Production Examples
[0039] Compounds 1 to 11 according to the present invention were produced as follows. For
comparison, compounds 12 to 14 were produced in the same manner as used in the production of the
compounds 1 to 11.
Production of 4-t-butyl-2-fluoroaniline
[0040] SELECTFLUOR (manufactured by Aldrich Chemical Company Inc.) (1-chloromethyl-4fluoro-1,4-diazoniabicyclo[2,2,2]octanebistetrafluoroborate) (15 g) was added to acetonitrile (200 ml),
and mixture was heated at 70 DEG C for 30 min to dissolve SELECTFLUOR in acetonitrile. The
reaction solution thus obtained was cooled to 60 DEG C, and 4-t-butyl-acetanilide (5.7 g) was added to
the cooled reaction solution. The mixture was stirred at 100 DEG C for one hr, and the reaction
solution was then allowed to stand for cooling. The cooled reaction solution was then added to water
(200 ml), followed by extraction with ethyl acetate (100 ml, twice). The ethyl acetate layer was washed
with saturated brine and was dried over anhydrous sodium sulfate, and the solvent was then removed
under the reduced pressure. The crude product thus obtained was purified by chromatography on silica
gel (Wako Gel C-200 manufactured by Wako Pure Chemical Industries, Ltd., elution solvent: nhexane-ethyl acetate (10 : 1)) to give 4-t-butyl-2-fluoro-acetanilide (3.06 g). This 4-t-butyl-2-fluoro-
55/2194
acetanilide (3.67 g) was added to a mixed solution composed of ethanol (30 ml) and concentrated
hydrochloric acid (15 ml), and the mixture was stirred at 95 DEG C for 2 hr. The reaction solution was
allowed to stand for cooling, and the cooled reaction solution was then poured into water, followed by
neutralization with a saturated aqueous sodium hydrogencarbonate solution and extraction with ethyl
acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate
solution and saturated brine, and was dried over anhydrous sodium sulfate. The solvent was then
removed under the reduced pressure to give 4-t-butyl-2-fluoroaniline (3.49 g). >;1;H-NMR data on this
compound in deutro-chloroform were as shown below.
[0041]
delta (ppm) : 7.01 (1H, dd), 6.95 (1H, dd), 6.73 (1H, m), 1.28 (9H,s)
Compound 1: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-hydroxyquinoline
[0042] 4-t-Butyl-2-fluoroaniline (4.79 g) prepared according to the above process and ethyl 2methyl-acetoacetate (4.96 g) were refluxed in toluene (60 ml) in the presence of trifluoroboron etherate
(0.3 ml) for 3 hr to obtain a reaction solution. The reaction solution thus obtained was washed with a
saturated aqueous sodium hydrogencarbonate solution and saturated brine and was dried over
anhydrous sodium sulfate. The solvent was then removed under the reduced pressure. The reaction
product was refluxed in diphenyl ether (80 ml) for one hr and was allowed to stand for cooling. The
precipitated product was then collected by filtration under the reduced pressure to give 2,3-dimethyl-6t-butyl-8-fluoro-4-hydroxyquinoline (compound 1, 1.66 g). >;1;H-NMR data on this compound in
deutro-DMSO (dimethyl sulfoxide) were as shown below.
[0043]
(9H, s)
delta (ppm) : 11.27 (1H, br.s), 7.83 (1H, s), 7.59 (1H, br.d), 2.41 (3H, s), 1.96 (3H, s), 1.31
Compound 2: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-acetyl-quinoline
[0044] The compound 1 (50 mg) was stirred in acetic anhydride (3 ml) at 120 DEG C for 3 hr to
obtain a reaction solution. Acetic anhydride was removed from the reaction solution under the reduced
pressure. The residue was dissolved in ethyl acetate. The solution was washed with a saturated aqueous
sodium hydrogencarbonate solution and saturated brine and was then dried over anhydrous sodium
sulfate, and the solvent was then removed under the reduced pressure. The crude product was purified
by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (5 : 1)) to
give 2,3-dimethyl-6-t-butyl-8-fluoro-4-acetylquinoline (compound 2, 35.7 mg). >;1;H-NMR data on
this compound in deutro-chloroform were as shown below.
[0045]
delta (ppm) : 7.43 (1H, dd), 7.37 (1H, d), 2.78 (3H, s), 2.51 (3H, s), 2.26 (3H, s), 1.38 (9H, s)
Compound 3: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-propionylquinoline
[0046] In tetrahydrofuran (3 ml) was suspended 60% sodium hydride (20 mg). The compound 1 (124
mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min. Further,
propionyl chloride (200 mu l) was added thereto, and the mixture was stirred for 3 hr. The reaction
solution thus obtained was poured into ice water, and the mixture was extracted with ethyl acetate. The
ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution and
saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then removed under
the reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4propionylquinoline (compound 3, 21 mg). >;1;H-NMR data on this compound in deutro-chloroform
were as shown below.
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[0047] delta (ppm) : 7.42 (1H, dd), 7.36 (1H, d), 2.81 (2H, q), 2.75 (3H, s), 2.25 (3H, s), 1.43 (3H,
t), 1.37 (9H, s)
Compound 4: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-butyryl-quinoline
[0048] In tetrahydrofuran (3 ml) was suspended 60% sodium hydride (20 mg). The compound 1 (124
mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min. Further,
butyryl chloride (200 mu l) was added thereto, and the mixture was stirred for 3 hr. The reaction
solution thus obtained was poured into ice water, and the mixture was extracted with ethyl acetate. The
ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution and
saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then removed under
the reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4butyrylquinoline (compound 4, 64 mg). >;1;H-NMR data on this compound in deutro-chloroform were
as shown below.
[0049] delta (ppm) : 7.43 (1H, dd), 7.37 (1H, d), 2.76 (2H, t), 2.75 (3H, s), 2.25 (3H, s), 1.94 (2H,
m), 1.37 (9H, s), 1.15 (3H, t)
Compound 5: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-valeryl-quinoline
[0050] In tetrahydrofuran (3 ml) was suspended 60% sodium hydride (20 mg). The compound 1 (124
mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min. Further,
valeryl chloride (200 mu l) was added thereto, and the mixture was stirred for 3 hr. The reaction
solution thus obtained was poured into ice water, and the mixture was extracted with ethyl acetate. The
ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution and
saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then removed under
the reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4valerylquinoline (compound 5, 120 mg). >;1;H-NMR data on this compound in deutro-chloroform
were as shown below.
[0051] delta (ppm) : 7.42 (1H, dd), 7.37 (1H, d), 2.78 (2H, t), 2.75 (3H, s), 2.25 (3H, s), 1.89 (2H,
m), 1.56 (2H, m), 1.37 (9H, s), 1.03 (3H, t)
Compound 6: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-methoxy-carbonylquinoline
[0052] In tetrahydrofuran (3 ml) was suspended 60% sodium hydride (20 mg). The compound 1 (124
mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min. Further,
methyl chloroformate (200 mu l) was added thereto, and the mixture was stirred for 3 hr. The reaction
solution thus obtained was poured into ice water, and the mixture was extracted with ethyl acetate. The
ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution and
saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then removed under
the reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4methoxycarbonyl-quinoline (compound 6, 100 mg). >;1;H-NMR data on this compound in deutrochloroform were as shown below.
[0053]
s)
delta (ppm) : 7.45 (1H, br.s), 7.43 (1H, dd), 4.00 (3H, s), 2.76 (3H, s), 2.31 (3H, s), 1.38 (9H,
Compound 7: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-ethoxy-carbonylquinoline
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[0054] In tetrahydrofuran (10 ml) was suspended 60% sodium hydride (60 mg). The compound 1
(200 mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min.
Further, ethyl chloroformate (200 mu l) was added thereto, and the mixture was stirred for 3 hr. The
reaction solution thus obtained was poured into ice water, and the mixture was extracted with ethyl
acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate
solution and saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then
removed under the reduced pressure. The crude product was purified by chromatography on silica gel
(Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8fluoro-4-ethoxycarbonyl-quinoline (compound 7, 220 mg).
[0055]
>;1;H-NMR data on this compound in deutro-chloroform were as shown below.
[0056] delta (ppm) : 7.45 (1H, br.s), 7.43 (1H, dd), 4.40 (2H, q), 2.32 (3H, s), 2.04 (3H, s), 1.44
(3H, t), 1.38 (9H, s)
Compound 8: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-n-propoxy-carbonylquinoline
[0057] In tetrahydrofuran (3 ml) was suspended 60% sodium hydride (20 mg). The compound 1 (124
mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min. Further, npropyl chloroformate (200 mu l) was added thereto, and the mixture was stirred for 3 hr. The reaction
solution thus obtained was poured into ice water, and the mixture was extracted with ethyl acetate. The
ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution and
saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then removed under
the reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4-npropoxycarbonyl-quinoline (compound 8, 96 mg). >;1;H-NMR data on this compound in deutrochloroform were as shown below.
[0058] delta (ppm) : 7.45 (1H, br.s), 7.43 (1H, dd), 4.35 (2H, t), 2.75 (3H, s), 2.31 (3H, s), 1.82 (2H,
m), 1.38 (9H, s), 1.04 (3H, t)
Compound 9: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-n-butoxy-carbonylquinoline
[0059] In tetrahydrofuran (10 ml) was suspended 60% sodium hydride (60 mg). The compound 1
(200 mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min.
Further, n-butyl chloroformate (200 mu l) was added thereto, and the mixture was stirred for 3 hr. The
reaction solution thus obtained was poured into ice water, and the mixture was extracted with ethyl
acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate
solution and saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then
removed under the reduced pressure. The crude product was purified by chromatography on silica gel
(Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8fluoro-4-n-butoxycarbonyl-quinoline (compound 9, 142 mg). >;1;H-NMR data on this compound in
deutro-chloroform were as shown below.
[0060] delta (ppm) : 7.45 (1H, d), 7.43 (1H, dd), 4.35 (2H, t), 2.75 (3H, s), 2.32 (3H, s), 1.77 (2H,
m), 1.48 (2H, m), 1.38 (9H, s), 0.99 (3H, t)
Compound 10: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-methoxy-acetylquinoline
[0061] In tetrahydrofuran (10 ml) was suspended 60% sodium hydride (165 mg). The compound 1
(680 mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min.
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Further, methoxyacetyl chloride (200 mu l) was added thereto, and the mixture was stirred for 3 hr. The
reaction solution thus obtained was poured into ice water, and the mixture was extracted with ethyl
acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate
solution and saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then
removed under the reduced pressure. The crude product was purified by chromatography on silica gel
(Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8fluoro-4-methoxyacetylquinoline (compound 10, 390 mg). >;1;H-NMR data on this compound in
deutro-chloroform were as shown below.
[0062] delta (ppm) : 7.42 (1H, dd), 7.35 (1H, d), 4.51 (2H, s), 3.62 (3H, s), 2.75 (3H, s), 2.26 (3H,
s), 1.37 (9H, s)
Compound 11: 2,3-Dimethyl-6-t-butyl-8-fluoro-4-acetoxy-acetylquinoline
[0063] In tetrahydrofuran (10 ml) was suspended 60% sodium hydride (44 mg). The compound 1
(200 mg) was added to the suspension under ice cooling, and the mixture was stirred for 30 min.
Further, acetoxyacetyl chloride (100 mu l) was added thereto, and the mixture was stirred for 3 hr. The
reaction solution thus obtained was poured into ice water, and the mixture was extracted with ethyl
acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate
solution and saturated brine and was then dried over anhydrous sodium sulfate. The solvent was then
removed under the reduced pressure. The crude product was purified by chromatography on silica gel
(Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3 : 1)) to give 2,3-dimethyl-6-t-butyl-8fluoro-4-acetoxyacetylquinoline (compound 11, 140 mg). >;1;H-NMR data on this compound in
deutro-chloroform were as shown below.
[0064] delta (ppm) : 7.43 (1H, dd), 7.42 (1H, br.s), 5.02 (2H, s), 2.75 (3H, s), 2.27 (3H, s), 2.23 (3H,
s), 1.40 (9H, s)
Compounds 12 to 14 (Comparative)
[0065] Compounds 12 to 14 having respective structures as shown in Table 1 below were produced
in the same manner as used in the production of the above compounds. These compounds 12 to 14 are
comparative compounds relative to the present invention.
Production of rice blast controlling agents
Production Example 1: Wettable powder
[0066] Intimate mixing was carried out according to the following formulation, and the mixture was
ground to produce wettable powder.
>;tb;>;TABLE; Columns=2
>;tb;Compound 2>;SEP;25 wt%
>;tb;Clay>;SEP;30 wt%
>;tb;Diatomaceous earth>;SEP;35 wt%
>;tb;Calcium lignin sulfonate>;SEP;3 wt%
>;tb;Polyoxyethylene alkylaryl ether>;SEP;7 wt%
>;tb;>;/TABLE;
Production Example 2: Dust
59/2194
[0067] Intimate mixing was carried out according to the following formulation to produce dust.
>;tb;>;TABLE; Columns=2
>;tb;Compound 2>;SEP;2 wt%
>;tb;Clay>;SEP;60 wt%
>;tb;Talc>;SEP;37 wt%
>;tb;Calcium stearate>;SEP;1 wt%
>;tb;>;/TABLE;
Production Example 3: Emulsifiable concentrate
[0068] Intimate mixing and dissolution were carried out according to the following formulation to
produce an emulsifiable concentrate.
>;tb;>;TABLE; Columns=2
>;tb;Compound 2>;SEP;20 wt%
>;tb;N,N-Dimethylformamide>;SEP;20 wt%
>;tb;Xylene>;SEP;50 wt%
>;tb;Polyoxyethylene alkylaryl ether>;SEP;10 wt%
>;tb;>;/TABLE;
Evaluation test
Test 1: Rice blast infection inhibition test (rice blast preventive test)
[0069] Full fourth-leaf stage rice seedlings (variety: Jikkoku) raised in each of plastic pots containing
compost for about 15 days after seeding were provided as a test plant.
[0070] The rice blast controlling agent according to the present invention was diluted with a 10%
aqueous acetone solution (with 2000-fold diluted Neoesterin TM added thereto) to predetermined
concentrations. Thus, test solution were prepared. Each of the test solution thus prepared was applied in
an amount of 10 ml per three pots by means of a spray gun to the test plant, followed by air drying.
[0071] Next, rice blast fungi, which have been previously cultured in petri dish, were collected and
were used to prepare a conidial suspension (1 to 5 x 10>;6;/ml). This conidial suspension was
homogeneously sprayed and inoculated into the pots. The pots were then allowed to stand in a moist
chamber of 25 DEG C for 24 hr. Thereafter, the pots were transferred to an environment controlled
greenhouse kept at 20 DEG C at night and at 25 DEG C in the daytime to induce the disease.
[0072] Seven days after the inoculation, the number of lesions which had appeared in the fourth leaf
were counted to obtain the results in the treated plot and the results in the nontreated plot. For each
case, the protective value was calculated by the following equation.
Protective value = [1 - (number of lesions in treated plot/number of lesions in nontreated plot)] x 100
[0073] The results were as summarized in Table 1.
EMI19.1
Test 2: Rice blast lesion evolution inhibition test (rice blast treatment test)
60/2194
[0074] Full fourth-leaf stage rice seedlings (variety: Jikkoku) raised in each of plastic pots containing
compost for about 15 days after seeding were provided as a test plant.
[0075] Rice blast fungi, which have been previously cultured in petri dish, were collected and were
used to prepare a conidial suspension (1 to 5 x 10>;6;/ml). This conidial suspension was
homogeneously sprayed and inoculated into the pots. The pots were then allowed to stand in a moist
chamber of 25 DEG C for 24 hr. Thereafter, the pots were transferred to an environment controlled
greenhouse kept at 20 DEG C at night and at 25 DEG C in the daytime to induce the disease.
[0076] After the elapse of 48 hr from the inoculation, the rice blast controlling agent according to the
present invention was brought to predetermined concentrations to prepare test solution. Each of the test
solution was applied in an amount of 10 ml per three pots by means of a spray gun to the test plant,
followed by air drying. Subsequently, the pots were again transferred to the environment controlled
greenhouse to induce the disease.
[0077] Seven days after the inoculation, the number of lesions which had appeared in the fourth leaf
were counted to obtain the results in the treated plot and the results in the nontreated plot. For each
case, the protective value was calculated in the same manner as used in the infection inhibition test.
[0078] The results were as shown in Table 2.
EMI21.1Data supplied from the esp@cenet database - Worldwide
Claims of corresponding document: EP1291344
Claims:
1. A compound of formula (1) or an acid addition salt thereof:
EMI22.1
wherein
R represents a hydrogen atom, -COR>;1;, -COOR>;1;, in which R>;1; represents alkyl having 1 to 4
carbon atoms,-COCH2OCH3, or -COCH2OCOCH3.
2. The compound of formula (1) or acid addition salt thereof according to claim 1, for use in the control
of rice blast.
3. A controlling agent for rice blast, comprising as an active ingredient at least one compound selected
from the group consisting of the compounds of formula (1) or acid addition salts thereof according to
claim 1.
4. A method for controlling rice blast, comprising the step of applying the compound or acid addition
salt thereof according to claim 1 to a rice plant per se, soil, or field water.
5. Use of the compound or acid addition salt thereof according to claim 1, for the production of a
controlling agent for rice blast.Data supplied from the esp@cenet database - Worldwide
61/2194
5. DE10245221
- 4/24/2003
COMPOSITION FOR SELECTIVE WEED CONTROL IN HERBICIDETOLERANT CROPS E.G. RICE CROPS, COMPRISES 1-(4,6-DIMETHOXY-2PYRIMIDINYL)-3-(2-METHOXYETHOXY)-2-PYRIDYLSULFONYL)-UREA
AND ANOTHER HERBICIDE E.G. N-PHOSPHONOMETHYLGLYCINE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE10245221
Inventor(s):
KOTZIAN GEORG RUEDIGER (CH)
Applicant(s):
SYNGENTA PARTICIPATIONS AG (CH)
IP Class 4 Digits: A01N
IP Class:A01N47/36; A01N47/38; A01N43/54; A01N43/50; A01N57/12; A01N57/26
E Class: A01N47/36
Application Number:
DE20021045221 (20020927)
Priority Number: CH20010001800 (20011001)
Family: DE10245221
Abstract:
Abstract of DE10245221
Composition (A) for selective weed control in herbicide-tolerant crops comprises: (i) 1-(4,6dimethoxy-2-pyrimidinyl)-3-((2-methoxyethoxy)-2-pyridylsulfonyl )-urea (I); and (ii) another
herbicide (II). Composition (A) for selective weed control in herbicide-tolerant crops comprises: (1) 1(4,6-dimethoxy-2-pyrimidinyl)-3-((2-methoxyethoxy)-2-pyridylsulfonyl )-urea (I) or its salts; and (2) a
compound (II) selected from: (a) N-phosphonomethylglycine and its salts; (b) ammonium 3-amino-3carboxylpropyl methylphosphinate and its (S)-isomer and salts; (c) alkali(ne earth) metal 1-(4,6dimethoxy-2-pyrimidinyl)-3-(3-(2,2,2-trifluoroethoxy)-2-pyridyl sulfonyl)-urea salts and their hydrates
and ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloroethane,
tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert.-butyl ether, chlorobenzene,
toluene or xylene solvates; (d) 3-(3-(2-allyloxycarbonyl-2-propoxycarbonyl)-4-chlorophenyl)-1methyl-6 -trifluoromethyl-1,2,3,4-tetrahydro-2,4-pyrimidinedione; (e) 2-(4-isopropyl-4-methyl-5(4H)oxo-1H-imidazol-2-yl)-3-pyridinecarboxylic acid and its 5-methoxymethyl, 5-methyl and 5-ethyl
derivatives; (f) 2-(4-isopropyl-4-methyl-5(4H)-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid; (g)
methyl 2-(4-isopropyl-4-methyl-5(4H)-oxo-1H-imidazol-2-yl)-5-methyl-3-pyridin ecarboxylate; and
(h) ethyl hexahydroazepine-1-carbothioate. An Independent claim is also included for a method for
controlling unwanted plant growth in herbicide-tolerant crops, comprising applying (A) to the crop
plants or their habitat.
62/2194
6. DE10245222
- 4/17/2003
SYNERGISTIC HERBICIDAL COMPOSITION, ESPECIALLY FOR SELECTIVE
WEED CONTROL IN CROPS SUCH AS RICE, CONTAINING
PHENYLSULFONYL-UREA DERIVATIVE AND ANOTHER HERBICIDE, E.G.
PICOLINAFEN, TRITOSULFURON, MESOTRIONE OR SULCOTRIONE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE10245222
Inventor(s):
KOTZIAN GEORG RUEDIGER (CH)
Applicant(s):
SYNGENTA PARTICIPATIONS AG (CH)
IP Class 4 Digits: A01N
IP Class:A01N47/36
E Class: A01N47/36
Application Number:
DE20021045222 (20020927)
Priority Number: CH20010001799 (20011001)
Family: DE10245222
Abstract:
Abstract of DE10245222
A synergistic herbicidal composition comprises an active agent combination of: (A) N-(2-(2methoxyethoxy)-phenylsulfonyl)-N'-(4,6-dimethoxy-1,3,5-triazin -2-yl)-urea (I) or its salt; and a
second herbicide (B), e.g. picolinafen, tritosulfuron, mesotrione or sulcotrione.Description:
Description of DE10245222
Die vorliegende Erfindung betrifft ein neues herbizides synergistisches Mittel, welches eine herbizide
Wirkstoffkombination enthält, die sich zur selektiven Unkrautbekämpfung in Nutzpflanzenkulturen,
wie beispielsweise in Kulturen von Reis eignet.
Die Erfindung betrifft ferner ein Verfahren zur Bekämpfung von Unkräutern in Nutzpflanzenkulturen,
sowie die Verwendung dieses neuen Mittels zu diesem Zweck.
Die Verbindung der Formel I
EMI1.1
sowie deren agronomisch verträgliche Salze, besitzt herbizide Wirkung, wie dies beispielsweise in USA-4,425,154 beschrieben ist.
Die folgenden unter A) und B) angegebenen Verbindungen sind ebenfalls als Herbizide bekannt:
A) Die Verbindungen der Formel II
EMI1.2
worin R1 Chlor oder Nitro bedeutet. Die Verbindung der Formel II, worin R1 für NO2 steht, ist unter
dem Namen Mesotrione bekannt und beispielsweise in US-A-5,006,158 beschrieben. Die Verbindung
63/2194
der Formel II, worin R1 für Chlor steht, ist unter dem Namen Sulcotrione bekannt und z. B. im
Pesticide Manual, eleventh ed., British Crop Protection Council, 1997 auf der Seite 1124 beschrieben.
B) Die im Pesticide Manual, eleventh ed., British Crop Protection Council, 1997 auf den
angegebenen Seiten aufgeführten Verbindungen Azafenidin (Seite 37), Tepraloxydim (Seite 80),
Pyriminobac-methyl (Seite 1071), Bispyribac-sodium (Seite 129), sowie die Verbindungen
Benzfendizone (Methyl 2-[2-[[4-[3,6-dihydro-3-methyl-2,6-dioxo-4- (trifluormethyl)-1(2H)pyrimidinyl]phenoxy]methyl]-5-ethylphenoxy]propanoat, CAS (Chemical Abstracts) Reg. Nr. 15875595-4), Benflubutamid (2-[4-fluoro-3-(trifluoromethyl)phenoxy]-N- (phenylmethyl)butanamid, CAS
Reg. Nr. 113614-08-7), Benzobicyclon (3-(2-Chlor-4- (methylsulfonyl)benzoyl]-4(phenylthio)bicyclo[3.2.1]oct-3-en-2-on, CAS Reg. Nr. 156963-66- 5), Cinidon-ethyl (Ethyl (22)-2chlor-3-[2-chlor-5-(1,3,4,5,6,7-hexahydro-1,3-dioxo-2H- isoindol-2-yl)phenyl]-2-propenoat, CAS Reg.
Nr. 142891-20-1), Dicfosulam (N-(2,6- Dichiorphenyl)-5-ethoxy-7-fluor[1,2,4]triazol[1,5-c]pyrimidin2-sulfonamid, CAS Reg. Nr. 145701-21-9), Flufenpyr ([2-Chlor-4-fluor-5-[5-methyl-6-oxo-4(trifluormethyl]-1(6H)- pyridazinyl]phenoxy]essigsäure, CAS Reg. Nr. 188490-07-5, sowie dessen
Ethylester CAS Reg. Nr. 188489-07-8), Mesosulfuron (2-[[[[(4,6-Dimethoxy-2pyrimidinyl)amino]carbonyl]amino]sulfonyl]-4-[[(methylsulfonyl)amino]methyl]benzoesäure und
dessen Methylester, CAS Reg. Nr. (Methylester) 208465-21-8), Penoxsulam (2-(2,2- Difluorethoxy)N-(5,8-dimethoxy[1,2,4]triazol[1,5-c]pyrimidin-2-yl)-6- (trifluormethyl)benzolsulfonamid, CAS Reg.
Nr. 219714-96-2), Picolinafen (N-(4- Fluorphenyl)-6-[3-(trifluormethyl)phenoxy]-2pyridincarboxamid, CAS Reg. Nr. 137641-05-5), Fentrazamide (4-(2-Chlorphenyl)-N-cyclohexyl-Nethyl-4,5-dihydro-5-oxo-1H-tetrazol-1- carboxamid, CAS Reg. Nr. 158237-07-1), Oxaziclomefone (3[1-(3,5-Dichlorphenyl)-1- methylethyl]-2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazin-4-on, CAS Reg.
Nr. 153197-14-9), Profoxidim (2-(1-[[2-(4-Chlorphenoxy)propoxy]imino]butyl]-3-hydroxy-5(tetrahydro-2H- thiopyran-3-yl)-2-cyclohexen-1-on, CAS Reg. Nr. 139001-49-3), Pyrazogyl (1-(3Chlor- 4,5,6,7-tetrahydropyrazolo[1,5a]pyridin-2-yl)-5-(methyl-2-propynylamino)-1H-pryazol-4carbonitril, CAS Reg. Nr. 158353-15-2), Profluazol (1-Chlor-N-[2-chlor-4-fluor-5-[(6S,7aR)-6fluorotetrahydro-1,3-dioxo-1H-pyrrolo[1,2-c]imidazol-2(3H)-yl]phenyl]methansulfonamid, CAS Reg.
Nr. 190314-43-3), Propoxycarbazone (Methyl 2-[[[(4,5-dihydro-4-methyl-5-oxo-3- propoxy-1H-1,2,4triazol-1-yl)carbonyl]amino]sulfonyl]benzoat, CAS Reg. Nr. 145026-81-9 und dessen Natriumsalz
CAS Reg. Nr. 181274-15-7), Amicarbazone (4-Amino-N (1,1- dimethylethyl)-4,5-dihydro-3-(1methylethyl)-5-oxo-1H-1,2,4-triazol-1-carboxamid, CAS Reg. Nr. 129909-90-6, bekannt z. B. aus USA-5,194,085), Trifloxysulfuron (N-[[(4,6-Dimethoxy-2- pyrimidinyl)amino]carbonyl]-3-(2,2,2trifluorethoxy)-2-pyridinsulfonamid, CAS Reg. Nr. 145099-21-4, sowie dessen Natriumsalz CAS Reg.
199119-58-9), Pyriminobac (2-[(4,6- Dimethoxy-2-pyrimidinyl)oxy]-6-[1(methoxyimino)ethyl]benzoesäure, CAS Reg. Nr. 136191- 56-5, sowie dessen Salze und Ester,
insbesondere der Methylester CAS Reg. Nr. 136191- 64-5), Indanofan (2-[[2-(3Chlorphenyl)oxiranyl]methyl]-2-ethyl-1H-inden-1,3(2H)-dion, CAS Reg. Nr. 133220-30-1),
Pyribenzoxim (Diphenylmethanon-O-[2,6-bis[(4,6-dimethoxy-2- pyrimidinyl)oxy]benzoyl]oxim, CAS
Reg. Nr. 168088-61-7), Fentrazamide (4-(2- Chlorophenyl)-N-cyclohexyl-N-ethyl-4,5-dihydro-5-oxo1H-tetrazol-1-carboxamid, CAS Reg. Nr. 15823-07-1) und Tritosulfuron (N-[[[4-Methoxy-6(trifluormethyl)-1,3,5-triazin-2- yl]amino]carbonyl]-2-(trifluormethyl)benzolsulfonamid, CAS Reg. Nr.
142469-14-5, z. B. bekannt aus DE-A-40 38 430).
Es hat sich nun überraschenderweise gezeigt, dass eine mengenmässig variable Kombination
mindestens zweier Wirkstoffe, d. h. mindestens eines Wirkstoffs der Formel I mit mindestens einem
der oben unter A) und B) aufgeführten Wirkstoffe eine synergistische Wirkung entfaltet, die die
Mehrzahl der vorzugsweise in Nutzpflanzenkulturen vorkommenden Unkräuter sowohl im Vorauflaufals auch im Nachauflaufverfahren zu bekämpfen vermag, ohne die Nutzpflanze wesentlich zu
schädigen.
Es wird daher gemäss der vorliegenden Erfindung ein neues synergistisches Mittel zur selektiven
Unkrautbekämpfung vorgeschlagen, das neben üblichen inerten Formulierungshilfsstoffen als
Wirkstoff eine Mischung aus
a) einer Verbindung der Formel I
EMI3.1
64/2194
sowie deren agronomisch verträgliche Salze, und
b) einer synergistisch wirksamen Menge einer Verbindung ausgewählt aus den Verbindungen der
Formel II
EMI4.1
worin R, Chlor oder Nitro bedeutet;
Azafenidin, Tepraloxydim, Pyriminobac-methyl, Bispyribac-sodium, Benflubutamid, Benzfendizone,
Benzobicyclon, Cinidon-ethyl, Diclosulam, Flufenpyr, Flufenpyr-ethylester, Mesosulfuron,
Mesosulfuron-methylester, Penoxsulam, Picolinafen, Fentrazamide, Oxaziclomefone, Profoxidim,
Pyrazogyl, Profluazol, Propoxycarbazone, Propoxycarbazonesodium, Amicarbazone, Trifloxysulfuronsodium, Pyriminobac-methyl, Pyribenzoxim, Fentrazamide und Tritosulfuron enthält.
Die Erfindung umfasst ebenfalls die Salze, die die Verbindungen der Formel I und die oben unter b)
aufgeführten Verbindungen mit Aminen, Alkali- und Erdalkalimetallbasen oder quaternären
Ammoniumbasen bilden können. Unter den Alkali- und Erdalkalimetallbasen sind als Salzbildner die
Hydroxide von Lithium, Natrium, Kalium, Magnesium oder Calcium, insbesondere die von Natrium
oder Kalium hervorzuheben. Als Beispiele für zur Ammoniumsalzbildung geeignete Amine kommen
sowohl Ammoniak wie auch primäre, sekundäre und tertiäre C1-C18-Alkylamine, C1-C4Hydroxyalkylamine und C2-C4- Alkoxyalkylamine in Betracht, beispielsweise Methylamin,
Ethylamin, n-Propylamin, iso- Propylamin, die vier isomeren Butylamine, n-Amylamin, Iso-amylamin,
Hexylamin, Heptylamin, Octylamin, Nonylamin, Decylamin, Pentadecylamin, Hexadecylamin,
Heptadecylamin, Octadecylamin, Methyl-ethylamin, Methyl-iso-propylamin, Methylhexylamin,
Methyl-nonylamin, Methyl-pentadecylamin, Methyl-octadecylamin, Ethylbutylamin, Ethylheptylamin, Ethyl-octylamin, Hexyl-heptylamin, Hexyl-octylamin, Dimethylamin, Diethylamin, Di-npropylamin, Di-iso-propylamin, Di-n-butylamin, Di-n- amylamin, Di-iso-amylamin, Dihexylamin,
Diheptylamin, Dioctylamin, Ethanolamin, n- Propanolamin, iso-Propanolamin, N,N-Diethanolamin, NEthylpropanolamin, N- Butylethanolamin, Allylamin, n-Butenyl-2-amin, n-Pentenyl-2-amin, 2,3Dimethylbutenyl-2- amin, Di-butenyl-2-amin, n-Hexenyl-2-amin, Propylendiamin, Trimethylamin,
Triethylamin, Tri-n-propylamin, Tri-iso-propylamin, Tri-n-butylamin, Tri-iso-butylamin, Tri-sek.butylamin, Tri-namylamin, Methoxyethylamin und Ethoxyethylamin; heterocyclische Amine wie z. B.
Pyridin, Chinolin, iso-Chinolin, Morpholin, Piperidin, Pyrrolidin, Indolin, Chinuclidin und Azepin;
primäre Arylamine wie z. B. Aniline, Methoxyaniline, Ethoxyaniline, o, m und p- Toluidine,
Phenylendiamine, Naphthylamine und o, m und p-Chloraniline; insbesondere aber Triethylamin, isoPropylamin und Di-iso-propylamin. Zur Salzbildung geeignete quartäre Ammoniumbasen sind
beispielsweise [N(Ra Rb Rc Rd)]>;+; OH>;-;, wobei Ra, Rb, Rc und Rd unabhängig voneinander für
C1-C4-Alkyl stehen. Weitere geeignete Tetraalkylammoniumbasen mit anderen Anionen können
beispielsweise durch Anionenaustauschreaktionen erhalten werden.
Es ist in hohem Masse überraschend, dass die Kombination des Wirkstoffs der Formel I mit einem
Wirkstoff der oben unter b) aufgeführten Wirkstoffe die prinzipiell zu erwartende additive Wirkung auf
die zu bekämpfenden Unkräuter übersteigt und so die Wirkungsgrenzen beider Wirkstoffe
insbesondere in zweierlei Hinsicht erweitert: Zum einen werden die Aufwandmengen der jeweiligen
Einzelverbindungen bei gleichbleibend guter Wirkung gesenkt. Zum anderen erzielt das
erfindungsgemässe Mittel auch dort noch einen hohen Grad der Unkrautbekämpfung, wo die
Einzelsubstanzen im Bereich geringer Aufwandmengen agronomisch nicht mehr brauchbar geworden
sind. Dies hat eine wesentliche Verbreiterung des Unkrautspektrums und eine zusätzliche Erhöhung der
Selektivität für die Nutzpflanzenkulturen zur Folge, wie es im Falle einer unbeabsichtigten
Wirkstoffüberdosierung notwendig und erwünscht ist. Des weiteren erlaubt das erfindungsgemässe
Mittel unter Beibehaltung der herausragenden Kontrolle der Unkräuter in Nutzpflanzen eine grössere
Flexibilität bei Nachfolgekulturen.
Das erfindungsgemässe Mittel kann gegen eine grosse Anzahl agronomisch wichtiger Unkräuter, wie
Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanüm, Phaseolus,
Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia,
Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium,
Viola und Veronica verwendet werden. Das erfindungsgemässe Mittel ist für alle in der Landwirtschaft
üblichen Applikationsmethoden wie z. B. preemergente Applikation, postemergente Applikation und
Saatbeizung geeignet. Das erfindungsgemässe Mittel eignet sich vorzugsweise zur Unkrautbekämpfung
65/2194
in Nutzpflanzenkulturen wie Getreide, Raps, Zuckerrübe, Zuckerrohr, Plantagen, Reis, Mais und Soja
sowie zur nicht-selektiven Unkrautkontrolle, und ganz besonders zur Unkrautbekämpfung in Reis.
Unter Nutzpflanzenkulturen sind auch solche zu verstehen, die durch konventionelle züchterische oder
gentechnologische Methoden gegen Herbizide bzw. Herbizidklassen tolerant gemacht worden sind.
Das erfindungsgemässe Mittel enthält den Wirkstoff der Formel I und die oben unter b) aufgeführten
Wirkstoffe in beliebigem Mischungsverhältnis, in der Regel mit einem Überschuss der einen über die
andere Komponente. Bevorzugte Mischungsverhältnisse zwischen dem Wirkstoff der Formel I und den
oben unter b) aufgeführten Mischpartnern sind 1 : 2000 bis 2000 : 1, insbesondere 200 : 1 bis 1 : 200.
Als ganz besonders wirksame Mittel haben sich Kombinationen der Verbindung der Formel I mit den
Verbindungen der Formel II erwiesen.
Die Aufwandmenge kann innerhalb weiter Bereiche variieren und hängt von der Beschaffenheit des
Bodens, der Art der Anwendung (pre- oder postemergent; Saatbeizung; Anwendung in der Saatfurche;
no tillage Anwendung etc.), der Kulturpflanze, dem zu bekämpfenden Unkraut, den jeweils
vorherrschenden klimatischen Verhältnissen und anderen durch Anwendungsart,
Anwendungszeitpunkt und Zielkultur bestimmten Faktoren ab. Im allgemeinen kann das
erfindungsgemässe Wirkstoffgemisch mit einer Aufwandmenge von 1 bis 5000 g Wirkstoffgemisch/ha
Wirkstoffgemisch/ha angewendet werden. In dem erfindungsgemässen Mittel ist die Komponente der
Formel I gegenüber der oben unter b) aufgeführten in einem Gewichtsverhältnis von 1 : 100 bis 1000 :
1 vorhanden.
Die Gemische der Verbindung der Formel (mit den oben unter b) aufgeführten Verbindungen können
in unveränderter Form, d. h. wie sie in der Synthese anfallen, eingesetzt werden. Vorzugsweise
verarbeitet man sie aber auf übliche Weise mit den in der Formulierungstechnik gebräuchlichen
Hilfsmitteln, wie Lösungsmittel, feste Träger oder Tenside, z. B. zu emulgierbaren Konzentraten,
direkt versprühbaren oder verdünnbaren Lösungen, verdünnten Emulsionen, Spritzpulvern, löslichen
Pulvern, Stäubemitteln, Granulaten oder Mikrokapseln, wie dies in WO 97/34483, Seiten 9 bis 13
beschrieben ist. Die Anwendungsverfahren wie Versprühen, Vernebeln, Verstäuben, Benetzen,
Verstreuen oder Giessen werden, gleich wie die Art der Mittel, den angestrebten Zielen und den
gegebenen Verhältnissen entsprechend gewählt. Die Formulierungen, d. h. die die Wirkstoffe der
Formeln I und die oben unter b) aufgeführten Wirkstoffe, sowie gegebenenfalls ein oder mehrere feste
oder flüssige Formulierungshilfsmittel enthaltenden Mittel, Zubereitungen oder Zusammensetzungen
werden in an sich bekannter Weise hergestellt, z. B. durch inniges Vermischen und/oder Vermahlen der
Wirkstoffe mit den Formulierungshilfsmitteln wie z. B. Lösungsmittel oder festen Trägerstoffe. Ferner
können zusätzlich oberflächenaktive Verbindungen (Tenside) bei der Herstellung der Formulierungen
verwendet werden.
Beispiele für Lösungsmittel und feste Trägerstoffe sind z. B. in der WO 97/34485 Seite 6 angegeben.
Als oberflächenaktive Verbindungen kommen je nach der Art des zu formulierenden Wirkstoffes der
Formel I nichtionogene, kation- und/oder anionaktive Tenside und Tensidgemische mit guten
Emulgier-, Dispergier- und Netzeigenschaften in Betracht. Beispiele für geeignete anionische,
nichtionische und kationische Tenside sind beispielsweise in der WO 97/34485, Seiten 7 und 8
aufgezählt. Ferner sind auch die in der Formulierungstechnik gebräuchlichen Tenside, die u. a. in "Mc
Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981,
Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, München/Wien, 1981 und M. und J. Ash,
"Encyclopedia of Surfactants", Vol I-III, Chemical Publishing Co., New York, 1980-81 beschrieben
sind, zur Herstellung der erfindungsgemässen herbiziden Mittel geeignet.
Die herbiziden Formulierungen enthalten in der Regel 0,1 bis 99 Gew.-%, insbesondere 0,1 bis 95
Gew.-% Wirkstoffgemisch aus der Verbindung der Formel I mit den oben unter b) aufgeführten
Wirkstoffen, 1 bis 99,9 Gew.-% eines festen oder flüssigen Formulierungshilfstoffes und 0 bis 25
Gew.-%, insbesondere 0,1 bis 25 Gew.-% eines Tensides.
Während als Handelsware üblicherweise konzentrierte Mittel bevorzugt werden, verwendet der
Endverbraucher in der Regel verdünnte Mittel. Die Mittel können auch weitere Zusätze wie
Stabilisatoren z. B. gegebenenfalls epoxydierte Pflanzenöle (epoxydiertes Kokosnussöl, Rapsöl oder
Sojaöl), Entschäumer, z. B. Silikonöl, Konservierungsmittel, Viskositätsregulatoren, Bindemittel,
66/2194
Haftmittel sowie Dünger oder andere Wirkstoffe enthalten. Insbesondere setzen sich bevorzugte
Formulierungen folgendermassen zusammen:
(% = Gewichtsprozent; Wirkstoffgemisch bedeutet eine Mischung aus der Verbindung der Formel I
mit einem oben unter b) aufgeführten Wirkstoff).
Emulgierbare Konzentrate
Aktives Wirkstoffgemisch: 1 bis 90%, vorzugsweise 5 bis 20%
oberflächenaktives Mittel: 1 bis 30%, vorzugsweise 10 bis 20%
flüssiges Trägermittel: 5 bis 94%, vorzugsweise 70 bis 85%.
Stäube
Aktives Wirkstoffgemisch: 0,1 bis 10%, vorzugsweise 0,1 bis 5%
festes Trägermittel: 99,9 bis 90%, vorzugsweise 99,9 bis 99%.
Suspensions-Konzentrate
Aktives Wirkstoffgemisch: 5 bis 75%, vorzugsweise 10 bis 50%
Wasser: 94 bis 24%, vorzugsweise 88 bis 30%
oberflächenaktives Mittel: 1 bis 40%, vorzugsweise 2 bis 30%.
Benetzbare Pulver
Aktives Wirkstoffgemisch: 0,5 bis 90%, vorzugsweise 1 bis 80%
oberflächenaktives Mittel: 0,5 bis 20%, vorzugsweise 1 bis 15%
festes Trägermaterial: 5 bis 95%, vorzugsweise 15 bis 90%.
Granulate
Aktives Wirkstoffgemisch: 0,1 bis 30%, vorzugsweise 0,1 bis 15%
festes Trägermittel: 99,5 bis 70%, vorzugsweise 97 bis 85%.
Die folgenden Beispiele erläutern die Erfindung weiter, ohne sie zu beschränken.
EMI8.1
Aus solchen Konzentraten können durch Verdünnung mit Wasser Emulsionen jeder gewünschten
Konzentration hergestellt werden.
EMI8.2
EMI9.1
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.
EMI9.2
Der Wirkstoff wird in Methylenchlorid gelöst, auf den Träger aufgesprüht und das Lösungsmittel
anschliessend im Vakuum abgedampft.
EMI9.3
67/2194
Der fein gemahlene Wirkstoff wird in einem Mischer auf das mit Polyethylenglykol angefeuchtete
Trägermaterial gleichmässig aufgetragen. Auf diese Weise erhält man staubfreie UmhüllungsGranulate.
EMI9.4
Der Wirkstoff wird mit den Zusatzstoffen vermischt, vermahlen und mit Wasser angefeuchtet. Dieses
Gemisch wird extrudiert und anschliessend im Luftstrom getrocknet.
EMI10.1
Man erhält anwendungsfertige Stäubemittel, indem der Wirkstoff mit den Trägerstoffen vermischt und
auf einer geeigneten Mühle vermahlen wird.
EMI10.2
Der feingemahlene Wirkstoff wird mit den Zusatzstoffen innig vermischt. Man erhält so ein
Suspensions-Konzentrat, aus welchem durch Verdünnen mit Wasser Suspensionen jeder gewünschten
Konzentration hergestellt werden können.
Es ist oft praktischer, den Wirkstoff der Formel I und den Mischungspartner einzeln zu formulieren
und sie dann kurz vor dem Ausbringen in Applikator im gewünschten Mischungsverhältnis als
"Tankmischung" im Wasser zusammenzubringen.
Biologische Beispiele
Ein synergistischer Effekt liegt immer dann vor, wenn die Wirkung z. B. der Wirkstoffkombination
grösser ist als die Summe der Wirkung der einzeln applizierten Wirkstoffe. Die zu erwartende
herbizide Wirkung We für eine gegebene Kombination zweier Herbizide kann nach der Methode von
COLBY, S. R., "Calculaling synergistic and antagonstic response of herbicide combinations", Weeds
15, Seiten 20-22, 1967 berechnet werden. Der synergistische Effekt der Kombinationen des Wirkstoffs
der Formel I mit den oben unter b) aufgeführten Wirkstoffen wird in den folgenden Beispielen
demonstriert.
Beispiel B1
Pre-emergenter Versuch
Die Versuchspflanzen werden unter Gewächshausbedingungen in Töpfen angesät. Als Kultursubstrat
wird eine Standarderde verwendet. In einem Vorauflaufstadium werden die Herbizide sowohl allein als
auch in Mischung auf die Bodenoberfläche appliziert. Die Aufwandmengen richten sich nach den unter
Feld- oder Gewächshausbedingungen ermittelten optimalen Dosierungen. Die Auswertung der
Versuche erfolgt nach 2 bis 4 Wochen (100% Wirkung = vollständig abgestorben; 0% Wirkung =
keine phytotoxische Wirkung). Die in diesem Versuch verwendeten Mischungen zeigen gute Resultate.
Beispiel B2
68/2194
Post-emergenter Versuch
Die Versuchspflanzen werden unter Gewächshausbedingungen in Töpfen bis zu einem
Postapplikationsstadium angezogen. Als Kultursubstrat wird eine Standarderde verwendet. In einem
Nachauflaufstadium werden die Herbizide sowohl allein als auch in Mischung auf die Testpflanzen
appliziert. Die Aufwandmengen richten sich nach den unter Feld- oder Gewächshausbedingungen
ermittelten optimalen Dosierungen. Die Auswertung der Versuche erfolgt nach 2 bis 4 Wochen (100%
Wirkung = vollständig abgestorben; 0% Wirkung = keine phytotoxische Wirkung). Die in diesem
Versuch verwendeten Mischungen zeigen gute Resultate.Data supplied from the esp@cenet database Worldwide
69/2194
7. DE19928453
- 12/28/2000
SYNERGISTIC SELECTIVE HERBICIDAL COMPOSITION, ESPECIALLY FOR
USE IN RICE, CONTAINING SULFURON AND E.G. CLETHODIM,
BENTAZONE OR NICOSULFURON
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE19928453
Inventor(s):
HACKER ERWIN (DE); BIERINGER HERMANN (DE); AULER THOMAS (DE);
MELENDEZ ALVARO (DE)
Applicant(s):
AVENTIS CROPSCIENCE GMBH (DE)
IP Class 4 Digits: A01N
IP Class:A01N47/36
E Class: A01N47/36
Application Number:
DE19991028453 (19990624)
Priority Number: DE19991028453 (19990624)
Family: DE19928453
Abstract:
Abstract of DE19928453
A herbicidal composition contains ethoxysulfuron and at least one of a wide range of other herbicides
which are selectively active in rice. A herbicidal composition contains as active agents: (A) 1-(2ethoxyphenoxysulfonyl)-3-(4,6-dimethoxy-2-pyrimidinyl)-urea of formula (I) (i.e. ethoxysulfuron)
and/or its salts; and (B) one or more of: (a) herbicides mainly for controlling grasses in rice, selected
from fentrazamide (NBA 061), haloxyfop, sethoxydim, dithiopyr, clefoxidim, KIH 6127 and
clethodim; (b) herbicides mainly for controlling dicotyledonous weeds and Cyperaceae in rice, selected
from 2,4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron-methyl, dicamba, acifluorfen,
carfentrazone, bentazone and trichlorpyr; and (c) herbicides mainly for controlling grasses,
dicotyledonous weeds and Cyperaceae in rice, selected from pendimethalin, clomazone, KIH 2023,
oxadiargyl, cyclosulfamuron (AC 322, 140), azimsulfuron (DPX-A-8947), nicosulfuron, cinmethylin,
indanofan, pentoxazone, pyribenzoxim, oxaziclomefone (MY-100), fluthiamide and
mesotrione.Description:
Description of DE19928453
Die Erfindung bezieht sich auf das technische Gebiet der Pflanzenschutzmittel, insbesondere betrifft
die Erfindung herbizide Mittel mit einem Gehalt an bestimmten Phenoxysulfonylharnstoffen und/oder
ihren Salzen, die sich hervorragend zur Bekämpfung von bislang nur schwer mit einzelnen Herbiziden
kontrollierbaren Unkräutern in Reis, insbesondere grasartigen, dikotylen und/oder Cyperaceenartigen
Unkräutern in Reis oder transgenen Reiskulturen, eignen.
Aus der IT 1270985 sind herbizide Mittel bekannt, gekennzeichnet durch einen wirksamen Gehalt
substituierter Phenoxysulfonylharnstoffe in Kombination mit herbiziden Wirkstoffen.
Es existieren insbesondere in Reis eine Reihe wirtschaftlich sehr wichtiger monokotyler Unkräuter, wie
z. B. in erster Linie Echinochloa crus galli, Ischaemum ssp. oder Leptochloa, die mit bislang bekannten
Reis-Herbiziden oder Mischungen davon alleine nicht in zufriedenstellender Weise zu bekämpfen sind.
Auch sind aus globalen Reisanbausystemen Schadpflanzen bekannt, wie Sagittaria spp., Eleocharis
70/2194
spp., z. B. Eleocharis kuroguwai, Cyperus serotinus, Scirpus juncoides, aber auch andere
Schadpflanzen, die überwiegend aus Dauerorganen im Boden auskeimen und dadurch schwieriger
bekämpft werden können als Unkräuter, die aus Samen auskeimen, und auch breitblättrige Arten, die in
der ganzen Breite des Spektrums von Unkräutern nicht einfach in optimaler Weise kontrollierbar sind.
Ferner werden zunehmend resistente Arten (unter anderem von Cyperus ssp. oder Echinochloa ssp.)
gefunden, die mit Einzelwirkstoffen aber auch mit herkömmlichen Kombinationen oft nicht mehr
bekämpfbar sind.
Angesichts des hierin angegebenen und diskutierten Standes der Technik war es mithin Aufgabe der
Erfindung Mischungen mit herbizider Wirksamkeit anzugeben, um den Praktiker in die Lage zu
versetzen, mit einer Applikation bzw. wenigen Applikationen von Herbiziden das Unkrautspektrum
oder einzelne schwer zu bekämpfende Unkrautspezies in Reis zu kontrollieren.
Überraschend wurde gefunden, dass unter anderem diese Aufgaben durch herbizide Mittel mit den
Merkmalen des Anspruchs 1 gelöst werden. So sind Gegenstand der vorliegenden Erfindung herbizide
Mittel, enthaltend
A) einen oder mehrere herbizide Wirkstoffe aus der Gruppe der substituierten
Phenoxysulfonylharnstoffe der Formel I und deren Salze
EMI2.1
und
A) eine oder mehrere herbizid wirksame Verbindungen aus der Gruppe der Verbindungen, welche
besteht aus
1. selektiv in Reis vorwiegend gegen Gräser wirksamen Herbiziden ausgewählt aus der Gruppe
bestehend aus Fentrazamid (NBA 061), Haloxyfop, Sethoxydim, Dithiopyr, Etobenzanid (MY-52),
Clefoxidim, KIH 6127, und Clethodim,
2. selektiv in Reis vorwiegend gegen dikotyle Schadpflanzen und Cyperaceen wirksamen Herbiziden,
ausgewählt aus der Gruppe, bestehend aus 2,4-D, MCPA, Mecoprop, Mecoprop-P, Tritosulfuron,
Halosulfuron-methyl, Dicamba, Acifluorfen, Carfentrazone, Bentazon und Triclopyr,
3. selektiv in Reis, vorwiegend gegen Gräser und dikotyle Schadpflanzen sowie Cyperaceen
wirksamen Herbiziden, ausgewählt aus der Gruppe, bestehend aus Pendimethalin, Clomazone, KIH
2023, Oxadiargyl, Cycloslulfamuron (AC 322, 140), Azimsulfuron (DPX-A-8947), Nicosulfuron,
Thenylchlor, Cinmethylin, Indanofan, Pentoxazone, Pyribenzoxim, Oxaziclomefone (MY-100),
Fluthiamid und Mesotrione.
Durch die erfindungsgemässen Kombinationen aus herbiziden Wirkstoffen der Typen A und B gelingt
es besonders vorteilhaft, die vom Praktiker geforderte Kontrolle des Unkrautspektrums zu erreichen,
wobei auch einzelne schwer zu bekämpfende Arten erfasst werden. Darüberhinaus lässt sich mit den
erfindungsgemässen Kombinationen der Aufwand an Wirkstoffmengen der einzelnen in der
Kombination enthaltenen Kombinationspartner deutlich reduzieren, was ökonomischere
Lösungsansätze seitens der Anwender erlaubt.
Schliesslich konnten überraschenderweise Wirkungssteigerungen erzielt werden, die über das zu
erwartende Mass hinausgehen, womit die herbiziden Mittel der Erfindung in breitem Umfang
synergistische Aktivitäten zeigen. Daneben lassen sich auch viele resistente Arten in hervorragender
Weise kontrollieren.
Die Verbindungen der Formel I können Salze bilden, bei denen der Wasserstoff der -SO2-NH-Gruppe
durch ein für die Landwirtschaft geeignetes Kation ersetzt wird. Diese Salze sind beispielsweise
Metall-, insbesondere Alkalisalze (z. B. Na- oder K- Salze) oder Erdalkalisalze, oder auch
Ammoniumsalze oder Salze mit organischen Aminen. Ebenso kann Salzbildung durch Anlagerung
einer starken Säure an den Heterocyclenteil der Verbindungen der Formel I erfolgen. Geeignet hierfür
71/2194
sind z. B. HCl, HNO3, Trichloressigsäure, Essigsäure oder Palmitinsäure. Besonders vorteilhafte
Verbindungen sind solche, bei denen das Salz des Herbizids der Formel (I) durch Ersatz des
Wasserstoffs der -SO2-NH-Gruppe durch ein Kation aus der Gruppe der Alkalimetalle,
Erdalkalimetalle und Ammonium, bevorzugt Natrium, gebildet wird.
Sofern die Verbindungen der Formel I ein oder mehrere asymmetrische C-Atome oder auch
Doppelbindungen enthalten, die in der allgemeinen Formel nicht gesondert angegeben sind, gehören
diese doch zu den Typ-A Verbindungen. Die durch ihre spezifische Raumform definierten möglichen
Stereoisomeren, wie Enantiomere, Diastereoisomere, Z- und E-Isomere sind alle von der Formel I
umfasst und können nach üblichen Methoden aus Gemischen der Stereoisomeren erhalten oder auch
durch stereoselektive Reaktionen in Kombination mit dem Einsatz von stereochemisch reinen
Ausgangsstoffen hergestellt werden. Die genannten Stereoisomeren in reiner Form als auch ihre
Gemische können somit erfindungsgemäss eingesetzt werden.
Phenoxysulfonylharnstoffe der Formel I sind zwar grundsätzlich z. B. von der allgemeinen Formel I
aus der IT 127 09 85 umfasst und auch deren Eignung als Synergismuspartner für in Kulturpflanzen
anzuwendende Herbizide ist dort beschrieben. Die herausragende Eignung der speziellen
Phenoxysulfonylharnstoffe der Gruppe A als Kombinationspartner in synergistischen Mischungen mit
anderen Herbiziden, die in Reis angewendet werden können, ist dem Stand der Technik allerdings nicht
entnehmbar. Insbesondere gibt es keine Anhaltspunkte in der bekannt gewordenen Literatur, dass
Kombinationen von Verbindungen der Gruppe A), mit den Reisherbiziden der Gruppe B eine solche
Ausnahmestellung bei der Bekämpfung der wichtigsten Schadpflanzen in Reiskulturen zukommt.
Dabei ist vor allem auch zu berücksichtigen, dass von der Anwendung einer Kombination in anderen
Kulturen nicht auf die Wirkung in Reiskulturen extrapoliert werden kann. Selbst wenn die
Verbindungen der Gruppe A) sich alleine zur Bekämpfung von Schadpflanzen in Reis eignen, kann
nicht mit überwiegender oder auch nur einiger Aussicht auf Erfolg vorhergesagt werden, ob
Kombinationen mit anderen Reisherbiziden über die additive Wirkung hinausgehende
Wirkungssteigerungen bei der Schadpflanzenbekämpfung zulassen.
Ein bevorzugter Kombinationspartner aus der Gruppe A) ist die Verbindung A1 (Ethoxysulfuron): 1[2-Ethoxy-Phenoxy)sulfonyl]-3-(4,6-dimethoxy-2-pyrimidyl)- harnstoff
EMI5.1
die u. a. bekannt ist aus Pesticide Manual (publ. British Crop Protection Council), 11. Auflage, 1997,
S. 488-489. Diese Verbindung wird bevorzugt als alleiniger Wirkstoff der Gruppe A) verwandt und
kann mit einem oder mehreren herbizid wirksamen Verbindungen der Gruppe B kombiniert werden.
Die speziellen Sulfonylharnstoffe der Gruppe A, insbesondere die Verbindung A1) sind in
Kombination mit anderen Herbiziden von Typ B) hervorragend dazu geeignet, schwer zu bekämpfende
Unkrautspezies in Reiskulturen wirkungsvoll zu kontrollieren. Insbesondere treten dabei unerwartete
spezielle Wirkungseffekte gegen resistente Schadgräder auf.
Die Kombinationspartner vom Typ B sind in der Regel Standardherbizide, die jedoch unter bestimmten
Kriterien ausgewählt sind. So handelt es sich ausnahmslos um selektiv in Reis gegen unerwünschte
Pflanzen wirksame Herbizide. Zu den zu bekämpfenden Schadpflanzen gehören dabei vor allem Gräser
und Dikotyle/Cyperaceen. Die Schreibweise "Dikotyle/Cyperaceen" soll dabei zum Ausdruck bringen,
dass die Wirksamkeit gegen Dikotyle und Cyperaceen gegeben ist, die Wirksamkeit gegen Dikotyle
jedoch im Vordergrund steht.
Hinsichtlich der Wirksamkeit der Standardherbizide vom Typ B wiederum kann man eine Abstufung in
Bezug auf den Schwerpunkt der bekämpften Pflanzen vornehmen.
So ist ein Teil der Typ-B Herbizide vorwiegend, respektive annähernd ausschliesslich, gegen Gräser
wirksam (Untergruppe Ba)), ein anderer Teil vorwiegend gegen Dikotyle und Cyperaceen
(Untergruppe Bb)), während eine weitere Gruppe sowohl gegen Gräser als auch Dikotylen/Cyperaceen
(Untergruppe Bc)) Wirksamkeit entfaltet.
72/2194
Es ergibt sich für die erfindungsgemässen Kombinationen ein optimiertes Wirkungsspektrum durch
Ergänzung und Intensivierung der herbiziden Eigenschaften der Verbindungen vom Typ A, so dass
auch Wirkungssteigerungen gegen Schadpflanzen in anderen Zielgruppen erreicht werden können.
In weiters ganz besonders zweckmässiger Ausgestaltung kennzeichnet sich die herbizid wirksame
Mischung der Erfindung dadurch, dass sie als Herbizide vom Typ B ein oder mehrere selektiv in Reis
gegen Gräser wirksame Herbizide aus der Gruppe Ba) enthält, die besteht aus
1. NBA 061 - Fentrazamid oder BAY YRC 2388
4-(2-Chlorphenyl)-5-oxo-4,5-dihydro-tetrazole-1-carboxylic acid cyclohexylethyl-amide
Tagungsband: The 1997 Brighton Crop Protection Conference, Weeds (publ. British Crop Protection
Council), S. 67-68,
2. Haloxyfop
(+/-)-2-[4-[[3-Chlor-5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propionsäure, umfassend u. a. die
Anwendungsform als Haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-methyl [(R)-Isomer],
wobei die vorgenannten Verbindungen B2) aus Pesticide Manual, 10. Aufl. 1994, S. 551-554 bekannt
sind;
3. Sethoxydim
(+/-)-(EZ)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2- enone,
Pesticide Mannual, 11. Auflage, 1997, S. 1101-1103 bekannt ist,
4. Dithiopyr
5,5'-dimethyl-2-(difluoromethyl-4-isobutyl-6-trifluoromethyl-pyrimidine-3,5- dicarbothioate
Pesticide Manual, 11. Auflage, 1997, S. 442-443,
5. Etobenzanid = MY-52
2',3'-dichloro-4-ethoxymethoxybenzanilide
Pesticide Manual, 11. Auflage, 1997, S. 492-493,
6. Clefoxidem = BAS 625 H
2-(1-(2-(4-chlorophenoxy)propoxyimino)butyl]-3-oxo-5-thione-3-ylcyclohex-1- enol
AG Chem, New Compound Review (publ. Agranova), Vol. 17, 1999, S. 26,
7. KIH 6127 = Pyriminobac-methyl
2-(4,6-Dimethoxy-2-pyrimidinyloxy)-6-(1-methoxyiminooethyl)- benzoesäuremethylester,
auch als Säure oder Natriumsalz
Pesticide Manual, 11. Aufl. 1997, S. 1071-1072,
1. Clethodim
(+/-)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]- 3-hydroxycyclohex-2enone
Pesticide Manual, 11. Auflage, 1997, S. 250-251.
Obwohl die Vertreter der Gruppe Ba) zum Teil auch relativ unterschiedliche chemische Strukturen
aufweisen, bilden sie dennoch aufgrund ihres Wirkungsspektrums sowie der Tatsache, dass sie
Synergisten für die Verbindungen des Typs A darstellen, eine zusammengehörige Untergruppe.
Von besonderem Interesse sind auch herbizide Mittel, die als Verbindung vom Typ B ein oder mehrere
selektiv in Reis gegen Dikotyle und teilweise auch Cyperaceen wirksame Verbindungen enthalten
(Untergruppe Bb)), welche aus der Gruppe ausgewählt sind, die besteht aus den Herbiziden
1. 2,4-D
(2,4-Dichlorphenoxy)essigsäure
häufig eingesetzte Formen: 2,4-D-butotyl, 2,4-D-butyl, 2,4-D- dimethylammonium, 2,4-D-diolamin,
2,4-D-iso-octyl, 2,4-D-isopropyl, 2,4-D- trolamin,
Pesticide Manual, 10. Aufl. 1994, S. 271-273,
2. MCPA
(4-Chlor-2-methylphenoxy)essigsäure,
73/2194
vorwiegend eingesetzte Formen sind u. a. MCPA-butotyl, MCPA- dimethylammonium, MCPAisoctyl, MCPA-Kalium, MCPA-Natrium,
Pesticide Manual, 10. Aufl. 1994, S. 638-640,
3. Mecoprop, Mecoprop-P
(RS)-2-(4-Chlor-o-tolyloxy)propionsäure
(R)-2-(4-Chlor-o-tolyloxy)propionsäure
Pesticide Manual, 10. Aufl. 1994, S. 646-647 und 647-648,
4. Tritosulfuron
N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]carbonyl]-2(trifluoromethylbenzenesulfonamide)
AG Chem, New Compound Review (publ. Agranova), Vol. 17, 1999, S. 24
5. Halosulfuron-methyl
methyl3-chloro-5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1- methylpyrazole-4carboxylate
Pesticide Manual, 11. Aufl. 1997, S. 657-659,
6. Dicamba
3,6-Dichlor-o-anissäure
angewendet u. a. als Dicamba-dimethylammonium, Dicamba-Kalium, Dicamba- Natrium, Dicambatrolamin,
Pesticide Manual, 10. Aufl. 1994, S. 298-300,
7. Acifluorfen
5-(2-Chlor- alpha , alpha , alpha -trifluor-p-tolyloxy)-2-nitrobenzoesäure,
auch verwendet als Acifluorfen-Natrium,
Pesticide Manual, 10. Aufl. 1994, S. 12-13,
8. Carfentrazone
ethyl (RS)-[2-chloro-3-[2-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo- 1H-1,2,4-triazol-1yl)-4-fluorophenyl]propionate
angewendet u. a. als Carfentrazone-ethyl (wie angegeben) oder auch als Säure, Pesticide Manual, 11.
Aufl. 1997, S. 191-193,
9. Bentazon
3-Isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-on-2,2-dioxid
Pesticide Manual, 10. Aufl. 1994, S. 90-91,
10. Triclopyr
[(3,5,6-trichloro-2-pyridinyl)oxy]essigsäure,
bevorzugt als Triclopyr, Triclopyr-butotyl, Triclopyr-triethylammonium, Pesticide Manual, 10. Aufl.
1994, S. 1015-1017.
In weiterhin bevorzugter Ausführungsform der vorliegenden Erfindung enthalten die herbizid
wirksamen Kombinationen als Herbizide vom Typ B ein oder mehrere selektiv in Reis vorwiegend
gegen Gräser und Dikotyle/Cyperaceen wirksame Herbizide (Untergruppe Bc)) aus der Gruppe, die
besteht aus
1. Pendimethalin
N-(1-Ethylpropyl)-2,6-dinitro-3,4-xylidin
Pesticide Manual, 10. Aufl. 1994, S. 779-780,
2. Clomazone
2-[(2-Chlorphenyl)-4,4-dimethyl-3-isoxazolidinon;
Pesticide Manual, 10. Aufl. 1994, S. 220-221,
3. KIH 2023
Natrium 2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoat,
bevorzugt ist die Form als Natriumsalz
Pesticide Manual, 10. Aufl. 1994, S. 620,
4. Oxadiargyl
5-tert-Butyl-3-[2,4-dichloro-5-(prop-2-ynyloxy)phenyl]-1,3,4-oxadiazol-2(3H)- one,
Pesticide Manual, 11. Aufl. 1997, S. 904-905,
5. AC 322,140 = Cyclosulfamuron
N-[([2-(cyclopropylcarbonyl)phenyl]amino]sulfonyl]-N1-(4,6- dimethoxypyrimidin-2-yl)harnstoff,
74/2194
Pesticide Manual, 10. Aufl. 1994, S. 8-9,
6. Azimsulfuron (DPX-A8947),
1-(4,6-dimethoxypyrimidin-2-yl)-3-[1-methyl-4-(2-methyl-2H-tetrazol-5- yl)pyrazol-5ylsulfonylharnstoff
Pesticide Mannual, 11. Auflage, 1997, S. 63-65,
7. Nicosulfuron
1-(4,6-Dimethoxypyrimidin-2-yl)-3-(3-dimethylcarbamoyl-2- pyridylsulfonyl)harnstoff
Pesticide Manual, 10. Aufl. 1994, S. 734-735,
8. Thenylchlor
2-chlor-N-(3-methoxy-2-thenyl)-2',6'-dimethylacetanilide
Pesticide Manual, 11. Auflage, 1997, S. 1182-1183,
9. Cinmethylin
(1RS, 25R, 4SR)-1,4-epoxy-p-menth-2-yl 2methylbenzylether
Pesticide Manual, 11. Auflage, 1997, S. 246-248,
10. Indanofan
(RS)-2-[2-(3-chlorophenyl)-2,3-epoxypropyl]-ethylindan-1,3-dione
Pesticide Manual, 11. Auflage, S. 715,
11. Pentoxazone
3-(4-Chloro-5-cyclopentyloxy-2-fluorphenyl)-5-isoprpyliden-1,3-oxazolidin-2,4- dion
Pesticide Manual, 11. Aufl. 1997, S. 942-943,
12. LGC-40863 = Pyribenzoxim
Benzophenone O-[2,6-bis-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzoyl]oxime
Tagesband: The 1997 Brighton Crop Protection Conference, Weeds (publ. British Crop Protection
Council) S. 39-40,
13. Oxaziclomefone = MY100
3-[1-(3,5-dichlorophenyl)-1-methylethyl]-2,3-dihydro-6-methyl-5-phenyl-4H-1,3- oxazim-4-one
Tagesband: The 1997 Brighton Crop Protection Conference, Weeds (publ. British Crop Protection
Council) S. 73-74,
14. Fluthiamid = BAY FOE 5043
4'-fluoro-N-isopropyl-2-(5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy)acetanilide
Pesticide Manual, 11. Auflage, 1997, S. 82-83,
15. Mesotrione
2-[4-(methylsulfonyl)-2-nitrobenzoyl]-1,3-cyclohexanedione
AG Chem, New Compound Review (publ. Agranova), Vol. 16, 1998, S. 51.
Bei den Verbindungen B1) bis B32) handelt es sich um beispielsweise aus der bei der jeweiligen
Verbindung angegebenen Quelle bekannte, speziell mit den Verbindungen der Gruppe A) der
Erfindung in Kombination angewandte, in Reis und in transgenem Reis selektive Herbizide. Neben der
Grundsubstanz, deren Formel regelmässig zur Verdeutlichung mit angegeben ist, wird in einigen Fällen
auch auf üblicherweise eingesetzte Abwandlungen der Grundsubstanzen hingewiesen, die ebenfalls im
Rahmen der vorliegenden Erfindung Verwendung finden können. Sofern optische aktive Formen der
Typ-B-Verbindungen üblich sind, gehören diese ebenfalls zur Erfindung, teilweise wurde auch auf
diese Formen Bezug genommen (z. B. Mecoprop und Mecoprop-P etc.).
Kombinationen aus den Wirkstoffen A + B zeigen überadditive Effekte, d. h. bei gleicher Kontrolle der
Schadpflanzen wird es durch die erfindungsgemässen herbiziden Mittel möglich, die Aufwandmenge
zu senken und/oder die Sicherheitsmarge in Reis-Kulturen zu erhöhen. Beides ist sowohl ökonomisch
als auch ökologisch sinnvoll. Die Wahl der von den Komponenten A + B einzusetzenden Mengen, das
Verhältnis der Komponenten A : B und die zeitliche Reihenfolge der Ausbringung sind dabei ebenso
wie beispielsweise die zu wählende Formulierung von einer ganzen Reihe von Faktoren abhängig.
In diesem Zusammenhang nicht unbedeutend sind u. a. die Art der Mischungspartner, das
Entwicklungsstadium der Unkräuter oder Ungräser, das zu bekämpfende Unkrautspektrum,
Umweltfaktoren, Klimabedingungen, Bodenverhältnisse etc.
In besonders bevorzugter erfindungsgemässer Ausführungsform kennzeichnen sich erfindungsgemässe
herbizide Mittel dadurch, dass sie einen synergistisch wirksamen Gehalt einer Kombination der
Verbindungen der Formel I oder deren Salze (Typ-A- Verbindungen) mit Verbindungen aus der
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Gruppe B aufweisen. Dabei ist vor allem hervorzuheben, dass selbst in Kombinationen mit
Aufwandmengen oder Gewichtsverhältnissen von A : B, bei denen ein Synergismus nicht in jedem
Falle ohne weiteres nachzuweisen ist - etwa weil die Einzelverbindungen üblicherweise in der
Kombination in sehr unterschiedlichen Aufwandmengen eingesetzt werden oder auch weil die
Kontrolle der Schadpflanzen bereits durch die Einzelverbindungen sehr gut ist - den herbiziden Mitteln
der Erfindung in der Regel eine synergistische Wirkung inhärent ist.
Die Aufwandmengen des Typ A Herbizids liegen im allgemeinen zwischen 1 und 120 g ai/ha (ai =
active ingredient, d. h. Aufwandmenge bezogen auf den aktiven Wirkstoff), bevorzugt zwischen 5 und
90 g ai/ha.
Die Gewichtsverhältnisse A : B der kombinierten Herbizide können wie erwähnt ebenso wie deren
Aufwandmengen innerhalb weiter Grenzen schwanken. Ein erfindungsgemässer Bereich der
Aufwandmengenverhältnisse (wt/wt) umfasst etwa A : B wie 1 : 20.000 bis etwa 200 : 1. Im Rahmen
der Erfindung sind Mittel bevorzugt, welche Verbindungen der Formel (oder deren Salze (Typ-AVerbindungen) und Verbindungen aus der Gruppe B in einem Gewichtsverhältnis von etwa 1 : 8000
bis 100 : 1 enthalten. Ganz besonders zweckmässig sind Mittel mit Aufwandmengenverhältnissen A :
B, die zwischen 1 : 4000 und 50 : 1 liegen. Im einzelnen ergibt sich für die verschiedenen Herbizide
der Gruppe B das folgende Bild, d. h. folgende Aufwandmengen und Gewichtsverhältnisse (A : B)
gelangen vorzugsweise zum Einsatz:
EMI14.1
EMI15.1
Die erfindungsgemässen Wirkstoffkombinationen können sowohl als Mischformulierungen der beiden
Komponenten vorliegen, die dann in üblicher Weise mit Wasser verdünnt zur Anwendung gebracht
werden, oder auch als sogenannte Tankmischungen durch gemeinsame Verdünnung der getrennt
formulierten Komponenten mit Wasser hergestellt werden.
Die Wirkstoffe der Typen A und B können auf verschiedene Art formuliert werden, je nachdem welche
biologischen und/oder chemisch-physikalischen Parameter vorgegeben sind.
Als Formulierungsmöglichkeiten kommen beispielsweise in Frage:
Spritzpulver (WP), emulgierbare Konzentrate (EC), wasserlösliche Pulver (SP), wasserlösliche
Konzentrate (SL), konzentrierte Emulsionen (EW) wie Öl-in-Wasser und Wasser-in-Öl-Emulsionen,
versprühbare Lösungen oder Emulsionen, Kapselsuspensionen (CS), Dispersionen auf Öl- oder
Wasserbasis (SC), Suspoemulsionen, Suspensionskonzentrate, Stäubemittel (DP), ölmischbare
Lösungen (OL), Beizmittel, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und
Adsorptionsgranulaten, Granulate für die Boden- oder Streuapplikation, wasserlösliche Granulate (SG),
wasserdispergierbare Granulate (WG), ULV- Formulierungen, Mikrokapseln und Wachse.
Bevorzugt sind hiervon wasserlösliche Spritzpulver (WP), wasserdispergierbare Granulate (WG),
wasseremulgierbare Granulate (EC), Suspoemulsionen (SE) und Öl-Suspensionskonzentrate (SC).
Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben
in: Winnacker-Küchler, "Chemische Technologie" Band 7, C. Hauser Verlag München, 4. Aufl. 1986;
Wade von Valkenburg, "Pesticide Formulations", Marcel Dekker N. Y., 1973; K. Martens, "Spray
Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere
Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of
Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N. J.; H. v. Olphen
"Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N. Y.; Marsden "Solvents Guide,
2nd Ed., Interscience, N. Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ.
Corp., Ridgewood N. J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co.
Inc., N. Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesellschaft,
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Stuttgart 1976; Winnacker-Küchler "Chemische Technologie", Band 7, C. Hauser Verlag München, 4.
Aufl. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen
Stoffen, Herbiziden, Insektiziden, Fungiziden, sowie Antidots, Safenern, Düngemitteln und/oder
Wachstumsregulatoren herstellen, z. B. in Form einer Fertigformulierung oder als Tankmix.
Besonders vorteilhaft werden die Herbizid-Kombinationen der Erfindung hergestellt, indem man die
Verbindungen der Formel I oder deren Salze (Typ-A-Verbindungen) mit einer oder mehreren
Verbindungen des Typs B analog einer üblichen Pflanzenschutzformulierung aus der Gruppe
enthaltend wasserlösliche Spritzpulver (WP), wasserdispergierbare Granulate (WDG),
wasseremulgierbare Granulate (WEG), Suspoemulsionen (SE) und Öl-Suspensionskonzentrate (SC)
formuliert.
Spritzpulver sind in Wasser gleichmässig dispergierbare Präparate, die neben den Wirkstoffen ausser
einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel,
Dispergiermittel), z. B. polyoxyethylierte Alkylphenole, polyoxyethylierte Fettalkohole und Fettamine,
Fettalkoholpolyglykolethersulfate, Alkansulfonate oder Alkylarylsulfonate, ligninsulfonsaures
Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalinsulfonsaures Natrium
oder auch oleylmethyltaurinsaures Natrium enthalten.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes oder der Wirkstoffe in einem
organischen Lösungsmittel, z. B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch
höhersiedenden Aromaten oder Kohlenwasserstoffen unter Zusatz von einem oder mehreren Tensiden
ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als Emulgatoren können
beispielsweise verwendet werden: Alkylarylsulfonsaure Calcium-Salze wie Ca- Dodecylbenzolsulfonat
oder nichtionische Emulgatoren wie Fettsäurepolyglykolester, Alkylarylpolyglykolether,
Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte (z. B.
Blockcopolymere), Alkylpolyether, Sorbitanfettsäureester, Polyoxyethylensorbitanfettsäureester oder
andere Polyoxyethylensorbitanester.
Stäubemittel erhält man durch Vermahlen des Wirkstoffes oder der Wirkstoffe mit fein verteilten
Stoffen, z. B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Pyrophyllit, oder Diatomeenerde.
Granulate können entweder durch Verdüsen des Wirkstoffes oder der Wirkstoffe auf
adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von
Wirkstoffkonzentraten mittels Klebemitteln, z. B. Polyvinylalkohol, polyacrylsaurem Natrium oder
auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem
Inertmaterial. Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie
Sprühtrocknung, Wirbelbettgranulierung, Tellergranulierung, Mischung mit
Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt. Auch können
geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.
Die agrochemischen Zubereitungen gemäss der Erfindung enthalten in der Regel 0,1 bis 99 Gew.-%,
insbesondere 2 bis 95 Gew.-%, ganz besonders bevorzugt 3 bis 92 Gew.-% Wirkstoffe der Typen A
und B, neben üblichen Formulierungshilfsmitteln.
Die Konzentrationen der Wirkstoffe A + B können in den Formulierungen verschieden sein. In
Spritzpulvern beträgt die Wirkstoffkonzentration z. B. etwa 10 bis 95 Gew.-%, der Rest zu 100 Gew.% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die
Wirkstoffkonzentration etwa 1 bis 85 Gew. %, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförmige
Formulierungen enthalten etwa 1 bis 25 Gew.-%, meistens 5 bis 20 Gew.-% Wirkstoffe, versprühbare
Lösungen etwa 0,2 bis 25 Gew.-%, vorzugsweise 2 bis 20 Gew.-% Wirkstoffe. Bei Granulaten wie
dispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung
flüssig oder fest vorliegt und welche Granulierhilfsmittel und Füllstoffe verwendet werden. In der
Regel liegt der Gehalt bei den in Wasser dispergierbaren Granulaten zwischen 10 und 90 Gew.-%.
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Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-,
Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösungsmittel, Füll-,
Farb- und Trägerstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert und die Viskosität
beeinflussende Mittel.
Aufgrund der relativ geringen Aufwandmenge der erfindungsgemässen Kombinationen A + B ist deren
Verträglichkeit in aller Regel schon sehr gut. Insbesondere wird durch die erfindungsgemässen
Kombinationen eine Senkung der absoluten Aufwandmenge erreicht, verglichen mit der
Einzelanwendung eines herbiziden Wirkstoffs. Um die Verträglichkeit und/oder Selektivität der
erfindungsgemässen Herbizidkombinationen gewünschtenfalls noch zu steigern ist es allerdings von
Vorteil, diese gemeinsam in Mischung oder zeitlich getrennt nacheinander zusammen mit Safenern
oder Antidots anzuwenden. Als Safener oder Antidots für die erfindungsgemässen Kombinationen in
Frage kommenden Verbindungen sind z. B. aus EP-A-333 131 (ZA-89/1960), EP-A-269 806 (US-A4,891,057), EP-A-346 620 (AU-A-89/34951) und den internationalen Patentanmeldungen PCT/EP
90/01966 (WO-91/08202) und PCT/EP 90/02020 (WO-91/078474) und dort zitierter Literatur bekannt
oder können nach den dort beschriebenen Verfahren hergestellt werden. Weitere geeignete Safener
kennt man aus EP-A-94 349 (US-A-4,902,304), EP-A-191 736 (US-A-4,881,966) und EP-A-0 492 366
und der dort zitierten Literatur.
Günstigenfalls kennzeichnen sich die herbiziden Mischungen oder Anwendungskombinationen der
Erfindung durch einen zusätzlichen Gehalt an C) einer oder mehrerer Verbindungen die als Safener
wirken.
Besonders bevorzugte Antidots oder Safener oder Gruppen von Verbindungen die sich als Safener oder
Antidots für die vorbeschriebenen Produktkombinationen der Erfindung bewährt haben sind unter
anderem:
a) Verbindungen vom Typ der Dichlorphenylpyrazolin-3-carbonsäure, vorzugsweise Verbindungen
wie 1-(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin- 3-carbonsäureethylester
(Verbindung C1-1) und verwandte Verbindungen, wie sie in der internationalen Anmeldung WO
91/07874 (PCT/EP 90/02020) beschrieben sind;
b) Derivate der Dichlorphenylpyrazolcarbonsäure, vorzugsweise Verbindungen wie 1-(2,4Dichlorphenyl)-5-methyl-pyrazol-3-carbonsäureethylester (Verbindung C1-2), 1-(2,4-Dichlorphenyl)5-isopropyl-pyrazol-3-carbonsäureethylester (Verbindung C1-3), 1-(2,4-Dichlorphenyl)-5-(1,1dimethyl-ethyl)pyrazol-3- carbonsäureethylester (Verbindung C1-4), 1-(2,4-Dichlorphenyl)-5phenylpyrazol-3-carbonsäureethylester (Verbindung C1-5) und verwandte Verbindungen, wie sie in
EP-A-0 333 131 und EP-A-0 269 806 beschrieben sind;
c) Verbindungen vom Typ der Triazolcarbonsäuren, vorzugsweise Verbindungen wie 1-(2,4Dichlorphenyl)-5-trichlormethyl-(1H)-1,2,4-triazol-3- carbonsäureethylester (Verbindung C1-6,
Fenchlorazol) und verwandte Verbindungen (siehe EP-A-0 174 562 und EP-A-0 346 620);
d) Verbindungen vom Typ der Dichlorbenzyl-2-isoxazolin-3-carbonsäure, Verbindungen vom Typ
der 5-Benzyl- oder 5-Phenyl-2-isoxazolin-3-carbonsäure, vorzugsweise Verbindungen wie 5-(2,4Dichlorbenzyl)-2-isoxazolin-3- carbonsäureethylester (Verbindung C1-7) oder 5-Phenyl-2-isoxazolin3- carbonsäureethylester (Verbindung C1-8) und verwandte Verbindungen wie sie in der
internationalen Patentanmeldung WO 91/08202 (PCT/EP 90/01966) beschrieben sind;
e) Verbindungen vom Typ der 8-Chinolinoxyessigsäure, vorzugsweise Verbindungen wie
(5-Chlor-8-chinolinoxy)-essigsäure-(1-methyl-hex-1-yl)-ester (C2-1),
(5-Chlor-8-chinolinoxy)-essigsäure-(1,3-dimethyl-but-1-yl)-ester (C2-2),
(5-Chlor-8-chinolinoxy)-essigsäure-4-allyl-oxy-butylester (C2-3),
(5-Chlor-8-chinolinoxy)-essigsäure-1-allyl-oxy-prop-2-ylester (C2-4),
(5-Chlor-8-chinolinoxy)-essigsäureethylester (C2-5),
(5-Chlor-8-chinolinoxy)-essigsäuremethylester (C2-6),
(5-Chlor-8-chinolinoxy)-essigsäureallylester (C2-7),
(5-Chlor-8-chinolinoxy)-essigsäure-2-(2-prpyliden-iminoxy)-1-ethylester (C2-8),
(5-Chlor-8-chinolinoxy)-essigsäure-2-oxo-prop-1-ylester (C2-9)
und verwandte Verbindungen wie sie in EP-A-0 086 750, EP-A-0 094 349 und EP-A-0 191 736 oder
EP-A-0 492 366 beschrieben sind;
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f) Verbindungen vom Typ der (5-Chlor-8-chinolinoxy)-malonsäure, vorzugsweise Verbindungen wie
(5-Chlor-8-chinolinoxy)-malonsäurediethylester, (5-Chlor-8- chinolinoxy)-malonsäurediallyester, (5Chlor-8-chinolinoxy)- malonsäuremethylethylester und verwandte Verbindungen wie sie in der
deutschen Patentanmeldung EP-A-0 582 198 beschrieben und vorgeschlagen worden sind;
g) Wirkstoffe vom Typ der Phenoxyessig- bzw. -propionsäurederivate bzw. der aromatischen
Carbonsäuren, wie z. B. 2,4-Dichlorphenoxyessigsäure(ester) (2,4-D), 4-Chlor-2-methyl-phenoxypropionester (Mecoprop), MCPA oder 3,6-Dichlor- 2-methoxy-benzoesäure(ester) (Dicamba).
h) Verbindungen vom Typ der 5,5-Diphenyl-2-isoxazolin-3-carbonsäure, vorzugsweise 5,5Diphenyl-2-isoxazolin-3-carbonsäureethylester (C3-1).
i) Verbindungen, die als Safener für Reis bekannt sind wie Fenclorim (= 4,6- Dichlor-2phenylpyrimidin, Pesticide Manual, 11. Auflage, 1997, S. 511-512), Dimepiperate (= Piperidin-1thiocarbonsäure-S-1-methyl-1-phenylethylester, Pesticide Manual, 11. Auflage, 1997, S. 404-405),
Daimuron (= 1-(1-Methyl-1 - phenylethyl)-3-p-tolyl-harnstoff, Pesticide Manual, 11. Auflage, 1997, S.
330), Cumyluron (= 3-(2-Chlorphenylmethyl)-1-(1-methyl-1-phenylethyl)-harnstoff, JP-A-60/087254),
Methoxyphenon (= 3,3'-Dimethyl-4-methoxy-benzophenon, CSB (= 1-Brom-4-(chlormethylsulfonyl)benzol, CAS-Reg. Nr. 54091-06-4)
Die genannten Verbindungen sind ausserdem zumindest teilweise in der EP-A-0 640 587 beschrieben,
auf die hiermit zu Offenbarungszwecken Bezug genommen wird.
a) Eine weitere wichtige Gruppe von als Safenern und Antidoten geeignete Verbindungen ist aus der
WO 95/07897 bekannt.
Die Safener (Antidote) der vorstehenden Gruppen a) bis j) reduzieren oder unterbinden phytotoxische
Effekte, die beim Einsatz der Produktkombinationen gemäss der Erfindung in Nutzpflanzenkulturen
auftreten können, ohne die Wirksamkeit der Herbizide gegen Schadpflanzen zu beeinträchtigen.
Hierdurch kann das Einsatzgebiet der erfindungsgemässen Mischungen von Herbiziden ganz erheblich
erweitert werden und insbesondere ist durch die Verwendung von Safenem der Einsatz von
Kombinationen möglich, die bislang nur beschränkt oder mit nicht ausreichendem Erfolg eingesetzt
werden konnten, d. h. von Kombinationen, die ohne Safener in niedrigen Dosierungen mit wenig
Breitenwirkung zu nicht ausreichender Kontrolle der Schadpflanzen führten.
Die herbiziden Mischungen gemäss der Erfindung und die erwähnten Safener können zusammen (als
fertige Formulierung oder im Tankmix-Verfahren) oder in beliebiger Reihenfolge nacheinander
ausgebracht werden. Das Gewichtsverhältnis Safener : Herbizid (Gruppe A, i. e. Verbindung der
Formel I und ihre Salze) kann innerhalb weiter Grenzen variieren und ist vorzugsweise im Bereich von
1 : 100 bis 100 : 1, insbesondere von 1 : 100 bis 50 : 1. Die jeweils optimalen Mengen an Herbiziden
(Typ-A- und Typ-B-Verbindungen) und Safener sind üblicherweise vom Typ der verwendeten
Herbizidmischung und/oder vom verwendeten Safener sowie von der Art des zu behandelnden
Pflanzenbestandes abhängig.
Die Safener vom Typ C) können je nach ihren Eigenschaften zur Vorbehandlung des Saatgutes der
Kulturpflanze (Beizung der Samen) verwendet werden oder vor der Saat in die Saatfurchen eingebracht
oder zusammen mit der Herbizidmischung vor oder nach dem Auflaufen der Pflanzen angewendet
werden.
Vorauflaufbehandlung schliesst sowohl die Behandlung der Anbaufläche vor der Aussaat als auch die
Behandlung der angesäten, aber noch nicht bewachsenen Anbauflächen ein. Bevorzugt ist die
gemeinsame Anwendung mit der Herbizidmischung. Hierzu können Tankmischungen oder
Fertigformulierungen eingesetzt werden.
Die benötigten Aufwandmengen der Safener können je nach Indikation und verwendetem Herbizid
innerhalb weiter Grenzen schwanken und sind in der Regel im Bereich von 0,001 bis 1 kg,
vorzugsweise 0,005 bis 0,2 kg Wirkstoff je Hektar. Besonders günstige und in Reis hervorragend
einsatztaugliche herbizide Mittel ergeben sich im Rahmen der Erfindung, wenn Herbizide aus der
Gruppe A) in Kombination mit Typ-B-Verbindungen und dem Safener C2-1 und/oder C3-1 eingesetzt
werden.
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Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen gegebenenfalls in
üblicher Weise verdünnt, z. B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und
wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw.
Streugranulate, sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr
mit weiteren inerten Stoffen verdünnt.
Gegenstand der Erfindung ist auch ein Verfahren zur Bekämpfung von unerwünschten Pflanzen, das
dadurch gekennzeichnet ist, dass man auf diese oder die Anbaufläche eine herbizid wirksame Menge
einer erfindungsgemässen Kombination von Wirkstoffen A + B appliziert. Die Wirkstoffe können auf
die Pflanzen, Pflanzenteile, Pflanzensamen oder die Anbaufläche ausgebracht werden.
In bevorzugter Verfahrensvariante werden die Verbindungen der Formel (I) oder deren Salze (Typ-AVerbindungen) in Aufwandmengen von 1 bis 120 g ai/ha, bevorzugt von 5 bis 90 g ai/ha, ganz
besonders bevorzugt zwischen 6 und 60 g ai/ha, ausgebracht, während die Aufwandmengen für die
Verbindungen vom Typ B im allgemeinen 1 bis 5000 g ai/ha betragen. Bevorzugt ist die Ausbringung
der Wirkstoffe der Typen A und B gleichzeitig oder zeitlich getrennt im Gewichtsverhältnis 1 : 20.000
bis 200 : 1. Weiterhin besonders bevorzugt ist die gemeinsame Ausbringung der Wirkstoffe in Form
von Tankmischungen, wobei die optimal formulierten konzentrierten Formulierungen der
Einzelwirkstoffe gemeinsam im Tank mit Wasser gemischt und die erhaltene Spritzbrühe ausgebracht
wird.
Da die Kulturverträglichkeit der erfindungsgemässen Kombinationen bei gleichzeitig sehr hoher
Kontrolle der Schadpflanzen ausgesprochen gut ist, können diese als selektiv angesehen werden. In
bevorzugter Verfahrensabwandlung werden herbizide Mittel mit den erfindungsgemässen
Wirkstoffkombinationen daher zur selektiven Bekämpfung unerwünschter Pflanzen eingesetzt.
Besonders günstig gestaltet sich das Verfahren zur selektiven Bekämpfung von Schadpflanzen, wenn
die herbiziden Mittel der Erfindung in Reis eingesetzt werden.
Die Kombinationspartner vom Typ A bekämpfen alleine angewendet in Reis ein limitiertes Spektrum
an annuellen und perennierenden Unkräutern und Cyperaceen. Das Wirkungsspektrum der Typ A
Verbindungen wird durch die Kombination mit den in der Erfindung genannten Typ-B-Partnern jedoch
noch deutlich weiter verbessert, wobei einzelne Artengruppen zusätzlich erfasst werden. Je nach Natur
des Kombinationspartners B können die erfindungsgemässen herbiziden Kombinationen vorteilhaft zur
Bekämpfung von unerwünschten Pflanzen auch in transgenen Reis- Kulturen eingesetzt werden.
Transgene Kulturen sind solche, in denen die Pflanzen durch genetische Manipulation gegen Herbizide
oder Pestizide resistent gemacht werden. Dergestalt veränderte Reis-Kulturpflanzen lassen dann einen
selektiven Einsatz zu.
Insgesamt betrifft die Erfindung damit auch die Verwendung von herbiziden Mitteln, enthaltend
A) eine oder mehrere herbizide Wirkstoffe aus der Gruppe der substituierten
Phenoxysulfonylharnstoffe der Formel I und deren Salze
EMI25.1
und
A) eine oder mehrere herbizid wirksame Verbindungen aus der Gruppe der Verbindungen, welche
besteht aus
1. selektiv in Reis vorwiegend gegen Gräser wirksamen Herbiziden ausgewählt aus der Gruppe
bestehend aus
Fentrazamid (NBA 061), Haloxyfop, Sethoxydim, Dithiopyr, Etobenzanid (MY-52), Clefoxidim, KIH
6127 und Clethodim,
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2. selektiv in Reis vorwiegend gegen dikotyle Schadpflanzen und Cyperaceen wirksamen Herbiziden,
ausgewählt aus der Gruppe, bestehend aus 2,4-D, MCPA, Mecoprop, Mecoprop-P, Tritosulfuron,
Halosulfuron-methyl, Dicamba, Acifluorfen, Carfentrazone, Bentazon und Triclopyr,
3. selektiv in Reis, vorwiegend gegen Gräser und dikotyle Schadpflanzen sowie Cyperaceen
wirksamen Herbiziden, ausgewählt aus der Gruppe bestehend aus Pendimethalin, Clomazone, KIH
2023, Oxadiargyl, Cycloslulfamuron (AC 322, 140), Azimsulfuron (DPX-A-8947), Nicosulfuron,
Thenylchlor, Cinmethylin, Indanofan, Pentoxazone, Pyribenzoxim, Oxaziclomefone (MY-100),
Fluthiamid und Mesotrione,
zur Bekämpfung unerwünschter Schadpflanzen, vorzugsweise in Pflanzenkulturen wie Reiskulturen.
Das Gewichtsverhältnis von Verbindungen der Formel I oder deren Salze (Typ-A-Verbindungen) und
Verbindungen aus der Gruppe B liegt im allgemeinen im Bereich von 1 : 20.000 bis 200 : 1, bevorzugt
1 : 8000 bis 100 : 1, besonders bevorzugt 1 : 4000 bis 50 : 1.
Eine bevorzugte Verwendung betrifft den Einsatz von Kombinationen, die Gehalte von A- und BVerbindungen in einer synergistisch wirksamen Menge aufweisen.
Ausserdem bevorzugt ist die Verwendung von Mischungen mit Kombinationen aus A) und Ba) zur
selektiven Bekämpfung von Gräsern in Reis. Bevorzugt ist auch die Verwendung von Mischungen mit
Kombinationen aus A) und Bb) zur selektiven Bekämpfung von Dikotylen und Cyperaceen in Reis.
Weiters bevorzugt ist die Verwendung von Mischungen mit Kombinationen aus A) und Bc) zur
selektiven Bekämpfung von Gräsern, Dikotylen und Cyperaceen in Reis.
Zur Erfindung gehören auch Mischungen von einem oder mehreren Kombinationspartnern A),
vorzugsweise nur A1 (Ethoxysulfuron), und einem oder mehreren Kombinationspartnern B),
gegebenenfalls in Kombination mit einem oder mehreren Safenern C).
Als bevorzugte Beispiele für die erfindungsgemässen Wirkstoffmischungen seien folgende
Kombinationen von A1 (Ethoxysulfuron) mit Mischungspartnern B1-B32 genannt, ohne dass dadurch
eine Einschränkung nur auf die explizit genannten Kombinationen erfolgen soll:
A1+B1: Fentrazamid, A1+B2: Haloxyfop, A1+B3: Sethoxydim, A1+B4: Dithiopyr, A1+B5:
Etobenzanid, A1+B6: Clefoxidim, A1+B7: KIH 6127, A1+B7a: Clethodim, A1+B8: 2,4-D, A1+B9:
MCPA, A1+B10: Mecoprop Mecoprop-P, A1+B11: Tritosulfuron, A1+812: Halosulfuron-methyl,
A1+B13: Dicamba, A1+B14: Acifluorfen, A1+815: Carfentrazone, A1+B16: Bentazon, A1+B17:
Triclopyr, A1+B18: Pendimethalin, A1+B19: Clomacone, A1+B20: KIH 2023, A1+B21: Oxadiargyl,
A1+B22: Cyclosulfamuron, A1+B23: Azimsulfuron, A1+B24: Nicosulfuron, A1+B25: Thenylchlor,
A1+B26: Sinmethylin, A1+B27: Indanofan, A1+B28: Pentoxazone, A1+B29: Pyribenzoxim, A1+B30:
Oxaziclomefone, A1+B31: Fluthiamid, A1+B32: Mesotrione.
Die vorbeschriebenen Mischungen können zweckmässig zusammen mit einem oder mehreren Safenern
eingesetzt werden. Beispiele für bevorzugte Safener sind (5-Chlor-8-chinolinoxy)-essigsäure-(1methyl-hex-1-yl)-ester (C2-1)und 5,5- Diphenyl-2-isoxazolin-3-carbonsäuremethylester (C3-1).
In den aufgeführten Kombinationen bietet der Einsatz eines Safeners erhebliche Vorteile, da hierdurch
mögliche Schäden an der Kulturpflanze wie Reis, die durch Sulfonylharnstoffderivate oder andere
herbizid wirksame Wirkstoffe entstehen können, verringert werden.
Ferner können die Safener C2-1 und C3-1 vorteilhaft durch eine oder mehrere Verbindungen der
folgenden Gruppe von Safenern ersetzt oder zusammen mit einer oder mehreren der folgenden
Verbindungen eingesetzt werden:
- 1-(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin-3- carbonsäureethylester (C1-1),
- 1-(2,4-Dichlorphenyl)-5-methyl-pyrazol-3-carbonsäureethylester (C1-2),
- 1-(2,4-Dichlorphenyl)-5-isopropyl-pyrazol-3-carbonsäureethylester (C1-3),
- 1-(2,4-Dichlorphenyl)-5-(1,1-dimethyl-ethyl)pyrazol-3-carbonsäureethylester (C1-4),
- 1-(2,4-Dichlorphenyl)-5-phenylpyrazol-3-carbonsäureethylester (C1-5),
- 1-(2,4-Dichlorphenyl)-5-trichlormethyl-(1 H)-1,2,4-triazol-3-carbonsäureethylester (C1-6,
Fenchlorazol),
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- 5-(2,4-Dichlorbenzyl)-2-isoxazolin-3-carbonsäureethylester (C1-7),
- 5-Phenyl-2-isoxazolin-3-carbonsäureethylester (C1-8),
- 5-Chlor-8-chinolinoxy)-essigsäure-(1,3-dimethyl-but-1-yl)-ester (C2-2),
- (5-Chlor-8-chinolinoxy)-essigsäure-4-allyl-oxy-butylester (C2-3),
- (5-Chlor-8-chinolinoxy)-essigsäure-1-allyl-oxy-prop-2-ylester (C2-4),
- (5-Chlor-8-chinolinoxy)-essigsäureethylester (C2-5),
- (5-Chlor-8-chinolinoxy)-essigsäuremethylester (C2-6),
- (5-Chlor-8-chinolinoxy)-essigsäureallylester (C2-7),
- (5-Chlor-8-chinolinoxy)-essigsäure-2-(2-propyliden-iminoxy)-1-ethylester (C2-8),
- (5-Chlor-8-chinolinoxy)-essigsäure-2-oxo-prop-1-ylester (C2-9),
- (5-Chlor-8-chinolinoxy)-malonsäurediethylester,
- (5-Chlor-8-chinolinoxy)-malonsäurediallyester,
- (5-Chlor-8-chinolinoxy)-malonsäuremethylethylester,
- 2,4-Dichlorphenoxyessigsäure(ester) (2,4-D),
- 4-Chlor-2-methyl-phenoxy-propionester (Mecoprop),
- MCPA,
- 3,6-Dichlor-2-methoxy-benzoesäure(ester) (Dicamba).
Daneben können in den Mischungen der Erfindung zur Abrundung der Eigenschaften, meist in
untergeordneten Mengen, zusätzlich eines, zwei oder mehrere der folgenden Pestizide (Herbizide,
Insektizide, Fungizide usw.) enthalten sein:
abamectin, AC94377, AC263222, AC3-103630, acephate, aclonifen, acrinathrin, acypectas, AKH7088, alachlor, alanycarb, aldicarb, aldoxycarb, allethrin, alloxydim, alpha-cypermethrin, ametryn,
amidosulfuron, amitraz, amitrole, ammonium sulfamate, ancymidol, anilazine, anthraquinone, asulam,
atrazine, azaconazole, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azocyclotin,
BAS480F, BAS490F, benalaxyl, benazolin, bendiocarb, benfluralin, benfuracarb, benomyl, benoxacor,
bensulide, bensultap, benzoximate, beta-cyfluthrin, beta- cypermethrin, bifenox, bifenthrin, bilanafos,
bioallethrin, bioallethrin (S- cyclopentenyl isomer), bioresmethrin, biphenyl, bitertanol, blasticidin-S,
borax, Bordeaux mixture, brodifacoum, bromacil, bromadiolone, bromethalin, bromofenoxim,
bromopropylate, bromoxynil, bromuconazole, bronopol, bupirimate, buprofezin, butamifos,
butocarboxim, butoxycarboxim, butralin, butylamine, butylate, cadusafos, calcium polysulfide,
captafol, captan, carbaryl, carbendazim, carbetamide, carbofuran, carbosulfan, carboxin, cartap,
CGA50439, CGA183893, CGA219417, chinomethionat, chlomethoxyfen, chloralose, chloramben,
chlorbromuron, chlorbufam, chlordane, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlorflurenol,
chloridazon, chlormephos, chlormequat, chlornitrofen, chloracetic acid, chlorobenzilate, chloroneb,
chlorophacinone, chloropicrin, chlorothalonil, chlorotoluron, chlorophonium, chlorpropham,
chlorpyrifos, chlorpyrifos-methyl, chlorsulfuron, chlorthal, chlorthiamid, chlozolinate, CL26691,
CL304415, clodinafop, cloethocarb, clofentezine, clomeprop, cloprop, clopyralid, cloquintocet,
cloxyfonac, copper hydroxide, copper oxychloride, copper sulfate, coumaphos, coumatetralyl, 4-CPA,
cuprous oxide, cyanamide, cyanazine, cyanophos, cycloate, cycloprothrin, cyfluthrin, beta-cyfluthrin,
cyhalothrin, lambda- cyhalothrin, cyhexatin, cymoxanil, cypermethrin, alpha-cypermethrin, betacypermethrin, zeta-cypermethrin, cyphenotrin, cyproconazole, cyromazine, daminozide, dazomet, 2,4DB, DCIP, debacarb, decan-1-ol, deltamethrin, demeton- S-methyl, desmedipham, desmetryn,
diafenthiuron, diazinon, dichlobenil, dichlofluanid, dichlone, dichlormid, dichlorophen, 1,3dichloropropene, dichlorprop, dichlorprop-P, dichlorvos, diclofop, diclomezine, dicloran, diclofol,
dicrotophos, dienochlor, diethofencarb, diethyltoluamide, difenacoum, diefenoconazole, difenzoquat,
difethialone, diflubenzuron, diflufenican, dikegulac, dimefuron, dimethachlor, dimethametryn,
dimethenamid, dimethipin, dimethirimol, dimethoate, dimethomorph, dimethyl phthalate,
dimethylvinphos, diniconazole, dinitramine, dinocap, dinoterb, diofenolan, dioxabenzofos,
diphacinone, diphenamid, diphenylamine, dipropyl pyridine-2,5-dicarboxylate, diquat, disulfuton,
dithianon, diuron, DKA-24, DNOC, dodemorph, dodine, edifenphos, empenthrin, endosulfan, endothal,
ENT8184, EPN, EPTC, ergocalciferol, esfenvalerate, esprocarb, ET751, ethalfluralin, ethametsulfuronmethyl, ethephon, ethiofencarb, ethion, ethirimol, ethofumesate, ethoprophos, ethoxyquin,
ethychlozate, ethylene dibromide, ethylene dichloride, etofenprox, etridiazole, F8426, famphur,
fenamiphos, fenarimol, fenazaquin, fenbuconazole, fenbutatin oxide, fenchlorazole, fenclorim,
fenfuram, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpiclonil, fenpropathrin, fenpropidin,
fenpropimorph, fenpyroximate, fenthion, fentin, fenuron, fenvalerate, ferbam, ferbam, ferimzone,
fipronil, flamprop, flamprop-M, flazasulfuron, flocoumafen, fluazifop, fluazifop-P, fluazinam,
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fluazuron, fluchloralin, flucycloxuron, flucythrinate, fludioxonil, flufenoxuron, flumetralin,
flumetsulam, flumiclorac, flumioxazin, fluometuron, fluoroacetamide, fluoroglycofen, fluoromide,
flupoxam, flupropanate, fluquinconazole, flurazole, flurenol, fluridone, flurochloridone, fluroxypyr,
flurprimidol, flurtamone, flusilazole, flusulfamide, flutolanil, flutriafol, taufluvalinate, fluxofenim,
folpet, fomesafen, fonofos, forchlorfenuron, formetanate, formothion, fosamine, fosetyl, fosthiazate,
fuberidazole, furalaxyl, furathiocarb, furilazole, gibberellic acid, gibberellin A4 gibberellin A7,
guazatine, GY-81, halfenprox, halosulfuron, HC-252, gamma-HCH, heptachlor, heptenophos,
hexachlorobenzene, hexaconazole, hexaflumuron, hexazinone, hexythiazox, hydramethylnon, 2hydrazinoethanol, hydroprene, 8-hydroxyquinoline sulfate, hymexazol, ICIA0858, ICIA5504, imazalil,
imazamethabenz, imazapyr, imazaquin, imazethapyr, imibenconazole, imidacloprid, iminoctadien,
inabenfide, indol-3- ylacetic acid, 4-indol-3-ylbutyric acid, ipconazole, iprobenfos, iprodione, isazofos,
isofenphos, isopamphos, isoprocarb, isoprothiolane, isoproturon, isouron, isoxaben, isoxapyrifop,
isoxathion, kasugamycin, KIH 9201, lactofen, lambda-cyhalothrin, lenacil, linuron, lufenuron,
malathion, maleic hydrazide, mancopper, mancozeb, maneb, MCPA-thioethyl, MCPB, mecarbam,
mefluidide, mepanipyrim, mephosfolan, mepiquat, mepronil, metalaxyl, metaldehyde, metam,
metamitron, metazachlor, metconazole, methabenzthiazuron, methacrifos, methamidophos,
methasulfocarb, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methylarsonic acid,
methyl bromide, methyldymron, methyl isothiocyanate, metiram, metobenzuron, metobromuron,
metolcarb, metoxuron, metribuzin, mevinphos, milbemectin, MK-243, monocrotophos, monolinuron,
muscalure, myclobutanil, nabam, naled, naphthenic acid, 2-(1-naphthyl)acetamide, (1-naphthyl)acetic
acid, (2-naphthoyloxy)acetic acid, napropamide, naptalam, natamycin, NC-330, neburon, NI-25, nickel
bis(dimethyldithiocarbamate), niclosamide, nicotine, nitenpyram, nithiazine, nitrapyrin, nitrothalisopropyl, norflurazon, nuarimol, octhilinone, 2- (octylthio)ethanol, ofurace, omethoate, orbencarb,
oryzalin, oxabetrinil, oxadixyl, oxamyl, oxine-copper, oxolinic acid, oxycarboxin, oxydemeton-methyl,
paclobutrazol, paraquat, parathion, parathion-methyl, pebulate, pefurazoate, penconazole, pencycuron,
pentachlorophenol, pentanochlor, permethrin, phenmedipham, phenothrin, phenthoate, 2-phenylphenol,
N-phenylphthalamic acid, phorate, phosalone, phosdiphen, phosmet, phosphamidon, phoxim,
phthalide, pindone, piperalin, piperonyl butoxide, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl,
polyoxins, prallethrin, pretilachlor, primisulfuron, probenazole, prochloraz, procymidone, prodiamine,
profenofos, prohexadione, prometon, propachlor, propamocarb, propaphos, propaquizafop, propargite,
propazine, propetamphos, propham, propiconazole, propineb, propisochlor, propoxur, propyzamide,
prosulfocarb, prosulfuron, prothiofos, pymetrozine, pyraclofos, pyrethrins, pyridaben, pyridaphenthion,
pyridate, pyrifenox, pyrimethanil, pyrimidifen, pyriproxyfen, pyrithiobac-sodium, pyroquilon,
quinalophos, quinmerac, quinoclamine, quintozene, quizalofop, quizalofop-P, resmethrin, rimsulfuron,
rotenone, RU15525, S421, siduron, silafluofen, smazine, sodium fluoroacetate, SSF-109, SSI-121,
streptomycin, strychnine, sulcofuron, sulfentrazone, sulfluramid, sulfometuron, sulfotep, sulfur,
sulprofos, tar oils, 2,3,6-TBA, TCA-sodium, tebuconazole, tebufenozide, tebufenpyrad, tebutam,
tebuthiuron, tecloftalam, tecnazene, teflubenzuron, tefluthrin, temephos, terbacil, terbufos, terbumeton,
terbuthylazine, terbutryn, tetrachlorvinphos, tetraconazole, tetradifon, tetramethrin, tetramethrin[(1R)isomers], thiabendazole, thidiazuron, thifensulfuron, thifluzamide, thiocyclam, thiodicarb, thiofanox,
thiometon, thiophanate-methyl, thiram, tiocarbazil, tolclofos-methyl, tolylfluanid, tralkoxydim,
trafomethrin, transfluthrin, triadimefon, triadimenol, tri-allate, triazamate, triazophos, triazoxide,
tribenuron, S,S,S-tributyl phosphorotrithioate, trichlorfen, tricyclazole, tridemorph, trietazine,
triflumizole, triflumuron, trifluralin, triflusulfuron, triforme, trimethacarb, trinexapac, triticonazole,
uniconazole, validamycin, vamidothion, vernolate, vinclozolin, warfarin, XDE537, XMC, xylylcarb,
zineb und ziram.
Damit ergeben sich zahlreiche Möglichkeiten mehrere Wirkstoffe miteinander zu kombinieren und
gemeinsam zur Unkrautbekämpfung in Reiskulturen einzusetzen, ohne vom Gedanken der Erfindung
abzuweichen.
Die erfindungsgemässen herbiziden Mittel (Kombinationen) weisen eine ausgezeichnete herbizide
Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler Schadpflanzen
auf. Auch schwer bekämpfbare perennierende Unkräuter, die aus Samen oder Rhizomen,
Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die Wirkstoffkombinationen gut
erfasst. Dabei ist es gleichgültig, ob die Substanzen im Vorsaat-, Vorauflauf- oder
Nachauflaufverfahren ausgebracht werden.
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Auf der Seite der monokotylen Unkrautarten werden zum Beispiel Echinochloa sowie Cyperusarten
aus der annuellen Gruppe auf seiten der perennierenden Spezies ausdauernde Cyperusarten gut erfasst.
Die unter spezifischen Kulturbedingungen in Reis vorkommenden Unkräuter, wie z. B. Sagittaria,
Alisma, Rotala, Monochoria, Eleocharis, Scirpus, Cyperus etc., werden von den erfindungsgemässen
Wirkstoffkombinationen hervorragend bekämpft.
Werden die erfindungsgemässen herbiziden Mittel vor dem Keimen appliziert, so wird entweder das
Auflaufen der Unkrautkeimlinge vollständig verhindert, oder die Unkräuter wachsen bis zum
Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schliesslich nach Ablauf
von drei bis vier Wochen vollkommen ab.
Bei Applikation der Wirkstoffkombination der Erfindung auf die grünen Pflanzenteile im
Nachauflaufverfahren tritt ebenfalls rasch nach der Behandlung ein drastischer Wachstumsstopp ein.
Die Unkrautpflanzen bleiben in dem zum Applikationszeitpunkt vorhanden Wachstumsstadium stehen
oder sterben nach einer gewissen Zeit mehr oder weniger schnell ab, so dass auf diese Weise eine für
Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig durch den Einsatz der neuen
erfindungsgemässen Mittel verhindert werden kann und auch damit verbundene quantitative und
qualitative Ertragseinbussen.
Obgleich die erfindungsgemässen Mittel eine ausgezeichnete herbizide Aktivität gegenüber mono- und
dikotylen Unkräutern aufweisen, wird die Kulturpflanze nur unwesentlich oder gar nicht geschädigt.
Die Mittel eignen sich aus diesem Grund besonders in Reis sehr gut zur selektiven Bekämpfung von
unerwünschtem Pflanzenwuchs.
Im speziellen gehören zu den zu bekämpfenden Schadpflanzen wie bereits ausgeführt vor allem Gräser,
Dikotyle und/oder ansonsten schwer bekämpfbare Cyperaceen. Zu bevorzugt mit den
erfindungsgemässen Kombinationen aus Typ A- und Typ B-Verbindungen zu bekämpfenden
Schadpflanzen gehören unter anderem Echinochloa colonum, Echinochloa chinesis, Echinochloa crus
galli, Leptochloa chin./fil., Paspalum dis., Brachiaria platyphylla, Digitaria spp., lschaemum, Leersia
hexandra, Oryza sativa (Red rice), Cenchrus echinatus, Rottboellia exaltata, Leersia und dergleichen
auf der Seite der Gräser, Monochoria vag., Potamogeton dis., Rotala indica, Marsilea crenata,
Ludwigia ad., Salvina mol., Ipomoea, Sesbania ex., Heteranthera, Commelinia, Butomus,
Aeschynomene, Alisma plantago, Eclypta, Murdania, Xanthium, Alteranthera spp., Spenodea zey.,
Sagittaria, Iuncus spp., Polygonum, Ammania ind. auf der Seite der Unkräuter und Cyperus diff.,
Cyperus iria, Fimbristylis litt., Cyperus ferax, Cyperus esculentes auf der Seite der annuellen
Cyperaceen sowie Eleocharis spp., Scirpus spp., Scirpus mucronatus und Cyperus rotundus auf Seiten
der perennierenden Cyperaceen.
Zusammenfassend kann gesagt werden, dass bei gemeinsamer Anwendung von Sulfonylharnstoffen
der Formel I und/oder ihren Salzen mit einem oder mehreren Wirkstoffen aus der Gruppe B
überadditive (= synergistische) Effekte auftreten. Dabei ist die Wirkung in den Kombinationen stärker
als die der eingesetzten Einzelprodukte bei alleiniger Anwendung.
Diese Effekte erlauben unter anderem eine Reduzierung der Aufwandmenge, die Bekämpfung eines
breiteren Spektrums von Unkräutern und Ungräsern, die Schliessung von Wirkungslücken, auch
hinsichtlich resistenter Arten, eine schnellere und sicherere Wirkung, eine längere Dauerwirkung, eine
komplette Kontrolle der Schadpflanzen mit nur einer oder wenigen Applikationen, und eine
Ausweitung des Anwendungszeitraumes der Wirkstoffe in Kombination.
Die genannten Eigenschaften sind in der praktischen Unkrautbekämpfung gefordert, um
landwirtschaftliche Kulturen von unerwünschten Konkurrenzpflanzen freizuhalten und damit die
Erträge qualitativ und quantitativ zu sichern und/oder zu erhöhen. Der technische Standard wird durch
die erfindungsgemässen Kombinationen bezüglich der beschriebenen Eigenschaften deutlich
übertroffen.
Darüberhinaus gestatten die erfindungsgemässen Kombinationen in hervorragender Weise die
Bekämpfung ansonsten resistenter Schadpflanzen.
84/2194
Folgende Beispiele dienen zu Erläuterung der Erfindung ohne limitierenden Charakter zu haben:
1. Formulierungsbeispiele
a) Ein Stäubemittel wird erhalten, indem man 10 Gew.-Teile einer erfindungsgemässen
Wirkstoffkombination und 90 Gew.-Teile Talkum als Inertstoff mischt und in einer Schlagmühle
zerkleinert.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 Gew.-Teile
Wirkstoffe A + B, 64 Gew.-Teile kaolinhaltigen Quarz als Inertstoff, 10 Gew.-Teile ligninsulfonsaures
Kalium und 1 Gew.-Teil oleoylmethyltaurinsaures Natrium als Netz- und Dispergiermittel mischt und
in einer Stiftmühle mahlt.
c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20 Gew.Teile Wirkstoffe A + B mit 6 Gew.-Teilen Alkylphenolpolyglykolether ( TM Triton x 207), 3 Gew.Teilen Isotridecanolpolyglykolether (8 EO) und 71 Gew.-Teilen paraffinischem Mineralöl
(Siedebereich z. B. ca. 255 bis 277 DEG C) mischt und in einer Reibkugelmühle auf eine Feinheit von
unter 5 Mikron vermahlt.
d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew.-Teilen Cyclohexanon als Lösemittel und
10 Gew.-Teilen oxethyliertes Nonylphenol als Emulgator.
e) Ein in Wasser dispergierbares Granulat wird erhalten, indem man
75 Gew.-Teile Wirkstoffe A + B,
10 Gew.-Teile ligninsulfonsaures Calcium,
5 Gew.-Teile Natriumlaurylsulfat,
3 Gew.-Teile Polyvinylalkohol und
7 Gew.-Teile Kaolin
mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch Aufsprühen von Wasser
als Granulierflüssigkeit granuliert.
f) Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man
25 Gew.-Teile Wirkstoffe A + B
5 Gew.-Teile 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium,
2 Gew.-Teile oleoylmethyltaurinsaures Natrium,
1 Gew.-Teil Polyvinylalkohol,
17 Gew.-Teile Calciumcarbonat und
50 Gew.-Teile Wasser
auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschliessend auf einer Perlmühle mahlt
und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse zerstäubt und trocknet.
g) Ein Extruder-Granulat erhält man, indem man 20 Gew.-Teile der Wirkstoffe A + B, 3
Gewichtsteile ligninsulfonsaures Natrium, 1 Gewichtsteil Carboxymethylcellulose und 76
Gewichtsteile Kaolin vermischt, vermahlt und mit Wasser anfeuchtet. Dieses Gemisch wird extrudiert
und anschliessend im Luftstrom getrocknet.
2. Biologische Beispiele
Die nachfolgend genannten Beispiele wurden im Gewächshaus und teilweise in Feldversuchen
erarbeitet:
i) Unkrautwirkung im Vorauflauf
Samen bzw. Rhizomenstücke von mono- und dikotylen Unkrautpflanzen werden in Plastiktöpfen von 9
cm Durchmesser in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Im Reisanbau
vorkommende Unkräuter werden im mit Wasser gesättigten Boden kultiviert, wobei soviel Wasser in
die Töpfe gefüllt wird, dass das Wasser bis zur Bodenoberfläche oder einige Millimeter darüber steht.
Die in Form von benetzbaren Pulvern oder Emulsionskonzentraten formulierten erfindungsgemässen
85/2194
Wirkstoffkombinationen sowie in parallelen Versuchen die entsprechend formulierten Einzelwirkstoffe
werden dann als wässrige Suspensionen bzw. als Emulsionen mit einer Wasseraufwandmenge von
umgerechnet 300 bis 600 l/ha, in unterschiedlichen Dosierungen auf die Oberfläche der Abdeckerde
appliziert oder beim Reis ins Bewässerungswasser gegossen.
Nach der Behandlung werden die Töpfe im Gewächshaus aufgestellt und unter guten
Wachstumsbedingungen (Temperatur, Luftfeuchtigkeit, Wasserversorgung) für die Unkräuter gehalten.
Die visuelle Bonitur der Pflanzen bzw. der Auflaufschäden erfolgte nach dem Auflaufen der
Versuchspflanzen nach einer Versuchszeit von 3 bis 4 Wochen im Vergleich zu unbehandelten
Kontrollen. Die Versuche werden statistisch mit mehrfacher, bis zu fünffacher, Wiederholung angelegt.
Die erfindungsgemässen herbiziden Mittel weisen eine gute herbizide Vorauflaufwirksamkeit gegen
ein breites Spektrum von Ungräsern und Unkräutern auf.
ii) Unkrautwirkung im Nachauflauf
Samen bzw. Rhizomenstücke von mono- und dikotylen Unkrautpflanzen werden in Plastiktöpfen in
sandigem Lehmboden ausgelegt, mit Erde abgedeckt und im Gewächshaus unter guten
Wachstumsbedingungen (Temperatur, Luftfeuchtigkeit, Wasserversorgung) angezogen. Im Reisanbau
vorkommende Unkräuter werden in Töpfen kultiviert, in denen Wasser bis zu 2 cm über der
Bodenoberfläche steht. Drei Wochen nach der Aussaat werden die Versuchspflanzen im
Dreiblattstadium behandelt. Die als Spritzpulver oder Emulsionskonzentrate formulierten
erfindungsgemässen Wirkstoffkombinationen sowie in parallelen Versuchen die entsprechend
formulierten Einzelwirkstoffe werden in verschiedenen Dosierungen mit einer Wasseraufwandmenge
von umgerechnet 300 bis 600 l/ha auf die grünen Pflanzenteile gesprüht und nach ca. 3 bis 4 Wochen
der Versuchspflanzen im Gewächshaus unter optimalen Wachstumsbedingungen (Temperatur,
Luftfeuchtigkeit, Wasserversorgung) die Wirkung der Präparate visuell im Vergleich zu unbehandelten
Kontrollen bonitiert. Bei Reis oder bei Unkräutern, die im Reisanbau vorkommen, werden die
Wirkstoffe auch direkt ins Bewässerungswasser gegeben (Applikation in Analogie zur sogenannten
Granulatanwendung) oder auf Pflanzen und ins Bewässerungswasser gesprüht. Die Versuche werden
mit mehrfacher, bis zu fünffacher, Wiederholung angelegt worden. Die erfindungsgemässen herbiziden
Mittel weisen auch im Nachauflauf eine gute herbizide Wirksamkeit gegen ein breites Spektrum
wirtschaftlich wichtiger Ungräser und Unkräuter auf.
iii) Feldversuche
Feldversuche werden auf praxisüblich bewirtschafteten Flächen mit natürlichen Versendungen
angelegt. Dabei werden nach Aussaat bzw. Auflauf der Kultur/Unkraut/-gräser Parzellen mit ca. 20 bis
10 m>;2; und 2 bis 4 Wiederholungen appliziert. Dazu werden Parzellenspritzgeräte verwendet. Die
Effekte der Herbizid/-kombinationen werden im Zeitraum von 1 bis 8 Wochen nach Applikation
visuell bonitiert und die Effekte prozentual (0-100%) im Vergleich zu unbehandelten Kontrollparzellen
festgehalten. Die Ergebnisse stellen Mittelwerte der 2 bis 4 Wiederholungen für die jeweilige Unkraut/gras-Spezies dar.
Bewertung der Kombinationseffekte in den Beispielen
Bei der Bewertung der Kombinationseffekte wird die Wirkung der Einzelkomponenten addiert und mit
der Wirksamkeit der dosierungsgleichen Mischungen verglichen. Oft zeigte sich, dass die
Kombinationen höhere Wirkungsgrade als die Summe der Einzelwirkungen zeigt.
In Fällen mit weniger deutlichen Effekten wird nach der COLBY-Formel der Erwartungswert errechnet
und mit dem empirisch ermittelten Ergebnis verglichen. Der errechnete, theoretisch zu erwartende
Wirkungsgrad einer Kombination wird ermittelt nach der Formel von S. R. Colby: "Calculation of
synergistic and antagonistic responses of herbicide combinations", Weeds 15 (1967), Seiten 20 bis 22.
86/2194
Die Formel lautet für Zweierkombinationen:
EMI39.1
Dabei kann von synergistischen Effekten ausgegangen werden, wenn der empirische Wert grösser als
der Erwartungswert ist. Bei Kombinationen mit wirkstoffgleichen Einzelkomponenten können auch
Vergleiche über die Summenformel angestellt werden.
In der Mehrzahl der Fälle ist die synergistische Wirkungssteigerung jedoch so hoch, dass auf das
Kriterium nach Colby verzichtet werden kann; die Wirkung der Kombination übersteigt dann deutlich
die formale (zahlenmässige) Summe der Wirkungen der Einzelstoffe.
Es sei besonders darauf hingewiesen, dass eine Beurteilung des Synergismus bei den hier eingesetzten
Wirkstoffen die stark unterschiedlichen Aufwandmengen der Einzelwirkstoffe berücksichtigen muss.
Es ist somit nicht sinnvoll, die Wirkungen der Wirkstoffkombinationen und die Einzelwirkstoffe
jeweils bei gleichen Aufwandmengen zu vergleichen. Die erfindungsgemäss einzusparenden
Wirkstoffmengen werden nur durch die überadditive Wirkungssteigerung bei Einsatz der kombinierten
Aufwandmengen oder durch die Verringerung der Aufwandmengen beider Einzelwirkstoffe in den
Kombinationen im Vergleich zu den Einzelwirkstoffen bei jeweils gleicher Wirkung erkennbar.
Spezielle Versuchsbeispiele
In den nachfolgenden Tabellen gelten:
g ai/ha = Gramm Aktivsubstanz (active ingredient) pro Hektar
Erwartungswerte für die Herbizidkombinationen sind in Klammern angegeben.
Tabelle 1
Ethoxysulfuron + Fentrazamid (B1)
EMI40.1
Gewächshausversuch: Behandlung in 1-2 Blattstadium
Bonitierung: 20 Tage nach Applikation
Tabelle 2
Ethoxysulfuron + Azimsulfuron (B23)
EMI40.2
Feldversuch: Behandlung in 2-3 Blattstadium
Bonitierung: 28 Tage nach Applikation
Tabelle 3
Ethoxysulfuron + (pentoxazone) (B28)
EMI41.1
Feldversuch: Behandlung in 1 Blattstadium
Bonitierung: 43 Tage nach Applikation
Tabelle 4
Ethoxysulfuron + Oxaziclomefone (B30)
EMI41.2
Gewächshausversuch: Behandlung in 2-4 Blattstadium
Bonitierung: 20 Tage nach Applikation
Tabelle 5
87/2194
Ethoxysulfuron + Clefoxidim (B6)
EMI42.1
Gewächshausversuch: Behandlung in 2-4 Blattstadium
Bonitierung: 20 Tage nach Applikation
Tabelle 6
Ethoxysulfuron + KIH 2023 (B20)
EMI43.1
Gewächshausversuch: Behandlung in 2 Blattstadium
Bonitierung: 22 Tage nach Applikation
Tabelle 7
Ethoxysulfuron + Oxadiargyl (B21)
EMI43.2
Gewächshausversuch: Behandlung in 1-2 Blattstadium
Bonitierung: 21 Tage nach Applikation
Tabelle 8
Ethoxysulfuron + KIH 6127 (B7)
EMI44.1
Gewächshausversuch: Behandlung in 1-2 Blattstadium
Bonitierung: 21 Tage nach Applikation
Tabelle 9
Ethoxysulfuron + Tritosulfuron (B11)
EMI44.2
Feldversuch: Behandlung in 2-4 Blattstadium
Bonitierung: 28 Tage nach Applikation
Tabelle 10
Ethoxysulfuron + Clomazone (B19)
EMI45.1
Feldversuch: Vorauflauf
Bonitierung: 53 Tage nach Applikation
Tabelle 11
Ethoxysulfuron + Nicusulfuron (B24)
EMI46.1
Feldversuch: Behandlung im 2-4 Blattstadium
Bonitierung: 28 Tage nach Applikation
Die Beispiele zeigen, dass durch die Einzelwirkstoffe einzelne Schadpflanzen nur mit hohen
Dosierungen gut bekämpft werden. Die Kombinationspartner in niedrigen Dosierungen appliziert,
zeigen in der Regel nur geringe, bei weitem nicht die in der Praxis geforderte Wirksamkeit. Nur durch
die gemeinsame Anwendung der Wirkstoffe lassen sich gute Effekte gegen alle geprüften
Schadpflanzen erzielen. Dabei wurde die additive Wirkung aus den Einzelkomponenten deutlich
übertroffen, d. h., dass das geforderte Bekämpfungsniveau durch deutlich niedrigere Aufwandmengen
erzielt wird. Durch diese Effekte wird das Wirkungsspektrum deutlich breiter.
Die Kulturverträglichkeit, in Form von Schädigungen bewertet, wird nicht negativ beeinflusst, d. h.
dass die Kombinationen als voll selektiv bewertet werden können.Data supplied from the esp@cenet
database - Worldwide
Claims:
88/2194
Claims of DE19928453
1. Herbizide Mittel, enthaltend
A) einen oder mehrere herbizide Wirkstoffe aus der Gruppe der substituierten
Phenoxysulfonylharnstoffe der Formel I und deren Salze
EMI47.1
und
A) eine oder mehrere herbizid wirksame Verbindungen aus der Gruppe der Verbindungen, welche
besteht aus
1. selektiv in Reis vorwiegend gegen Gräser wirksamen Herbiziden ausgewählt aus der Gruppe
bestehend aus
Fentrazamid (NBA 061), Haloxyfop, Sethoxydim, Dithiopyr, Etobenzanid (MY-52), Clefoxidim, KIH
6127 und Clethodim,
2. selektiv in Reis vorwiegend gegen dikotyle Schadpflanzen und Cyperaceen wirksamen Herbiziden,
ausgewählt aus der Gruppe, bestehend aus 2,4-D, MCPA, Mecoprop, Mecoprop-P, Tritosulfuron,
Halosulfuron-methyl, Dicamba, Acifluorfen, Carfentrazone, Bentazon und Triclopyr,
3. selektiv in Reis, vorwiegend gegen Gräser und dikotyle Schadpflanzen sowie Cyperaceen
wirksamen Herbiziden, ausgewählt aus der Gruppe bestehend aus Pendimethalin, Clomazone, KIH
2023, Oxadiargyl, Cycloslulfamuron (AC 322, 140), Azimsulfuron (DPX-A-8947), Nicosulfuron,
Thenylchlor, Cinmethylin, Indanofan, Pentoxazone, Pyribenzoxim, Oxaziclomefone (MY-100),
Fluthiamid und Mesotrione.
2. Herbizide Mittel nach einem oder mehreren der vorhergehenden Ansprüche, dadurch
gekennzeichnet, dass sie einen synergistisch wirksamen Gehalt einer Kombination der Verbindungen
der Formel I oder deren Salze (Typ-A-Verbindung) mit Verbindungen aus der Gruppe B aufweisen.
3. Herbizide Mittel nach einem oder mehreren der vorhergehenden Ansprüche, dadurch
gekennzeichnet, dass sie die Verbindungen der Formel I oder deren Salze (Typ-A- Verbindungen) und
die Verbindungen aus der Gruppe B in einem Gewichtsverhältnis von 1 : 20.000 bis 200 : 1, bevorzugt
1 : 8000 bis 100 : 1, besonders bevorzugt 1 : 4000 bis 50 : 1, enthalten.
4. Herbizide Mittel nach einem oder mehreren der vorhergehenden Ansprüche, dadurch
gekennzeichnet, dass sie eine oder mehrere weitere Komponenten aus der Gruppe enthaltend
Pflanzenschutzmittelwirkstoffe anderer Art, Safenerwirkstoffe, im Pflanzenschutz übliche Zusatzstoffe
und Formulierungshilfsmittel enthalten.
5. Verfahren zur Bekämpfung von Schadpflanzen dadurch gekennzeichnet, dass man die Herbizide der
herbiziden Mittel, definiert gemäss einem oder mehreren der Ansprüche 1 bis 4, gemeinsam oder
getrennt im Vorauflauf, Nachauflauf oder im Vor- und Nachauflauf auf die Pflanzen, Pflanzenteile,
Pflanzensamen oder die Anbaufläche appliziert.
6. Verfahren nach Anspruch 5 zur selektiven Bekämpfung von Schadpflanzen in Pflanzenkulturen.
7. Verfahren nach Anspruch 6 zur Bekämpfung von Schadpflanzen in Reis.
8. Verwendung der nach einem der Ansprüche 1 bis 4 definierten herbiziden Mittel zur Bekämpfung
von Schadpflanzen.
9. Verwendung nach Anspruch 8 zur Bekämpfung von Schadpflanzen in Reiskulturen.
89/2194
10. Verfahren zur Herstellung herbizider Mittel, definiert gemäss einem oder mehreren der Ansprüche
1 bis 4, wobei die Verbindung(en) der Formel I oder deren Salze (Typ-A-Verbindungen) mit einer oder
mehreren Verbindungen des Typs B analog einer üblichen Pflanzenschutzformulierung aus der Gruppe
enthaltend Spritzpulver, emulgierbare Konzentrate, wässrige Lösungen, Emulsionen, versprühbare
Lösungen (tank-mix), Dispersionen auf Öl- oder Wasserbasis, Suspoemulsionen, Stäubemittel,
Granulate zur Boden- oder Streuapplikation, wasserdispergierbare Granulate, ULV-Formulierungen,
Mikrokapseln und Wachse, formuliert werden.Data supplied from the esp@cenet database - Worldwide
90/2194
8. DE2034734
- 4/15/1971
MIXED FUNGICIDE ACTIVE AGAINST RICE DISEASES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE2034734
E Class: A01N47/22
Application Number:
DE19702034734 (19700714)
Priority Number: JP19690055756 (19690716)
Family: DE2034734
Abstract:
Abstract of DE2034734
Fungicidal compsn. active against both Piricularia oryzae and Hypochnus sasakii, contains as active
ingredients: 3-chloro-2,4,6-tribromophenyl-N-butylcarbamate and O-ethyl (or propyl)- S,Sdiphenylphosphorodithioate.Description:
Description of DE2034734
Gemischte fungizide Komposition für Reiskulturen
Die Erfindung betrifft neue gemischte fungizide Mittel für Reiskulturen. Insbesondere bezieht sich die
vorliegende erfindung auf neue fungizide Kompositionen für Reiskulturen, die dadurch gekennzeichnet
sind, dass sie ausgezeichnete schützende heilende und dauerhafte Wirkungen synergistisch
hervorbringen u.zw. gegen Piricularia oryzae und PelliculariasesStkii und dass sie ausserdem
ausgezeichnete Anpassungsfähigkeit im praktischen Gebrauch zeigen. Diese Verbindungen sind
gegenMenschen undhaustiere wenig toxisch.
Bisher war folgendes bekannt: Die insektizide Wirkung wurde verdoppelt, wennzwei-bekannte
Insektizide miteinander vermischt wurden (Japanisches PatentNrO 438.268 Japanische PatentVeröffentlichungNrO Sho 39-20729).
Sowohl der anfängliche wie auch der verbleibende insektizide Effekt wurde vergrössert9 verglichen
mit derEinzel-Anwen- dung jedesInsektizidesa wenn sie miteinander vermischt wurden. (Japanisches
Patent Nr. 490.900, Japanische PatentveröffentlichungNrO Sho41-1003890 Sowohl eine fungizide
wie auch insektizide Wirkung wurde erreicht, wenn bekannte Fungizide undIns-ektizlde in Mischung
miteinander verwendet wurden0 (Japanisches PatentNrO 414130, Japanische Patentveröffentlichung
Nr. Sho 38-14944).Ein breiterer Anwendungsbereich wurde erhalten, wenn zwei bekannte Insektizide
mit verschiedenenAnwendungsmoglich- keiten miteinander gemischt wurden (Japanisches Patent Nr.
469.435, JapanischePatentveröffentlichung Nr. Sho 40-22399). Diese Erfindungen zielen daraufabD
diebekannte ten biologischen Aktivitäten der verwendetenChemiMalien synergistisch zu stärken, oder
ihre Eigenschaften zu kumulieren.
Die gemischten fungiziden Mittel gemäss der vorliegenden Erfindung sind dadurch gekennzeichnet,
dass sie als aktive Substanzen zwei Typen von Verbindungen mit ver-schiedenen
fungizidenEigenschaften nämlich Carbamid- säureester und organische Phosphorsäureester
inMischung enthalten. Die vorliegenden Kompositionen besitzenausge zeichnete synergistische
Wirksamkeit bei der Bekämpfung von piricularia oryzae und von hypochnus sasakii des Reises, die bei
Gebrauch der beiden Verbindungen einzeln kaum zu erreichen ist.
Die Bekämpfungswirkung gegen hypochnus sasakii von Reis ist stark genug, um im praktischen
Gebrauch verglichen mit der Anwendung jeder einzelnen dieserVerbin- dungen wirksam zu sein. Bei
der Bekämpfung von piricularia oryzae werden die heilenden und schützenden Wirkungen, die jede
Verbindung einzeln besitzt, synergistisch erhöht. Daher wird die Anwendungsperiode der Chemikalien
91/2194
verlängert und eine Begrenzung der Anwendungsperiode für jede einzelne Verbindung zum
Verschwinden gebracht. Diese Eigenheiten bringen es mit sich, dass eine Mischung der zwei
Verbindungen die gleichzeitige Bekämpfung von piricularia oryzae und hypochnus sasakii des Reises
ermöglicht. Die ausgezeichneten fungiziden Kompositionen ergeben demnach auch vom Standpunkt
der Arbeitsersparnis in der Landwirtschaft Vorteile.
Die vorliegende Erfindung betrifft gemischte, fungizide Kompositionen, die dadurch
gekennzeichnetsind ; dass sie
EMI3.1
3-Chlor-2,4,6-tribrom- phenyl-N-n-butylcarbamat der folgenden Formel
EMI3.2
undO- thyl(oder propyl)-S,S-diphenyl-phosphordithiolat der allgemeinen Formel
EMI3.3
in der R einen Athyl- oder Propylrest bedeutet als Wirkstoffe und inerte flüssige oder feste
Trägermaterialien und/oder Verdünnungsmittel und Hilfsmittel wie Lösungsmittel, emulgierende
Substanzen je nach Bedarf und Methode ihrer Anwendung, enthalten. Das Mischungsverhältnis der
aktiven Verbindungen I und II beträgt von 2 : 1 bis 1 : 1 Gew.-Teile und die aktiven Verbindungen
werden dann in herkömmliche pestizide Formulierungen übergeführt und verwendet.
Es ist eine Vielzahl von Verbindungen unter welchen auch die speziellen Verbindungen der oben
genannten allgemeinen Formel II, die gemäss der vorliegenden Erfindung verwendet werden,
aufscheinen, in ihrer Verwendung als Fungizide aus dem niederländischen Patent Nr. 6,611.860
bekannt. Jedoch ist bekannte dass unter den besagten Verbindungen, die Alkylreste mit 2 oder 3
Kohlenstoffatomen für R und einen nicht substituierten Phenylrest aufwiesen, gegen piricularia oryzae
sehr wirksam waren.Weiters wurde überraschend gefunden, dass neue und ganz hervorragende
Eigenschaften für ein Bekämpfungsmittel von Reispflanzen Krankheiten wie oben erwähnt, erreicht
werden, wenn insbesondere3-Chlor-2,4,6-tribromphenyl-N-n butylcarbamat der oben genannten
Formel I undO-Alkyl-S,S-diphenylphosphor- dithiolat der oben genannten allgemeinen Formel II
miteinander gemischt werden.
Die Reispflanzen werden während ihrer Wachstumsperiode nicht nur durch Insektenschädlinge
sondern auch durch Arten von pflanzenpathogenen Pilzen befallen. Unter ihnen verursachen piricularia
oryzae und hypochnus sasakii den grössten Schaden, wobei beide sehr oft zur selben Zeit während der
Wachstumsperiode der Reispflanzen auftreten.
Daher sind Chemikalien, die gute Wirksamkeit gegen piricularia oryzae aber praktisch keine Aktivität
gegen hypochnus sasakii oder vice versa aufweisen, vom Standpunkt der praktischen
Krankheitsbekämpfung nicht so voll, da hier die Anwendung der Chemikalien während der Periode, in
der beide Krankheiten ausbrechen würden, erforderlich ist. Zu diesem Zweck wurden bis jetzt
gemischte Kompositionen die aus einem Chemikal, welches gegen piricularia oryzae wirksam ist und
eine organische Arsenverbindung die gegen hypochnus sasakii wirksam ist, verwendet. Jedoch sind
Mischungen von chemischen Verbin dungen, die Schwermetalle und andere Chemikalien enthalten,
vom Standpunkt der Formulierungstechnik wie auch vom Standpunkt derToxizitätsprobleme auf
Mensch und Haustier nicht besonders vorteilhaft.Daher sind Kompositionen gemäss der vorliegenden
Erfindung bei der gleichzeitigen Bekämpfung beider Krankheiten grossartig wirksam.
Wie sich herausgestellt hat, gehen beim Gebrauch der Verbindungen der Formeln I oder II einzeln
sowie bei den bisher dafür entwickelten organischen Phosphorsäureestern ein, zwei oder drei Elemente
verloren, nämlich der schützende, der heilende und der verbleibende Effekt (Dauer-Effekt) gegen
Reiskrankheiten. Insbesondere waren die Verbindung bei der gleichzeitigen Bekämpfung von
piricularia oryzae und hypochnus sasakii,den ernsten Krankheiten der Reispfalnzen, die unter den oben
genannten Bedingungen auftreten, nicht genügend wirksam im Vergleich zu sehr kraftvollen
Fungiziden, die Schwermetalle enthielten und bisher verwendet wurden.
Es war ein kaum erwartetes Resultat, das dieses Problem gelöst werden könnte, wenn der
Carbamidsäureester der Formel I und organische Phosphorsäureester der allgemeinen Formel II,
gemäss der vorliegenden Erfindung in Kombination verwendet wurden. Die gemischte fungizide
Komposition gemäss der vorliegenden Erfindung löste die allgemeinen Nachteile synthetischer
organischer Verbindungen, die bisher auf dem Markt waren und verweist auf die Entwicklung von
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Reisfungiziden welche anstelle der organischenQuecksilberverbindungen, die für Mensch und Tier
schädliche Schwermetalle enthalten, verwendet werden können.
Der Einfluss von Bromatomen, die am Phenylkern hängen und ihre Anzahl in denVerbindun"der oben
genannten Formel 1 gemäss. der vorliegendenErfindung,ist für die Spezifität und Dauerhaftigkeit des
fungiziden Effektes entscheidend.
Als Beispiele für die organischen Phosphorsäure ester der allgemeinen Formel II seiO-Äthyl-S,Sdiphenyl- phosphordithiolat angeführt. Diese Verbindungen werden nach einer Methode, die in der
niederländischen PatentschriftNr. 6,611.810 beschrieben ist, erhalten0
Die gemischten fungiziden Kompositionen gemäss der vorliegenden Erfindung zeigen eine
bemerkenswert ausgezeichnete Wirkung gegen ernste Reispflanzenkrankheiten, wie piricularia oryzae
und hypochnus sasakii wie schon erwähnt. Jedoch sind sie auch bei der Bekämpfung anderer
Krankheiten der Reispflanzen, wiezoBo von Helminthosporium-orycae (Cochliobolus
miyabeanus),helminthosporium sigmoideum und xanthomonasorycae wirksam.
Die gemischten fungizidenKompositlonen der vorliegenden Erfindung werden durch Vermischen der
aktiven Bestandteile, nämlich der Verbindung der allgemeinen Formel I und einer oder mehreren
Verbindungen der allgemeinen Formel II mit verschiedenen inerten Lösungsmitteln und/oder
Trägermaterialien in Form von Gasen, Flüssigkeiten und Feststoffen, weiters mit Hilfsmitteln
sowieoberflachenaktio ven Mitteln, emulgierenden Mitteln, dispergierenden Mittel, entwickelnden
Mitteln, Spreitmitteln und adhäsiven Mitteln in FormulierungenübergeführtR die dann verwendet
werden.
Als Gas, Verdünnungsmittel oder Trägermaterialien werden Freon oder andere Treibmittel und Gases
dienor- malerweise für Aerosolgebrauch Verwendung findenangel wendet. Als flüssigeVerdünnungsoder Trägermaterialien dienen Wasser und organische Lösungsmittel, insbesondere aromatische
Kohlenwasserstoffe, wie Xylol, Toluol, Benzol, Dimethylnaphthalin, aromatische Erdölfraktionen
usw; aliphatische Kohlenwasserstoffe, wie Benzin, Cyclohexan, Paraffin usw; chlorierte aromatische
oder aliphatische Kohlenwasserstoffe, wie Chlorbenzol, Chlormethylen, Chlor äthylen,
Tetrachlorkohlenstoff, usw. Alkohole, wie Methanol, Äthanol, Propanol, Butanol, usw; Ketone, wie
Aceton, Methyläthylketon, Cyclohexanon usw; stark polare Lösungsmittel wie Acetonitril,
Dimethylformamid, Dimethylsulfoxid usw.Als feste Verdünnungs- oder Trägermaterialien dienen
gemahlene natürliche Mineralien, wie Atapulgite,Ton,Bentonitj Kreide, Talk, Kaolin,Montmorilo- nit,
Diatomeenerde, Calciumcarbonat usw; gemahlene synthetische Mineralien, wie hochdisperse
Kieselsäure, Aluminiumoxid, Silikate usw. Als Hilfsmittel kommen nichtionische und anionische
oberflächenaktive Mittel oder emulgierende Mittel wie z.B.
Polyoxyäthylenfettsäureester,Polyoxyäthylenfettalkoholäther, z.B. Alkyl-,Aryl- Polyglycoläther,
Alkylsulfonate, Arylsulfonate und dis pergierende Mittel, wie Lignin, Sulfitablaugen,Methylcellulo.
se usw. in Frage.
Je nach Bedarf können auch andereAgrikulturchemika- lien wie Insektizide, Nematozide, Fungizide
(einschliesslich Antibiotika), Herbizide, Pflanzen-Wachstumsregulatoren oder Düngemittel in diesen
fungiziden Kompositionen vorhanden sein.
Die gemischten fungiziden Kompositionen, gemäss dieser Erfindung enthalten 0,1 - 95Gew.-%,
vorzugsweise 0,5 - 90 Gew.-% der Mischung der aktiven Verbindungen.-Die Menge aktiver
Verbindungen, die in den Kompositionen enthalten ist, kann je nach Typ der Formulierung,
Anwendungsmethode, Zweck, Zeit und Ort der Anwendung wie auch entsprechend der
Ausbruchsbedingungen der Krankheiten variiert werden.
Die aktiven Verbindungen gemäss der vorliegenden Erfindung können als solche oder in Form ihrer
Formulierungen jeder Art, die auf dem Gebiet der Herstellung von Agrikulturchemikalien üblich sind,
verwendet werden, wie als Flüssigkeiten, Emulsionen, emulgierbare Konzentrate, benetzbare Pulver,
lösliche Pulver, Öle, Aerosole, Pasten, Rauch,Stäube,.Körner, Pellets, Tabletten usw.
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Die Anwendung dieser Verbindungen kann durch Mischen,Såssern, Giessen, Versprühen. Zerstäuben,
Verstreuen, Verräuchern usw. erfolgen, indem man die pflanzenpathogenen Pilze und/oder ihren
Lebensraum behandelt.
Die aktiven Verbindungen gemäss der vorliegenden Erfindung können auch in Zusammenhang mit
dem bekannten Ultra-Low Volume-Verfahren angewendet werden. Nach dieser Methode enthält die
Formulierung bis zu 95 Gew.-% der aktiven Verbindungen oder sogar die aktiven Verbindungen allein.
Die Menge der Verbindungen in den gebrauchsfertigen Formulierungen kann in einem ziemlich
weiten Bereich aus denselben Gründen, die bei den Typen der Formulierungen dargelegt wurden,
variiert werden.
Im allgemeinen enthalten sie 0,005 bis 10Gew.-%, vorzugsweiseO,Q1 bis 5 Gew.-% aktive Substanz.
Die Dosierungsmenge pro Flächeneinheit betrug im allgemeinen zwischen 15 und 1000 g,
vorzugsweise zwischen 40 und 600 g aktive Substanz pro 10 a. Jedoch ist es in Sonderfällen möglich,
diese Menge zu über- oderunteFschrei- ten und manchmal ist dies auch notwendig.
Gemäss der vorliegenden Erfindung sind folgende Methoden der Krankheitsbekämpfung vorgesehen,
wenn dievorliegendngemischten fungiziden Kompositionen, wie oben erwähnt, verwendet werden.
1. Eine Bekämpfungsmethode der Krankheiten von Reispflanzen, die dadurch charakterisiert ist, dass
man eine gemischte aktive Verbindung und/oder eine gemischte fungizide Komposition gemäss der
vorliegenden Erfindung auf die Anbaufläche (einschliesslich der Wasseroberfläche und des Bodens des
Reisfeldes) und/oder die Reispflanzen anwendet.
2. Eine Bekämpfungsmethode für piricularia oryzae undhypochnus.sasakii der Reispflanzen, die
dadurch charakterisiert ist, dass man die aktiven Verbindungen und/oder die gemischten fungiziden
Kompositionen gemäss der vorliegenden Erfindung auf Reisanbauflächen (einschliesslich der
Oberfläche des wassers und des Bodens des Reisfeldes)und/oder die Reispflanzen, bevor, während und
nach Entwicklung von piricularia oryzae und von hypochnus sasakii anwendet.
Die vorliegende Erfindung wird im einzelnen durch die folgenden Arbeitsbeispiele erläutert, die in
keiner Weise einschränkend wirken.
Arbeitsbeispiel l:
50 Gew.-% einer Mischung (1:1) von aktiven Verbindungen der Formel I und der allgemeinen Formel
II, 20Gew.-% eines emulgierenden Agens (Alkylarylpolyglykol äther) und 30 Gew.-% eines
Lösungsmittels (Xylol) werden gemischt und gerührt und bilden ein homogenes emulgierbares
Konzentrat. Dieses wird mit Wasser verdünnt (1000bis2QOO-fach) und ergibt eine gebrauchsfertige
Komposition, die aufgesprüht werden kann und gegen die pflanzenpathogenen Pilze und deren
Lebensraum mit Hilfe einer Sprühvorrichtung angewendet wird.
Arbetsbeispiel 2s
Jede der aktiven Verbindungen der Formel I und der allgemeinen Formel II wird knapp vor deren
Anwendung zu einer emulgierbaren Konzentration bzw. zu einer gewünschten Konzentration(50O bis
1000-fach) verdünnt und gemischt(1:1, Tank-Mischungsmethode). Die nun gebrauchsfertige
Präparierung wird gemäss der Methode im Arbeitsbeispiel 1 aufgesprüht.
Arbeitsbeispiel 3:
25 Gew.-% einer Mischung (1,5o 1) der aktiven Verbindung der Formel1 und der allgemeinen Formel
II, 7 Gew.-% eines emulgierenden Agens(Alkylarylpoly glykoläther) und 68Gew.-% eines feinen
inertenMineral- pulvers (eine Mischung von Diatomeenerde und Tonhut5) werden miteinander
pulverisiert und ein benetzbares Pulver erhalten.Dieses wird nach Verdünnung mit Wasser zur
gewünschten Konzentration verdünnt (etwa2500 bis 1000-fach) und ergibt eine
gebrauchsfertigePräparation,die dann gemäss den Methoden nach Beispiel 1 Verwendung findet,
Arbeitsbeispiel 4: 2Ges. % einer Mischung (1 : 1) einer aktiven Verbindung der FormelI und einer der
allgemeinen Formel II und 98 Gew.-% einer Mischung (3 : 1) von Talk und Ton, werden in einem
Mischapparat gemischt (z.B. Lödecke-Mixer) und in einer Mühle homogenisiert und dabei eine
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staubförmige Formulierung erhalten0 Diese wird auf die Reispflanzen in einer Menge von 3 bis 4 kg
pro 10 a mit Hilfe einesVerstäubers aufgebracht.
Arbeitsbeispiel 5:
Eine Mischung (1:1) der aktiven Substanz der Formel I und der allgemeinen Formel II wird in einem
Lösungsmittel (z.B. Aceton) gelöst. Dies wird dann auf Tonkörner mit 0,2 - 1 mm Durchmesserunter
Umwälzung in einem Mischapparat (z.B.V förmiger Mischer), aufgesprüht, so dass etwa 5Gew.-%
der gemischten aktiven Verbindung darin enthalten sind. Die körnige Formulierung wird dann nach
dem Abdampfen des Lösungsmittels und Trocknung erhalten. Die Formulierung wird dann auf die
Oberfläche des Wassers oder des Bodens in den Reisfeldern in einer Menge von 4 bis 6 kg pro 10 a
mittels einer Sprühvorrichtung auf gebracht.
Im folgenden werden Ergebnisse von Tests, die mit den fungitoxisch aktiven Verbindungen und den
gemischten fungiziden Kompositionen gemäss der vorliegenden Erfindung, die ausgezeichnete
synergistische Wirkungen zeigten, durchgeführt wurden, beschrieben.
Testbeispiell:
DerSchutz-,Dauer- und Heil-Effekttest gegen piricularia oryzae von Reispflanzen, wurde unter
Verwendung von 3-Chlor-2,4,6-tribromphenyl-N-n-butylcarbamat der Formel I undO-Athyl(oder isopropyl)-S,Sdiphenyl-phosphordithiolaten der allgemeinen Formel II bzw. von Mischung dieser beiden,
ausgeführt. Das Ergebnis zeigt TabelleIr
Testverfahren:
A) Schutz- und Dauer-Effekttest gegen piricularia oryzae.
Reispflanzen (Jukkoku-Art) wurden in Töpfen von 12 cm Durchmesser kultiviert. Die aktiven
Verbindungen und gemischten fungiziden Kompositionen gemäss der vorliegenden Erfindung wurden
in den vorgeschriebenen Konzentrationen auf die Reispflanzen im Sprossstadium aufgebracht.
Die Emulsionen wurden in einer Menge von 50 ml pro 3 Töpfen bei einem Druck von 1,5 kg/cm2
aufgesprüht, so dass die Blätter der Reispflanzen tropfnass wurden. Das Besprühen wurde ausgeführt,
indem die Töpfe auf drehbaren Tischen, die sichin~Verbindung mit der Chemikalienabgabe aus dem
Ventil der Sprühpistole bewegten, montiert waren. Die vorgeschriebene Menge der staubförmigen
Formulierung wurde einheitlich auf die Testpflanzenaufgestäubt und zwar unter reduziertem Druck von
200 mm Hg, indem man einen grossen"Bell-Jar-Verstäuber" verwendete.
Die besprühten Reispflanzen wurden dann jeweils 1 oder 5 Tage nach der chemischen Behandlung in
eine feuchte Kammer gegeben und bei25 0C bei 100 % Feuchtigkeit 2 Tage stehen gelassen. Während
dieser Zeit wurde eine Sporen-Suspension von piricularia oryzae (50.000 - 100.000 Sporen proml) die
vorher gezuchtet wurden, auf die Reispflanzen zur Beimpfung aufgesprüht.
Der direkte schützende Effekt wurde an Reispflanzen ausgewertet, welche einen Tag nach der
chemischen Behandlung beimpft wurden und der Dauer- und Schutz-Effekt wurde an jenen Pflanzen
ausgewertet, die 5 Tage nach der chemischen Behandlung geimpft worden waren.
7 Tage nach der Beimpfung wurden die Infektionsgrade ausgewertet, indem man die ersten und
zweiten Entwicklungablätter von 10 ausgesuchten Stengel pro Topf, gemäss der folgenden Definition
bewertete. Dann wurde die Schädigungsrate gemäss der unten angeführten Gleichung errechnet.
Die Phytotoxizität gegen Reispflanzen wurde gleichzeitig ausgewertet:
Prozentsatz der Krankheitsflecken Infektionsgrad Fläche 0 0 % 0,5 >; 2 % 1 3-5 % 2 6-10 % 3 11-20
% 4 21-40 % ; 41 %
1/2n0,5 + n1 + 2n2 + 4n3 + 8n4 + 10n5 Schädigungsrate = x 100
10 N
Darin bedeutet N die Zahl aller beobachteten Blätter, n0,5 die Zahl der Blätter mit dem Infektionsgrad
0,5, .... n5 die Zahl der Blätter mit dem Infektionsgrad 5.
B) Heil-Effekt-Test gegen piricularia oryzae. Dieser Test wurde ausgeführt, um den Heil-Effekt der
vorliegenden Verbindungen gegen pathogene Pilze, die in denPf lanzenkörper eingebracht wurden, zu
überprüfen.
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Reis-Pflanzen, wie sie im Test A) verwendet wurden, wurden in einer feuchten Kammer bei 25 C und
100 % Feuchtigkeit zwei Tage lang stehen gelassen. Während dieser Zeit wurde eine Sporensuspension
von piricularia oryzae zur Beimpfung aufgesprüht. Am nächsten Tage der Infektion wurden die aktiven
Verbindungen und gemischten fungiziden Kompositionen gemäss der vorliegenden Erfindung in der
vorgeschriebenen Konzentration aufgesprüht und zwar in derselben Weise wie beim Heil-Effekt-Test.
C) Test gegen hypochnuns sasakii des Reises.
Reispflanzen (Kinmaze-Art) werden in unglasierten Töpfen mit einem Durchmesser von 12 cm
kultiviert. Eine verdünnte Lösung einer Verbindung gemäss der vorliegenden Erfindung wurde wie im
Testbeispiel gegen piricularia oryzae vorbereitet und auf die Reispflanzen am Beginn des
Sprossstadiums (100 ml/3 Töpfe, im Fall eines benetzbaren Pulvers), aufgesprüht.
Am nächsten Tag wurde das Sklerotium von hypochnus sasakii, welches aufGertenkörnern 10 Tage
langgeachtet wurde, am Fuss der Testreispflanzen eingeimpft.
Die behandelten Pflanzen wurden in eine Kammer mit einer relativen Feuchtigkeit von 95 % oder mehr
bei Temperaturen von 28 bis 30 C acht Tage lang stehen gelassen und die Krankheit zur Entwicklung
gebracht.
Der Entwicklungsstand der Krankheit wurde dann ausgewertet und auf Grund der Entwicklung der
Krankheitsflecken vom Fuss der Reispflanzen her, wo die Beimpfung stattfand, beobachtet. 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, auf denen keine
Ent- wicklung der Krankheit zu sehen war;;nl die Zahl der Stengel auf denen die Entwicklung der
Krankheit bis zur er sten Blatt scheide vom Boden her, n2 die Zahl der Stengel auf dem die
Entwicklung der Krankheit bis zur zweiten Blatt scheide vom Boden und n3 die Zahl der Stengel auf
denen die Entwicklung der Krankheit bis zur dritten Blatt- scheide vom Boden her beobachtet werden
konnte Ergebnis des Tests gegen piricularia oryzae und hypochnus sasakii von Reispflanzen
Benetzbares Tabelle I: Pulver Wirkstoff Wirkstoff- Wirkung gegen piricularia oryzae Wirkung gegen
Phytotoxizikonz. % Schutzeffekt Dauereffekt Heil-Effekt hypochnus tät auf Reis sasakii I 0,02 2,8 9,9
43,3 53,3 0,04 0 4,0 48,2 12,0 II-a 0,02 8,5 21,7 7,7 68,5 0,04 0 18,1 3,6 39,7 II-b 0,02 4,3 23,7 19,0
70,2 0,04 0 12,2 6,4 28,4 I + II - a 0,02 3,3 14,8 15,3 20,7 (1,7 : 1) 0,04 0 8,0 9,1 9,5 I + II - b 0,02 0
12,5 22,7 25,3 (1,7 : 1) 0,04 0 6,4 14,2 11,3 Urbazid (Vergleich) 0,008 - - - 14,0 unbehandelt - 32,6
41,8 44,3 82,9 - >;RTI Tabelle I: (Fortsetzung) Ergebnis des Tests gegen piricularia oryzae und
hypochnus sasakii von Reispflanzen Benetzbares Pulver: Wirkstoff Wirkstoff- Wirkung gegen
piriculariz oryzae Wirkung gegen Phytotokonz. % Schutzeffekt Dauereffekt Heil-Effekt hypochnus
xizität auf sasakii Reis I 60 3,5 10,0 57,2 30,4 120 0 4,4 49,0 11,7 II-a 30 9,4 26,3 18,5 - 60 3,3 20,1
16,6 30,9 II-b 60 3,5 12,5 12,0 - 120 0 6,7 5,3 22,0 I + II - a 60 2,0 8,6 20,2 7,1 (2 : 1) 120 0 4,4 13,4
1,5 I + II - b 60 4,4 11,7 16,3 7,0 (1 : 1) 120 0 6,7 12,8 2,0 Urbazid (Vergleich) 24 18,3 29,0 56,6 0,8
unbehandelt - 30,7 45,7 48,0 66,7 - Anmerkungen: 1. Die Zahlen in der Tabelle geben die
Durchschnitts schädigungsrate von 3 Töpfen an.
2.(I) 3-Chlor-2,4,6-tribromphenyl-N-n-butylcarbamat (II-a): O-Äthyl-S,S-diphenylphosphordithiolat
(II-b):0-Isopropyl-S,S-diphenylphosphordithiolat 3. Urbazid: Methylarsin-bis-dimethyldithiocarbamat
4. (-) in der Phytotoxizität bedeutet keinen negativen
Einfluss auf das Wachstum der ReispflanzenData supplied from the esp@cenet database - Worldwide
Claims:
Claims of DE2034734
Patentansprüche 1) Fungizides Mittel, gekennzeichnet durch einen Gehalt an einer
Wirkstoffkombination bestehend aus3-Chlor-2,4,6-tribrom- phenyl-N-n-butylcarbamat der Formel
EMI18.1
und O-Äthyl(oder Propyl)-S,S-diphenyl-phosphordithiolat der Formel
EMI18.2
96/2194
in welcher R einen Äthyl- oder Propylrest bedeutet
EMI18.3
>;tb; 2 >;SEP; f >;SEP; .r, >;SEP; L >;SEP; -, >;SEP; D
>;tb; dass >;SEP; man >;SEP; eine >;SEP; Wirtnaria'"nspr, >;SEP; åS >;SEP; Änsprych >;SEP; 1
>;SEP; auf >;SEP; Pilze
>;tb; 2#) Verwendung von Wirkstoffkombinationen gemäss Anspruch 1 zur
Bekämpfung von Pilzen.
3/) Verfahren zur Herstellung vonfungiziden Mitteln, dadurch gekennzeichnet, dass man eine
Wirkstoffkombination gemässAnspruo
1 mit Streckmitteln und/oder oberflächenaktiven Mitteln ver mischt.Data supplied from the esp@cenet
database - Worldwide
97/2194
9. DE2056651
- 6/9/1971
FUNGICIDE FOR RICE CULTURES
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE2056651
E Class: A01N47/20; C22F1/10
Application Number:
DE19702056651 (19701118)
Priority Number: JP19690093492 (19691122)
Family: DE2056651
Abstract:
Abstract of DE2056651
The fungicide contains 4,5,6,7-tetrachlorophthalide and a 2-(1-pyrazolyl)-5-(lower
alkoxycarbonylamino)-benzimidazole. The combination is particularly useful against Piricularia and
Hypochnus, and has low toxicity to man and animals.Description:
Description of DE2056651
Fungizides Kombinationspräparat für Reiskulturen
Die vorliegende Erfindung betrifft eine fungizide Wirkstoffkombination. Genauer ausgedrückt, bezieht
sich die Erfindung auf ein neues fungizides Kombinationspräparatfiir den Reisanbau, das sich durch
einen Synergismus auszeichnet und eino vorzügliche protektive und kurative Wirkung, sowieeine
Dauerwirkunggegen die "Brusone-Krankheit" des Reises,(verur- sach durch Pyricularia pryzae) und
die "Hypochnus sasakii" Reiskrankheit (verursacht durch Pellicularia sasakii) hat und sich für die
Praxis hervorragend eignet. Die Verbindungen weisen eine geringe Toxizität gegendber Menschen und
Tieren auf.
Es ist bereits bekannt geworden, dass die insektizide Wirkung durch Zusammenmischen von zwei
bekannten Insektiziden verdoppelt werden kann (Japanische Patentschrift Nr. 438 268) und die Sofortund die Dauerwirkung der Insektizide im Vergleich zu der Anwendung der einzelnen Insektizide
verstärkt werden kann (Japanische Patentschrift Nr. 490 900;Bek. Nr.
Sho 41-10038). Perner ist auch bekannt, dass durch Mischung bekannter Insektizide und Fungizide ihre
insektizide und fungizide Wirkungen addiert werden (Japanische Patentschrift Nr. 414 130) und dass
das Wirkungsspektrum bei der Mischung von zwei bekannten Insektiziden mit verschiedenen
Wirkungsspektren vergrössert wird (Japanische Patentschrift Nr. 469 435).
Das fungizide Kombinationspräparat gemäss vorliegender Erfindung besteht aus zwei verschiedenen
chemischen Komponenten, von denen jede eine andere Eigenschaft besitzt, und zwar aus einer
Mischung von einem substituierten Phthalid und einemCarbaminsäureester- benzimida ol-DeriBat. Bei
der Mischung der beiden Komponenten ergibt sich ein synergistischer Effekt, und deren protektive und
kurative Wirkung gegen Piricularia wird so stark erhöht, wie man es bei der Anwendung der einzelnen
Komponenten nicht hätte erwarten können. Auch die Wirkung gegen Hypochnus wird durch die
Mischung verstärkt und der Zeitraum, in dem die Anwendung erfolgen kann, wird stark ausgedehnt,
sodass man gegen Piricularia und Hypochnus eine gleichzeitige Bekämpfung erreichen kann.Dies ist
im Hinblick auf eine Arbeitsersparnis in der Landwirtschaft vongrolXem Vcrteil.
Die vorliegende Erfindung betrifft eine fungizide Kombination, welche aus den Wirkstoffen 4,5,6,7Tetrachlorphthalid der Formel
EMI3.1
und einem 2-Lpyrazolyl-(i )7 -5-alkoxycarbonylamino-benzimiduzol der allgemeinen Formel
EMI3.2
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worin R für niedrige Alkyl-Reste steht, besteht, und die Verwendung dieser Kombination.
Je nach den Erfordernissen, werden flüssige oder feste Formulierungen mit Hilfe
vonVerdíinnungsmitteln, Lösungsmitteln, Emulgatoren u. a. Formulierungshilfsmitteln vorgenommen.
DasMischungs-Gewichtsverhältnis der beiden Wirkstoffe von Formel (I) zu allgemeiner Formel (II) ist
5:1 - 1:1; die Mischung lässt sich nach einer im Pflanzenschutz üblichen Methode formulieren.
Beispiele für die von der allgemeinen Formel(TI) umfalten chemischen Verbindung sind: 1) 2[Pyrazolyl-(1)]-5-methoxycarbonylamino-benzimidazol 2) 2-[razoly-(1 ? -5-äthoxycarbonylaminobenzimidazol 3) 2-[Pyrazolyl-(1)]-5-n-propxycarbonylamino-benzimidazol 4) 2-[Pyrazolyl-(1)]-5-isopropxycarbonylamino-benzimidazol 5) 2-CPyrazolyl-(1 n -5-n-butoxycarbonylamino-benzimidazol 6)
2- [Pyrazolyl-(1)]-5-iso-butoxycarbonylamino-benzimida zol Aus der Gruppe von chemischen
Verbindungen, in der die erwähnten Wirkstoffe der allgemeinen Formel (II) eingeschlossen sind, ist
eine Verwendung als Fungizide, Nematozide und Insektizide bereits bekannt (Bekannt gemachte
Holländische Patentanmeldung 68-12312).Nun wurde unter anderem gefunden, dass unter den bereits
erwähnten Verbindungen besonders 2 [Pyrazolyl-(1)]-5-alkoxycarbonylamino-benzimidazol zur
Bekämpfung von Hypochnus sehr wirksam ist und auch gegen Piricularia eine gute kurative Wirkung
hat. Ausserdem wurde gefunden, dass die genannte chemische Verbindung der Formel (II) gegen
Piricularia eine vorzügliche protektive Wirkung hat.
Ferner wurde überraschenderweise gefunden, dass, was bis jetzt noch nicht bekannt war, ganz neue
undgtinstige Eigenschaften gegen Krankheiten im Reisanbau vorhanden sind, wenn 4,5,6,7
Tetrachlorphthalid entsprechend derPormel (T) und 2- [Pyrazolyl- (1)]-5-alkoxycarbonylaminobenzimidazol der Formel (II) gemischt werden. Reispflanzenwerden nicht nur von Schädlingen
angegriffen, sondern auch von verschiedenen phytopathogenen Pilzen befallen. Insbesondere bedeutet
der von Piricularia undHypo(hnus verursachte Schaden grosse Verluste im Reisanbau und die beiden
Krankheiten treten oft im gleichen Zeitpunkt während derWaehstumszeit der Reispflanzen
auf.Ausdiesem Grunde sind Präparate, die gegen Piricularia eine hohe Aktivität besitzen, die jedoch
gegen Hypochnus keinepraktisch verwertbare Wirkunghaben, oder umgekehrt, vom standpunkt der
Praxis aus gesehen, nicht wertvoll; d.h. eine Applikation während des Zeitraumes, in welchem beide
Krankheiten wahrscheinlichaus- brechen, ist gefragt. Aus diesem Grund werden zur Zeit
Kombinations-Präparate verwendet, die aus einem gegen Piricularia wirksamen Wirkstoff und einer
gegen Hypochnus wirksamen organischen Arsen-Verbindung bestehen. Die Mischung von einer
Schwermetall enthaltenden chemischen Verbindung und einem anderen Wirkstoff ist jedoch vom
Blickpunkt der Formulierungstechnik aus, ebenso wie aus Gründen der Toxizität für Menschen und
Tiere, nicht wünschenswert.DasKombinationspräparat vorliegender Erfindung ist daher auch in
diesem Punkt sehr günstig.
Entsprechend eigenen Untersuchungen fehlen bei der alleinigen Verwendung von Verbindungen der
Formel (I) oder(II), ferner bei Anwendung aller bis jetzt entwickelten organischen Verbindungen, eine
oder zwei von den drei für die Bekämpfung von Reiskrankheiten wesentlichen Faktoren; und zwar sind
dies die protektive Wirkung,de kurative Wirkung und die Dauerwirkung.
Insbesondere sind diese Verbindungen, im Vergleich zu bisher gebrauchten stark wirksamen
schwermetallhaltigen Fungiziden, nicht ausreichend wirksam für die gleichzeitige Bekämpfung der
wichtigen Reiskrankheiten Piricularia und Hypochnus.
Es ist ein überraschendes Resultat, dass diese Aufgabe auf einmal gelöst werden kann, wenn die
Tetrachlorphthalid-Verbindung der Formel (I) und das Carbaminsäureester-benzimidazol-Derivat der
allgemeinen Formel (II) in Kombination angewendet werden.
Die fungizide Kombinationgemä vorliegender Erfindungschlielft eine Lücke unter den zur Zeit auf
dem Markte vorhandenen organischen synthetischen Präparaten.S^; wurde einReisfungizid
entwickelt, welches anstelle der giftigenorganischen vueck- ;ilber-Präparate angewendet werden kann.
Das erfindungsgemässe fungizide Kombinationspräparat zeigt, wie bereits mehrfach erwähnt, eine
vorzügliche Wirkung gegen die wichtigsten Reiskrankheiten Piricularia und Hypochnus; und dar über
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hinaus dient es zur Bekämpfung von Erregern anderer Reis krankheiten, wie z.B. von Cochliobolus
miyabeanus, Helminthosporium sigmoideum und Xanthomonas oryzae.
Die erfindungsgemässe Kombination, bestehend aus einer Verbindung der Formel (I) und einer oder
mehreren mit der allgemeinen Formel(II), kann in die üblichen Formulierungen übergeführt werden,
wie Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate. Diese verschiedenen
Formulierungen werden in bekannter Weise hergestellt, z.B. durch Mischung der Wirkstoffe mit
verschiedenen inerten gasförmigen, flüssigen oder festen Verdünnungsmitteln und/oder Trägern, und
gegebenenfalls unter Verwendung von Hilfsmitteln, z.B.Grenzflächen-Aktivatoren, Emulgatoren,
Diffusionsmitteln, Verteilungsmitteln und Haftmitteln. Als Verdünnungsmittel oder Träger werden für
rosole geeignete Treibmittel, die unter normalen Zuständen gasartig sind, empfohlen.Als flüssige
Verdünnungsmittel oder Träger sind z.B. zu nennen: Wasser, organische Lösungsmittel, aromatische
Kohlenwasserstoffe (z.B. Xylol, Toluol, Benzol, Dimethylnaphthol, aromatisches Naphtha u.s.w.);
chlorierte aromatische oder aliphatische Kohlenwasserstoffe (z.B. Chlorbenzol, Chlormethylen,
Chloräthylen, Tetrachlorkohlenstoff u.s.w.); aliphatische Kohlenwasserstoffe (z.B. Benzin,
Cyclohexan, Paraffin u.s.w.); stark polare Lösungsmittel, wie Acetonitril, Dimethylformamid,
Dimethylsulfoxidu.s.w.). Als feste Verdünnungsmittel oder Träger sind natiirliche Gesteinsmehle (z.B.
Apatit, Lehm, Benthonit, Kalk, Talkum, Kleie, Kaolin, Montmorillonit,Infusorienerde,
Kalziumkarbonat u.s.w.), und Dispergiermittel (z.B.Lignin-Sulfit-Papierbrei-Abfallauge,
Methylcellulose, u.s.w.) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure,
Aluminiumoxid (Tonerde), Silikate u.s.w.) aufzuzählen. Als Hilfsmittel können nichtionogene und
anionischeGrenzflächenaktivatoren oderSmulgatoren (z,B.
Polyoxyäthylenfettsäureester,Polyoxyäthylenfettsäurealkoholäther, oderstlkylarylpolyglykoläther,
alkylsulfonsäure Salze,arylaulfon- saure Salze, u.s.w.), und Dispergiermittel (z.B. Lignin, Sulfit
Papierbrei-Abfallauge, Methylcellulose,u.s.w.) genannt werden.
Ferner, falls erforderlich, können andere Pflanzenschutzmittel, z.B. Insektizide, Nematizide, Fungizide
(einschliesslich Antibiotika), Herbizide,Pflanzenwuchs-Regulåtoren oder Düngemittel diesem
fungiziden Kombinationspräparat zugegeben werden.
Das fungizide Kombinationspräparat gemäss vorliegender Erfindung enthält 0,1 - 95 Gewichtsprozent,
bevorzugt 0,5 - 90% von der genannten Wirkstoffkombination.
Die Menge der aktiven Bestandteile in dem Kombinationspräparat kann entsprechend den
Formulierungstypen, Applikationsmethoden und -zwecken, Zeit und Ort der Anwendung, sowie
entsprechend den Befallsbedingungen variiert werden. Als Formulierungstypen sind alle für
Pflanzenschutzmittel üblichen Formulierungen zu nennen; nämlich Lösungen,
Emulsionen,Enulsionakonzentrate, Spritzpulver, wasserlösliches Pulver, Öle, Aerosole, Pasten,
Räuchermittel, Stäube, Granulate, Tabletten, u.s.w.
Die Applikation dieses Kombinationspräparates ist direkt oder mit einem Gerät durch
Spritzung,Versprühung, Vernebelung, Verstäuben, Verstreuen, Räuchern, Giessen, Düngen, u.s.w.
an den von den Erregern befallenen Stellendurchzufihren.
Auch für die Sogenannte "Ultra-low-volume-Methode" ("ULV-Verfahren") ist dieses
Kombinationspräparat gut geeignet. Bei der ULV-Anwendung kann die Wirkstoffmischung in bis zu
95%iger Konzentration oder sogar als solche Verwendung finden.
Die Menge der >; ktiven Bestandateile ist bei der praktischen Anwendung infolge derLrit
obenerwähnten Grunde ziemlich variationsfähig. Im allgemeinen ist jedoch einesnw(ndungskonzentration von 0,005 - 10%, bevorzugt 0,01 -5, zu empfehlen.
Die Applikationsmenge pro Flächeneinheit beträgt fUrdig Wirkstoffkombination im allgemeinen
zwischen 1,5 und 100 gr., bevorzugt 4 bis 60 gr. pro ar. Jedoch in besonderen Fällen ist es möglich,
oder manchmal sogar notwendig, diesen Konzentrationsbereich nach oben oder unten zu überschreiten.
Die obenbeschriebene Erfindung lässt sich in folgender Weise zusammenfassen:(1) Verfahren zur
Bekämpfung und Verhütung von Reiskrankheiten, dadurch gekennzeichnet, dass man eine
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Wirkstoffkombination gemäss dieser Erfindung an dem Ort, wo Reispflanzen wachsen (einschliesslich
Wasseroberfläche, Boden, u.s.w. des Wasser reisfeldes) und/oder auf den Reispflanzen anwendet.
(2) Verfahren zur Bekämpfung von Piricularia oryzae und Pelli cularia sasakii, gekennzeichnet durch
die Verwendung einer
Wirkstoffkombination gemäss dieser Erfindung an dem Ort, wo
Reispflanzen wachsen (einschliesslich Wasseroberfläche,
Boden, u.s.w. des Wasserfeldes), bevor, während, oder nach dem Auftreten von Piricularia oryzae
und/oder Pellicularia sasakii.
Imfolgenden.wird die vorliegende Erfindung durch die folgenden Arbeitsbeispiele speziell illustriert,
die allerdings keineswegs einschränkende Wirkung besitzen.
Arbeitsbeispiel 1 50% einer Mischung (1:1) der erfindungsgemässen beiden Wirkstoffe der Formel (I)
und der allgemeinen Formel (II), 20% eines Emulgators(Alkylarylpolyglykoläther) und30 eines
Lösungsmittels (Xylol) werden gemischt und gerührt, wobei ein homogenisiertes emulgierbares
Konzentrat erhalten wird. Dieses emulgierbare Konzentrat wird mit Wasser auf die gewünschte
Wirkstoffkonzentration(0,05 - 0,1%) verdünnt und das sogenannte anwendungsfertige Präparat mit
einem Spritzgerät auf Krankheitskeime oder deren Lebensraum gespritzt.
Arbeitsbeispiel 2 Nach derselben Methode, wie in Beispiel 1 angegeben, wird ein emulgierbares
Konzentrat aus jedem Wirkstoff der Formel (I) und der allgemeinen Formel (II) jeweils getrennt
erhalten, und jedes Konzentrat wird jeweils mit Wasser auf die gewünschte Wirkstoffkonzentration
(0,1 - 0,2%) verdünnt. Diese beiden Wirkstoffzubereitungen werden erst kurz vor der Applikation
gemischt (Verhältnis 1:1, sogenanntes"Tank-Mix"-Verfahren) und zu einem anwendungsfertigen
Präparat verfertigt. Die Bespritzung erfolgt gleich wie beim Beispiel 1. Arbeitsbeispiel S 25 5 Teile
der erfindungsgemässen Wirkstoffkombination der Formel (I) und der allgemeinen Formel (II) im
Gewichtsverhältnis 2:1, 7 Teile eines Emulgators (Alkylarylpolyglykoläther) und 68 Teile
einesfeingepulverten inerten Gesteinsmehl3 (eine Mischung im Verhältnis 1:5 von Infusorienerde und
Kleie) werden gemischt und zu einem benetzbaren Pulver vermahlen undveiarbaitet.
Dieses Pulver wird mit Wasser auf die gewünschte Wirkstoff konzentration (0,1 - 0,4%) verdünnt und
somit ein anwendungsfertiges Präparat erhalten. Das Präparat wird nach der gleichen Methode wie
beim Beispiel 1 ausgebracht.
Arbeitsbeispiel 4 2 Teile der Wirkstoffkombination der Formel (I) und der allgemeinen Formel (II) im
Gewichtsverhältnis 1:1 und 98 Teile einer 3:1 Mischung von Talkum und Kleie werden in einem
Mischgerät gemischt, in einer Mühle homogenisiert, und eine Staub-Formulierung erhalten. Dieser
Staub wird direkt an Halmen und Blättern von Reispflanzen in einer Aufwandmenge von 0,3 - 0,4 kg
pro ar. mit einem Verstäuber ausgebracht.
Arbeitsbeispiel 5 Eine Wirkstoffkombination (3:1) der Formel (I) und der allgemeinen Formel (II)
wird in einem Lösungsmittel (z.B. Aceton) aufgelöst. Diese Wirkstofflösung wird auf Kleie-Körnern
von 0,2 -imm Xeilchen-Durchme9qer ein einem Misch-Apparat aufgespritzt, bis die Konzentration der
Wirkstoffkombination in den Körnern 5% erreicht. Nach Verdampfung des Lösungsmittels werden die
Körner getrocknet und eine Granulat-Formulierung erhalten. Dieses Granulat wird auf die
Wasseroberfläche oder den Boden eines Wasserreisfeldes in einer Menge von 0,4 - 0,6 kg pro ar. mit
einem Granulat-Streuer ausgebracht.
Im folgenden werden dieErgebiese der Wirksamkeitsteste der erfindungsgemässen Fungizid-Mischung
(und der bis jetzt unbekannten hervorragenden synergistischen Wirkung durch Mischung der beiden
Fungizide)gezeigt. ~ Test beispiel 1 Piricularia-Test Die Wirkungen der Wirkstoffe.4,5,6,7Tetrachlorphthalid der Formel (I) und 2-Pyrazolyl-(i) -5-alkoxycarbonylamino-benzimidazol der
Formel(11), und die Wirkung der erfindungsgemässen Kombination werden gegen Piricularia oryzae
und Pellicularia sasakii nach folgender Testmethode protektiv, durativ (Prüfung der Dauerwirkung)
und kurativ geprüft.
Die Resultate werden auf Tabelle 1 und 2 gezeigt.
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Testverfahren (a) Test auf protektive Wirkung und Dauerwirkung gegen Piri cularia oryzae (Topf-Test)
Wasserreispflanzen (Sorte: Jukkoku) wurden in Töpfen mit 12 cm Durchmesser aufgezogen. Die
erfindungsgemässe Wirkstoffkombination und jeder der einzelnen Wirkstoffe wurden getrennt in der
jeweils vorgeschriebenen Konzentration aufgespritzt. Zur Durchführung verdünnte man ein
Spritzpulver mit Wasser und stellte die Töpfe auf einen drehbaren Tisch, der sich in Verbindung mit
der aus der Düse derSpritpistole abgegebenenPräparatmenge bewegte. Die Spritzflüssigkeit wurde in
einer Menge von 50 cm pro 4 Töpfe, bei einem Druck von 1,5 kg/cm gespritzt, sodass die Blätter der
Reis pflanzen tropfnass wurden.
Eine Hälfte der so bespritztenReispflanen wurde am nächsten Tag und die andere Hälfte der Pflanzen
wurde 5 Tage nach der Bespritzung in eine Feuchtkammer gegeben und dort bei einer relativen
Feuchtigkeit von1004 und einer Temperatur von 250C zwei Tage lang gehalten.
In dieser Zeit wurde eine wässrige Sporensuspension von Piricularia oryzae (50 000 bis 100 000
Sporen pro ml) durch zweimaliges SprUhen zur Infektion der Reispflanzen aufgebracht.
Die Hälfte der Pflanzen, die am Tage nach der Applikation inokuliert wurde, diente zur Auswertung
der direkten protektiven Wirkung und die andere Hälfte der Pflanzen, die 5 Tage nach der Applikation
inokuliert wurde, diente zur Auswertung der Dauerwirkung.
7 Tage nach der Inokulation wurden 10 Stengel pro Topf ausgewählt und auf den ersten und zweiten
Blättern von oben wurde der Krankheitsbefall je nach dessen Stärke in 7 Klassen eingestuft und daraus
wurde ein Befallsgrad nach der unten angegebenen Gleichung errechnet. Gleichzeitig wurde die
Phytotoxizität gegenüber den Reispflanzen ermittelt.
Befallaklasse Prozentsatz der Fläche der Krankheits flecken
0 0%
0,5 weniger als 2%
1 3 bis 5%
2 6 bis 10%
3 11 bis 20%
4 21 bis 40%
5 mehr als 41% 1/2n0,5+n1+2n2+4n3+8n4+10n5 Befallsgrad= x 100
10
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(Topf-Test) Um die kurative Wirkung der erfindungsgemässen Verbindungen gegen die schon in
denPflanzenkdrper eingedrungenen Krankheitskeime zu prüfen, wurde dieser Test durchgeführt.
Wasserreispflanzen (gleiche Sorte wie bei Test a.) wurden in einer Feuchtkammer bei einer relativen
Feuchtigkeit von 100% und einer Temperatur von 250C zwei Tage lang gehalten. In dieser Zeit wurde
eine wässrige Sporensuspension von Piricularia oryzae zur Infektion der Reispflanzen auf dieselben
aufgesprüht.
km Tag nach der Inokulation wurden dieSpritzlösungen von jedem einzelnen Wirkstoff und der
Wirkstoffkombination auf die von Piricularia oryzae infizierten Pflanzen in gleicher Weise wie bei Test
(a) gespritzt.
6 Tage nach der Applikation wurde der Befallsgrad von Piricularia oryzae auf die Pflanzen nach
gleicher Methode wie bei Test (a) untersucht und der Befallsgrad wurde nach derselben Gleichung wie
bei Test (a) errechnet.
Tabelle 1 Testergebnis der Wirkung gegen Piricularia oryzae (Topf-Test) Spritzpulver-Formulierung
EMI14.1
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1) I :4,5,6,7-Tetrachlorphthalid
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2)Phytotoxizität: "-" bedeutet, dass kein schädlicher Ein flug auf das Wachstum der Reispflanzen
beobachtet wurde.
(c) Test zur Prüfung der Wirkung gegen Pellicularia sasakii (2Hypochnus sasakii) (TopfTest)Wasserreispflanzen (Sorte:Kinmaze) wurden in Töpfen mit einem Durchmesser von12cm
aufgezogen. Beim Jungährenbildungs Stadium wurden dieselben Präparate wie beim Test gegen
Piricularia oryzae ausgebracht. Die Applikationsmethode ist die gleiche wie beim Test gegen
Piricularia oryzae. (Die Präparate wurden jedoch bei diesem Test in einer Menge von100ml pro 3
Töpfe verwendet.) Am Tag nach der Applikation wurde -dasSclerotium von Pellicularia sasakii,
welches auf Gerstennährboden zehn Tage lang gezüchtet worden war, am Fuss der Test-Reispflanzen
aufgebracht.
Die behandelten Pflanzen wurden in einer Feuchtkammer bei einer relativen Feuchtigkeit von 95% und
Temperaturen von 28 bis 300C zehn Tage lang stehen gelassen, um die Erkrankung zur Wirkung zu
bringen. Danach wurden die Pflanzen ausgewertet.
Bei derAuowertung wurde dieBefallastärke aufgrund der Entwicklung von Krankheitsflecken vom
Fuss der Reispflanzen her, wo die Infektion stattfand,klassifiziert und der Befallsgrad wurde nach der
folgenden Gleichung ausgerechnet: 3n3 + 2n2 + n1 + 0n0 Befallsgrad = x 100
3 N Darin bedeutet;
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>;tb; >;SEP; vom >;SEP; Boden >;SEP; befallenen >;SEP; Stengel
>;tb;
Tabelle 2 Testergebnis der Wirkung gegen Pellicularia sasakii (Topf-Test) Spritzpulver-Formulierung
EMI18.1
>;tb; Präparate >;SEP; irkstoffs- >;SEP; Befallsgrad >;SEP; von >;SEP; Phytotoxi
>;tb; >;SEP; ILEonzent >;SEP; rat;i >;SEP; on >;SEP; PelXicula >;SEP; ria >;SEP; iasakii >;SEP;
zität
>;tb; >;SEP; ~ >;SEP; . >;SEP; , >;SEP; , >;SEP; ; >;SEP; ~ >;SEP; , >;SEP; .
>;tb;
>;SEP; I >;SEP; 0,05 >;SEP; 8Q.5 >;SEP;
>;tb; >;SEP; II >;SEP; 0.025 >;SEP; 8.2
>;tb; >;SEP; 0.05 >;SEP; 2.8
>;tb; I >;SEP; + >;SEP; II
104/2194
>;tb; (2x1) >;SEP; 0.025 >;SEP; 12.1
>;tb; (2s1 >;SEP; ) >;SEP; 0025 >;SEP; 12.1 >;SEP; ~
>;tb; Kombina >;SEP; t >;SEP; i >;SEP; onos
>;tb; präp. >;SEP; der >;SEP; vor- >;SEP; 0.05 >;SEP; 4.3
>;tb; liegenden >;SEP; Er
>;tb; findung
>;tb; Urbazid >;SEP; 0.008 >;SEP; 3.5
>;tb; >;SEP; w >;SEP; 7
>;tb; unbehandelte
>;tb; Kontrolle >;SEP; 77.8
>;tb; (Anmerkungen)
1) DiePräparatenummern entsprechen denen in Tabelle 1.
2) Urbazid: Methylarsin-bis-dimethyldithiocarbamat (Handelsprodukt, zum Vergleich)
3) Phytotoxizität:t t bedeutet, dass kein schädlicher Ein fluss auf das Wachstum der Reispflanzen
beobachtet wurde.Data supplied from the esp@cenet database - Worldwide
105/2194
10. DE2138017
- 2/3/1972
SYNERGISTIC SELECTIVE HERBICIDE - CONTG PHENYLUREA AND
BENZYL CARBAMATE CPDS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE2138017
E Class: A01N47/30
Application Number:
DE19712138017 (19710729)
Priority Number: JP19700066530 (19700731)
Family: DE2138017
Abstract:
Abstract of DE2138017
Agent for selectively combatting weeds in agricultural cultures (esp. rice cultures) contain a
combination of a phenylurea of formula (I): (where X1 and X2 are H, Cl or S-CF2-Cl, at least one of
X1 and X2 being S-CF2-Cl) and a benzyl carbamate of formula (II) (where n is 1 or 2, each Y is H,
halogen or lower alkyl or alkoxy, Z is O or S, and R1 and Ri are lower alkyl, allyl or cycloalkyl, or
R1+R2 is 4-6C polymethylene optionally substituted by a methyl group) in a ratio of ca 1:1 to 1:10. (I) and (II) act synergistically, and phytotoxicity to rice is low. The period during which the herbicide
can be applied is prolonged, extending from 1 week before to 2 weeks after transplanting of rice
seedlings.
106/2194
11. DE4241629
- 6/16/1994
SYNERGISTIC HERBICIDAL COMPSNS. - CONTG. SULPHONYL-UREA
DERIV. AND OTHER HERBICIDE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE4241629
Applicant(s):
HOECHST AG (DE)
IP Class 4 Digits: A01N; C07D
IP Class:A01N47/36; A01N43/42; A01N47/18; A01N47/16; A01N57/14; A01N47/12; A01N47/38;
A01N43/78; A01N43/76; A01N43/40; A01N37/26; A01N37/22; A01N43/56; A01N57/16;
A01N37/38; A01N43/12; A01N37/18; C07D215/48; C07D295/194; C07D213/79; C07D277/68;
A01N47/30; A01N43/70; C07D263/58; C07D231/20; C07D403/12; C07D239/46
E Class: A01N47/36; C07D521/00S
Application Number:
DE19924241629 (19921210)
Priority Number: DE19924241629 (19921210)
Family: DE4241629
Abstract:
Abstract of DE4241629
Herbicidal compsns. contain sulphonylurea derivs. of formula (I) or their salts in combination with one
or more other herbicides (II). (a) R1 = 2-3C alkoxy, R2 = halogen, NO2, CF3 etc., (b) R1 = opt. unsatd.
1-8C alkoxy (substd. by halogen, opt. unsatd. 1-6C alkoxy, 1-6C alkylthio, 1-6C alkylsulphinyl etc., R2
= opt. unsatd. 1-8C alkyl, phenyl, phenoxy etc. and n = 0-3 or (c) R1 = 1-8C alkoxy, R2 = 2-8C
alkenyl, 2-8C alkynyl, phenyl etc., (d) R1 = halogen, OMe, Et or Pr, R2 = 2-5C alkoxycarbonyl in the 6
position and n = 1, R3 = H, opt. unsatd. 1-8C alkyl or 1-4C alkoxy, R4, R5 = H, halogen or 1-4C alkyl,
alkoxy etc. Y = O or S, E = CH or N. (II) are selected from quinchlorac (B1) or its salts, molinate (B2),
thiobencarb (B3), butachlor (B4), pretilachlor (B5), dithiopyr (B6), mefenacet (B7), fenoxaprop ethyl
(B8), dimepiperate (B9), pyrazolynate (B10), pyrazoxyfen (B11), benzofenap (B12), naproanilid
(B13), bensulfuron methyl (B14) etc. Combinations of (I) with a single cpd. (II) selected from B1-B9,
B14-B16 and B28 are excluded. (I) are described in DE3933543, B1-B27 are described in 'The
Pesticide Manual' (1991), B28 in EP238070, B29 in 'Weed Research' (1989), B30 in 'Weed Research'
(1990, B31 in EP332133 and B32 in J-6 0087254 (sic). Also claimed is the use of cpds. (II) for
protecting crop plants from the phytotoxic side effects of herbicides. USE/ADVANTAGE - The
compsns. are useful for pre- and post-emergence control of mono- and dicot weeds, esp. for selective
control of monocot weeds in rice and maize crops. Combinations of (I) and (II) have synergistically
enhanced herbicidal activity and in some cases (B19 and B32) synergistically reduced phytotoxicity to
rice.Description:
Description of DE4241629
[0001] Die Erfindung liegt auf dem Gebiet der Pflanzenschutzmittel, die gegen monokotyle und
dikotyle Unkräuter eingesetzt werden können.
Stand der Technik
[0002] Aus EP-A-03 42 569, EP-A-03 42 568 und EP-A-03 88 771 sind heterocyclisch substituierte
Phenoxysulfonylharnstoffe bekannt, mit denen ein breites Spektrum mono- und dikotyler Unkräuter
bekämpft werden kann. Sie können sowohl als Bodenherbizid als auch übers Blatt eingesetzt werden
107/2194
und zeigen auch eine besonders hohe Selektivität in monokotylen Kulturpflanzen wie Getreide, Mais,
Reis und Sorghum.
[0003] Aus EP-A-04 94 988 und EP-04 80 306 sind Wirkstoffmischungen bekannt, die eine
synergistische Steigerung des Bekämpfungserfolges gegenüber wichtigen Problemunkräutern in
Getreide und Reis zeigen.
[0004] Sowohl im Getreide als auch im Mais und Reis existieren jedoch eine Reihe wirtschaftlich
sehr wichtiger monokotyler Unkräuter, wie z. B. Alopecurus myosuroides, Avena fatua, Echinochloa
crus-galli oder Setaria viridis, die mit den erwähnten Mischungen alleine nicht in optimaler Weise zu
bekämpfen sind.
[0005] Überraschenderweise konnten nun in biologischen Versuchen herbizide Wirkstoffe
identifiziert werden, die bei gemeinsamer Anwendung mit den obengenannten Einzelverbindungen
ausgesprochen synergistische Eigenschaften hinsichtlich der Effektivität gegen Unkräuter haben und
somit den aus P 39 33 543.7 bekannten Zweierkombinationen überlegen sind.
Aufgabenstellung
[0006] Gegenstand der vorliegenden Erfindung sind herbizide Mittel, gekennzeichnet durch einen
wirksamen Gehalt an
A) Verbindungen der allgemeinen Formel (I) oder deren Salzen
[image - see original document]
worin
a1) R Ethoxy, Propoxy oder Isopropoxy und
R Halogen, NO2, CF3, CN, C1-C4-Alkyl, C1-C4-Alkoxy, C1- C4-Alkylthio oder (C1-C4-Alkoxy)carbonyl und
n 0, 1, 2 oder 3 oder
a2) R gegebenenfalls ungesättigtes C1-C8-Alkoxy, das substituiert ist durch Halogen, gegebenenfalls
ungesättigtes C1-C6-Alkoxy, einen Rest der Formel (C1-C6-Alkyl)-S-, (C1-C6-Alkyl)-SO-, (C1-C6Alkyl)-SO2-, (C1-C6- Alkyl)-O-CO-, NO2, CN oder Phenyl; ferner C2-C8-Alkenyloxy oder Alkinyloxy und
R gesättigtes oder ungesättigtes C1-C8-Alkyl, Phenyl, Phenoxy, C1-C4-Alkoxy, C1-C4-Alkylthio,
(C1-C4-Alkoxy)- carbonyl, wobei alle vorstehenden Reste für R durch Halogen, C1-C4-Alkoxy oder
C1-C4-Alkylthio substituiert sein können, oder Halogen, NO2, C1-C4-Alkylsulfonyl oder -sulfinyl
und
n 0, 1, 2 oder 3 oder
a3) R C1-C8-Alkoxy und
R C2-C8-Alkenyl oder -Alkinyl, Phenyl oder Phenoxy, wobei die genannten Reste für R
unsubstituiert oder durch Halogen, C1-C4-Alkoxy oder -Alkylthio substituiert sind, oder C1-C4Alkylsulfonyl oder -Alkylsulfinyl und
n 1, 2 oder 3 oder
a4) R jeweils in 2-Stellung am Phenylrest-Halogen, Methoxy, Ethyl oder Propyl,
R (C1-C4-Alkoxy)-carbonyl in 6-Stellung im Phenylrest und
n=1
sowie in allen Fällen a1)-a4)
R Wasserstoff, gesättigtes oder ungesättigtes C1-C8-Alkyl oder C1-C4-Alkoxy,
R>;4;, R>;5; unabhängig voneinander Wasserstoff, Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4Alkylthio, wobei die letztgenannten drei Reste unsubstituiert oder durch Halogen, C1-C4-Alkoxy oder
C1-C4-Alkylthio substituiert sind,
Y O oder S und
E CH oder N
bedeuten, in Kombination mit
B) einer, zwei oder mehr Verbindungen aus der Gruppe, welche die Verbindungen
B1) 3,7-Dichlorchinolin-8-carbonsäure und deren Salze, (Quinchlorac)
[image - see original document]
B2) N-(Ethylthio-carbonyl)-azepan (Molinate),
[image - see original document]
108/2194
B3) N,N-Diethyl-carbaminsäure-4-chlorbenzylthioester (Thiobencarb),
[image - see original document]
B4) N-(Butoxymethyl)-2-chlor-N-(2,6-diethylphenyl)-acetamid (Butachlor)
[image - see original document]
B5) N-(2-Propoxyethyl)-2-chlor-N-(2,6-diethylphenyl)acetamid (Pretilachlor)
[image - see original document]
B6) 3,5-Bis(methylthio-carbonyl)-2-difluormethyl-4-(2- methylpropyl)-6-trifluormethyl-pyridin,
(MON-7200, Dithiopyr)
[image - see original document]
B7) 2-(1,3-Benzthiazol-2-yloxy)-N-methyl-acetanilid, (Mefenacet)
[image - see original document]
B8) 2-[4-(6-Chlor-benzoxazol-2-yloxy)-phenoxy]-propionsäureethylester, (Fenoxapropethyl)
[image - see original document]
B9) N-(2-Phenyl-prop-2-yl-thiocarbonyl)-piperidin (MY-93, Dimepiperate)
[image - see original document]
B10) 4-(2,4-Dichlorbenzoyl)-1,3-dimethyl-pyrazol-5-yl-toluyl-4-sulfonat (Pyrazolynate, Pyrazolate)
[image - see original document]
B11) 2-[4-(2,4-Dichlorbenzoyl)-1,3-dimethyl-pyrazol-5-yloxy]-acetophenon (Pyrazoxyfen)
[image - see original document]
B12) 2-[4-(2,4-Dichlor-m-tolyl)-1,3-dimethylpyrazol-5-yloxy-4'- methylacetophenon (Benzofenap),
[image - see original document]
B13) 2-(2-Naphthyloxy)-propionanilid (Naproanilid),
[image - see original document]
B14) [alpha]-(4,6-Dimethoxypyrimidin-2-yl-carbamoyl-sulfamoyl)-O- toluolsäure-methylester
(Bensulfuron-methyl)
[image - see original document]
B15) 5-(4,6-Dimethoxypyrimidin-2-yl-carbamoylsulfamoyl)-1- methylpyrazol-4carbonsäuremethylester (Pyrazosulfuron-ethyl),
[image - see original document]
B16) 1-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-3- [2-(2-methoxyethoxy)-phenylsulfonyl]-harnstoff
(Cinosulfuron),
[image - see original document]
B17) 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl-ethansulfonat (Benfuresate),
[image - see original document]
B18) 2-Brom-3,3-dimethyl-N-(1-methyl-1-phenylethyl)- butyramid (Bromobutide),
[image - see original document]
B19) 1-(1-methyl-1-phenylethyl)-3-p-toluyl-harnstoff (Dymuron, Daimuron),
[image - see original document]
B20) N -(1,2-Dimethylpropyl)-N>;4;-ethyl-6-methylthio-1,3,5- triazin-2,4-diamin (Dimethametryn),
[image - see original document]
B21) S-Benzyl-1,2-dimethylpropyl(ethyl)-thiocarbamat (Esprocarb),
109/2194
[image - see original document]
B22) O-3-tert-Butylphenyl-6-methoxy-2-pyridyl-(methyl)- thiocarbamat (Pyributicarb, TSH-888)
[image - see original document]
B23) (Z)-N-but-2-enyloxymethyl-2-chlor-2',6'-diethylacetanilid (Butenachlor, KH-218),
[image - see original document]
B24) S-2-Methylpiperidinocarbonylmethyl-O,O-dipropylphosphorodithionat (Piperophos),
[image - see original document]
B25) S-4-Chlor-N-isopropylcarbaniloylmethyl-O,O-dimethylphosphorodithioat (Anilofos),
[image - see original document]
B26) (1RS,2SR,4SR)-1,4-Epoxy-p-menth-2-yl-2-methylbenzylether (Cinmethylin),
[image - see original document]
B27) N-(3,4-dichlorophenyl)-propanamid (Propanil),
[image - see original document]
B28) Imazosulfuron (TH-913),
[image - see original document]
B29) [alpha]-Chlor-N-(3-methoxy-2-thienyl)-methyl-2',6'- dimethylacetanilid (NSK-850),
B30) 4-Ethoxybenz-2',3'-dihydrochloranilid (HW-52),
B31) 1-Diethylcarbamoyl-3-(2,4,6-trimethylphenylsulfonyl)-1,2,4-triazol (CH-900)
[image - see original document]
B32) 3-(2-Chlorphenylmethyl)-1-(1-methyl-1-phenylethyl)- harnstoff (JC-940)
[image - see original document]
B33) 2-(2-Chlor-4-mesylbenzoyl)-cyclohexan-1,3-dion (ICIA-0051)
[image - see original document]
enthält, ausser Mitteln mit einem wirksamen Gehalt an A in Kombination mit nur einer Verbindung B
aus der Gruppe B1 bis B9, B14 bis B16 oder B28.
[0007] Die Verbindungen A (Verbindungen der Formel (I)) sind aus den anfangs genannten
deutschen Patentanmeldungen bekannt.
[0008] Die Verbindungen B1)-B27) sind in "The Pesticide Manual", British Crop Protection
Council, 9th Ed., 1991 beschrieben; siehe B1) "Quinchlorac", S. 749; B2) "Molinate", S. 594, B3)
"Thiobencarb", S. 815; B4) "Butachlor", S. 106; B5) "Pretilachlor", S. 699; B6) "Dithiopyr", S. 321;
B7) "Mefenacet", S. 544; B8) "Fenoxaprop", S. 374; B9) "Dimepiperat", S. 289; B10) "Pyrazolynate",
S. 733; B11) "Pyrazoxyfen", S. 736; B12) "Benzofenap", S. 67; B13) "Naproanilid", S. 610; B14)
"Bensulfuron-methyl", S. 62; B15) "Pyrazosulfuron-ethyl"; S. 735; B16) "Cinosulfuron", S. 174; B17)
"Benfuresate", S. 58; B18) "Bromobutide", S. 97; B19) "Daimuron", S. 221; B20) "Dimethametryne",
S. 291; B21) "Esprocarb", S. 338; B22) "Pyributicarb", S. 741; B23) "Butenachlor", S. 108; B24)
"Piperophos", S. 688; B25) "Anilofos", S. 36; B26) "Cinmethylin", S. 173; B27) "Propanil" (STAM),
S. 715.
[0009] Verbindung B28) "Imazosulfuron" (TH-913) ist bekannt aus der Patentanmeldung EP-A-02
38 070.
Verbindung B29) ist als NSK-850 bekannt und von M. Ogasawara et al. in "Weed Research", (Tokyo),
1989, Seiten 131-137, beschrieben.
Verbindung B30) ist als HW-52 bekannt und von N. Ichizen et al. in "Weed Research", (Tokyo), 1990,
Seiten 261-267, beschrieben.
Verbindung B31) ist als CH-900 bekannt und in EP-332 133 beschrieben.
Verbindung B32) ist als JC-940 bekannt und in J-6 0087 254 beschrieben.
[0010] Von besonderem Interesse sind erfindungsgemässe herbizide Mittel mit Verbindungen der
genannten Formel (I) oder deren Salzen, worin
110/2194
a1) R Ethoxy, Propoxy oder Isopropoxy und
R in Position 6 orientiert ist und die obengenannte Bedeutung hat, und
n 0 oder 1 oder
a2) R gegebenenfalls ungesättigtes C1-C4-Alkoxy, das substituiert ist durch Halogen, C1-C4-Alkoxy,
C1-C4-Alkylthio oder -sulfinyl oder -sulfonyl, (C1-C4-Alkoxy)-carbonyl, NO2, CN oder Phenyl;
ferner C2-C5-Alkenyloxy oder C2-C4-Alkinyloxy und
R C1-C4-Alkyl, C2-C5-Alkenyl, (C1-C4-Alkoxy)-carbonyl, C1-C4-Alkoxy oder C1-C4-Alkylthio,
die wie oben angegeben substituiert sein können, oder Halogen und
n 0 oder 1 oder
a3) R Methoxy, Ethyl oder Propyl und
R 6-Methoxycarbonyl oder 6-Ethoxycarbonyl und
n 1 sowie
in allen Fällen a1)-a3)
R Wasserstoff, C1-C4-Alkyl, insbesondere Wasserstoff oder Methyl,
R>;4;, R>;5; Halogen, C1-C4-Alkyl, C1-C4-Alkoxy oder C1-C4-Alkylthio, wobei die letztgenannten
3 Reste unsubstituiert oder durch Halogen, C1-C4- Alkoxy oder C1-C4-Alkylthio substituiert sind,
Y O oder S, insbesondere O,
E CH oder N, insbesondere CH,
bedeuten.
[0011] Gesättigtes oder uungesättigtes Alkyl und Alkoxy bedeutet entsprechend geradkettiges oder
verzweigtes Alkyl bzw. Alkoxy, Halogen bedeutet F, Cl, Br und J, vorzugsweise F und Cl.
[0012] Die Verbindungen der Formel (I) können Salze bilden, bei denen der Wasserstoff der -SO2NH-Gruppe durch ein für die Landwirtschaft geeignetes Kation ersetzt wird. Diese Salze sind im
allgemeinen Metall-, insbesondere Alkali-, Erdalkali-, gegebenenfalls alkylierte Ammonium- oder
organische Aminsalze.
[0013] Bei den genannten Formeln für die Verbindungen A und B wurde die Stereochemie nicht im
einzelnen angegeben. Sofern Stereoisomere vorkommen können, sind mit den Formeln auch alle
geometrischen Isomeren, Enantiomeren und Diastereomeren sowie deren Gemische umfasst. Bei der
Verbindung B8) ist insbesondere auch D-Fenoxapropethyl umfasst und bevorzugt.
[0014] Bevorzugte herbizide Mittel enthalten als Verbindungen A ein oder mehrere Verbindungen
der Formeln A1, A2 und A3, wobei die Formeln folgendes bedeuten:
[image - see original document]
[0015] Als spezielle Beispiele für die beanspruchten Wirkstoffmischungen seien hier genannt, ohne
dass dadurch eine Einschränkung erfolgen soll:
A1 + pyrazolate + mefenacet
A1 + pyrazolate + mefenacet + dymuron
A1 + pyrazolate + mefenacet + dimethametryn
A1 + pyrazolate + esprocarb
A1 + pyrazolate + esprocarb + dymuron
A1 + pyrazolate + esprocarb + dimethametryn
A1 + pyrazolate + benthiocarb
A1 + pyrazolate + benthiocarb + dymuron
A1 + pyrazolate + benthiocarb + dimethametryn
A1 + pyrazolate + dimepiperate
A1 + pyrazolate + dimepiperate + dymuron
A1 + pyrazolate + dimepiperate + dimethametryn
A1 + pyrazolate + TSH 888
A1 + pyrazolate + TSH 888 + dymuron
A1 + pyrazolate + TSH 888 + dimethametryn
A1 + pyrazolate + molinate
A1 + pyrazolate + molinate + dymuron
A1 + pyrazolate + molinate + dimethametryn
A1 + pyrazolate + pretilachlor
A1 + pyrazolate + pretilachlor + dymuron
A1 + pyrazolate + pretilachlor + dimethametryn
A1 + pyrazolate + butachlor
A1 + pyrazolate + butachlor + dymuron
111/2194
A1 + pyrazolate + butachlor + dimethametryn
A1 + pyrazolate + NSK 850
A1 + pyrazolate + NSK 850 + dymuron
A1 + pyrazolate + NSK 850 + dimethametryn
A1 + pyrazolate + KH218
A1 + pyrazolate + KH218 + dymuron
A1 + pyrazolate + KH218 + dimethametryn
A1 + pyrazolate + CH900
A1 + pyrazolate + CH900 + dymuron
A1 + pyrazolate + CH900 + dimethametryn
A1 + pyrazolate + fenoxaprop-ethyl
A1 + pyrazolate + fenoxaprop-ethyl + dymuron
A1 + pyrazolate + fenoxaprop-ethyl + dimethametryn
A1 + pyrazolate + dithiopyr
A1 + pyrazolate + dithiopyr + dymuron
A1 + pyrazolate + dithiopyr + dimethametryn
A1 + pyrazolate + anilofos
A1 + pyrazolate + anilofos + dymuron
A1 + pyrazolate + anilofos + dimethametryn
A1 + benfuresate + mefenacet
A1 + benfuresate + mefenacet + dymuron
A1 + benfuresate + mefenacet + dimethametryn
A1 + benfuresate + esprocarb
A1 + benfuresate + esprocarb + dymuron
A1 + benfuresate + esprocarb + dimethametryn
A1 + benfuresate + benthiocarb
A1 + benfuresate + benthiocarb + dymuron
A1 + benfuresate + benthiocarb + dimethametryn
A1 + benfuresate + dimepiperate
A1 + benfuresate + dimepiperate + dymuron
A1 + benfuresate + dimepiperate + dimethametryn
A1 + benfuresate + TSH 888
A1 + benfuresate + TSH 888 + dymuron
A1 + benfuresate + TSH 888 + dimethametryn
A1 + benfuresate + molinate
A1 + benfuresate + molinate + dymuron
A1 + benfuresate + molinate + dimethametryn
A1 + benfuresate + pretilachlor
A1 + benfuresate + pretilachlor + dymuron
A1 + benfuresate + pretilachlor + dimethametryn
A1 + benfuresate + butachlor
A1 + benfuresate + butachlor + dymuron
A1 + benfuresate + butachlor + dimethametryn
A1 + benfuresate + NSK 850
A1 + benfuresate + NSK 850 + dymuron
A1 + benfuresate + NSK 850 + dimethametryn
A1 + benfuresate + KH218
A1 + benfuresate + KH218 + dymuron
A1 + benfuresate + KH218 + dimethametryn
A1 + benfuresate + CH900
A1 + benfuresate + CH900 + dymuron
A1 + benfuresate + CH900 + dimethametryn
A1 + benfuresate + fenoxaprop-ethyl
A1 + benfuresate + fenoxaprop-ethyl + dymuron
A1 + benfuresate + fenoxaprop-ethyl + dimethametryn
A1 + benfuresate + dithiopyr
A1 + benfuresate + dithiopyr + dymuron
A1 + benfuresate + dithiopyr + dimethametryn
A1 + benfuresate + anilofos
112/2194
A1 + benfuresate + anilofos + dymuron
A1 + benfuresate + anilofos + dimethametryn
[0016] Die erfindungsgemässen herbiziden Mittel weisen eine ausgezeichnete herbizide
Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler Schadpflanzen
auf. Auch schwer bekämpfbare perennierende Unkräuter, die aus Rhizomen, Wurzelstöckchen oder
anderen Dauerorganen austreiben, werden durch die Wirkstoffkombinationen gut erfasst. Dabei ist es
gleichgültig, ob die Substanzen im Vorsaat-, Vorauflauf- oder Nachauflaufverfahren ausgebracht
werden. Im einzelnen seienn beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora
genannt, die durch die erfindungsgemässen Mittel kontrolliert werden können, ohne dass durch die
Nennung eine Beschränkung auf bestimmte Arten erfolgen soll.
[0017] Auf der Seite der monokotylen Unkrautarten werden z. B. Avena, Lolium, Alopecurus,
Phalaris, Echinochloa, Digitaria, Setaria sowie Cyperusarten aus der annuellen Gruppe und auf seiten
der perennierenden Spezies Agropyron, Cynodon, Imperata sowie Sorghum und auch ausdauernde
Cyperusarten gut erfasst.
[0018] Bei dikotylen Unkrautarten erstreckt sich das Wirkungsspektrum auf Arten wie z. B. Galium,
Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon und Sida auf
der annuellen Seite sowie Convolvulus, Cirsium, Rumex und Artemisia bei den perennierenden
Unkräutern.
[0019] Unkräuter, die unter den spezifischen Kulturbedingungen im Reis vorkommen, wie z. B.
Sagittaria, Alisma, Eleocharis, Scirpus und Cyperus werden von den erfindungsgemässen
Wirkstoffkombinationen ebenfalls hervorragend bekämpft.
[0020] Unter den spezifischen Kulturbedingungen im Mais und Reis werden wirtschaftlich wichtige
monokotyle Unkräuter, wie z. B. Alopecurus myosuroides, Avena fatua, Echinochloa crus-galli und
Setaria viridis, bekämpft.
[0021] Werden die erfindungsgemässen herbiziden Mittel vor dem Keimen auf die Erdoberfläche
appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert, oder die
Unkräuter wachsen bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und
sterben schliesslich nach Ablauf von drei bis vier Wochen vollkommen ab.
[0022] Bei Applikation der Wirkstoffkombinationen auf die grünen Pflanzenteile im
Nachauflaufverfahren tritt ebenfalls sehr rasch nach der Behandlung ein drastischer Wachstumsstop
ein, und die Unkrautpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wuchsstadium
stehen oder sterben nach einer gewissen Zeit mehr oder weniger schnell ab, so dass auf diese Weise
eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig durch den Einsatz
der neuen erfindungsgemässen Mittel beseitigt werden kann.
[0023] Obgleich die erfindungsgemässen Mittel eine ausgezeichnete herbizide Aktivität gegenüber
mono- und dikotylen Unkräutern aufweisen, werden Kulturpflanzen wirtschaftlich bedeutender
Kulturen, wie z. B. Weizen, Gerste, Roggen, Reis und Mais, nur unwesentlich oder gar nicht
geschädigt. Die Mittel eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von
unerwünschtem Pflanzenwuchs in landwirtschaftlichen Nutzpflanzungen.
[0024] Mit den erfindungsgemässen Wirkstoffkombinationen wird eine herbizide Wirkung erreicht,
die über das hinausgeht, was als additive Wirkung der Einzelkomponenten zu erwarten ist. Solche
Wirkungssteigerungen erlauben es, die Einsatzmengen der einzelnen Wirkstoffe erheblich zu
reduzieren. Darüberhinaus kann die Dauerwirkung der Kombinationen verbessert oder eine
Beschleunigung der Wirkungsgeschwindigkeit beobachtet werden. Diese vorteilhaften Eigenschaften
der erfindungsgemässen Wirkstoffkombinationen bieten dem Anwender erhebliche Vorteile bei der
praktischen Unkrautbekämpfung, indem er Unkräuter billiger oder rascher oder dauerhafter
bekämpfen kann und dadurch in einem Kulturpflanzenbestand bessere Erträge erzielt.
[0025] Ferner wurde gefunden, dass bei den erfindungsgemässen Wirstoffkombinationen eine
Safener- oder Antidotwirkung ausgeprägt vorhanden ist, d. h. dass phytotoxische Nebenwirkungen der
verwendeten Wirkstoffe bei Kulturpflanzen, wie z. B. dem Reis, herabgesetzt oder gänzlich vermieden
werden. Von besonderem Interesse sind die Safener Dymuron (Verbindung B19) und JC940
(Verbindung B32).
[0026] Die Mischungsverhältnisse A : B können innerhalb weiter Grenzen schwanken und liegen in
der Regel bei Zweiermischungen zwischen 2 : 1-1 : 200 und bei Dreier- bzw. Vierermischungen
(Wirkstoff A mit zwei bzw. drei Wirkstoffen B) entsprechend zwischen 2 : 1 : 1 bzw. 2 : 1 : 1 : 1-1 :
200 : 200 bzw. 1 : 200 : 200 : 200. Die Wahl des Mischungsverhältnisses ist abhängig vom
Mischungspartner, Entwicklungsstadium der Unkräuter, Unkrautspektrum und Klimabedingungen.
113/2194
[0027] Vorzugsweise werden bei Zweiermischungen Mischungsverhältnisse von 1 : 1- 1 : 100 und
bei Dreier- bzw. Vierermischungen Mischungsverhältnisse zwischen 1 : 1 : 1 bzw. 1 : 1 : 1 : 1 bis 1 :
100 : 100 bzw. 1 : 100 : 100 : 100 angewendet. Die Aufwandmengen des Herbizids A in
Wirkstoffmischungen liegen bevorzugt zwischen 10 und 100 g/ha, die Aufwandmengen von B
zwischen 0,02 und 4,0 kg/ha.
[0028] Die optimalen Mengenverhältnisse können in systematischen Versuchen ermittelt werden.
Beim Einsatz von Dymron als Safener sind die Mengenverhältnisse 1 : 0,1- 1 : 50, vorzugsweise 1 : 1-1
: 30, insbesondere 1 : 10-1 : 30 geeignet.
[0029] Die erfindungsgemässen Wirkstoffkombinationen können sowohl als Mischformulierungen
der beiden Komponenten vorliegen, die dann in üblicher Weise mit Wasser verdünnt zur Anwendung
gebracht werden, oder als sogenannte Tankmischungen durch gemeinsame Verdünnung der getrennt
formulierten Komponenten mit Wasser hergestellt werden. Die Verbindungen A und B oder deren
Kombinationen können auf verschiedene Art formuliert werden, je nachdem welche biologischen
und/oder chemisch-physikalischen Parameter vorgegeben sind. Als Formulierungsmöglichkeiten
kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche Pulver (SP), wasserlösliche
Konzentrate, emulgierbare Konzentrate (EC), wässrige Lösungen (SL), Emulsionen (EW) wie Öl-inWasser- und Wasser-in-Öl-Emulsionen, versprühbare Lösungen oder Emulsionen, Dispersionen auf
Öl- oder Wasserbasis, Suspensionskonzentrate (SC), (Suspoemulsionen), ölmischbare Lösungen,
Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel, Granuzlate zur Boden- oder
Streuapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulate,
wasserlösliche Granulate (SG), wasserdispergierbare Granulate (WG), ULV-Formulierungen,
Mikrokapseln oder Wachse.
[0030] Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise
beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München,
4. Aufl. 1986; van Valkenburg, "Pesticides Formulations", Marcel Dekker H. Y., 2nd Ed. 1972-73; K.
Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
[0031] Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und
weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins,
"Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H. v.
Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley Sons, N. Y., Marsden, "Solvents
Guide", 2nd Ed., Interscience, N. Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC
Publ. Gorp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem.
Publ. Co. Inc., H. Y. 1964; Schönfeldt, Grenzflächenaktive Äthylenoxidaddukte", Wiss.
Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Band 7, G. Hauser
Verlag München, 4. Aufl. 1986.
[0032] Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid
wirksamen Stoffen, wie anderen Herbiziden, Fungiziden oder Insektiziden, sowie Düngemitteln
und/oder Wachstumsregulatoren herstellen, z. B. in Form einer Fertigformulierung oder als Tankmix.
[0033] Spritzpulver sind in Wasser gleichmässig dispergierbare Präparate, die neben dem Wirkstoff
ausser einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art
(Netzmittel, Dispergiermittel), z. B. polyoxethylierte Alkylphenole, polyoxethylierte Fettalkohole oder
Fettamine, Fettalkoholpolyglykolethersulfate, Alkansulfonate, Alkylbenzolsulfonate,
ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalinsulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der
Spritzpulver werden die herbiziden Wirkstoffe beispielsweise in üblichen Apparaturen wie
Hammermühlen, Gebläsemühlen und Luftstrahlmühlen feingemahlen und gleichzeitig oder
anschliessend mit den Formulierungshilfsmitteln vermischt.
[0034] Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen
Lösungsmittel, z. B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden
Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösungsmittel unter Zusatz
von einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt.
Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calcium-Salze wie
Ca-Dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester,
Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-EthylenoxidKondensationsprodukte, Alkylpolyether, Sorbitanfettsäureester, Polyoxyethylensorbitanfettsäureester
oder Polyoxethylensorbitester.
[0035] Stäubemittel erhält man durch Vermahlen des Wirkstoffes mit fein verteilten festen Stoffen,
z. B. Talkum, natürlichen Tonen wie Kaolin, Bentonit und Pyrophyllit oder Diatomeenerde.
114/2194
[0036] Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise
durch Nass-Vermahlung mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden,
wie sie z. B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, hergestellt werden.
[0037] Emulsionen, z. B. Öl-in-Wasser-Emulsionen (EW), lassen sich beispielsweise mittels
Rührern, Kolloidmühlen und/oder statischen Mischern unter Verwendung von wässrigen organischen
Lösungsmitteln und gegebenenfalls Tensiden, wie sie z. B. oben bei den anderen Formulierungstypen
bereits aufgeführt sind, herstellen.
[0038] Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges,
granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels
Klebemitteln, z. B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die
Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können
geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.
[0039] Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie
Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit
Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt.
[0040] Die agrochemischen Zubereitungen enthalten in der Regel 0,1 bis 99 Gewichtsprozente,
insbesondere 2 bis 95 Gew.-%, Wirkstoffe A bzw. B. Die Konzentrationen der Wirkstoffe A und B
können in den Formulierungen verschieden sein.
[0041] In Spritzpulvern beträgt die Wirkstoffkonzentration z. B. etwa 10 bis 95 Gew.-%, der Rest zu
100 Gew.-% besteht aus übliche Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann
die Wirkstoffkonzentration etwa 1 bis 85 Gew.-%, vorzugsweise 5 bis 80 Gew.-% betragen.
Staubförmige Formulierungen enthalten etwa 1 bis 25 Gew.-%, meistens 5 bis 20 Gew.-% an
Wirkstoff, versprühbare Lösungen etwa 0,2 bis 25 Gew.-%, vorzugsweise 2 bis 20 Gew.-% Wirkstoff.
Bei Granulaten wie wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab,
ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel und Füllstoffe
verwendet werden. In der Regel liegt der Gehalt bei den in Wasser dispergierbaren Granulaten
zwischen 10 und 90 Gew.-%.
[0042] Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils
üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und
Lösungsmittel, Füll-, Träger- und Farbstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert
und die Viskosität beeinflussende Mittel.
[0043] Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen
gegebenenfalls in üblicher Weise verdünnt, z. B. bei Spritzpulvern, emulgierbaren Konzentraten,
Dispersionen und wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen,
Boden- bzw. Streugranulate, sowie versprühbare Lösungen werden vor der Anwendung üblicherweise
nicht mehr mit weiteren inerten Stoffen verdünnt.
[0044] Mit den äusseren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten
Herbizids u. a. variiert die erforderliche Aufwandmenge der Verbindungen der Formel (I).
Auführungsbeispiel
[0045]
Folgende Beispiele dienen zur Erläuterung der Erfindung:
A. Formulierungsbeispiele
a) Ein Stäubmittel wird erhalten, indem man 10 Gew.-Teile einer erfindungsgemässen
Wirkstoffkombination und 90 Gew.-Teile Talkum als Inertstoff mischt und in einer Schlagmühle
zerkleinert.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 Gewichtsteile
Wirkstoff A+B 64 Gewichtsteile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile
ligninsulfonsaures Kalium und 1 Gew.-Teil oleoylmethyltaurinsaures Natrium als Netz- und
Dispergiermittel mischt und in einer Stiftmühle mahlt.
c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20
Gewichtsteile Wirkstoff A+B mit 6 Gew.-Teilen Alkylphenolpolyglykolether ( Triton X 207), 3 Gew.Teile Isotridecanolpolyglykolether (8 EO) und 71 Gew.-Teilen paraffinisches Mineralöl (Siedebereich
z. B. ca. 255 bis über 277 C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron
vermahlt.
d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew.-Teilen Wirkstoff A+B, 75 Gew.-Teilen
Cyclohexanon als Lösemittel und 10 Gew.-Teilen oxethyliertes Nonylphenol als Emulgator.
115/2194
e) Ein in Wasser dispergierbares Granulat wird erhalten, indem man
75 Gewichtsteile Wirkstoffe A+B,
10 Gewichtsteile ligninsulfonsaures Calcium,
5 Gewichtsteile Natriumlaurylsulfat,
3 Gewichtsteile Polyvinylalkohol und
7 Gewichtsteile Kaolin
micht, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch Aufsprühen von Wasser
als Granulierflüssigkeit granuliert.
f) Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man
25 Gewichtsteile Wirkstoffe A+B,
5 Gewichtsteile 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium,
2 Gewichtsteile oleoylmethyltaurinsaures Natrium,
1 Gewichtsteil Polyvinylalkohol,
17 Gewichtsteile Calciumcarbonat und
50 Gewichtsteile Wasser
auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschliessend auf einer Perlmühle mahlt
und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse zerstäubt und trocknet.
g) Ein Spritzpulver wird erhalten, indem man 3 Gewichtsteile Wirkstoff A, 30 Gewichtsteile Wirkstoff
B, 3 Gewichtsteile ligninsulfonsaures Natrium, 63 Gewichtsteile kaolinhaltigen Quarz und 1
Gewichtsteil dioctylsulfonsuccinatsaures Natrium mischt und mahlt.
h) Ein Granulat wird erhalten, indem man
0,1 Gewichtsteile Wirkstoff A,
1,5 Gewichtsteile Wirkstoff B,
0,5 Gewichtsteile Neochol,
35 Gewichtsteile Bentonit und
62,9 Gewichtsteile Talk
mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett granuliert.
Biologische Beispiele
1. Unkrautwirkung im Vorauflauf
[0046] Samen bzw. Rhizomstücke von mono- und dikotylen Unkrautpflanzen wurden in
Plastiktöpfen von 9 cm Durchmesser in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Im
Reisanbau vorkommende Unkräuter wurden im mit Wasser gesättigten Boden kultiviert, wobei so viel
Wasser in die Töpfe gefüllt wird, dass das Wasser bis zu Bodenoberfläche oder einige Millimeter
darüber steht. Die in Form von benetzbaren Pulvern oder Emulsionskonzentraten formulierten
erfindungsgemässen Wirkstoffkombinationen sowie in parallelen Versuchen die entsprechend
fomulierten Einzelwirkstoffe wurden dann als wässrige Suspensionen bzw. Emulsionen mit einer
Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha in unterschiedlichen Dosierungen auf die
Oberfläche der Abdeckerde appliziert oder beim Reis ins Bewässerungswasser gegossen.
[0047] Nach der Behandlung wurden die Töpfe im Gewächshaus aufgestellt und unter guten
Wachstumsbedingungen für die Unkräuter gehalten. Die optische Bonitur der Pflanzen- bzw. der
Auflaufschäden erfolgte nach dem Auflaufen der Versuchspflanzen nach einer Versuchszeit von 3 bis
4 Wochen im Vergleich zu unbehandelten Kontrollen. Die erfindungsgemässen herbiziden Mittel
wiesen eine gute herbizide Verauflaufwirksamkeit gegen ein breites Spektrum von Ungräsern und
Unkräutern auf.
[0048] In allen Fällen wurde bei den Kombinationen zwischen dem errechneten und dem
gefundenen Wirkungsgrad unterschieden. Der errechnete, theoretisch zu erwartende Wirkungsgrad
einer Kombination wird ermittelt nach der Formel von S. R. Colby: Calculation of synergistic and
antagonistic responses of herbicide combinations, Weeds 15, Seiten 20-22 (1967).
[0049] Diese Formel lautet für Zweierkombinationen:
[image - see original document]
und für die Kombination von drei herbiziden Wirkstoffen entsprechend:
[image - see original document]
wobei
X=% Schädigung durch Herbizid A bei x kg/ha Aufwandmenge;
Y=% Schädigung durch ein Herbizid B bei y kg/ha Aufwandmenge;
Z=% Schädigung durch ein Herbizid B bei z kg/ha Aufwandmenge;
116/2194
E=die zu erwartende Schädigung durch die Herbizide A+B (bzw. A+B+C) bei x+y (bzw. x+y+z)
kg/ha.
[0050] Ist die tatsächliche Schädigung grösser als die rechnerisch zu erwartende, so ist die Wirkung
der Kombination mehr als additiv, d. h. es liegt ein synergistischer Wirkungseffekt vor.
[0051] Die erfindungsgemässen Wirkstoffkombinationen haben eine herbizide Wirkung, die höher
ist als sie aufgrund der beobachteten Wirkungen der Einzelkomponenten bei alleiniger Anwendung
nach Colby zu erwarten ist. Die Wirkstoffkombinationen sind somit synergistisch.
2. Unkrautwirkung im Nachauflauf
[0052] Samen bzw. Rhizomstücke von mono- und dikotylen Unkräutern wurden in Plastiktöpfen in
sandigem Lehmboden ausgelegt, mit Erde abgedeckt und im Gewächshaus unter guten
Wachstumsbedingungen angezogen. Im Reisanbau vorkommende Unkräuter wurden in Töpfen
angezogen, in denen Wasser bis zu 2 cm über der Bodenoberfläche steht, und während der
Versuchsphase kultiviert. Drei Wochen nach der Aussaat werden die Versuchspflanzen im
Dreiblattstadium behandelt.
[0053] Die als Spritzpulver bzw. als Emulsionskonzentrate formulierten erfindungsgemässen
Wirkstoffkombinationen sowie in parallelen Versuchen die entsprechend formulierten
Einzelwirkstoffe wurden in verschiedenen Dosierungen mit einer Wasseraufwandmenge von
umgerechnet 300 bis 600 l/ha auf die grünen Pflanzenteile gesprüht und nach ca. 3 bis 4 Wochen
Standzeit der Versuchspflanzen im Gewächshaus unter optimalen Wachstumsbedingungen die
Wirkung der Präparate optisch im Vergleich zu unbehandelten Kontrollen bonitiert. Bei Unkräutern,
die im Reisanbau vorkommen, wurden die Wirkstoffe auch direkt ins Bewässerungswasser gegeben
(Applikation in Analogie zur sogenannten Granulatanwendung) oder auf Pflanzen und ins
Bewässerungswasser gesprüht. Die erfindungsgemässen Mittel wiesen auch im Nachauflauf eine gute
herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger Ungräser und Unkräuter
auf. Die Wirkungen der erfindungsgemässen Mittel sind nach der Colby-Anlyse synergistisch.
3. Safenerwirkung in Reis
[0054] Jeweils 2 Reispflanzen (2-Blatt-Stadium) werden in Töpfen (0,01 m ) im Gewächshaus
kultiviert. Die erfindungsgemässe Wirkstoffkombination sowie die entsprechend formulierten
Einzelwirkstoffe wurden in Form von 10 ml Spritzbrühe 2 Tage nach dem Einpflanzen appliziert. Die
pflanzen wurden so kultiviert, dass das Wasser 2 cm über der Bodenoberfläche stand. Die tatsächlich
eingesetzten Konzentrationen der Wirkstoffe sind in der folgenden Tabelle angegeben. Das Gewicht
der Wurzeln und Triebe wurde 25 Tage nach der Applikation gemessen und im Verhältnis zum
Gewicht der unbekannten Kontrollen (100%) angegeben.
Safenerwirkung in Reis (Pflanztiefe 0,5 cm)
[image - see original document]
Safenerwirkung in Reis (Pflanztiefe 2,0 cm)
[image - see original document]
Synergistische Wirkung von Dymuron in Reis
[image - see original document]Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of DE4241629
1. Herbizide Mittel, gekennzeichnet durch einen wirksamen Gehalt an
A) Verbindungen der allgemeinen Formel (I) oder deren Salze
[image - see original document]
worin
a1) R Ethoxy, Propoxy oder Isopropoxy und
R Halogen, NO2, CF3, CN, C1-C4-Alkyl, C1-C4-Alkoxy, C1- C4-Alkylthio oder (C1-C4-Alkoxy)carbonyl und
n 0, 1, 2 oder 3 oder
a2) R gegebenenfalls ungesättigtes C1-C8-Alkoxy, das substituiert ist durch Halogen, gegebenenfalls
ungesättigtes C1-C6-Alkoxy, einen Rest der Formel (C1-C6-Alkyl)-S-, (C1-C6-Alkyl)-SO-, (C1-C6-
117/2194
Alkyl)-SO2-, (C1-C6- Alkyl)-O-CO-, NO2, CN oder Phenyl; ferner C2-C8-Alkenyloxy oder Alkinyloxy und
R gesättigtes oder ungesättigtes C1-C8-Alkyl, Phenyl, Phenoxy, C1-C4-Alkoxy, C1-C4-Alkylthio,
(C1-C4-Alkoxy)- carbonyl, wobei alle vorstehenden Reste für R durch Halogen, C1-C4-Alkoxy oder
C1-C4-Alkylthio substituiert sein können, oder Halogen, NO2, C1-C4-Alkylsulfonyl oder -sulfinyl
und
n 0, 1, 2 oder 3 oder
a3) R C1-C8-Alkoxy und
R C2-C8-Alkenyl oder -Alkinyl, Phenyl oder Phenoxy, wobei die genannten Reste für R
unsubstituiert oder durch Halogen, C1-C4-Alkoxy oder -Alkylthio substituiert sind, oder C1-C4Alkylsulfonyl oder -Alkylsulfinyl und
n 1, 2 oder 3 oder
a4) R jeweils in 2-Stellung am Phenylrest-Halogen, Methoxy, Ethyl oder Propyl,
R (C1-C4-Alkoxy)-carbonyl in 6-Stellung im Phenylrest und
n=1
sowie in allen Fällen a1)-a4)
R Wasserstoff, gesättigtes oder ungesättigtes C1-C8-Alkyl oder C1-C4-Alkoxy,
R>;4;, R>;5; unabhängig voneinander Wasserstoff, Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4Alkylthio, wobei die letztgenannten drei Reste unsubstituiert oder durch Halogen, C1-C4-Alkoxy oder
C1-C4-Alkylthio substituiert sind,
Y O oder S und
E CH oder N
bedeuten, in Kombination mit
B) einer, zwei oder mehr Verbindungen aus der Gruppe, welche die Verbindungen
B1) 3,7-Dichlorchinolin-8-carbonsäure und deren Salze, (Quinchlorac)
[image - see original document]
B2) N-(Ethylthio-carbonyl)-azepan (Molinate),
[image - see original document]
B3) N,N-Diethyl-carbaminsäure-4-chlorbenzylthioester (Thiobencarb),
[image - see original document]
B4) N-(Butoxymethyl)-2-chlor-N-(2,6-diethylphenyl)-acetamid (Butachlor)
[image - see original document]
B5) N-(2-Propoxyethyl)-2-chlor-N-(2,6-diethylphenyl)acetamid (Pretilachlor)
[image - see original document]
B6) 3,5-Bis(methylthio-carbonyl)-2-difluormethyl-4-(2- methylpropyl)-6-trifluormethyl-pyridin,
(MON-7200, Dithiopyr)
[image - see original document]
B7) 2-(1,3-Benzthiazol-2-yloxy)-N-methyl-acetanilid, (Mefenacet)
[image - see original document]
B8) 2-[4-(6-Chlor-benzoxazol-2-yloxy)-phenoxy]-propionsäureethylester, (Fenoxapropethyl)
[image - see original document]
B9) N-(2-Phenyl-prop-2-yl-thiocarbonyl)-piperidin (MY-93, Dimepiperate)
[image - see original document]
B10) 4-(2,4-Dichlorbenzoyl)-1,3-dimethyl-pyrazol-5-yl-toluyl-4-sulfonat (Pyrazolynate, Pyrazolate)
[image - see original document]
B11) 2-[4-(2,4-Dichlorbenzoyl)-1,3-dimethyl-pyrazol-5-yloxy]-acetophenon (Pyrazoxyfen)
[image - see original document]
118/2194
B12) 2-[4-(2,4-Dichlor-m-tolyl)-1,3-dimethylpyrazol-5-yloxy-4'- methylacetophenon (Benzofenap),
[image - see original document]
B13) 2-(2-Naphthyloxy)-propionanilid (Naproanilid),
[image - see original document]
B14) [alpha]-(4,6-Dimethoxypyrimidin-2-yl-carbamoyl-sulfamoyl)-O- toluolsäure-methylester
(Bensulfuron-methyl)
[image - see original document]
B15) 5-(4,6-Dimethoxypyrimidin-2-yl-carbamoylsulfamoyl)-1- methylpyrazol-4carbonsäuremethylester Pyrazosulfuronethyl),
[image - see original document]
B16) 1-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-3- [2-(2-methoxyethoxy)-phenylsulfonyl]-harnstoff
(Cinosulfuron),
[image - see original document]
B17) 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl-ethansulfonat (Benfuresate),
[image - see original document]
B18) 2-Brom-3,3-dimethyl-N-(1-methyl-1-phenylethyl)-butyramid (Bromobutide),
[image - see original document]
B19) 1-(1-methyl-1-phenylethyl)-3-p-toluyl-harnstoff (Dymuron, Daimuron),
[image - see original document]
B20) N -(1,2-Dimethylpropyl)-N>;4;-ethyl-6-methylthio-1,3,5-triazin- 2,4-diamin (Dimethametryn),
[image - see original document]
B21) S-Benzyl-1,2-dimethylpropyl(ethyl)-thiocarbamant (Esprocarb),
[image - see original document]
B22) O-3-tert-Butylphenyl-6-methoxy-2-pyridyl-(methyl)- thiocarbamat (Pyributicarb, TSH-888)
[image - see original document]
B23) (Z)-N-but-2-enyloxymethyl-2-chlor-2',6'-diethylacetanilid (Butenachlor, KH-218),
[image - see original document]
B24) S-2-Methylpiperidinocarbonylmethyl-O,O-dipropylphosphorodithionat (Piperophos),
[image - see original document]
B25) S-4-Chlor-N-isopropylcarbamiloylmethyl-O,O-dimethylphosphorodithionat (Anilofos),
[image - see original document]
B26) (1RS,2SR,4SR)-1,4-Epoxy-p-menth-2-yl-2- methylbenzylether (Cinmethylin),
[image - see original document]
B27) N-(3,4-dichlorophenyl)-propanamid (Propanil),
[image - see original document]
B28) Imazosulfuron (TH-913),
[image - see original document]
B29) [alpha]-Chlor-N-(3-methoxy-2-thienyl)-methyl-2',6'- dimethylacetanilid (NSK-850),
B30) 4-Ethoxybenz-2',3'-dihydrochloranilid (HW-52),
B31) 1-Diethylcarbamoyl-3-(2,4,6-trimethylphenylsulfonyl)-1,2,4-triazol (CH-900)
[image - see original document]
119/2194
B32) 3-(2-Chlorphenylmethyl)-1-(1-methyl-1-phenylethyl)- harnstoff (JC-940)
[image - see original document]
B33) 2-(2-Chlor-4-mesylbenzoyl)-cyclohexan-1,3-dion (ICIA-0051)
[image - see original document]
enthält, ausser Mitteln mit einem wirksamen Gehalt an A in Kombination mit nur einer Verbindung B
aus der Gruppe B1 bis B9, B14 bis B16 oder B28.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, dass es Verbindungen der Formel (I) oder deren
Salze enthält, worin
a1) R Ethoxy, Propoxy oder Isopropoxy und
R in Position 6 orientiert ist und die obengenannte Bedeutung hat, und
n 0 oder 1 oder
a2) R gegebenenfalls ungesättigtes C1-C4-Alkoxy, das substituiert ist durch Halogen, C1-C4-Alkoxy,
C1-C4-Alkylthio oder -sulfinyl oder -sulfonyl, (C1- C4-Alkoxy)-carbonyl, NO2, CN oder Phenyl;
ferner C2-C5-Alkenyloxy und
R C1-C4-Alkyl, C2-C5-Alkenyl, (C1-C4-Alkoxy)-carbonyl C1-C4- Alkoxy oder
C1-C4-Alkylthio, die wie oben angegeben substituiert sein können, oder Halogen und
n 0 oder 1 oder
a3) R Methoxy, Ethyl oder Propyl und
R 6-Methoxycarbonyl oder 6-Ethoxycarbonyl und
n 1 sowie
in allen Fällen a1)-a3)
R Wasserstoff, C1-C4-Alkyl,
R>;4;, R>;5; Halogen, C1-C4-Alkyl, C1-C4-Alkoxy oder C1-C4-Alkylthio, wobei die letztgenannten
3 Reste unsubstituiert oder durch Halogen, C1-C4-Alkoxy oder C1-C4-Alkylthio substituiert sind,
Y O oder S,
E CH oder N
bedeuten.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass sie ein oder mehrere Verbindungen
der Formel A1, A2 und A3 oder deren Salze
[image - see original document]
enthalten.
4. Mittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie 0,1 bis
99 Gew.-% der Wirkstoffe A und B neben üblichen Formulierungshilfsmitteln enthalten.
5. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie die
Wirkstoffe bei Zweiermischungen im Gewichtsverhältnis zwischen 2 : 1-1 : 200 und bei
Dreiermischungen zwischen 2 : 1 : 1-1 : 200 : 200, vorzugsweise bei Zweiermischungen von 1 : 1-1
:100 und bei Dreiermischungen zwischen 1 : 1 : 1-1 : 100 : 100 enthalten.
6. Verfahren zur Herstellung eines Mittels nach einem oder mehreren der Ansprüche 1 bis 5, dadurch
gekennzeichnet, dass man ein oder mehrere Verbindungen A mit einer oder mehreren Verbindungen B
analog einer üblichen Pflanzenschutzmittelformulierung aus der Gruppe, enthaltend Spritzpulver,
emulgierbare Konzentrate, wässrige Lösungen, Emulsionen, versprühbare Lösungen, Dispersionen auf
Öl- oder Wasserbasis, Suspoemulsionen, Suspensionskonzentrate, ölmischbare Lösungen,
Kapselsuspensionen, Granulate in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten,
Stäubemittel, Beizmittel, Boden- oder Streugranulate, wasserdispergierbare Granulate, ULVFormulierungen, Mikrokapseln und Wachse, formuliert.
7. Verfahren zur Bekämpfung von unerwünschten Pflanzen, dadurch gekennzeichnet, dass man auf
diese oder deren Anbauflächen eine herbizid wirksame Menge eines Mittels nach einem oder
mehreren der Ansprüche 1 bis 5 appliziert.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass Unkräuter in Nutzpflanzenkulturen
bekämpft werden.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die Nutzpflanzenkultur eine aus der
Gruppe Weizen, Gerste, Roggen, Reis und Mais ist.
10. Verwendung der herbiziden Mittel nach einem oder mehreren der Ansprüche 1 bis 5 zur
Unkrautbekämpfung in Nutzpflanzenkulturen.
11. Verwendung der Verbindungen vom Typ B, wie sie in Anspruch 1 definiert sind, zum Schutz von
Kulturpflanzen vor phytotoxischen Nebenwirkungen von Herbiziden.
120/2194
12. Verwendung der Verbindungen vom Typ B zum Schutz von Kulturpflanzen vor phytotoxischen
Nebenwirkungen von Herbiziden vom Typ A, wobei die Verbindungen vom Typ A und B wie in
Anspruch 1 definiert sind.
13. Verwendung der Verbindungen der Formel B19 oder B32 gemäss Anspruch 1 zum Schutz von
Kulturpflanzen vor phytotoxischen Nebenwirkungen von Herbiziden.
14. Verwendung der Verbindungen der Formel B19 oder B32 zum Schutz von Kulturpflanzen vor
phytotoxischen Nebenwirkungen von Herbiziden vom Typ der Verbindung der Formel (I), wobei die
Verbindungen der Formel B19, B32 und (I) wie in Anspruch 1 definiert sind.
15. Verfahren zum Schutz von Nutzpflanzen gegen phytotoxische Nebenwirkungen von Herbiziden,
dadurch gekennzeichnet, dass man Herbizide in Kombination mit Verbindungen vom Typ B gemäss
Anspruch 1 auf die Pflanzen, Pflanzensamen oder die Anbaufläche appliziert.
16. Verfahren gemäss Anspruch 15, dadurch gekennzeichnet, dass man Herbizide vom Typ A mit
Verbindungen vom Typ B kombiniert, wobei Typ A und B wie in Anspruch 1 definiert sind.
17. Verfahren gemäss Anspruch 15, dadurch gekennzeichnet, dass man Herbizide in Kombination mit
den Verbindungen der Formel B19 oder B32 gemäss Anspruch 1 einsetzt.
18. Verfahren gemäss Anspruch 16, dadurch gekennzeichnet, dass Herbizide vom Typ der Verbindung
A mit Verbindungen der Formel B19 oder B32 eingesetzt werden, wobei die Verbindungen vom Typ
A und der Formel B19 uund B32 wie in Anspruch 1 definiert sind.
19. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass bei einer
Mischung der Verbindung vom Typ A mit Dymron die Mengenverhältnisse 1 : 0,1-1 : 50,
vorzugsweise 1 : 1-1 : 30, insbesondere 1 : 10-1 : 30 lauten.Data supplied from the esp@cenet
database - Worldwide
121/2194
12. DE4440121
- 5/18/1995
SYNERGISTIC HERBICIDE COMBINATIONS FOR USE IN RICE CROPS
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=DE4440121
Inventor(s):
SCHUBERT HANS-HERBERT DR (DE); NAKAJIMA TAKEHIKO (JP); BAUER
KLAUS DR (DE); BIERINGER HERMANN DR (DE)
Applicant(s):
HOECHST SCHERING AGREVO GMBH (DE)
IP Class 4 Digits: A01N
IP Class:A01N43/36; A01N37/34
E Class: A01N47/36
Application Number:
DE19944440121 (19941110)
Priority Number: DE19944440121 (19941110); DE19934338843 (19931113)
Family: DE4440121
Abstract:
Abstract of DE4440121
A herbicide contains (A) a substd. N-phenoxysulphonyl-N'-(4,6-disubstd. pyrimid-2-yl)urea deriv. of
formula (I) or its salt; and (B) a (2-fluoro-4-cyanophenoxy)phenoxypropionic acid ester of formula (II)
or its salt. In (I), either (a) R>;1; = OEt, OPr or O-i-Pr; R>;2; = halogen, NO2, CF3, CN, 1-4C alkyl, 14C alkoxy, 1-4C alkylthio or (1-4C alkoxy)carbonyl; and n = 0-3; or (b) R>;1; = halogen, OMe, Et or
Pr; R>;2; = (1-4C alkoxy) carbonyl in position 6 on the Ph ring; and n = 1: R>;3; = H, opt. satd. 1-8C
alkyl or 1-4C alkoxy; R>;4;, R>;5; = H, halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio (these 3 opt.
substd. with halogen, 1-4C alkoxy or 1-4C alkylthio); Y = O or S; E = CH or N; R>;6; = H or 1-6C
alkyl.Description:
Description of DE4440121
Die Erfindung liegt auf dem Gebiet der Pflanzenschutzmittel, die gegen monokotyle und dikotyle
Unkräuter eingesetzt werden können. In den deutschen Patentanmeldungen P 38 16 704.2 (EP-A-0 342
569), P 38 16 703.4 (EP-A-0 342 568) und P 39 09 053.1 (EP-A-0 388 771) werden heterocyclisch
substituierte Phenoxysulfonylharnstoffe beschrieben, mit denen ein breites Spektrum mono- und
dikotyler Unkräuter bekämpft werden kann. Sie können sowohl als Bodenherbizid als auch übers Blatt
eingesetzt werden und zeigen auch eine besonders hohe Selektivität in monokotylen Kulturpflanzen
wie Getreide, Mais und Reis.
Aus P 39 33 543.7 und P 40 31 799.4 und P 42 09 475.5 sind Wirkstoffmischungen bekannt, die eine
synergistische Steigerung des Bekämpfungserfolges gegenüber wichtigen Problemunkräutern in
Getreide und Reis zeigen.
Im Reis existieren jedoch eine Reihe wirtschaftlich sehr wichtiger monokotyler Unkräuter, wie z. B.
Cyperus serotinus, Sagittaria spp., Eleocharis spp., Scirpus spp., Echinochloa spp. u. a. die mit den
erwähnten Mischungen alleine nicht in optimaler Weise zu bekämpfen sind.
Überraschenderweise konnten nun in biologischen Versuchen herbizide Wirkstoffe identifiziert
werden, die bei gemeinsamer Anwendung mit den obengenannten Einzelverbindungen ausgesprochen
synergetische Eigenschaften hinsichtlich der Effektivität gegen Unkräuter haben und somit den aus P
39 33 543.7 und P 42 09 475.5 bekannten Kombinationen überlegen sind.
122/2194
Gegenstand der vorliegenden Erfindung sind herbizide Mitteln, gekennzeichnet durch einen wirksamen
Gehalt an
A) Verbindungen der allgemeinen Formel (I) oder deren Salzen
EMI2.1
worin
a1) R>;1; Ethoxy, Propoxy oder Isopropoxy und
R>;2; Halogen, NO2, CF3, CN, C1-C4-Alkyl, C1-C4-Alkoxy, C1C4-Alkylthio oder (C1-C4-Alkoxy)-carbonyl und n 0, 1, 2 oder 3 oder
a2) R>;1; jeweils in 2-Stellung am Phenylrest - Halogen, Methoxy, Ethyl oder Propyl,
R>;2; (C1-C4-Alkoxy)-carbonyl in 6-Stellung im Phenylrest und
n =1
sowie in allen Fällen a1) und a2)
R>;3; Wasserstoff, gesättigtes oder ungesättigtes C1-C8-Alkyl oder C1-C4-Alkoxy,
R>;4;, R>;5; unabhängig voneinander Wasserstoff, Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4Alkylthio, wobei die letztgenannten drei Reste unsubstituiert oder durch Halogen, C1-C4-Alkoxy oder
C1-C4-Alkylthio substituiert sind,
Y O oder S und
E CH oder N
bedeuten,
in Kombination mit der Verbindung der Formel II (DEH-112, 2-Fluor-4cyanaphenoxyphenoxypropionsäureester, B) oder deren Salzen
EMI3.1
worin R>;6; Wasserstoff oder (C1-C6)-Alkyl bedeutet.
Als weitere Kombinationspartner können bei Bedarf ein oder mehrere bekannte Reisherbizide
unterschiedlichster Strukturklassen verwendet werden. Von besonderem Interesse sind Verbindungen
aus der Klasse der Sulfonylharnstoffe, der Harnstoffe, der Amide, der Cyclohexandione, der
Thiocarbamate oder der Chloracetanilide.
Als spezielle Beispiele für solche Kombinationspartner seien die folgenden Verbindungen genannt,
ohne dass dadurch eine Einschränkung erfolgen soll: C1, AC-014
C2, Anilofos
C3, Bentazone
C4, Bensulfuron-methyl
C5, Benzofenap
C6, Bromobutide
C7, Butachlor
C8, Butenachlor
C9, Cinmethylin
C10, Cinosulfuron
C11, alpha -Chlor-N-(3-methoxy-2-thienyl)-methyl-2 min ,6 min -dimethylacetanilid (NSK-850)
C12, Daimuron (1-(1-Methyl-1-phenylethyl)-3-p-tolyl-harnstoff)
C13, 1-Diethylcarbamoyl-3-(2,4,6-trimethylphenylsulfonyl-1,2,4-triazol (CH-900)
C14, Dimepiperate
C15, Dimethametryn
C16, Dithiopyr
C17, DPX-47
C18, Esprocarb
C19, 4-Ethoxybenz-2 min ,3 min -dihydrochloranilid (HW-52)
C20, Fenoxaprop-ethyl bzw.Fenoxaprop-P-ethyl
C21, Imazosulfuron
C22, JC 940 (1-(2-Chlorbenzyl)-3-( alpha , alpha -dimethylbenzyl)-harnstoff
C23, MCPB
C24, Mefenacet
C25, Molinate
C26, Naproanilide
123/2194
C27, Piperophos
C28, Pretilachlor
C29, Propanil
C30, Pyrazosulfuron-ethyl
C31, Pyrazoxyfen
C32, Pyrazolate
C33, Quinchlorac
C34, Simetryn
C35, Sulcotrione (Chlormesulone, ICI-A0051)
C36, Thiobencarb
C37, 2,4-D
Aber auch andere Reisherbizide können gemeinsam mit der erfindungsgemässen Kombination
vorteilhaft eingesetzt werden.
Die Verbindung A ist aus den anfangs genannten deutschen Patentanmeldungen bekannt. Die
Verbindung der Formel B ist aus der europäischen Patentanmeldung EP 0 302 203 bekannt geworden.
Bei den genannten Formeln für die Verbindungen A und B wurde die Stereochemie nicht im einzelnen
angegeben. Sofern Stereoisomere vorkommen können, sind mit den Formeln auch alle geometrischen
Isomeren, Enantiomeren und Diastereomeren sowie deren Gemische umfasst.
Die Verbindung DPX-47 = DPX-A8947, N-(((4-6-Dimethoxypyrimidin-2-yl)-aminocarboxyl)-1methyl-4-(2-methyl-2H-tetrazol-5-yl)-1-H-pyrazol-5-sulfo-namid hat die folgende Strukturformel: Die
Verbindung AC-014, 1-(2-(Cyclopropylcarbonylphenyl)-sulfamoyl)-3-(4,6- dimethoxy-pyrimidin-2yl)-harnstoff hat die folgende Strukturformel
EMI5.2
und ist aus dem US-Patent 5,009,699 vom 22.6.90 bekannt.
Die Verbindung JC 940 ist aus der japanischen Patentanmeldung J-60087254 bekannt.
Die Verbindung Imazosulfuron (TH-913) ist bekannt aus der Patentanmeldung EP- A-0 238 070 (s.
Beispiel 1).
Die Verbindung NSK-850 ( alpha -Chlor-N-(3-methoxy-2-thienyl)-methyl-2 min ,6 min dimethylacetanilid) ist von M. Ogasawara et al. in "Weed Research", (Tokyo), 1989, Seiten 131 bis
137, beschrieben.
Die Verbindung HW-52 (4-Ethoxybenz-2,3-dihydrochloranilid) ist von N. Ichizen et al. In "Weed
Research", (Tokyo), 1990, Seiten 261 bis 267, beschrieben.
Die Verbindung CH-900 (1-Diethylcarbamoyl-3-(2,4,6-trimethylphenylsulfonyl)-1,2,4- triazol) ist in
EP-332 133 beschrieben.
Die Verbindung Sulcotrione (Chlormesulone, 2-(2-Chlor-4-mesylbenzoyl)- cyclohexan-1,3-dion) ist
aus der EP 0 298 680 (s. Seite 13, Verbindung Nr. 51A) bekannt. Die anderen Verbindungen vom Typ
C sind in "The Pesticide Manual", British Crop Protection Council, 9th Ed., 1991 beschrieben.
Von besonderem Interesse sind erfindungsgemässe herbizide Mittel mit Verbindungen der genannten
Formel (I) oder deren Salzen, worin
a1) R>;1; Ethoxy, Propoxy oder Isopropoxy und
R>;2; in Position 6 orientiert ist und die obengenannte Bedeutung hat, und
n O oder 1 oder
in allen Fällen a1) und a2)
R>;3;, Wasserstoff, C1-C4-Alkyl, insbesondere Wasserstoff oder Methyl,
R>;4;, R>;5; Halogen, C1-C4-Alkyl, C1-C4-Alkoxy oder C1-C4-Alkylthio, wobei die letztgenannten
3 Reste unsubstituiert oder durch Halogen, C1-C4- Alkoxy oder C1-C4-Alkylthio substituiert sind,
Y Q, und
E CH bedeuten.
124/2194
Gesättigtes oder ungesättigtes Alkyl und Alkoxy bedeutet entsprechend geradkettiges oder verzweigtes
Alkyl bzw. Alkoxy, Halogen bedeutet F, Cl, Br und J, vorzugsweise F und Cl.
Die Verbindungen der Formel (I) können Salze bilden, bei denen der Wasserstoff der -SO2-NHGruppe durch ein für die Landwirtschaft geeignetes Kation ersetzt wird. Diese Salze sind im
allgemeinen Metall-, insbesondere Alkali-, Erdalkali-, gegebenenfalls alkylierte Ammonium- oder
organische Aminsalze.
Bevorzugte herbizide Mittel enthalten als Verbindungen A ein oder mehrere Verbindungen der
Formeln A1, A2 und A3, wobei die Formeln folgendes bedeuten: Als spezielle Beispiele für die
beanspruchten Wirkstoffmischungen seien hier genannt, ohne dass dadurch eine Einschränkung
erfolgen soll: 1. A1 + B
2. A1 + B + C10 (NSK 850)
3. A1 + B + C11 (CH 900)
4. A1 + B + C25 (Pretilachlor)
Die erfindungsgemässen Kombinationen zeigen bei gemeinsamer Anwendung eine ausserordentlich
gute Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler
Schadpflanzen auf. Auch schwer bekämpfbare perennierende Unkräuter, die aus Rhizomen,
Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die Wirkstoffkombinationen gut
erfasst. Dabei ist es gleichgültig, ob die Substanzen im Vorsaat-, Vorauflauf- oder
Nachauflaufverfahren ausgebracht werden. Im einzelnen seien beispielhaft einige Vertreter der monound dikotylen Unkrautflora genannt, die durch die erfindungsgemässen Mittel kontrolliert werden
können, ohne dass durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll.
Auf der Seite der monokotylen Unkrautarten werden z. B. Echinochloa sowie Cyperusarten aus der
annuellen Gruppe und auf seiten der perennierenden Spezies ausdauernde Cyperusarten gut erfasst. Die
unter den spezifischen Kulturbedingungen im Reis vorkommenden Unkräuter, wie z. B. Sagittaria,
Alisma, Rotala, Monochoria, Eleocharis, Scirpus, Cyperus etc., werden von den erfindungsgemässen
Wirkstoffkombinationen hervorragend bekämpft.
Werden die erfindungsgemässen herbiziden Mittel vor dem Keimen auf die Erdoberfläche appliziert, so
wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert, oder die Unkräuter wachsen
bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schliesslich nach
Ablauf von drei bis vier Wochen vollkommen ab.
Bei Applikation der Wirkstoffkombinationen auf die grünen Pflanzenteile oder im das
Bewässerungswasser der Reiskultur im Nachauflaufverfahren tritt ebenfalls sehr rasch nach der
Behandlung ein drastischer Wachstumsstop ein. Die Unkrautpflanzen bleiben in dem zum
Applikationszeltpunkt vorhandenen Wuchsstadium stehen oder sterben nach einer gewissen Zeit mehr
oder weniger schnell ab, so dass auf diese Weise eine für die Kulturpflanzen schädliche
Unkrautkonkurrenz sehr früh und nachhaltig durch den Einsatz der neuen erfindungsgemässen Mittel
beseitigt werden kann.
Obgleich die erfindungsgemässen Mittel eine ausgezeichnete herbizide Aktivität gegenüber mono- und
dikotylen Unkräutern aufweisen, wird die Kulturpflanze Reis nur unwesentlich oder gar nicht
geschädigt. Die Mittel eignen sich aus diesen Gründen besonders in Reis sehr gut zur selektiven
Bekämpfung von unerwünschtem Pflanzenwuchs.
Sie sind bezüglich Wirkungsbreite und Wirkungsstärke den bekannten Herbiziden und
Herbizidkombinationen überlegen und können in geringen Aufwandmengen eingesetzt werden.
Weitere Vorteile dieser neuen Kombinationen sind deren anhaltende Dauerwirkung, die mehrere
Wochen anhält und dadurch nachfolgende Herbizidapplikationen gegen neu keimende Unkräuter
erübrigt. So kann ein zweiter Arbeitsgang eingespart werden, indem mit einer einzigen Applikation der
konkurrierende Unkrautaufwuchs beseitigt wird.
Mit den erfindungsgemässen Wirkstoffkombinationen wird eine herbizide Wirkung erreicht, die über
das hinausgeht, was auf Grund der Wirkung der Einzelkomponenten zu erwarten ist. Diese
125/2194
Wirkungssteigerungen erlauben es, die Einsatzmengen der einzelnen Wirkstoffe erheblich zu
reduzieren. Die Kombination der Herbizide kann auch eine Beschleunigung der
Wirkungsgeschwindigkeit verursachen. Solche Eigenschaften bieten dem Anwender erhebliche
Vorteile bei der praktischen Unkrautbekämpfung. Er kann Unkräuter billiger, rascher, mit weniger
Arbeitsaufwand sowie dauerhafter bekämpfen und dadurch in einem Kulturpflanzenbestand mehr
Ertrag ernten.
Ferner wurde gefunden, dass bei einer Reihe der Wirkstoffkombinationen eine Safener- oder
Antidotwirkung ausgeprägt vorhanden ist, d. h. dass phytotoxische Nebenwirkungen der verwendeten
Wirkstoffe bei Kulturpflanzen, wie z. B. dem Reis, herabgesetzt oder gänzlich vermieden werden.
Die Mischungsverhältnisse A: B können innerhalb weiter Grenzen schwanken und liegen in der Regel
zwischen 1 : 1 bis 1 : 40. Die Wahl des Mischungsverhältnisses ist abhängig vom Mischungspartner,
Entwicklungsstadium der Unkräuter, Unkrautspektrum und Klimabedingungen.
Vorzugsweise werden Mischungsverhältnisse für A : B von 1 : 5 bis 1 : 30 angewendet. Die
Aufwandmengen des Herbizids A in den Wirkstoffmischungen liegen bevorzugt zwischen 10 und 100
g/ha, die Aufwandmengen von B zwischen 50 und 600 g/ha. Die Aufwandmengen für Verbindungen
aus der Gruppe C sind, da es sich zum Teil um verschiedene Strukturklassen handelt, sehr
unterschiedlich und liegen je nach Wirkstoff im Bereich von wenigen Gramm bis zu 3 kg AS/ha.
Die erfindungsgemässen Wirkstoffkombinationen können sowohl als Mischformulierungen der beiden
Komponenten vorliegen, die dann in üblicher Weise mit Wasser verdünnt zur Anwendung gebracht
werden, oder als sogenannte Tankmischungen durch gemeinsame Verdünnung der getrennt
formulierten Komponenten mit Wasser hergestellt werden.
Die Verbindungen A und B oder deren Kombinationen mit C können auf verschiedene Art formuliert
werden, je nachdem welche biologischen und/oder chemisch-physikalischen Parameter vorgegeben
sind.
Als Formulierungsmöglichkeiten kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche
Pulver (SP), wasserlösliche Konzentrate, emulgierbare Konzentrate (EC), wässrige Lösungen (SL),
Emulsionen (EW) wie Öl-in Wasser- und Wasser-in-Öl-Emulsionen, versprühbare Lösungen oder
Emulsionen, Dispersionen auf Öl- oder Wasserbasis, Suspensionskonzentrate (SC),
(Suspoemulsionen), ölmischbare Lösungen, Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel,
Granulate zur Boden- oder Streuapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugsund Adsorptionsgranulate, wasserlösliche Granulate (SG), wasserdispergierbare Granulate (WG),
ULV-Formulierungen, Mikrokapseln oder Wachse.
Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben
in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986;
van Valkenburg, "Pesticide Formulations", Marcel Dekker H. Y., 2nd Ed. 1972-73; K. Martens, "Spray
Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere
Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of
Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H. v. Olphen,
"Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley Sons, N.Y., Marsden, "Solvents Guide",
2nd Ed., Interscience, N.Y. 1950; McCutcheon min s, "Detergents and Emulsifiers Annual", MG Publ.
Gorp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co.
Inc., N. Y 1964; Schönfeldt, Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart
1976; Winnacker-Küchler, "Chemische Technologie", Band 7, G. Hauser Verlag München, 4. Aufl.
1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen
Stoffen, wie anderen Herbiziden, Fungiziden oder Insektiziden, sowie Düngemitteln und/oder
Wachstumsregulatoren herstellen, z. B. in Form einer Fertigformulierung oder als Tankmix.
126/2194
Spritzpulver sind in Wasser gleichmässig dispergierbare Präparate, die neben dem Wirkstoff ausser
einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel,
Dispergiermittel), z. B. polyoxethylierte Alkylphenole, polyoxethylierte Fettalkohole oder Fettamine,
Fettalkoholpolyglykolethersulfate, Alkansulfonate, Alkylbenzolsulfonate, ligninsulfonsaures Natrium,
2,2 min -dinaphthylmethan-6,6 min -disulfonsaures Natrium, dibutylnaphthalin-sulfonsaures Natrium
oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der Spritzpulver werden die
herbiziden Wirkstoffe beispielsweise in üblichen Armaraturen wie Hammermühlen, Gebläsemühlen
oder Luftstrahlmühlen feingemahlen und gleichzeitig oder anschliessend mit den
Formulierungshilfsmitteln vermischt.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen
Lösungsmittel, z. B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden
Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösungsmittel unter Zusatz von
einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als
Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calcium-Salze wie CaDodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester,
Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-EthylenoxidKondensationsprodukte, Alkylpolyether, Sorbitanfettsäureester, Polyoxyethylensorbitanfettsäureester
oder Polyoxethylensorbitester.
Stäubemittel erhält man durch Vermahlen des Wirkstoffes mit fein verteilten festen Stoffen, z. B.
Talkum, natürlichen Tonen wie Kaolin, Bentonit und Pyrophyllit oder Diatomeenerde.
Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise durch NassVermahlung mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden, wie sie z. B.
oben bei den anderen Formulierungstypen bereits aufgeführt sind, hergestellt werden.
Emulsionen, z. B. Öl-in-Wasser-Emulsionen (EW), lassen sich beispielsweise mittels Rührern,
Kolloidmühlen und/oder statischen Mischern unter Verwendung von wässrigen organischen
Lösungsmitteln und gegebenenfalls Tensiden, wie sie z. B. oben bei den anderen Formulierungstypen
bereits aufgeführt sind, herstellen.
Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes
Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels
Klebemitteln, z. B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die
Oberfläche von Trägerstoffen wie Sand, Kaoliniten oder von granuliertem Inertmaterial. Auch können
geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.
Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie
Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit
Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt.
Die agrochemischen Zubereitungen enthalten in der Regel 0,1 bis 99 Gewichtsprozente, insbesondere 2
bis 95 Gew.-%, Wirkstoffe A bzw. B und gegebenenfalls C. Die Konzentrationen der Wirkstoffe A, B
und C können in den Formulierungen verschieden sein.
In Spritzpulvern beträgt die Wirkstoffkonzentration z. B. etwa 10 bis 95 Gew.-%, der Rest zu 100
Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die
Wirkstoffkonzentration etwa 1 bis 85 Gew. -%, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförmige
Formulierungen enthalten etwa 1 bis 25 Gew.-%, meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare
Lösungen etwa 0,2 bis 25 Gew.-%, vorzugsweise 2 bis 20 Gew.-% Wirkstoff. Bei Granulaten wie
wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame
Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel und Füllstoffe verwendet
werden. In der Regel liegt der Gehalt bei den in Wasser dispergierbaren Granulaten zwischen 10 und
90 Gew.-%.Bei Streugranulaten, die direkt ins Bewässerungswasser ausgestreut werden, werden in der
Regel Wirkstoffgehalte von 1 bis 10% bevorzugt.
127/2194
Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-,
Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösungsmittel, Füll-,
Träger- und Farbstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert und die Viskosität
beeinflussende Mittel.
Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen gegebenenfalls in
üblicher Weise verdünnt, z. B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und
wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw.
Streugranulate, sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr
mit weiteren inerten Stoffen verdünnt.
Mit den äusseren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten Herbizids u. a.
variiert die erforderliche Aufwandmenge der Verbindungen A und B. Die erforderliche
Aufwandmenge der zusätzlich eingesetzten Reisherbizide (C) schwankt ebenfalls in Abhängigkeit von
den äusseren Bedingungen.
Folgende Beispiele dienen zur Erläuterung der Erfindung:
A. Formulierungsbeispiele
a) Ein Stäubmittel wird erhalten, indem man 10 Gew.-Teile einer erfindungsgemässen
Wirkstoffkombination und 90 Gew.-Teile Talkum als Inertstoff mischt und in einer Schlagmühle
zerkleinert.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25
Gewichtsteile Wirkstoff A + B, 64 Gewichtsteile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile
ligninsulfonsaures Kalium und 1 Gew.-Teil oleoylmethyltaurinsaures Natrium als Netz- und
Dispergiermittel mischt und in einer Stiftmühle mahlt.
c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20
Gewichtsteile Wirkstoff A + B mit 6 Gew.-Teilen Alkylphenolpolyglykolether ( TM Triton X 207), 3
Gew.-Teile Isotridecanolpolyglykolether (8 E0) und 71 Gew.-Teilen paraffinisches Mineralöl
(Siedebereich z. B. ca. 255 bis über 277 DEG C) mischt und in einer Reibkugelmühle auf eine Feinheit
von unter 5 Mikron vermahlt.
d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew.-Teilen Wirkstoff A + B, 75 Gew.-Teilen
Cyclohexanon als Lösemittel und 10 Gew.-Teilen oxethyliertes Nonylphenol als Emulgator.
e) Ein in Wasser dispergierbares Granulat wird erhalten, indem man 75 Gewichtsteile Wirkstoffe A +
B,
10 Gewichtsteile ligninsulfonsaures Calcium,
5 Gewichtsteile Natriumlaurylsulfat,
3 Gewichtsteile Polyvinylalkohol und
7 Gewichtsteile Kaolin mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch
Aufsprühen von Wasser als Granulierflüssigkeit granuliert.
f) Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man 25 Gewichtsteile
Wirkstoffe A + B,
5 Gewichtsteile 2,2 min -dinaphthylmethan-6,6 min -disulfonsaures Natrium,
2 Gewichtsteile oleoylmethyltaurinsaures Natrium,
1 Gewichtsteil Polyvinylalkohol,
17 Gewichtsteile Calciumcarbonat und
50 Gewichtsteile Wasser auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschliessend auf
einer Perlmühle mahlt und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse
zerstäubt und trocknet.
Biologische Beispiele
1. Unkrautwirkung im Vorauflauf
128/2194
Samen bzw. Rhizomstücke von, mono- und dikotylen Unkrautpflanzen werden in Plastiktöpfen von 9
cm Durchmesser in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Im Reisanbau
vorkommende Unkräuter werden im mit Wasser gesättigten Boden kultiviert, wobei so viel Wasser in
die Töpfe gefüllt wird, dass das Wasser bis zu Bodenoberfläche oder einige Millimeter darüber steht.
Die in Form von benetzbaren Pulvern oder Emulsionskonzentraten formulierten erfindungsgemässen
Wirkstoffkombinationen sowie in parallelen Versuchen die entsprechend formulierten Einzelwirkstoffe
werden dann als wässrige Suspensionen bzw. Emulsionen mit einer Wasseraufwandmenge von
umgerechnet 600 bis 800 l/ha in unterschiedlichen Dosierungen auf die Oberfläche der Abdeckerde
appliziert oder beim Reis ins Bewässerungswasser gegossen.
Nach der Behandlung werden die Töpfe im Gewächshaus aufgestellt und unter guten
Wachstumsbedingungen für die Unkräuter gehalten. Die optische Bonitur der Pflanzen- bzw. der
Auflaufschäden erfolgte nach dem Auflaufen der Versuchspflanzen nach einer Versuchszeit von 3 bis 4
Wochen im Vergleich zu unbehandelten Kontrollen. Die erfindungsgemässen herbiziden Mittel weisen
eine gute herbizide Vorauflaufwirksamkeit gegen ein breites Spektrum von Ungräsern und Unkräutern
auf.
In allen Fällen wurde bei den Kombinationen zwischen dem errechneten und dem gefundenen
Wirkungsgrad unterschieden. Der errechnete, theoretisch zu erwartende Wirkungsgrad einer
Kombination wird ermittelt nach der Formel von S. R. Colby: Calculation of synergistic and
antagonistic responses of herbicide combinations, Weeds 15, Seiten 20-22 (1967).
Diese Formel lautet für Zweierkombinationen:
EMI16.1
und für die Kombination von drei herbiziden Wirkstoffen entsprechend:
EMI17.1
wobei
X = % Schädigung durch Herbizid A bei x kg/ha Aufwandmenge;
Y = % Schädigung durch ein Herbizid B bei y kg/ha Aufwandmenge;
Z = % Schädigung durch ein Herbizid C bei z kg/ha Aufwandmenge;
E = die zu erwartende Schädigung durch die Herbidzide A + B (bzw. + C) bei x + y (bzw. + z) kg/ha.
Ist die tatsächliche Schädigung grösser als die rechnerisch zu erwartende, so ist die Wirkung der
Kombination mehr als additiv, d. h. es liegt ein synergistischer Wirkungseffekt vor.
Die erfindungsgemässen Wirkstoffkombinationen haben eine herbizide Wirkung, die höher ist als sie
aufgrund der beobachteten Wirkungen der Einzelkomponenten bei alleiniger Anwendung nach Colby
zu erwarten ist. Die Wirkstoffkombinationen sind somit synergistisch.
2. Unkrautwirkung im Nachauflauf
Samen bzw. Rhizomstücke von mono- und dikotylen Unkräutern werden in Plastiktöpfen in sandigem
Lehmboden ausgelegt, mit Erde abgedeckt und im Gewächshaus unter guten Wachstumsbedingungen
angezogen. Im Reisanbau vorkommende Unkräuter werden in Töpfen angezogen, in denen Wasser bis
zu 3 cm über der Bodenoberfläche steht, und während der Versuchsphase kultiviert.
Ca. zwei bis drei Wochen nach der Aussaat werden die Versuchspflanzen im Zwei- Dreiblattstadium
behandelt.
Die als Spritzpulver bzw. als Emulsionskonzentrate formulierten erfindungsgemässen
Wirkstoffkombinationen sowie in parallelen Versuchen die entsprechend formulierten Einzelwirkstoffe
werden in verschiedenen Dosierungen mit einer Wasseraufwandmenge von umgerechnet 300 bis 600
l/ha auf die grünen Pflanzenteile gesprüht und nach ca. 3 bis 4 Wochen Standzeit der Versuchspflanzen
im Gewächshaus unter optimalen Wachstumsbedingungen die Wirkung der Präparate optisc Vergleich
zu unbehandelten Kontrollen bonitiert. Bei Unkräutern, die im Reisanbau vorkommen, werden die
Wirkstoffe auch direkt ins Bewässerungswasser gegeb (Applikation in Analogie zur sogenannten
129/2194
Granulatanwendung) oder auf Pflanzen und ins Bewässerungswasser gesprüht. Die
erfindungsgemässen Mittel weisen auch im Nachauflauf eine gute herbizide Wirksamkeit gegen ein
breites Spektrum wirtschaftlich wichtiger Ungräser und Unkräuter auf. Die Wirkungen der
erfindungsgemässen Mittel sind nach der Colby-Analyse synergistisch.
3. Kulturpflanzenverträglichkeit
In weiteren Versuchen im Gewächshaus werden Samen einer grösseren Anzahl von Kulturpflanzen
und Unkräutern in sandigem Lehmboden ausgelegt und mit Erde abgedeckt. Reis wird als Wasserreis
im wassergesättig Boden angezogen und kultiviert.
Ein Teil der Töpfe wird sofort wie unter 1. beschrieben behandelt, die übrigen im Gewächshaus
aufgestellt, bis die Pflanzen zwei bis drei echte Blätter entwickelt haben und dann mit den
erfindungsgemässen Wirkstoffkombinationen und zum Vergleich nur mit einem Einzelwirkstoff in
unterschiedlichen Dosierungen, wie unter 2. beschrieben besprüht. Bei Wasserreis erfolgt die
Applikatio teilweise auch durch Giessen der Wirkstoffe bzw. deren Formulierung in das
Bewässerungswasser.
Zwei Wochen nach der Applikation und Standzeit im Gewächshaus wird mittels optischer Bonitur
festgestellt, dass die erfindungsgemässen Wirkstoffkombinationen verschiedene Kulturen im Vor- und
Nachauflaufverfahren selbst bei hohen Wirkstoffdosierungen ungeschädigt lassen. Sie schonen
Gramineen-Kulturen wie z. B. Weizen und Reis. Die erfindungsgemässen Wirkstoffkombinationen
weisen somit eine hohe Selektivität bei Anwendung zur Bekämpfung von unerwünschten
Pflanzenwuchs in landwirtschaftlichen Kulturen auf.
Im folgenden sind die Ergebnisse ausgewählter Versuche in Tabellenform wiedergegeben:
Tabelle 1
Herbizide Wirkung gegen ECCR; Applikation im Wuchsstadium 2,5 Blätter; Beurteilung 15 Tage nach
Applikation
EMI20.1
Tabelle 2
Herbizide Wirkung gegen ECCR; Applikation im Wuchsstadium 3 Blätter; Beurteilung 12 Tage nach
Applikation
EMI21.1
Tabelle 3
Kulturpflanzenverträglichkeit gegenüber verpflanztem Reis; Applikation: 0 Tage nach Verpflanzung;
Beurteilung 15 Tage nach Verpflanzung
EMI22.1Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of DE4440121
1. Herbizide Mittel gekennzeichnet durch einen wirksamen Gehalt an
A) Verbindungen der allgemeinen Formel (I) oder deren Salzen
EMI23.1
worin
a1) R>;1; Ethoxy, Propoxy oder Isopropoxy und
R>;2; Halogen, NO2, CF3, CN, C1-C4-Alkyl, C1-C4-Alkoxy, C1- C4-Alkylthio oder (C1-C4Alkoxy)-carbonyl und
130/2194
n 0, 1, 2 oder 3 oder
a2) R>;1; jeweils in 2-Stellung am Phenylrest - Halogen, Methoxy, Ethyl oder Propyl,
R>;2; (C1-C4-Alkoxy)-carbonyl in 6-Stellung im Phenylrest und
n =1
sowie in allen Fällen a1) - a2)
R>;3; Wasserstoff, gesättigtes oder ungesättigtes C1-C8-Alkyl oder C1-C4-Alkoxy,
R>;4;, R>;5; unabhängig voneinander Wasserstoff, Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4Alkylthio, wobei die letztgenannten drei Reste unsubstituiert oder durch Halogen, C1-C4-Alkoxy oder
C1-C4-Alkylthio substituiert sind,
Y O oder S und
E CH oder N
bedeuten, in Kombination mit
B) einer Verbindung B der Formel (II) oder deren Salze
EMI24.1
worin
R>;6; Wasserstoff oder (C1-C6-Alkyl bedeutet.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, dass es Verbindungen der Formel (I) oder deren
Salze enthält, worin
a1) R>;1; Ethoxy, Propoxy oder Isopropoxy und
R>;2; in Position 6 orientiert ist und die obengenannte Bedeutung hat, und
n 0 oder 1 oder
in allen Fällen a1) und a2)
R>;3; Wasserstoff, C1-C4-Alkyl,
R>;4;, R>;5; Halogen, C1-C4-Alkyl, C1-C4-Alkoxy oder C1-C4-Alkylthio, wobei die letztgenannten
3 Reste unsubstituiert oder durch Halogen, C1-C4- Alkoxy oder C1-C4-Alkylthio substituiert sind,
Y O und
E CH bedeuten.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass sie Verbindungen der Formeln A1, A2
und A3 oder deren Salze
EMI25.1
enthalten.
4.Mittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie 0,1 bis 99
Gew.-% der Wirkstoffe A und B neben üblichen Formulierungshilfsmitteln enthalten.
5. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie die
Wirkstoffe A und B im Gewichtsverhältnis 1 : 1 bis 1 : 40 enthalten.
6.Verfahren zur Herstellung eines Mittels nach einem oder mehreren der Ansprüche 1 bis 5, dadurch
gekennzeichnet, dass man eine Verbindung A mit einer Verbindung B analog einer üblichen
Pflanzenschutzmittelformulierung aus der Gruppe, enthaltend Spritzpulver, emulgierbare Konzentrate,
wässrige Lösungen, Emulsionen, versprühbare Lösungen, Dispersionen auf Öl- oder Wasserbasis,
Suspoemulsionen, Suspensionskonzentrate, ölmischbare Lösungen, Kapselsuspensionen, Granulate in
Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, Stäubemittel, Beizmittel, Boden- oder
Streugranulate, wasserdispergierbare Granulate, ULV-Formulierungen, Mikrokapseln und Wachse,
formuliert.
7. Verfahren zur Bekämpfung von unerwünschten Pflanzen, dadurch gekennzeichnet, dass man auf
diese oder deren Anbauflächen eine herbizid wirksame Menge eines Mittels nach einem oder mehreren
der Ansprüche 1 bis 5 appliziert.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass Unkräuter in Nutzpflanzenkulturen
selektiv bekämpft werden.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die Nutzpflanzenkultur Reis ist.
131/2194
10. Verwendung der herbiziden Mittel nach einem oder mehreren der Ansprüche 1 bis 5 zur selektiven
Unkrautbekämpfung in Reis.Data supplied from the esp@cenet database - Worldwide
132/2194
13. EA2090
- 12/24/2001
SYNERGISTIC HERBICIDAL COMBINATION
URL EPO = http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=EA2090
Inventor(s):
FRANZ RICHARD LYNN (US); HAWTREE JOHN (GB); KHODAYARI
KHOSRO (US)
Applicant(s):
DOW AGROSCIENCES LLC (US)
IP Class 4 Digits: A01N
IP Class:A01N47/16
E Class: A01N47/16
Application Number:
EA20000000277 (19980827)
Priority Number: WO1998GB02573 (19980827); US19970922416 (19970903)
Family: EA2090
Equivalent:
WO9911130; EP1009233; AU734581
Abstract:
Abstract of EA2090
1. A herbicidal composition comprising molinate and acetochlor in a weight ratio of from about
250:1.5 to about 5:1. 2. A herbicidal composition according to claim 1 in which the weight ratio is from
about 250:3.25 to about 12:1. 3. A herbicidal composition according to claim 1 in which the weight
ratio is from about 36:1 to about 12:1. 4. A liquid herbicidal composition according to claim 1. 5. A
solid herbicidal composition according to claim 1. 6. A controlled release herbicidal composition
according to claim 1. 7. A herbicidal composition according to claim 6 in which at least one ingredient
of molinate and acetochlor is contained in microcapsules. 8. A method of controlling weeds in the
presence of a rice crop comprising applying to said crop, said weeds, or the locus of said crop and/or
said weeds, a herbicidally-effective amount of a composition according to claim 1. 9. A method of
controlling weeds in the presence of a rice crop comprising applying to said crop, said weeds, or the
locus of said crop and/or said weeds, a herbicidally-effective amount of a composition according to
claim 2. 10. A method of controlling weeds in the presence of a rice crop comprising applying to said
crop, said weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a
composition according to claim 3. 11. A method of controlling weeds in the presence of a rice crop
comprising applying to said crop, said weeds, or the locus of said crop and/or said weeds, a
herbicidally-effective amount of a composition according to claim 4. 12. A method of controlling
weeds in the presence of a rice crop comprising applying to said crop, said weeds, or the locus of said
crop and/or said weeds, a herbicidally-effective amount of a composition according to claim 5. 13. A
method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 6. 14. A method of controlling weeds in the presence of a rice crop comprising
applying to said crop, said weeds, or the locus of said crop and/or said weeds, a herbicidally-effective
amount of a composition according to claim 7.Description:
Description of corresponding document: WO9911130
SYNERGISTIC HERBICIDAL COMBINATION
Background and Prior Art
This invention pertains to synergistic herbicidal combinations, particularly such combinations for use
in controlling weeds in a rice crop.
133/2194
Molinate (S-ethylhexahydro-lH-azepine-l-carbothioate) is a thiocarbamate herbicide which has been
used to control weeds in rice crops for a number of years, and is generally sold under products bearing
the trademarkORDRAM. In different formulations and strengths, molinate is applied pre-plant, preflood or post-flood to control a wide range of weeds in rice crops, and is generally applied at rates
ranging from about 500 to about 11,000 g/ha. However, as with many pesticides, it would be desirable
to be able to achieve weed control while using a lower application rate of molinate. This could also
result in less impact upon the environment and/or upon workers handling the product.
It has now been found that, surprisingly, combining of a lesser amount of the herbicide acetochlor with
molinate can produce a synergistic effect such that equivalent weed control can be obtained with a
lesser amount and/or application rate of molinate.
Acetochlor, or 2-chloro-2' -methyl-6'-ethyl-N(ethoxymethyl)acetanilide is an acetamide or
haloacetanilide herbicide which is sold under several trademarks, notablySURPASS(E) and
HARNESS, and in microencapsulated formulations under trademarks such as TOPNOTCHTM
ANDFULTIMETM. This herbicide is sold primarily for use in corn crops, and also is known to be
useful for certain other crops such as soybeans. However, acetochlor is generally considered to be too
injurious to rice to be used as the primary herbicide for controlling weeds in rice crops. In accordance
with the present invention, however, the use of acetochlor in an amount which produces substantially
no phytotoxicity to a rice crop, in combination with molinate, particularly a lesser amount or lower
application rate than is normally used, produces a synergistic effect, resulting in good control of weeds
in rice crops in either pre-flood or post-flood applications.
Summarv of the Invention
This invention comprises a herbicidal composition as well as a method of controlling weeds in rice
crops.
In one aspect, this invention relates to a synergistic herbicidal composition comprising molinate and
acetochlor.
In a second aspect, it comprises a herbicidal composition comprising molinate and acetochlor in a
weight ratio of from about 250:1.5 to about 5:1, respectively.
In another aspect, this invention comprises a method of controlling weeds in a rice crop comprising
applying to said crop, said weeds or the locus of either or both, a synergistic combination comprising
molinate and acetochlor, particularly in a weight ratio of from about 250:1.5 to about 5:1, respectively.
Detailed Description of the Invention
The invention involves the use of the combination of the herbicides molinate and acetochlor to control
weeds in a rice crop. The combination, within the scope of this invention, demonstrates synergistic
effects, that is, effects that would have been unexpected from the performance of the two herbicides
individually against the same weeds under similar circumstances.
According to the invention, weeds are controlled in the presence of a rice crop by treating the crop, the
weeds, or the locus of either or both, with a herbicidally effective amount of a synergistic combination
of the herbicides molinate and acetochlor. In general, we have found that synergy is demonstrated
when the combination includes these two herbicides in a weight ratio respectively, of from about
250:1.5 to about 5: 1, preferably, from about 250:3.25 to about 12:1, most preferably from about 36:1
to about 12:1.
However, our discovery is that of synergism between molinate and acetochlor, and is not necessarily
limited to combinations of these herbicides within these weight ratios, as synergy may exist at others.
This combination produces synergistic or unexpected control of weeds in rice when applied at various
times, and to rice planted in different ways. To control the weeds, the combination may be applied
prior to planting, after planting but prior to flooding (preflood, post-emergence) or after emergence of
the rice and flooding (post-flood, postemergence) and may be applied to either direct seeded or
transplanted rice.
134/2194
To be used in combination, it is not necessary that the two herbicides molinate and acetochlor, be
applied in a physically combined form, or even at the same time. The combination effect results so long
as the two herbicides are present at the same time in the rice crop, regardless of when they were
applied. Thus, for instance, a physical combination of the two herbicides could be applied, or one could
be applied earlier than the other. For instance, one of the two herbicides could be applied even prior to
planting the rice in a controlled release formulation such as a microencapsulated formulation, and the
other applied subsequently in a conventional liquid or solid formulation, so long as the earlierapplied
herbicide is still present in the soil when the second is applied, and so long as the weight ratio of
available herbicides falls within that disclosed and claimed herein.
Either herbicide could thus be applied in liquid or solid form, or a combination product containing
both herbicides could be produced, again, in either liquid or solid form.
Typical liquid formulations include emulsions, suspensions (including suspensions containing
microcapsules), solutions, emulsifiable concentrates, and flowables. Solid products include forms such
as granules, wettable powders, water-dispersible solid products (including water-dispersible granules
containing microencapsulated pesticides) or dusts. Both types of compositions will generally contain,
in addition to the active herbicide, other ingredients such as solvents, wetting agents, suspending
agents, anti-caking agents, dispersing agents, emulsifiers, antifreeze agents, antifoam agents, and other
additives.
Either herbicide, or both, may be utilized in one of a number of known forms of controlled release
compositions. Such compositions provide relatively slow or controlled release of the active ingredient
into the environment and include, for example, encapsulations, microencapsulations, and various forms
of controlled release granules.
Combination products or compositions according to this invention, may contain the two herbicides in
numerous different physical forms. In some cases, a combination product may be produced by simply
physically mixing ("tank-mixing") commercially available products containing the active herbicides,
for example, two emulsifiable concentrates containing the herbicides, so long as all the ingredients of
the two products are relatively compatible. Alternatively, a package may be manufactured and sold
which contains overall the two herbicides in separate containers, but packaged together, commonly
termed a "twin-pack". A twin-pack is particularly suitable for the herbicidal compositions herein, since
the amount of molinate is substantially greater than that of acetochlor, so that an overall product
package can be produced containing a relatively large container of a molinate-containing herbicide
product together with a relatively small container of an acetochlor-containing herbicidal product.
Alternatively, previously prepared compositions ("premixes") containing the two herbicides can be
produced. Since both acetochlor and molinate are liquids under normal conditions, liquid compositions
would tend to be preferred. Typical liquid compositions would include an emulsifiable concentrate
containing both herbicides, and a two-phase emulsion (or microemulsion) with one herbicide in each
phase. One typical type of premixed liquid formulation containing the two herbicides would be an
emulsifiable concentrate and would contain, for example, 900 g/l molinate and either 25 or 37.5 g/l
acetochlor, using kerosene as the solvent and including, as emulsifiers, 1.50 weight percent
Sponto 217 and 3.50 weight percent Sponto221ER. The Sponto products are emulsifiers comprising
blends of ethoxylated nonylphenyl alcohols and calcium dodecylbenzene sulfonates.
However, in practice, both herbicides are currently also sold as solid formulations, that is, impregnated
granules, so that a similar solid product containing both herbicides could likewise be produced, as
impregnated granules. Similarly, other solid formulations such as wettable powders or dusts could be
prepared.
Again similarly, using appropriate ingredients and conditions, it would be possible to prepare
microencapsulated products in which one or both herbicides are contained within a microcapsule and
said microencapsulated products could be sold in either liquid form (i.e., capsule suspensions) or solid
form (i.e., water-dispersible granules produced by drying of microcapsule suspensions). One type of
liquid form would be a microcapsule suspension in which one of the herbicides is contained within the
capsules while the other is present in a nonencapsulated form, in the continuous liquid phase.
135/2194
Another type would be a suspension containing molinate and acetochlor separately encapsulated. The
types of formulations or compositions which may contain these two herbicides is not limited by those
enumerated herein, as other types of formulations would likely be envisaged by those skilled in the art.
The control of weeds by the combination of acetochlor and molinate is illustrated by the following
examples:
EXAMPLE 1. This example simulates application of the combination of molinate and acetochlor in a
direct seeded rice culture under conditions typical of the Americas.
Combinations of molinate and acetochlor in the indicated amounts were applied in the greenhouse at
the application rates shown in Table 1 (in terms of grams per hectare of the herbicide or herbicides) to
flats containing rice (orvza sativa, variety Katy) and the weeds barnyardgrass (Echinochloacrusgalli,
ECHCG) and smallflower flatsedge(Cyperus difformis. CYPDI) at the pre-flood postemergence stage,
and at the 2-leaf growth stage of the barnyardgrass. The weeds had been grown separately to the 2-leaf
stage, then transplanted to the rice flats. Results of these tests are shown in Table1, below, in terms of
percent control or injury as compared to an untreated check flat. A rating of 100% indicates complete
control; of 0% indicates no effect.
Table I
EMI6.1
>;tb; >;SEP; Compound(s) >;SEP; Rate >;SEP; of >;SEP; Rate >;SEP; of >;SEP; Rice >;SEP; Rice
>;SEP; ECHCG >;SEP; CYPDI
>;tb; >;SEP; molinate >;SEP; acetochlor >;SEP; injury >;SEP; % >;SEP; injury >;SEP; % >;SEP; (%
>;tb; >;SEP; (9 >;SEP; /ha) >;SEP; (g >;SEP; /ha) >;SEP; (7 >;SEP; days) >;SEP; (27 >;SEP;
control) >;SEP; control)
>;tb; >;SEP; days)>;/RTI; >;SEP;
>;tb; molinate >;SEP; 250 >;SEP; 0 >;SEP; 0 >;SEP; 66 >;SEP; 0
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 6 >;SEP; 1 >;SEP; 0 >;SEP; 93 >;SEP; 8
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 13 >;SEP; 5 >;SEP; 0 >;SEP; 100 >;SEP; 13
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 25 >;SEP; 36 >;SEP; 0 >;SEP; 100 >;SEP; 73
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 50 >;SEP; 59 >;SEP; 0 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 100 >;SEP; 44 >;SEP; 4 >;SEP; 100 >;SEP; 100
>;tb; molinate >;SEP; 500 >;SEP; 0 >;SEP; 0 >;SEP; 80 >;SEP; 3
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 6 >;SEP; 4 >;SEP; 0 >;SEP; 88 >;SEP; 8
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 13 >;SEP; 29 >;SEP; 1 >;SEP; 100 >;SEP; 36
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 25 >;SEP; 53 >;SEP; 1 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 50 >;SEP; 54 >;SEP; 4 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 100 >;SEP; 55 >;SEP; 3 >;SEP; 100 >;SEP; 100
>;tb; molinate >;SEP; 1000 >;SEP; 0 >;SEP; 0 >;SEP; 80 >;SEP; 3
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 6 >;SEP; 6 >;SEP; 0 >;SEP; 96 >;SEP; 44
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 13 >;SEP; -1 >;SEP; >;SEP; 53 >;SEP; 3 >;SEP; 100
>;SEP; 81
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 25 >;SEP; 44 >;SEP; 0 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 50 >;SEP; 55 >;SEP; 10 >;SEP; 100 >;SEP; - >;SEP;
100
>;tb;molinatelacetochlor >;SEP; 1000 >;SEP; 100 >;SEP; 63 >;SEP; 8 >;SEP; 100 >;SEP; 100
>;tb; molinate >;SEP; 2000 >;SEP; 6 >;SEP; 1 >;SEP; 90 >;SEP; 69
>;tb;molinatelacetochlor >;SEP; 2000 >;SEP; 6 >;SEP; 9 >;SEP; 0 >;SEP; 100 >;SEP; 79
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 13 >;SEP; 45 >;SEP; 0 >;SEP; 99 >;SEP; 100
>;tb;molinatelacetochlor >;SEP; 2000 >;SEP; 25 >;SEP; 44 >;SEP; 4 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 50 >;SEP; 61 >;SEP; 6 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 100 >;SEP; 60 >;SEP; 4 >;SEP; 100 >;SEP; 100
>;tb; acetochlor >;SEP; tech >;SEP; 6 >;SEP; 1 >;SEP; 0 >;SEP; 93 >;SEP; 0
>;tb; >;SEP; 1.3 >;SEP; 5 >;SEP; - >;SEP; >;SEP; 0 >;SEP; 99 >;SEP; 6
>;tb; >;SEP; 25 >;SEP; 21 >;SEP; 0 >;SEP; 99 >;SEP; 24
>;tb; >;SEP; 50 >;SEP; 50 >;SEP; 0 >;SEP; 100 >;SEP; 100
136/2194
>;tb; >;SEP; 100 >;SEP; 48 >;SEP; 0 >;SEP; 100 >;SEP; ~1 >;SEP; >;SEP; 100
>;tb;
EXAMPLE 2. This example demonstrates preflood postemergence application of molinate and
acetochlor to a direct seeded rice culture under auditors typically Southeast
Asia. Dry rice seed (Kaybonnet variety) is soaked for 24 hours or more. The soil is puddled to the right
consistency and partially drained. The pre-germinated seeds are then broadcast to the surface of the
soil and are grown to the 3 leaf stage. Weeds are grown separately to the 2 leaf growth stage and added
to the tubs. Herbicide application is by spraying or broadcasting of chemical. Tubs are flooded 1 week
or more after application.
The results of these are shown in the following Table 2.
Table 2
EMI7.1
>;tb; >;SEP; Compound(s) >;SEP; ) >;SEP; Rate >;SEP; of >;SEP; Rate >;SEP; of >;SEP; Rice
>;SEP; T >;SEP; >;SEP; Rice >;SEP; >;SEP; ECHCG >;SEP; CYPDI >;SEP;
>;tb; >;SEP; molinate >;SEP; acetochlor >;SEP; injury >;SEP; % >;SEP; injury >;SEP; % >;SEP; (%
>;tb; >;SEP; (g >;SEP; /ha) >;SEP; (g >;SEP; /ha) >;SEP; (7 >;SEP; days) >;SEP; (28 >;SEP;
control) >;SEP; control)
>;tb; >;SEP; days)
>;tb; molinate >;SEP; 250 >;SEP; 1 >;SEP; 0 >;SEP; 0 >;SEP; 0
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 6 >;SEP; 1 >;SEP; 0 >;SEP; 0 >;SEP; 54
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 13 >;SEP; 11 >;SEP; 1 >;SEP; 30 >;SEP; 61
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 25 >;SEP; 15 >;SEP; 3 >;SEP; 54 >;SEP; 85
>;tb;molinate/acetochlor >;SEP; 250 >;SEP; 50 >;SEP; 54 >;SEP; 6 >;SEP; 100 >;SEP; 96
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 100 >;SEP; 69 >;SEP; 15 >;SEP; 100 >;SEP; 95
>;tb; molinate >;SEP; 500 >;SEP; 3 >;SEP; 0 >;SEP; 0 >;SEP; 8
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 6 >;SEP; 0 >;SEP; 1 >;SEP; 8 >;SEP; 33
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 13 >;SEP; 6 >;SEP; 3 >;SEP; 54 >;SEP; 73
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 25 >;SEP; 29 >;SEP; 0 >;SEP; 100- >;SEP; 89
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 50 >;SEP; 58 >;SEP; 3 >;SEP; 100 >;SEP; 90
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 100 >;SEP; 65 >;SEP; 25 >;SEP; 100 >;SEP; 99
>;tb; molinate >;SEP; 1000 >;SEP; 0 >;SEP; 0 >;SEP; 8 >;SEP; 25
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 6 >;SEP; 1 >;SEP; 0 >;SEP; 63 >;SEP; 71
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 13 >;SEP; 3 >;SEP; 3 >;SEP; 92 >;SEP; 79
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 25 >;SEP; 50 >;SEP; 1 >;SEP; 100 >;SEP; 96
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 50 >;SEP; 56 >;SEP; 6 >;SEP; 100 >;SEP; 93
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 100 >;SEP; 65 >;SEP; 39 >;SEP; 100 >;SEP; 95
>;tb; molinate >;SEP; 2000 >;SEP; 11 >;SEP; 0 >;SEP; 90 >;SEP; 58
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 6 >;SEP; 6 >;SEP; 3 >;SEP; 100 >;SEP; 73
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 13 >;SEP; 5 >;SEP; 1 >;SEP; 100 >;SEP; 86
>;tb;molinatelacetochlor >;SEP; 2000 >;SEP; 25 >;SEP; 46 >;SEP; 3 >;SEP; 100 >;SEP; 95
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 50 >;SEP; 59 >;SEP; 4 >;SEP; 100 >;SEP; 96
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 100 >;SEP; 59 >;SEP; ~ >;SEP; >;SEP; 13 >;SEP; 100
>;SEP; 99
>;tb; acetochlor >;SEP; tech >;SEP; 6 >;SEP; 5 >;SEP; 0 >;SEP; 0 >;SEP; 24
>;tb; >;SEP; 13 >;SEP; 3 >;SEP; 3 >;SEP; 28 >;SEP; 73
>;tb; >;SEP; 25 >;SEP; 14 >;SEP; 0 >;SEP; 38 >;SEP; 65
>;tb; >;SEP; 50 >;SEP; 39 >;SEP; 4 >;SEP; 65 >;SEP; 91
>;tb; >;SEP; 100 >;SEP; 64 >;SEP; 10 >;SEP; 79 >;SEP; 91
>;tb;
EXAMPLE 3.- This example involved tests conducted using postflood, postemergence application (at
the 2-leaf stage of barnyardgrass) in transplanted rice variety Kushiki kari).
Rice is grown to the 2-4 leaf stage away separately from the trial tubs. The soil in the tub is puddled
until a blend is achieved. The rice plants are then transplanted into this blend.
137/2194
Weeds (2 leaf stage) are either grown separately and transplanted in or are grown in the tub on the
blended soil. Herbicide application typically takes place by injection or broadcasting of chemical after
flooding. The results are shown in the following Table 3.
Table 3
EMI8.1
>;tb; >;SEP; Compound(s) >;SEP; Rate >;SEP; of >;SEP; Rate >;SEP; of >;SEP; Rice >;SEP; Rice
>;SEP; ECHCG >;SEP; CYPDI
>;tb; >;SEP; molinate >;SEP; acetochlor >;SEP; injury >;SEP; % >;SEP; injury >;SEP; % >;SEP; (%
>;tb; >;SEP; (g >;SEP; /ha) >;SEP; (g/ha) >;SEP; (7 >;SEP; days) >;SEP; (28 >;SEP; control) >;SEP;
control)
>;tb; >;SEP; days)
>;tb; molinate >;SEP; 250 >;SEP; 0 >;SEP; 0 >;SEP; 63 >;SEP; 20
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 6 >;SEP; 0 >;SEP; 0 >;SEP; 100 >;SEP; 85
>;tb;molinatelacetochlor >;SEP; 250 >;SEP; 13 >;SEP; 0 >;SEP; 5 >;SEP; 100 >;SEP; 90
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 25 >;SEP; 0 >;SEP; 0 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 50 >;SEP; 43 >;SEP; 33 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 250 >;SEP; 100 >;SEP; 45 >;SEP; 35 >;SEP; 100 >;SEP; 95
>;tb; molinate >;SEP; 500 >;SEP; 0 >;SEP; 0 >;SEP; 88 >;SEP; 25
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 6 >;SEP; 0 >;SEP; 3 >;SEP; 100 >;SEP; 90
>;tb;molinatelacetochlor >;SEP; 500 >;SEP; 13 >;SEP; 3 >;SEP; 0 >;SEP; 99 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 25 >;SEP; 5 >;SEP; 0 >;SEP; 100 >;SEP; 90
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 50 >;SEP; 43 >;SEP; 15 >;SEP; 100 >;SEP; 95
>;tb; molinate/acetochlor >;SEP; 500 >;SEP; 100 >;SEP; 58 >;SEP; 45 >;SEP; ~ >;SEP; >;SEP; 100
>;SEP; 100
>;tb; molinate >;SEP; 1000 >;SEP; 0 >;SEP; 0 >;SEP; 98 >;SEP; 43
>;tb;molinatelacetochlor >;SEP; 1000 >;SEP; 6 >;SEP; 8 >;SEP; 8 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 13 >;SEP; 8 >;SEP; 18 >;SEP; 100 >;SEP; 93
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 25 >;SEP; 10 >;SEP; 3 >;SEP; 100 >;SEP; 100
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 50 >;SEP; 35 >;SEP; 30 >;SEP; 100 >;SEP; 95
>;tb; molinate/acetochlor >;SEP; 1000 >;SEP; 100 >;SEP; 68 >;SEP; 73 >;SEP; 100 >;SEP; 100
>;tb; molinate >;SEP; 2000 >;SEP; 0 >;SEP; 0 >;SEP; 99 >;SEP; 75
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 6 >;SEP; 0 >;SEP; 0 >;SEP; 100 >;SEP; 90
>;tb;molinste/acetochlor >;SEP; 2000 >;SEP; 13 >;SEP; 5 >;SEP; 10 >;SEP; 100 >;SEP; 95
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 25 >;SEP; 5 >;SEP; 3 >;SEP; 100 >;SEP; ~ >;SEP;
>;SEP; 93
>;tb;
EMI9.1
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 50 >;SEP; >;SEP; 40 >;SEP; 25 >;SEP; i >;SEP; 100
>;SEP; 100
>;tb; molinate/acetochlor >;SEP; 2000 >;SEP; 100 >;SEP; 65 >;SEP; 78 >;SEP; 100 >;SEP; 100
>;tb; acetochlor >;SEP; 6 >;SEP; 5 >;SEP; 15 >;SEP; 45 >;SEP; 73
>;tb; >;SEP; 13 >;SEP; 3 >;SEP; 13 >;SEP; 90 >;SEP; 78
>;tb; >;SEP; 25 >;SEP; 13 >;SEP; 33 >;SEP; 100 >;SEP; 88
>;tb; >;SEP; 50 >;SEP; 45 >;SEP; 43 >;SEP; 100 >;SEP; 100
>;tb; >;SEP; 100 >;SEP; 60 >;SEP; 58 >;SEP; 100 >;SEP; ~ >;SEP; >;SEP; 100
>;tb;
From the foregoing examples, the following can be noted:
1. In these tests, molinate applied alone at a rate of 2,000 g/ha provided sufficiently good control of
weeds such that further control when acetochlor was added, even in small amounts, appears to have
been no more than additive.
2. In some tests, combinations of molinate and acetochlor within the ranges described herein did not
show synergy, and this is not unexpected, as synergy is normally not shown for all possible
combinations of herbicides within a given range, or on all weeds.
138/2194
3. In some cases, combinations within this range showed early injury to rice (at 7 days after
application) but subsequently (at 27-28 days after application), the injury was no longer apparent or
had lessened markedly. Such injury to rice is acceptable if the rice recovers within 3-4 weeks.Data
supplied from the esp@cenet database - Worldwide
Claims:
Claims of corresponding document: WO9911130
CLAIMS
1. A herbicidal composition comprising molinate and acetochlor in a weight ratio of from about
250:1.5 to about 5:1.
2. A herbicidal composition according to claim 1 in which the weight ratio is from about 250:3.25 to
about 12:1.
3. A herbicidal composition according to claim 1 in which the weight ratio is from about 36:1 to about
12:1.
4. A liquid herbicidal composition according to claim 1.
5. A solid herbicidal composition according to claim 1.
6. A controlled release herbicidal composition according to claim 1.
7. A herbicidal composition according to claim 6 in which at least one of molinate and acetochlor is
contained in microcapsules.
8. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 1.
9. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 2.
10. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 3.
11. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 4.
12. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 5.
13. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 6.
14. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 7.Data supplied from the esp@cenet database - Worldwide
139/2194
14. EA2152
- 12/24/2001
SYNERGISTIC HERBICIDAL COMPOSITION
URL EPO = http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=EA2152
Inventor(s):
(CH)
FRANZ RICHARD LYNN (US); KHODAYARI KHOSRO (US); FUA JEE MOK
Applicant(s):
ZENECA LTD (GB)
IP Class 4 Digits: A01N
IP Class:A01N47/16; A01N31/16
E Class: A01N47/16
Application Number:
EA20000000276 (19980827)
Priority Number: WO1998GB02574 (19980827); US19970922785 (19970903)
Family: EA2152
Equivalent:
WO9911131; EP1009234; AU753747
Abstract:
Abstract of EA2152
1. An anthracycline glycoside of formula I wherein the wavy line means that the hydroxy group at 13position may be at [alpha] or [beta] position, or a mixture thereof. 2. A compound according to claim 1
which is 4-demethoxy-13 (S/R) dihydro-3'-deamino-3'-aziridinyl-4'-methansulfonyl daunorubicin, 4demethoxy-13(S) dihydro-3'-deamino-3'-aziridinyl-4'-methansulfonyl daunorubicin or 4-demethoxy13(R) dihydro-3'-deamino-3'-aziridinyl-4'-methansulfonyl daunorubicin. 3. A process for the
preparation of an anthracycline glycoside of formula (I) as defined in claim 1, which process comprises
reducing the anthracycline of the formula II in presence of a reductive agent in a mixture of organic
solvents and, if desired and necessary, separating the resultant mixture of 13(R) and 13(S) compounds
into the single diastereoisomer. 4. The process according to claim 3, in which the reductive agent is
sodium borohydride. 5. The process according to claims 4, in which the reduction is carried out at a
temperature below 50 degree C. 6. The process according to claims 6 in which the reduction is carried
out at a temperature of -70 degree C. 7. A pharmaceutical composition comprising an anthracycline
glycoside of formula I as defined in claim 1, and a pharmaceutically acceptable carrier or diluent. 8.
Use of the compound as defined in claim 1 or 2 for treating a human or an animal organism
conservatively. 1. A herbicidal composition comprising molinate and oxyfluorfen in a weight ratio of
from about 500:1 to about 30:1. 2. A herbicidal composition according to claim I in which the weight
ratio is from about 250:3.25 to about 5:1. 3. A herbicidal composition according to claim I in which the
weight ratio is from about 250:1 to about 40:1. 4. A herbicidal composition according to claim 1 which
is liquid. 5. A herbicidal composition according to claim 1 which is solid. 6. A herbicidal composition
according to claim 1 characterized by a controlled release of active substances. 7. A herbicidal
composition according to claim 6 in which at least one of molinate and oxyfluorfen is contained in
microcapsules. 8. A method of controlling weeds in the presence of a rice crop comprising applying to
said crop, said weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a
composition according to any of claims 1 to 7.Description:
Description of corresponding document: WO9911131
SYNERGISTIC HERBICIDAL COMBINATION
Background and Prior Art
140/2194
This invention pertains to synergistic herbicidal combinations, particularly such combinations for use
in controlling weeds in a rice crop.
Molinate (S-ethylhexahydro- I H-azepine- 1 -carbothioate) is a thiocarbamate herbicide which has
been used to control weeds in rice crops for a number of years, and is generally sold under products
bearing the trademarkORDRAMB. In different formulations and strengths, molinate is applied preplant, pre-flood or post-flood to control a wide range of weeds in rice crops, and is generally applied at
rates ranging from about 500 to about 11,000 g/ha. However, as with many pesticides, it would be
desirable to be able to achieve weed control while using a lower application rate of molinate. This
could also result in less impact upon the environment and/or upon workers handling the product.
It has now been found that, surprisingly, combining of a much lower amount of the herbicide
oxyfluorfen with molinate can produce a synergistic effect such that equivalent weed control can be
obtained with a lesser amount and/or application rate of molinate.
Oxyfluorfen or2-chioro- I -(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethylbenzene) is a diphenyl ether
herbicide sold primarily under the trademarkGOAL. Primarily, oxyfluorfen is sold for control of
weeds in fruit, nut and vegetable crops, and in cotton. It is not usually used for control of weeds in rice
crops because the rate of application needed to control weeds tends to cause unacceptable damage to
the rice. Oxyfluorfen is used, however, in China on a small scale to control weeds in rice. In
accordance with the present invention, however, the use of oxyfluorfen in an amount which produces
substantially no phytotoxicity to a rice crop, in combination with molinate, particularly a lesser amount
or lower application rate of molinate than is normally used, produces a synergistic effect, resulting in
good control of weeds in rice crops in either pre-flood or post-flood applications.
Summarv of the Invention
This invention comprises a herbicidal composition as well as a method of controlling weeds in rice
crops.
In one aspect, this invention relates to a synergistic herbicidal composition comprising molinate and
oxyfluorfen.
In a second aspect, it comprises a herbicidal composition comprising molinate and oxyfluorfen in a
weight ratio of from about 500:1 to about 30:1, respectively.
In another aspect, this invention comprises a method of controlling weeds in a rice crop comprising
applying to said crop, said weeds or the locus of either or both, a synergistic combination comprising
molinate and oxyfluorfen, preferably in a weight ratio of from about 500:1 to about 30:1, respectively.
Detailed Description of the Invention
The invention involves the use of the combination of the herbicides molinate and oxyfluorfen to
control weeds in a rice crop. The combination, within the scope of this invention, demonstrates
synergistic effects, that is effects that would have been unexpected from the performance of the two
herbicides individually against the same weeds under similar circumstances.
According to the invention, weeds are controlled in the presence of a rice crop by treating the crop, the
weeds, or the locus of either or both, with a herbicidally effective amount of a synergistic combination
of the herbicides molinate and oxyfluorfen. In general, we have found that synergy is demonstrated
when the combination includes these two herbicides, respectively, in a weight ratio of from about 500:1
to about 30: 1, preferably, from about 250:1 to about 40:1.
However, Applicants' discovery is that of synergism between molinate and oxyfluorfen, and is not
necessarily limited to combinations of these herbicides within these weight ratios, as synergy may exist
at others.
This combination produces synergistic or unexpected control of weeds in rice when applied at the
various times, and to rice planted in different ways. To control the weeds, the combination may be
applied prior to planting, after planting but prior to flooding (pre-flood, postemergence) or after
141/2194
emergence of the rice and flooding (post-flood, post-emergence) and may be applied to either direct
seeded or transplanted rice.
To be used in combination, it is not necessary that the two herbicides, molinate and oxyfluorfen, be
applied in a physically combined form, or even at the same time. The combination effect results so long
as the two herbicides are present at the same time in the rice crop, regardless of when they were
applied. Thus, for instance, a physical combination of the two herbicides could be applied, or one could
be applied earlier than the other. For instance, one of the two herbicides could be applied even prior to
planting the rice in a controlled release formulation such as a microencapsulated formulation, and the
other applied subsequently in a conventional liquid or solid formulation, so long as the earlier-applied
herbicide is still present in the soil when the second is applied, and so long as the weight ratio of
available herbicides falls within that disclosed and claimed herein.
Either herbicide could thus be applied in liquid or solid form, or a combination product containing
both herbicides could be produced, again, in either liquid or solid form. Typical liquid formulations
include emulsions, suspensions (including suspensions containing. microcapsules), solutions,
emulsifiable concentrates, and flowables. Solid products include forms such as granules, wettable
powders, water-dispersible solid products (including water-dispersible granules containing
microencapsulated pesticides) or dusts. Both types of compositions will generally contain, in addition
to the active herbicide, other ingredients such as solvents, wetting agents, suspending agents, anticaking agents, dispersing agents, emulsifiers, antifreeze agents, antifoam agents, and other additives.
Either herbicide, or both, may be utilized in one of a number of known forms of controlled release
compositions. Such compositions provide relatively slow or controlled release of the active ingredient
into the environment and include, for example, encapsulations, microencapsulations, and various forms
of controlled release granules.
Combination products or compositions according to this invention may contain the two herbicides in
numerous different physical forms. In some cases, a combination product may be produced by simply
physically mixing ("tank-mixing") commercially available products containing the active herbicides,
for example, two emulsifiable concentrates containing the herbicides, so long as all the ingredients of
the two products are relatively compatible. Alternatively, a package may be manufactured and sold
which contains, overall, the two herbicides in separate containers, but packaged together, commonly
termed a "twin-pack". A twin-pack is particularly suitable for the herbicidal compositions herein, since
the amount of molinate is substantially greater than that of oxyfluorfen, so that an overall product
package can be produced containing a relatively large container of a molinate-containing herbicide
product together with a relatively small container of an oxyfluorfen-containing herbicidal product.
Alternatively, previously prepared compositions ("premixes") containing the two herbicides can be
produced. Molinate is a liquid and oxyfluorfen in a solid which is soluble in many organic solvents. For
that reason, liquid compositions appear preferable for products containing the two herbicides. Typical
liquid compositions would include an emulsifiable concentrate containing both herbicides, or a twophase emulsion (or microemulsion) with one herbicide in each phase.
However, in practice, both herbicides are currently also sold as solid formulations, that is, impregnated
granules, so that a similar solid product containing both herbicides could likewise be produced, as
impregnated granules. Similarly, other solid formulations such as wettable powders or dusts could be
prepared.
Again similarly, using appropriate ingredients and conditions, it would be possible to prepare
microencapsulated products in which one or both herbicides are contained within a microcapsule and
said microencapsulated products could be sold in either liquid form (i.e., capsule suspensions) or solid
form (i.e., water-dispersible granules produced by drying of microcapsule suspensions). One type of
liquid form would be a microcapsule suspension in which one of the herbicides is contained within the
capsules while the other is present in a nonencapsulated form, in the continuous liquid phase. Another
type would be a suspension containing molinate and oxyfluorfen separately encapsulated. The types of
formulations or compositions which may contain these two herbicides is not limited by those
enumerated herein, as other types of formulations would likely be envisaged by those skilled in the art.
142/2194
The control of weeds by the combination of oxyfluorfen and molinate is illustrated by the following
example:
EXAMPLE 1. This example demonstrates application of the combination of molinate and oxyfluorfen
for weed control applied post-flood/postemergence in transplanted rice. Rice was grown to the 2-4 leaf
stage away separately from the trial tubs. The soil in the tub was flooded and tilled (puddled) until a
blend was achieved. The rice plants were then transplanted into this blend.
Weeds (2 leaf stage) were either grown separately and transplanted in or were grown in the tub on the
blended soil. Herbicide application typically was made by injection or broadcasting of chemical after
flooding. Combinations of molinate and oxyfluorfen in the indicated amounts were applied in the
greenhouse at the application rates shown (in terms of grams per hectare of the herbicide or herbicides)
to flats containing rice (Koshikari variety) and the weeds barnyardgrass (?) (Echinochloacrusgalli.
ECHCG),smallflower flatsedge(Cvperus difformis. CYPDI), and monochoria (Monochoria vaginalis,
MOOVA) at the post-flood postemergence stage. At the time of application the rice was in the 3-leaf
stage, the barnyardgrass was in the 2-leaf stage and the other two weeds were intermediate the 2- and
3-leaf stages. Results of these tests are shown in
Table 1, below, in terms of percent control or injury as compared to an untreated check flat.
Table I
EMI5.1
Rate, Rate, Injury % % Control
Compound(s) molinate oxyfluorfen
g /ha g/ha Rice, Rice, ECHCG MOOVA CYPDI
7da S 28da
S
molinate 726 0 0 1 4 0
969 0 0 69 4 29
1453 1 0 51 0 38
oxyfluorfen 3 1 0 0 24 8
6 1 0 0 35 14
13 0 0 0 35 38 23
25 3 0 0 100 50 30
>;tb; >;SEP; 969 >;SEP; 3 >;SEP; 4 >;SEP; 0 >;SEP; 100 >;SEP; 26 >;SEP; 44
>;tb; >;SEP; 1453 >;SEP; 3 >;SEP; 1 >;SEP; 0 >;SEP; 100 >;SEP; 19 >;SEP; 44
>;tb; molinate/oxyfluorfen >;SEP; 726 >;SEP; 6 >;SEP; 3 >;SEP; 0 >;SEP; 100 >;SEP; 34 >;SEP; 30
>;tb; >;SEP; 969 >;SEP; 6 >;SEP; 4 >;SEP; 1 >;SEP; 100 >;SEP; 34 >;SEP; 54
>;tb; >;SEP; 1453 >;SEP; 6 >;SEP; 1 >;SEP; 0 >;SEP; 100 >;SEP; 49 >;SEP; 64
>;tb; 726 >;SEP; 13 >;SEP; 1 >;SEP; 0 >;SEP; 100 >;SEP; 45 >;SEP; 29
>;tb; >;SEP; 969 >;SEP; 13 >;SEP; O >;SEP; >;SEP; 3 >;SEP; 100 >;SEP; 43 >;SEP; 55
>;tb; >;SEP; 1453 >;SEP; 13 >;SEP; 1 >;SEP; 0 >;SEP; 100 >;SEP; 44 >;SEP; 66
>;tb;molinate/oxyfluorfen >;SEP; 726 >;SEP; 25 >;SEP; 5 >;SEP; 0 >;SEP; 100 >;SEP; 63 >;SEP; 55
>;tb; >;SEP; 969 >;SEP; 25 >;SEP; 1 >;SEP; 0 >;SEP; 100 >;SEP; 59 >;SEP; 88
>;tb; >;SEP; 1453 >;SEP; 25 >;SEP; 1 >;SEP; 0 >;SEP; 100 >;SEP; 61 >;SEP; 96
>;tb;
From the foregoing examples, the following can be noted:
1. Molinate sparyed on barnyardgrass at 726 g/ha showed no control. Yet, when only 3 g/ha
oxyfluorfen (which also showed no control) was added, control was 99%. At higher application rates,
molinate alone controlled barnyardgrass to some extent. Yet when only 3-6 g/ha oxyfluorfen was
added, complete control was achieved.
2. Unexpected results were not obtained on monochoria, and were only obtained on smallflower
flatsedge at higher application rates of oxyfluorfen (25 g/ha). However, these higher rate combinations
are within the scope of this invention.
3. In some tests, combinations of molinate and oxyfluorfen within the ranges described herein did not
show synergy, and this is not unexpected, as synergy is normally not shown for all possible
combinations of herbicides within a given range, or on all weeds.Data supplied from the esp@cenet
database - Worldwide
Claims:
143/2194
Claims of corresponding document: WO9911131
CLAIMS
1. A herbicidal composition comprising molinate and oxyfluorfen in a weight ratio of from about
500:1 to about 30:1.
2. A herbicidal composition according to claim I in which the weight ratio is from about 250:3.25 to
about 5:1.
3. A herbicidal composition according to claim I in which the weight ratio is from about 250:1 to
about 40:1.
4. A liquid herbicidal composition according to claim 1.
5. A solid herbicidal composition according to claim 1.
6. A controlled release herbicidal composition according to claim 1.
7. A herbicidal composition according to claim 6 in which at least one of molinate and oxyfluorfen is
contained in microcapsules.
8. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 1.
9. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 2.
10. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 3.
11. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 4.
12. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 5.
13. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 6.
14. A method of controlling weeds in the presence of a rice crop comprising applying to said crop, said
weeds, or the locus of said crop and/or said weeds, a herbicidally-effective amount of a composition
according to claim 7.Data supplied from the esp@cenet database - Worldwide
144/2194
15. EA4313
- 2/26/2004
METHOD FOR FIGHTING SOIL INSECTS WITH PHENYL-PYRAZOLES
URL EPO = http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=EA4313
Inventor(s):
GAULLIARD JEAN-MICHEL (FR); SEGAUD CHRISTIAN (FR)
Applicant(s):
AVENTIS CROPSCIENCE SA (FR)
IP Class 4 Digits: A01N
IP Class:A01N43/56; A01N47/02; A01N25/12; A01N25/00
E Class: A01N47/02; A01N25/00B4; A01N43/56
Application Number:
EA20020000340 (20000907)
Priority Number: FR19990011312 (19990907); WO2000FR02460 (20000907)
Family: EA4313
Equivalent:
AU770778
WO0117354; EP1209976; US6939830; FR2798042; CA2383087; CZ294602;
Abstract:
Abstract of EA4313
1. An insecticide composition comprising: a) between 0.001 and 5 %, preferably between 0.05 and 1
%, more preferably between 0.05 and 0.5% of a compound of formula I: in which: R1 is a halo atom or
a CN group, or a methyl group, or a CH3CO group; R2 is S(O)nR3; R3 is C1-C6 alkyl or haloalkyl; R4
is a hydrogen or halo atom, or a NR5R6 radical, S(O)mR7, C(O)R7 or C(O)O-R7, C1-C6 alkyl,
haloalkyl containing 1-6 carbon atoms or OR8; or a -N=C(R9)(R10) radical; R5 and R6 are
independently a hydrogen atom or an alkyl C1-C6 radical, haloalkyl, containing 1-6 carbon atoms, C
(O) alkyl C1-C6, S(O)rrCF3; or R5 and R6 can together form divalent alkylene radical which can be
interrupted by one or two divalent hetero atoms such as oxygen and sulfur; R7 is an alkyl C1-C6
radical or haloalkyl, containing 1-6 carbon atoms; R8 is an alkyl C1-C6 radical, haloalkyl, containing
1-6 carbon atoms or a hydrogen atom; R9 is an alkyl C1-C6 radical or a hydrogen atom; R10 is a
phenyl radical or heteroaryl optionally substituted by one or a plurality of halo atoms or by groups such
as OH, -O-alkyl C1-C6, -S-alkyl C1-C6, cyano, or alkyl C1-C6; X is a trivalent nitrogen or a C1-C12
radical, in which three other valences of a carbon atom constitute a portion of an aromatic cycle; R1
and R12 are independently a hydrogen or halo atom; R13 is a halo atom or a haloalkyl radical,
haloalkoxy, containing 1-6 carbon atoms, S (O)qCF3 or SF5; m, n, q and r are independently integers
0, 1 or 2; provided that when R1 is methyl than R3 haloalkyl, R4 is NH2, R11 is Cl, R13 is CF3, and X
is N; b) between 0.05 to 10%, preferably between 0.1 to 5 % one (or a plurality of) agent(s) retaining
moisture, preferably an agent retaining moisture of organic nature; and c) between 40 to 99%,
preferably between 50 to 98% (and more preferably between 70 to 97%) vegetable flour. 2. The
insecticide composition according to claim 1, characterized in that the flour is produced by milling
cereals such as wheat, barley, rye, triticale, oats, and also rice, sorghum, soy and maize. 3. The
insecticide compositions according to claim 1 and 2, characterized in that the flour is maize flour. 4.
The insecticide composition according to any one of claims 1 to 3, characterized in that hydrophilic
macromolecular derivatives of vegetable origin, in particular, hydrophilic derivatives of cellulose and
more definite cellulose are used as a water-retentive agent of organic nature. 5. The insecticide
composition according to any one of claims 1 to 4, characterized in that the composition contains
between 3 to 30%, preferably between 4 to 20% of sugar. 6. The insecticide composition according to
any one of claims 1 to 4, characterized in that the sugar is selected, in particular, from mono-, oligo- or
polyorganosaccharides, and more definitely from sucrose, lactose, fructose, dextrose, glucose or also
from molasses or honey. 7. The insecticide composition according to any one of claims 1 to 6,
145/2194
characterized in that comprises a conservative agent formed during flour degradation, such as sodium
benzoate, 1,2 benzisothiazoline-3-one, benzoic acid, p-hydroxybenzoic acid, esters thereof, and salts
thereof with alkali or alkali-earth metals, in particular, sodium salt, 2-phenylphenol, and salts thereof
with alkali or alkali-earth metals, in particular, sodium salt, paranitrophenol. 8. The insecticide
composition according to any one of claims 1 to 7, characterized in that comprises other additives, such
as dying agents or attractive agents for pests or repulsive agents for birds and animals which are useful
or to be protected, and/or other additives used for ready formulations such as gluing, agglomerating,
causing appetite, agglutinating, gel-forming, bloating, antiadhesive and other additives. 9. The
insecticide composition according to any one of claims 1 to 8, characterized in that the compound of
formula I is 5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-4-[(trifluoromethyl)
sulfinyl]-1H-pyrazole. 10. The insecticide composition according to any one of claims 1 to 9,
characterized in that the ready formulations are in the form of granules between 0.1 mm to 3 mm,
preferably between 0.5 mm to 4 mm, said granules are preferably insoluble in water. 11. A method for
fighting insects, characterized in that an effective amount of the composition according to any one of
claims 1 to 10 in the form of granules between 0.2 mm to 2 cm in size is applied on soil or in soil
(preferably in soil) in a zone to be cultivated. 12. The method according to claim 11, characterized in
that the compound of formula I is used for crop protection. 13. The method according to claim 11 or
12, characterized in that cereals are protected, preferably maize or beet, or sun flower, or potato, or
rape. 14. The method according to any one of claims 11 to 13, characterized in that an effective amount
of one of compositions is used for fighting insects, in particular, against click beetles. 15. The method
according to any one of claims 12 to 14, characterized in that an effective amount of the composition
corresponds to the dose of the composition of formula I, which is between 1 to 50g/ha, preferably
between 3 to 40 g/ha. 16. The method for fighting insects, comprising applying on or in soil the
composition as defined in one claims 1 to 10, comprising a dose which is not lethal in contact, but
lethal in ingestion. 17. The method according to claim 16 used against click beetles.Description:
Description of corresponding document: US6939830
BACKGROUND OF THE INVENTION
[0001] A The subject of the present invention is novel compositions intended for controlling soil
insects in their various developmental forms, and in particular compositions useful for controlling click
beetles. The invention also relates to a method of control using the said compositions.
DESCRIPTION OF RELATED ART
[0002] Insecticidal compounds of the phenylpyrazole type which can be used in controlling insects
are known in particular from patent applications EP 295117, WO 87/3781, 93/6089 and 94/21606.
Patent applications EP 295117 and 836386 also mention compositions comprising from 0.01% to 5%
of such active substances.
[0003] Click beetles constitute a family of insects which are particularly harmful for certain crops,
more particularly for maize, beet, sunflower, potato and rape crops. Their harmful character is all the
more marked since the larval forms of click beetles can remain for very long periods in the soil,
extending up to 5 years.
[0004] Baits have indeed been proposed for various sorts of insects, as well as formulas which can be
consumed by ingestion, but these formulas are not necessarily active for all the types of insect and the
need remains to find insecticidal forms or formulations which are particularly effective for the most
diverse applications, and in particular for controlling click beetles.
[0005] In addition, as regards the insecticides applied over or into the soil, it is desirable to find
conditions and formulations which make it possible to obtain good efficacy at doses which are as low
as possible.
[0006] One aim of the invention is to overcome these difficulties completely or in part.
[0007] Another aim of the invention is to provide advantageous and effective compositions for
controlling non-gregarious insects.
[0008] Another aim of the invention is to provide advantageous and effective compositions for
controlling soil insects, especially click beetles, and more particularly click beetles in the larval state.
[0009] Another aim of the invention is to provide compositions comprising at least one insecticidal
active substance of the phenylpyrazole type and which are easily applicable over or into the soil.
[0010] Another aim of the invention is to provide insecticide compositions whose performance is
good in spite of low applicable doses.
146/2194
SUMMARY OF THE INVENTION
[0011] It has found that these aims could be achieved, completely or in part, by means of the
compositions and the control method according to the invention which are described in detail below. It
is specified that the percentages indicated in the present text are weight/weight percentages, unless
otherwise indicated.
[0012] The subject of the present invention is therefore, firstly, insecticidal compositions comprising:
[0013] a) between 0.001 and 5%, preferably between 0.05 and 1% and still more advantageously
between 0.05 and 0.5% of the compound of formula (I):
EMI1.0
[0014] in which:
[0015] R1 is a halogen atom or a CN group or a methyl group or a CH3CO group;
[0016] R2 is S(O)nR3;
[0017] R3 is alkyl or haloalkyl;
[0018] R4 represents a hydrogen or halogen atom, or an NR5R6, S(O)mR7, C(O)R7 or C(O)O-R7,
alkyl, haloalkyl or OR8 radical or an -N-C(R9)(R10) radical;
[0019] R5 and R6 independently represent a hydrogen atom or an alkyl, haloalkyl, C(O)alkyl or
S(O)rCF3 radical, or R5 and R6 can together form a divalent alkylene radical which may be interrupted
by one or two divalent heteroatoms such as oxygen or sulphur;
[0020] R7 represents an alkyl or haloalkyl radical;
[0021] R8 represents an alkyl or haloalkyl radical or a hydrogen atom;
[0022] R9 represents an alkyl radical or a hydrogen atom;
[0023] R10 represents a phenyl or heteroaryl group optionally substituted with one or more halogen
atoms or groups such as OH, -O-alkyl, -S-alkyl, cyano or alkyl;
[0024] X represents a trivalent nitrogen atom or a C-R12 radical, the other three valencies of the
carbon atom forming part of the aromatic ring;
[0025] R11 and R12 represent, independently of each other, a hydrogen or halogen atom;
[0026] R13 represents a halogen atom or a haloalkyl, haloalkoxy, S(O)qCF3 or SF5 group;
[0027] m, n, q, r represent, independently of each other, an integer equal to 0, 1 or 2;
[0028] with the proviso that when R1 is methyl, then R3 is haloalkyl, R4 is NH2, R11 is Cl, R13 is
CF3 and X is N;
[0029] b) between 0.05 and 10%, preferably between 0.1 and 5% of one (or more) moisture-retaining
agents, preferably a moisture-retaining agent of an organic nature; and
[0030] c) between 40 and 99%, preferably between 50 and 98% (and more preferably between 70 and
97%) of vegetable meal.
[0031] The alkyl radicals of the definition of formula (I) generally comprise from 1 to 6 carbon
atoms. The ring formed by the divalent alkylene radical representing R5 and R6 as well as by the
nitrogen atom to which R5 and R6 are attached is generally a 5-, 6- or 7-membered ring.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0032] The compound of formula (I) may be prepared according to one of the methods described in
patent applications WO 87/3781, 93/6089, 94/21606, EP 295117 or alternatively by another method
within the general knowledge of persons skilled in the art competent in chemical synthesis. This
compound is generally designated in the present text by the term active substance.
[0033] Among the vegetable meals which can be used, there may be mentioned the meals derived
from the grinding of cereal grains such as wheat, barley, rye, triticale, oats, or also rice, sorghum,
soyabean, maize, the preferred meal being that based on maize. A mixture of these vegetable meals can
also be envisaged in the context of the present invention.
[0034] Among the moisture-retaining agents of an organic nature, there may be mentioned the
macromolecular hydrophilic derivatives of plant origin, and in particular the cellulosic hydrophilic
derivatives, and more particularly cellulose, but also one or more disintegrating agents. It may be
advantageous to use these compounds in particular when meals such as hard wheat meals are used in
the granules. Disintegrating agents include: starch, sodium carboxymethyl starch, cellulose such as
microcrystalline cellulose; modified celluloses such as sodium carboxymethylcellulose; bentonite,
aluminium and magnesium silicate; sodium polynaphthalenesulphonate, sodium
dodecylbenzenesulphonate, sodium dioctylsulphosuccinate, lignin sulphonate; a saccharide derivative
such as lactose, fructose, sucrose, mannitol, dextrose; a cross-linked derivative of
polyvinylpyrrolidone. When a disintegrating agent is used, the composition according to the invention,
147/2194
may contain from 0.5 to 30%, and preferably from 1 to 20%, by weight of the dry substance, of the said
agent(s).
[0035] According to a variant of the composition according to the invention, the composition also
comprises from 3 to 30%, preferably from 4 to 20% of sugars. The sugars are chosen in particular from
mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose or
alternatively molasses or honey.
[0036] The compositions which are the subject of the invention may also comprise a preservative
preventing the degradation of the meals, such as sodium benzoate, 1,2-benzisothiazolin-3-one, benzoic
acid, para-hydroxybenzoic acid and its ester derivatives and its alkali or alkaline-earth metal salts, in
particular the sodium salt, 2-phenylphenol and its alkali or alkaline-earth metal salts, in particular the
sodium salt, para-nitrophenol.
[0037] Other additives may also be included such as colourings or attractants for pests or repellents
for birds or animals which are useful or which should be protected.
[0038] Other formulation additives may be used such as binding, agglomerating, appetite-enhancing,
agglutinating, gelling, swelling or antiadherent agents and the like.
[0039] A preferred class of compounds of formula (I) comprises compounds such that R1 is CN,
and/or R3 is haloalkyl, and/or R4 is NH2, and/or R11 and R12 are, independently of each other, a
halogen atom, and/or R13 is haloalkyl.
[0040] According to a particularly advantageous variant of the invention, the compound of formula
(I) used in the invention is 5-amino-3-cyano-1-[2,6-di-chloro-4-(trifluoromethyl)phenyl]-4[(trifluoromethyl)-sulphinyl]-1H-pyrazole, to which reference is made in the examples under the term
"fipronil".
[0041] The formulations according to the invention are generally in the form of granules. The size of
the granules is advantageously between 0.1 mm and 3 cm, preferably between 0.5 and 4 mm. These
granules are advantageously insoluble in water (in the sense that they resist disintegration with water).
[0042] The compositions according to the invention may be prepared by simply mixing the various
constituents, preferably by extrusion or compression in the cold or hot state according to any
granulation or pelleting technique known per se. For the production of such granules, reference can be
easily made to the European patent application published under the number EP 0575838 and/or to other
techniques, for example extrusion techniques, known to persons skilled in the art.
[0043] The invention also relates to a method of protecting crops from insects, especially click
beetles, characterized in that an effective quantity of a composition in the form of granules having a
size of between 0.2 mm and 2 cm comprising an active substance chosen from the group consisting of
the products of formula I, imidacloprid, acetamiprid, nitenpyram and thiamethoxam, is applied over or
into the soil (preferably into the soil) of the area which has to be cultivated.
[0044] The invention thus relates more particularly to a method of protecting cereal, preferably maize
or beet or sunflower or potato or rape, crops. The application of the formulations according to the
invention takes place advantageously before sowing the said crop, or simultaneously with this sowing.
[0045] The invention also relates to a method of controlling insects, especially click beetles,
characterized in that an effective quantity of one of the compositions according to the invention is
applied over or into the soil (preferably into the soil) where they are present or are likely to be present.
[0046] As effective quantity, quantities of composition corresponding to a dose of compound of
formula (I) of between 1 and 50 g/ha, preferably between 3 and 40 g/ha are often used.
[0047] A specific characteristic of the method of controlling insects according to the invention
consists in the application, over or into the soil, of a composition providing a dose which is nonlethal
through contact but lethal through ingestion.
[0048] In other words, in the specific case of click beetles, the method consists in killing the click
beetles by application of a dose which is nonlethal through contact but lethal through ingestion. A
hypothesis for the good efficacy of the method of treatment according to the invention, which makes it
possible to greatly reduce the applicable doses of compounds of formula I in particular, is based on the
fact that once the bait according to the invention has caused the death of a click beetle, the latter can
itself serve as bait for other click beetles, which therefore also ingest a product (dead click beetle)
containing the insecticide.
[0049] For the purposes of the present text, the words insecticide and insect should be taken in their
broad ordinary-sense and not in their strictly scientific (zoological) sense. Accordingly, the term insect
is understood to mean any animal of a very small size such as arthropods (insects in the strict and
zoological sense, arachnids, myriapods) and nematodes.
[0050] As soil insects against which the invention is particularly effective, there may be mentioned
for example:
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[0051] The Coleoptera (wireworms (Agriotes spp.), false wireworms, white grubs) such as for
example:
[0052] Agriotes lineatus (European click beetle, Elateridae),
[0053] Agriotes sordidus (European click beetle, Elateridae),
[0054] Agriotes obscurus (European click beetle, Elateridae),
[0055] Agriotes sputator (European click beetle, Elateridae),
[0056] Athous spp. (Elateridae),
[0057] Atomaria linearis (Cryptophagidae)
[0058] Melolontha spp. (white grubs, Scarabaeidae),
[0059] Bothynoderes
[0060] Limonius spp. (US click beetle),
[0061] Melanotus spp. (US click beetle),
[0062] Diabrotica spp. (cornrootworms, Crysomelidae),
[0063] Tanymecus pallidus (beet leaf weevil, Curculionidae).
[0064] The Lepidoptera (Noctuidae) such as:
[0065] Autographa spp., Mamestra spp., Agrotis spp. (cutworms, grey grubs), Euxoa spp. (cutworms,
grey grubs), Spodoptera spp. (Spodoptera exigua, Spodoptera littorlis).
[0066] The Diptera such as Tipula spp.).
[0067] The Myriapoda (Myriapoda):
[0068] Diplopoda=Millipedes,
[0069] Centipede.
[0070] Among the soil click beetles against which the invention is particularly effective, there may be
mentioned Agriotes spp., Athous spp., Limonius spp.
[0071] The granules according to the invention are advantageously inserted into the soil at a depth of
between 1 and 5 cm.
[0072] The compositions according to the invention are particularly advantageous in that they allow
the use of lower doses of active product than similar known compositions.
[0073] The following examples illustrate the invention without however constituting a limitation
thereto. In these examples, the compound of formula (I) used is fipronil.
EXAMPLE 1
[0074] A surface of 0.1 ha is sown with maize at the rate of about 8000 untreated seeds. This surface
is divided into 40-m>;2 ; plots.
[0075] At the same time as the sowing, there are incorporated into the soil, in the sowing row, 2 mm
granules containing a composition consisting of:
[0076] 0.25% of fipronil,
[0077] 93.5% of maize meal,
[0078] 2% of cellulose,
[0079] 4% of lactose,
[0080] 0.2% of para-nitrophenol,
[0081] 0.05% of pigment blue 15.3.
[0082] The quantities of granules thus spread vary from 2.5 to 10 kg per hectare. Untreated plots are
kept to serve as control and to verify the extent of the damage by the insects. Likewise, the plots will be
treated with a commercial insecticide which is reputed effective and called reference. Each modality is
repeated four times.
[0083] Approximately 20 days after sowing, the maize plants which have emerged are counted.
[0084] In the locality of St Hilaire (30), 22 days after sowing, 19 plants-are observed in the furrow of
the 4 untreated plots per 10 meters of furrow. In the plots treated according to the invention with the
dose of fipronil of 6 g per hectare, 49 plants are observed per 10 meters of furrow.
[0085] With the dose of fipronil of 12.5 g per hectare, 48 to 50.5 plants are observed per 10 meters of
furrow.
[0086] With the dose of fipronil of 25 g per hectare, 45.5 to 51.3 plants are observed per 10 meters of
furrow.
[0087] With the dose of fipronil of 50 g per hectare, 49 plants are observed per 10 meters of furrow.
[0088] To obtain the same result with a conventional granule (clay carrier), 200 g of fipronil have to
be provided per hectare.
[0089] The soil is dug out and scraped in order to capture and identify the insects responsible for the
damage; a large presence of larvae of click beetles of the genus Agriotes, in particular Agriotes
sordidus, is observed for the untreated control.
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EXAMPLE 2
[0090] A surface of 1 ha is sown with maize at the rate of about 98, 100 untreated seeds. This surface
is divided into 27-m>;2 ; plots.
[0091] At the same time as the sowing, there are incorporated into the soil, in the sowing row, 2 mm
granules containing a composition consisting of:
[0092] 0.25% of- fipronil,
[0093] 93.5% of maize meal
[0094] 2% of cellulose,
[0095] 4% of lactose,
[0096] 0.2% of para-nitrophenol,
[0097] 0.05% of pigment blue 15.3.
[0098] The quantities of granules thus spread vary from 2.5 to 10 kg per hectare. Untreated plots are
kept to serve as control and to verify the extent of the damage by the insects. Likewise, the plots will be
treated with a commercial insecticide which is reputed effective and called reference. Each modality is
repeated four times.
[0099] Approximately 50 days after sowing, the maize plants which have emerged are counted.
[0100] In the locality of Beaufort (62), 50 days after sowing, 30 plants are observed in the furrow of
the 4 untreated plots per 10 meters of furrow. In the plots treated according to the invention with the
dose of fipronil of 6 g per hectare, 40 plants are observed per 10 meters of furrow.
[0101] With the dose of fipronil of 12.5 g per hectare, 43 to 46 plants are observed per 10 meters of
furrow.
[0102] With the dose of fipronil of 25 g per hectare, 44.5 to 50 plants are observed per 10 meters of
furrow.
[0103] With the dose of fipronil of 50 g per hectare, 49.8 plants are observed per 10 meters of furrow.
[0104] To obtain the same result (52 plants per 10 meters) with a conventional granule (clay carrier),
200 g of fipronil have to be provided per hectare.
[0105] The soil is dug out and scraped in order to capture and identify the insects responsible for the
damage; a large presence of larvae of click beetles of the genus Agriotes, in particular Agriotes
lineatus.
EXAMPLE 3
[0106] Test of efficacy of the bait granules according to the invention on potato crop.
[0107] At the same time as the sowing, there are incorporated into the soil, in the sowing row,
granules according to the invention consisting of:
[0108] 12.5 g/kg of fipronil (from an SC containing 500 g/l of fipronil),
[0109] 945.5 g/kg of a) maize meal (granules A) or b) rice meal (granules B),
[0110] 40 g/kg of lactose,
[0111] 2 g/kg of para-nitrophenol.
[0112] The efficacy against Agriotes (click beetles), 90 days after sowing, of the two granules A and
B above, used at the doses of 5 and 2.5 g of fipronil per hectare, and of the same fipronil used by
spraying at the doses of 50 and 25 g/ha (from Regent(R) 800WG) (compound C), was compared.
[0113] The following results, expressed as number of holes per 10 tubers (=N) are then observed:
[0114]
>;tb;Product>;sep;A>;sep;A>;sep;B>;sep;B>;sep;C>;sep;C>;sep;Control*
>;tb;Dose (g.ha)>;sep;2.5>;sep;5>;sep;2.5>;sep;5>;sep;25>;sep;50>;sep;>;tb;N>;sep;6>;sep;1>;sep;7>;sep;3>;sep;6>;sep;1>;sep;14
>;tb;*untreated control.
[0115] This result indeed shows the good control of click beetles which is obtained by the granules
according to the invention which give the same result as Regent(R) 800WG but with a dose reduced by
a factor of 10.Data supplied from the esp@cenet database - Worldwide
Claims:
Claims of corresponding document: US6939830
1. An insecticidal composition comprising:
(a) between 0.001 and 5% of a compound of formula (I):
EMI2.0
in which:
150/2194
R1 is a halogen atom or a CN group or a methyl group or a CH3CO group;
R2 is S(O)nR3;
R3 is alkyl or haloalkyl;
R4 represents a hydrogen or halogen atom, or an NR5R6, S(O)mR7, C(O)R7 or C(O)O-R7, alkyl,
haloalkyl or OR8 radical or an -N-C(R9)(R10) radical;
R5 and R6 independently represent a hydrogen atom or an alkyl, haloalkyl, C(O)alkyl or S(O)rCF3
radical, or R5 and R6 together form a divalent alkylene radical optionally interrupted by one or two
divalent heteroatoms;
R7 represents an alkyl or haloalkyl radical;
R8 represents an alkyl or haloalkyl radical or a hydrogen atom;
R9 represents an alkyl radical or a hydrogen atom;
R10 represents a phenyl or heteroaryl group optionally substituted with at least one halogen atom or
radical selected from the group consisting of OH, -O-alkyl, -S-alkyl, cyano and alkyl;
X represents a trivalent nitrogen atom or a C-R12 radical, the other three valences of the carbon atom
forming part of the aromatic ring;
R11 and R12 represent, independently of each other, a hydrogen or halogen atom;
R13 represents a halogen atom or a haloalkyl, haloalkoxy, S(O)qCF3 or SF5 group;
m, n, q, r represent, independently of each other, an integer equal to 0, 1 or 2;
with the proviso that when R1 is methyl, then R3 is haloalkyl, R4 is NH2, R11 is Cl, R13 is CF3 and X
is N;
(b) between 0.05 and 10% of cellulose as a moisture-retaining agent; and
(c) between 40 and 99% of at least one vegetable meal.
2. An insecticidal composition according to claim 1, wherein the vegetable meal is derived from the
grinding of a cereal grain.
3. An insecticidal composition according to claim 1, wherein the vegetable meal is a maize.
4. An insecticidal composition according to claim 1, wherein the composition also comprises from 3 to
30% of a sugar.
5. An insecticidal composition according to claim 1, wherein the sugar is selected from mono, oligo- or
polyorganosaccharides.
6. An insecticidal composition according to claim 1, further comprising a preservative.
7. An insecticidal composition according to claim 1, further comprising one or more additives selected
from the group consisting of colorings, attractants for pests, repellents for birds or animals, binding
agents, agglomerating agents, appetite-enhancing agents, agglutinating agents, gelling agents, swelling
agents and antiadherent agents.
8. An insecticidal composition according to claim 1, wherein the compound of formula (I) is 5-amino3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole.
9. An insecticidal composition according to claim 1, which is in the form of granules of a size between
0.1 mm and 3 cm.
10. An insecticidal composition according to claim 1, wherein the compound of formula (I) is present
in an amount of between 0.05 and 1%.
11. An insecticidal composition according to claim 10, wherein the compound of formula (I) is present
in an amount of between 0.05 and 0.5%.
12. An insecticidal composition according to claim 1, wherein the moisture-retaining agent is present in
an amount of between 0.1 and 5%.
13. An insecticidal composition according to claim 1, wherein the vegetable meal is present in an
amount of between 50 and 98%.
151/2194
14. An insecticidal composition according to claim 13, wherein the vegetable meal is present in an
amount of between 70 and 97%.
15. An insecticidal composition according to claim 2, wherein said cereal grain is selected from the
group consisting of wheat, barley, rye, triticale, oats, rice, sorghum, soyabean and maize.
16. An insecticidal composition according to claim 4, wherein the sugar is present in an amount of
between 4 to 20%.
17. An insecticidal composition according to claim 5, wherein the sugar is sucrose, lactose, fructose,
dextrose, glucose, molasses or honey.
18. An insecticidal composition according to claim 6, wherein the preservative is selected from the
group consisting of sodium benzoate, 1,2-benzisothiazolin-3-one, benzoic acid, para-hydroxybenzoic
acid and its esters and alkali and alkaline-earth metal salts, 2-phenylphenol and its alkali and alkalineearth metal salts, and para-nitrophenol.
19. An insecticidal composition according to claim 9, wherein the granules are of a size between 0.5
and 4 mm and are water-insoluble.
20. An insecticidal composition according to claim 1, further including from 0.5 to 30% of at least one
disintegrating agent.
21. An insecticidal composition according to claim 20, wherein the disintegrating agent is present in an
amount of 1 to 20% and is selected from the group consisting of starch, sodium carboxymethyl starch,
microcrystalline cellulose, modified celluloses, bentonite, aluminum silicate, magnesium silicate,
sodium polynaphthalenesulfonate, sodium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate,
lignin sulfonate, a saccharide derivative.
22. A method of controlling insects which comprises applying an effective quantity of an insecticidal
composition comprising:
(a) between 0.001 and 5% of a compound of formula (I):
EMI3.0
in which:
R1 is a halogen atom or a CN group or a methyl group or a CH3CO group;
R2 is S(O)nR3;
R3 is alkyl or haloalkyl;
R4 represents a hydrogen or halogen atom, or an NR5R6, S(O)mR7, C(O)R7 or C(O)O-R7, alkyl,
haloalkyl or OR8 radical or an -N-C(R9)(R10) radical;
R5 and R6 independently represent a hydrogen atom or an alkyl, haloalkyl, C(O)alkyl or S(O)rCF3
radical, or R5 and R6 together form a divalent alkylene radical optionally interrupted by one or two
divalent heteroatoms;
R7 represents an alkyl or haloalkyl radical;
R8 represents an alkyl or haloalkyl radical or a hydrogen atom;
R9 represents an alkyl radical or a hydrogen atom;
R10 represents a phenyl or heteroaryl group optionally substituted with at least one halogen atom or
radical selected from the group consisting of OH, -O-alkyl, -S-alkyl, cyano and alkyl;
X represents a trivalent nitrogen atom or a C-R12 radical, the other three valences of the carbon atom
forming part of the aromatic ring;
R11 and R12 represent, independently of each other, a hydrogen or halogen atom;
R13 represents a halogen atom or a haloalkyl, haloalkoxy, S(O)qCF3 or SF5 group;
m, n, q, r, represent, independently of each other, an integer equal to 0, 1 or 2;
with the proviso that when R1 is methyl, then R3 is haloalkyl, R4 is NH2, R11 is Cl, R13 is CF3 and X
is N;
(b) between 0.05 and 10% of cellulose as a moisture-retaining agent; and
(c) between 40 and 99% of at least one vegetable meal;
in the form of granules having a size of between 0.2 mm and 2 cm over or into the soil in an area which
is to be cultivated.
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23. A method according to claim 22, wherein the effective quantity is selected to provide a dosage
which is nonlethal through contact but lethal through ingestion.
24. A method according to claim 22, wherein the insect being controlled is a click beetle.
25. A method according to claim 22, wherein the effective quantity is between 1 and 50 g/ha.
26. A method according to claim 25, wherein the effective quantity is between 3 and 40 g/ha.
27. A method according to claim 22, wherein the vegetable meal is maize.
28. A method according to claim 22, wherein the composition also comprises from 3 to 30% of a sugar
and from 0.5 to 30% of at least one disintegrating agent.
29. A method according to claim 28, wherein the sugar is lactose and the disintegrating agent is lactose.
30. A method according to claim 22, wherein the compound of formula (I) is 5-amino-3-cyano-1-[2,6dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl)-1H-pyrazole.
31. A method according to claim 30, wherein the vegetable meal is maize and the composition also
comprises from 3 to 30% of a sugar and from 0.5 to 30% of at least one disintegrating agent.
32. A method according to claim 31, wherein the sugar is lactose and the disintegrating agent is lactose.
33. A method of protecting crops which comprises applying over or into the soil before or
simultaneously with sowing the crops, an effective amount of an insecticidal composition comprising:
(a) between 0.001 and 5% of a compound of formula (I):
EMI4.0
in which;
R1 is a halogen atom or a CN group or a methyl group or a CH3CO group;
R2 is S(O)nR3;
R3 is alkyl or haloalkyl;
R4 represents a hydrogen or halogen atom, or an NR5R6, S(O)mR7, C(O)R7 or C(O)O-R7, alkyl,
haloalkyl or OR8 radical or an -N-C(R9)(R10) radical;
R5 and R6 independently represent a hydrogen atom or an alkyl, haloalkyl, C(O)alkyl or S(O)rCF3
radical, or R5 and R6 together form a divalent alkylene radical optionally interrupted by one or two
divalent heteroatoms;
R7 represents an alkyl or haloalkyl radical;
R8 represents an alkyl or haloalkyl radical or a hydrogen atom;
R9 represents an alkyl radical or a hydrogen atom;
R10 represents a phenyl or heteroaryl group optionally substituted with at least one halogen atom or
radical selected from the group consisting of OH, -O-alkyl, -S-alkyl, cyano and alkyl;
X represents a trivalent nitrogen atom or a C-R12 radical, the other three valences of the carbon atom
forming part of the aromatic ring;
R11 and R12 represent, independently of each other, a hydrogen or halogen atom;
R13 represents a halogen atom or a haloalkyl, haloalkoxy, S(O)qCF3 or SF5 group;
m, n, q, r represent, independently of each other, an integer equal to 0.1 or 2;
with the proviso that when R1 is methyl, then R3 is haloalkyl, R4 is NH2, R11 is Cl, R13 is CF3 and X
is N;
(b) between 0.05 and 10% of cellulose as a moisture-retaining agent; and
(c) between 40 and 99% of at least one vegetable meal; in the form of granules.
34. A method according to claim 33, wherein the crop to be protected is a cereal, beet, sunflower,
potato or rape.
35. A method according to claim 33, wherein the effective amount comprises between 1 and 50 g/ha.
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36. A method according to claim 35, wherein the amount is between 3 and 40 g/ha.
37. A method according to claim 34, wherein the vegetable meal is maize.
38. A method according to claim 34, wherein the composition also comprises from 3 to 30% of a sugar
and from 0.5 to 30% of at least one disintegrating agent.
39. A method according to claim 38, wherein the sugar is lactose and the disintegrating agent is lactose.
40. A method according to claim 33, wherein the compound of formula (I) is 5amino-3-cyano-1-[2,6dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl)]-1H-pyrazole.
41. A method according to claim 40, wherein the vegetable meal is maize and the composition also
comprises from 3 to 30% of a sugar and from 0.5 to 30% of at least one disintegrating agent.
42. A method according to claim 41, wherein the sugar is lactose and the disintegrating agent is lactose.
43. An insecticidal composition comprising;
(a) between 0.001 and 5% of the compound 5-amino-3-cyano-1-[2,6-dichloro-4(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole;
(b) between 0.05 and 10% of cellulose as a moisture-retaining agent; and
(c) between 40 and 99% of at least one vegetable meal.
44. An insecticidal composition according to claim 43, wherein the vegetable meal is maize.
45. An insecticidal composition according to claim 43, wherein the composition also comprises from 3
to 30% of a sugar and from 0.5 to 30% of at least one disintegrating agent.
46. An insecticidal composition according to claim 45, wherein the vegetable meal is maize.
47. An insecticidal composition according to claim 45, wherein the sugar is lactose and wherein the
disintegrating agent is lactose.
48. An insecticidal composition according to claim 47, wherein the vegetable meal is maize.
49. A method of controlling insects which comprises applying an effective quantity of an insecticidal
composition comprising:
(a) between 0.001 and 5% of the compound 5-amino-3-cyano-1-[2,6-dichloro-4(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole;
(b) between 0.05 and 10% of cellulose as a moisture-retaining agent; and
(c) between 40 and 99% of at least one vegetable meal;
in the form of granules having a size of between 0.2 mm and 2 cm over or into the soil in an area which
is to be cultivated.Data supplied from the esp@cenet database - Worldwide
154/2194
16. EA4458
- 4/29/2004
HERBICIDES CONTAINING N-[(4,6-DIMETHOXYPYRIMIDINE-2YL)AMINOCARBONYL]-5-METHYLSULPHONAMIDOMETHYL-2ALKOXYCARBONYLBENZENE SULPHONAMIDES
URL EPO = http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=EA4458
Inventor(s):
HACKER ERWIN (DE); BIERINGER HERMANN (DE); LORENZ KLAUS (DE)
Applicant(s):
HOECHST SCHERING AGREVO GMBH (DE)
IP Class 4 Digits: A01N
IP Class:A01N47/36
E Class: A01N47/36
Application Number:
EA19990000456 (19971118)
Priority Number: DE19961050955 (19961207); WO1997EP06416 (19971118)
Family: EA4458
Equivalent:
WO9824320; EP0946100; US6221809; DE19650955; CA2274091; TR9901272T;
SK283810B; BG64030; AU731739
Abstract:
Abstract of EA4458
1. A herbicidal composition comprising A) at least one compound from the group of the substituted
phenylsulfonylureas of the formula (I) in which R>;1; is (C1-C8)alkyl, (C1-C4)alkyl, which is monoto tetrasubstituted by radicals selected from the group consisting of halogen and (C1-C2)alkoxygroup
and agriculturally acceptable salts thereof, and Ba) at least one compound from the group comprising
B1) phenoxaprop, phenoxaprop-P B2) isoproturon B3) diclophop B4) clodinaphop B5) a compound
from B4) and clokvintocete B6) chlorotoluron B7) metabenzthiazuron B8) imasametabenz B9)
tralcoxidim B10) difenzoquate B11) flamprop, flamprop-M B12) pendimetaline wherein compounds of
formula (I) or salts thereof and compounds from Ba) group are taken in synergistically active content.
2. The herbicide compound comprising A) at least one compound from the group containing
substituted phenylsulfonylureas of the formula (I) in which R>;1; is (C1-C8)-alkyl or (C1-C4)-alkyl,
which is mono- to tetrasubstituted by radicals selected from the group consisting of halogen and (C1C2)alkoxygroup and agriculturally acceptable salts thereof, and Bb) at least one compound from the
group comprising B13) mecoprop, mecoprop-P B14) MCPA B15) dichloroprop, dichloroprop-P B16)
2,4-D B17) dicamba B18) fluoroxipir B19) ioxinyl B20) bromoxinyl B21) bifenox methyl-5-(2,4dichlorophenoxy)-2-nitrobenzoat B22) fluoroglycofen B23) lactofen B24) phomesafen B25)
oxifluorfen B26) ET-751 B27) azole of the formula (II) in which R>;1; is (C1-C4)-alkyl, R>;2; is (C1C4)-alkyl, (C1-C4)-alkylthio- or (C1-C4)-alkoxygroup, each of which may be substituted by one or
more halogen atoms, or R>;1; and R>;2; together form the group (CH2)m where m =3 or 4, R>;3; is
hydrogen or halogen, R>;4; is hydrogen or (C1 -C4)-alkyl, R>;5; is hydrogen, nitro-, cyano or one of
the groups -COOR>;7;, -C(=X)NR>;7;R>;8; or -C(=X)R>;10;, R>;6; is hydrogen, halogen,
cyanogroup, (C1-C4)-alkyl, (C1-C4)-alkylthio or -NR>;11; R>;12;, R>;7; and R>;8; are identical or
different and each is hydrogen or (C1-C4)-alkyl, or R>;7; and R>;8; join with the nitrogen to which
they are attached to form a saturated 5- or 6-membered carbocyclic ring, R>;10; is hydrogen or (C1C4)-alkyl, the latter optionally being substituted by one or more halogen atoms, and R>;11; and R>;12;
are identical or different and each is hydrogen, (C1-C4)-alkyl or (C1-C4)-alkoxycarbonyl, where
R>;11; and R>;12; may join with the nitrogen to which they are attached to form a 3-, 5- or 6membered carbocyclic or aromatic ring in which one carbon atom may be replaced by an oxygen atom;
155/2194
and B28) F 8426 B29) diflufenican B30) bentazon wherein compounds of the formula (I) and salts
thereof and compounds from the group Bb) are taken in synergistically active content. 3. The herbicide
compound comprising A) at least one compound from the group containing substituted
phenylsulfonylureas of the formula (I) in which R>;1; is (C1-C8)-alkyl or (C1-C4)-alkyl, which is
mono- to tetrasubstituted by radicals selected from the group consisting of halogen and (C1C2)alkoxygroup and agriculturally acceptable salts thereof, and Bb) at least one compound from the
group comprising B31) metribucine B32) metosulam B32a) flupoxam B33) prosulfocarb B34)
flurtamon B35) amidosulfuron B36) metsulfuron B37) tribenuron B38) tifensulfuron B39) triasulfuron
B40) chlorosulfuron B41) sulfonylureas of the formula (III) in which R>;1; is methyl, ethyl, n-propyl,
isopropyl or allyl, R>;2; is -CO-R>;5;, COOR>;6;, -CO-NR>;8;R>;9;, -CS-NR>;10;R>;11;,
SO2R>;14; or SO2NR>;15;R>;16;, R>;3; is -COR>;17;, -COOR>;18;, -CONR>;19;R>;20; or -COON=CR>;22;R>;23;, R>;4; is hydrogen or (C1-C4)-alkyl, R>;5; is hydrogen, (C1-C4)-alkyl, (C1-C2)haloalkyl, cyclopropyl, phenyl, benzyl or heteroaryl having 5 or 6 ring atoms, the last 3 radicals being
unsubstituted or substituted by one or more halogen atoms, R>;6; is (C1-C4)-alkyl, allyl, propargyl or
cyclopropyl, R>;8; is hydrogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl or (C1-C4-alkoxy)-carbonyl, R>;9; R>;11; are independently of one another identical or different and each is hydrogen or (C1-C4)-alkyl,
R>;14; is (C1-C4)-alkyl, R>;15; and R>;16; are independently of one another identical or different and
each is hydrogen or (C1-C4)-alkyl, R>;17; is hydrogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C3-C6)cycloalkyl, phenyl or heteroaryl, the last two radicals being unsubstituted or substituted, R>;18; is
hydrogen, (C1-C4)-alkyl, (C2 -C6)-alkenyl or (C2-C6)-alkynyl, the last three radicals being
unsubstituted or substituted by one or more radicals selected from the group consisting of halogen,
(C1-C4)-alkoxy, (C1-C4)-alkylthio and NR>;31;R>;32;, or (C3-C6)-cycloalkyl or (C3-C6)cycloalkyl(C1-C3)-alkyl, R>;19; is analogous to R>;8;, R>;20; is analogous to R>;9;, R>;22; and
R>;23; are independently of one another, identical or different, each is hydrogen or (C1-C2)-alkyl,
R>;31; and R>;32; are independently of one another, identical or different, each is hydrogen or (C1C4)-alkyl, W is oxygen or sulfur, X is (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)alkylthio, halogen or mono- or di-C1-C2 -alkyl)-amino, Y is (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)haloalkyl or (C1-C4)-alkylthiogroup, and Z is CH or N, B42) sulfonylureas of the formula (IV) and
agriculturally acceptable salts thereof, in which R>;1; is (C1-C8)-alkyl, (C3-C4)-alkenyl, or (C3-C4)alkynyl or (C1-C4)-alkyl which is mono- to tetrasubstituted by radicals selected from the group
consisting of halogen and (C1-C2)-alkoxy, where in the herbicide of the formula (IV) or the salt
thereof, especially preferable if R>;1; is methyl, and where those salts have favorable activity, where
the salt of the herbicide of the formula (IV) is formed by replacing the hydrogen of the -SO2-NH-COgroup by a cation selected from the group of the alkali metals, alkaline earth metals and ammonium,
preferably natrium, B43) flupirsulfuron (DPX-KE459) B44) MON 48500 and B45) sulfosulfuron
(MON 37500) wherein compounds of the formula (I) and salts thereof and compounds from the group
Bb) are taken in synergistically active content. 4. The herbicide compound comprising A) at least one
compound from the group containing substituted phenylsulfonylureas of the formula (I) in which R>;1;
is (C1-C8)-alkyl or (C1-C4)-alkyl, which is mono- to tetrasubstituted by radicals selected from the
group consisting of halogen and (C1-C2)alkoxygroup and agriculturally acceptable salts thereof, and
Bd) at least one compound from the group comprising B46) glufozinat, glufozinat-P B47) glifozat
wherein compounds of the formula (I) or salts thereof and compounds from the group Bg) are taken in
synergistically active content. 5. The composition as claimed in claim 4 comprising as a compound Bg)
glufozinat-ammonium. 6. The composition as claimed in claims 1-5, comprising the herbicide of the
formula (I), in which R>;1; is methyl, ethyl, n- or isopropyl, n-, tert-, 2-butyl or isobutyl, n-pentyl,
isopentyl, n-exyl, isohexyl, 1,3-dimethylbutyl, n-heptyl, 1 -methylhexyl or 1,4-dimethylpentyl and salts
thereof. 7. The composition as claimed in claim 1, wherein in the herbicide of the formula (I) or the salt
thereof R>;1; is methyl. 8. The composition as claimed in any of previous claims, wherein the salt of
the herbicide of the formula (I) is formed by replacing the hydrogen of the -SO2 -NH-CO-group by a
cation selected from the group of the alkali metals, alkaline earth metals and ammonium, preferably
natrium. 9. The composition as claimed in any of above mentioned claims, which comprises 0.1 to 99%
by weight of the active compounds A and Ba)-Bd), in addition to customary formulation auxiliaries.
10. A process for preparing a composition as claimed in any of above mentioned claims, which
comprises mixing the compounds of the formula I or salts thereof (group A compounds) with one or
more compounds of group B and, if appropriate, with one or more compounds of group C using a
customary crop protection formulation selected from the group consisting of wettable powders,
emulsifiable concentrates, aqueous solutions, emulsions, sprayable solutions (tank-mix), oil- or waterbased dispersions, suspoemulsions, dusts, seed dressings, granules for soil application or application by
broadcasting, water-dispersible granules, ULV formulations, microcapsules and waxes. 11. A method
156/2194
for controlling undesirable plants, which comprises applying a herbicidally effective amount of one of
the combinations of active compounds A+B as claimed in any of claims 1-9 onto the plants or the
cultivated area. 12. The method as claimed in claim 11, wherein the application rate for the compounds
of the formula (I) or salts thereof (group A compounds) is from 0.1 to 100 g of ai/ha, preferably from 2
to 40 g of ai/ha, and the application rates for the compounds of group B are from 1 to 5000 g of ai/ha.
13. The method as claimed in claims 11 and 12, wherein the active compounds of groups A and B are
applied simultaneously or at different times in a weight ratio of 1:2500 to 20:1. 14. The method as
claimed in one of claims 11-13, wherein the combinations are employed for the selective control of
undesirable plants. 15. The method as claimed in claim 14, wherein the combinations are employed in
transgenic crops. 16. The method as claimed in claim 15, wherein the combinations are employed in
cereals, maize, rice, sugar cane, crop plantations, meadows or pasture land. 17. The method as claimed
in one of claims 11-13, wherein the combinations are employed in crops of useful plants. 18. The
method as claimed in one of claims 11-13, wherein the combinations are employed in non-crop areas.
19. The method as claimed in claim 11, wherein harmful plants, which are usually resistant are
controlled.Description:
Description of corresponding document: US6221809
The invention relates to the technical field of crop protection agents, in particular to herbicidal
compositions comprising N-[(4,6dimethoxypyrimidin-2-yl)aminocarbonyl]-5methylsulfonamidomethyl-2- alkoxycarbonylbenzenesulfonamides and/or salts thereof.
WO 95/10507 (PCT/EP94/03369) discloses phenylsulfonylureas of the formula I and salts thereof
##STR2##
where the formula 1, owing to the extensive and wide definition of the radicals A, W, R@1, R@2,
R@3, R@4, R@5, R@6 and R@7, includes a large number of possible individual compounds.
Table 1 of WO 95/10507 lists compounds of the formula 1a ##STR3##
the examples having the numbers 105, 209, 217, 395, 399, 403, 407, 497 and 536 relating to those
compounds of the formula 1 a where Z is CH, X and Y are methoxy, R@7 is hydrogen, R@1 is
alkoxycarbonyl, R@4 is hydrogen and R@5 is a radical containing a sulfonyl group (SO2 CH3, SO2
NHCH3, SO2 N(CH3)2, SO2 N(CH3)2, SO2 CH2 F, SO2 CF3, SO2 C2 H5, SO2 -n-C3 H7, SO2 CH3
or SO2 CH3). However, the melting point is only given for Examples 105 (R@1 =methoxycarbonyl,
R@5 =methylsulfonyl) and 217 (R@1 =methoxycarbonyl, R@5 =SO2 N(CH3)2) and for Example 536
(sodium salt of the compound 105).
In WO 95/10507, biological examples for the compounds mentioned individually above are given
insofar as it is stated in general terms that the compounds of Examples 105, 217 and 536--in addition to
a series of other compounds--have very good activity against harmful plants such as Sinapis alba,
Stellaria media, Chrysanthemum segetum and Lolium multiflorum in the pre- and post-emergence
method at an application rate of 0.3 kg to 0.005 kg of active substance per hectare. The crop plant
safety of the compounds of the formula 1 is not documented by examples in the International Published
Specification mentioned.
Furthermore, general mention is made of the possibility that the compounds of the formula 1 can be
applied together with other herbicides. This mention is followed by an exemplary list of more than
about 250 different standard active compounds of which, inter alia, amidosulfurone, bentazone,
bifenox, bromoxynil, cafentrazon (ICI-A0051), chlortoluron, chlorsulfuron, clodinafop and its ester
derivatives (for example clodinafop-propargyl), dicamba, dichlorprop, diclofop and its esters such as
diclofop-methyl, difenzoquat, diflufenican, fenoxaprop and fenoxaprop-P and esters thereof such as,
for example, fenoxaprop-P-ethyl and fenoxaprop-ethyl, flamprop-methyl, fluoroglycofen-ethyl,
fluroxypyr, flurtamone, fomesafen, glufosinate, glyphosate, imazamethabenz-methyl, ioxynil,
isoproturon, lactofen, MCPA, mecoprop, methabenzthiazuron, metribuzin, metsulfuron-methyl,
pendimethalin, prosulfocarb, thifensulfuron-methyl, tralkoxydim, triasulfuron and tribenuron-methyl
are explicitly mentioned. Other than just mentioning the substances, WO 95/10507 does not provide
additional information with regard to the particular essence and purpose of a joint application, nor does
it provide a reason for the intended selection and combination of particular active compounds.
157/2194
Most phenylsulfonylureas disclosed in formula 1 and 1a of WO 95/10507 have useful to good activity
against a broad spectrum of economically important mono- and dicotyledonous harmful plants, and
active compounds of the formula 1 or 1 a also allow control of weeds encountered in rice under the
specific cultivation conditions such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus, Cyperus,
etc., however, in many cases the individual active compounds are not sufficient to control the range of
mono- and dicotyledonous weeds encountered in agricultural practice in particular in cereals or maize,
but also in other crop species.
With respect to the prior art mentioned and discussed herein, it was therefore an object of the invention
to provide novel mixtures having herbicidal activity to enable the expert to control, with a single
application or a small number of applications of herbicides in cereals and other crop species, the range
of weeds or specific weeds which are difficult to control. Furthermore, the mixtures of herbicidal active
compounds which are known in principle are meant to contribute to close so-called "activity gaps" and,
if possible, to reduce at the same time the application rates of the individual active compounds and to
increase flexibility in the timing of the application.
This object, and other objects which have not been specifically mentioned, is achieved by herbicidal
compositions having the features of in claim 1. Thus, the invention provides herbicidal compositions,
comprising
A) at least one herbicidal active compound from the group of the substituted phenylsulfonylureas of
the formula I and agriculturally acceptable, i.e. safe or usable, salts thereof ##STR4##
in which
R@1 is (C1 -C8)-alkyl, (C3 -C4)-alkenyl, or (C3 -C4)-alkynyl or (C1 -C4)-alkyl which is mono- to
tetrasubstituted by radicals selected from the group consisting of halogen and (C1 -C2)-alkoxy, and
B) at least one herbicidally active compound selected from the group of the compounds consisting of
Ba) herbicides which have selective activity against grasses in cereals,
Bb) herbicides which have selective activity against dicotyledons in cereals,
Bc) herbicides which have selective activity against grasses and dicotyledons in cereals and
Bd) herbicides which are active against weed grasses and broad-leaved weeds and which are
nonselective in non-crop areas or perennial crops (plantations) and/or selective in transgenic crops.
The combinations of herbicidally active compounds of types A and B according to the invention
permit, in a particularly advantageous manner, the control of the range of weeds required by the expert,
even including certain species which are difficult to control. In addition, using the combinations
according to the invention it is possible to reduce the active compound application rates of the
individual combination partners which are comprised in the combination, thus allowing more
economical approaches by the user. Finally, in a not readily foreseeable way, it was possible to achieve
increases in activity which surpassed expectations, the herbicidal compositions according to the
invention thus showing extensive synergistic effects.
Furthermore, it was particularly surprising in the context of the invention that the sulfonylureas of the
formula I carrying a methylsulfonamidomethyl substituent in position 5 of the phenyl ring in
combination with other herbicides proved to be outstandingly suitable for the effective control of weed
species which are difficult to control. In particular, unexpected specific activities against resistant weed
grasses were observed.
Altogether, the quality of the activities found for the combinations according to the invention is
generally also better than for example that found for similar combinations comprising sulfonylureas of
the closest prior art, as represented for example by phenylsulfonylureas carrying iodine substituents in
position 4 of the phenyl ring according to formula 2 of WO 92/13845 ##STR5##
where the radicals according to the prior art in formula 2 are, inter alia, Q.dbd.O, R.dbd.methyl,
W.dbd.O, R@1.dbd.H, R@2.dbd.OCH3, R@3.dbd.CH3, Z and Y.dbd.N.
With respect to the specifically substituted phenylsulfonylureas of the formula I according to the
invention it has to be stated that they are in principle embraced for example by the formula 1 of WO
95/10507, but that their outstanding suitability as combination partners for synergistic mixtures with
158/2194
other herbicides is not evident from the prior art. In particular, there are no indications in the known
literature that the narrow and clearly defined group of the N-[(4,6dimethoxypyrimidin-2yl)aminocarbonyl]-5methylsulfonamidomethyl-2-a lkoxycarbonylbenzenesulfonamides, which may be
present in the form of their salts, occupies such an exceptional position. Likewise, neither the
application rates nor the ratios of the amounts of the individual compounds to be employed in the
combinations according to the invention are evident from the prior art. Finally, the combinations
according to the invention are advantageous in comparison with other herbicidal combinations
comprising similar sulfonylureas.
Particularly interesting combination partners of type A for the combinations according to the invention
are compounds of the formula I or salts thereof where R@1 is methyl, ethyl, n- or isopropyl, n-, tert-,
2-butyl or isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 1,3-dimethylbutyl, n-heptyl, 1-methylhexyl
or 1,4-dimethylpentyl.
In a very particularly preferred embodiment, herbicidal compositions according to the invention
comprise a type A compound of the formula I or a salt thereof in which R@1 is methyl.
The compounds of type A (formula 1) can form salts where the hydrogen of the SO2 --NH--CO-group is replaced by an agriculturally suitable cation. These salts are, for example, metal, in particular
alkali metal salts (for example sodium or potassium salts) or alkaline earth metal salts, or else
ammonium salts or salts with organic amines. Likewise, salt formation can occur by addition of a
strong acid to the heterocycle moiety of the compounds of the formula 1. Suitable for this purpose are,
for example, HCl, HNO3, trichloroacetic acid, acetic acid or palmitinic acid.
Particularly advantageous type A compounds are those where the salt of the herbicide of the formula
(I) is formed by replacing the hydrogen of the --SO2 --NH--CO-- group by a cation selected from the
group of the alkali metals, alkaline earth metals and ammonium, preferably sodium.
Even if the compounds of the formula I contain one or more asymmetric carbon atoms or else double
bonds which are not specifically indicated in the general formula, they nevertheless belong to the type
A compounds. The stereoisomers which are possible and which are defined by their specific spatial
form, such as enantiomers, diastereoisomers, Z isomers and E isomers, are all embraced by formula I,
and they can be obtained from stereoisomer mixtures by customary methods, or else be prepared by
stereoselective reactions in combination with the use of stereochemically pure starting materials. Thus,
the mentioned stereoisomers can be employed according to the invention in pure form or else as their
mixtures.
The combination partners of type B are generally standard herbicides which are, however, selected
according to certain criteria. Thus, except for two (subgroup Bd)), they are herbicides which act
selectively against undesirable plants in cereals. The harmful plants to be controlled include in
particular grasses and/or dicotyledons. Grasses which are to be particularly controlled include, inter
alia, Alopecurus myosuroides, Avena fatua, Apera spica venti, Lolium ssp., Phalares ssp., Setaria ssp.,
Agropyron repens, Bromus ssp., Sorghum ssp.; dicotyledonous harmful plants which can be controlled
particularly effectively include, inter alia, Lamium ssp., Veronica ssp., Viola ssp., Stellaria media,
Matricaria ssp., Galium aparine, Sinapis album, Raphanus raphanistrum, Myosotes arcensis,
Polygonum ssp., Chenopodium ssp., Rochia ssp./Cirsium, Galeopsis tetra., Capsella bursa pastoris,
Paphaver rhoeas, Physallis angulata, Brassica napus, Descurainia richardsonii, Oxalis ssp.; the
combinations according to the invention have particularly favorable activity inter alia in the control of
Lolium multiflorum, Avena fatua, Apera spica venti, Galium aparine, Oxalis spp, Phalaris minor,
Descurainia richardssonii, Capsella bursa pastoris, Polygonum convovulus, Chenopdium album,
Paphaver rhoeas, Physalis angulata, Brassica napus, Lamium purpreum, Kochia scorp., etc.
With regard to the activity of the standard herbicides of type B it is in turn possible to grade or classify
them with respect to the plants which are controlled most effectively. Thus, some of the type B
herbicides are effective almost exclusively against grasses, others predominantly against dicotyledons,
whereas the herbicides of type B from subgroup Bc) are employed both against grasses and against
dicotyledons. However, in each case an optimized activity spectrum results for the combinations
according to the invention by complementation and intensification of the herbicidal properties of the
compounds of type A which, on their own have a particularly advantageous range of properties in the
159/2194
control of harmful plants in cereals. Last, but not least, the intensification and complementation of the
activity spectrum also applies to the type B compounds of group Bd), which includes the herbicides
which are active against weed grasses and broad-leaved weeds and which are nonselective in non-crop
areas or in perennial crops (plantations) and/or selective in transgenic crops.
In a preferred variant, a composition according to the invention is characterized in that it comprises, as
herbicide(s) of type B, one or more herbicides which have selective activity against grasses in cereals
and which are selected from the group consisting of the 2-(4-aryloxyphenoxy)propionic acids and
esters thereof, ureas, cyclohexanedione oximes, arylalanins, 2,6-dinitroanilins, imidazolinones and
difenzoquat. In addition to the individual substances mentioned, the classes of chemical substances
mentioned include a number of grass herbicides which are suitable as combination partners of the
compounds of type A.
Preferred compositions according to the invention comprise, as herbicides of type B, one or more
herbicides which have selective activity against grasses in cereals and which are selected from the
group consisting of
B1) fenoxaprop, fenoxaprop-P ##STR6##
(.+-.) -2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionic acid, including, inter alia, the use
form as fenoxaprop-ethyl ##STR7##
(R)-2-[4-(6 chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionic acid, including, inter alia, the most
common use form fenoxaprop-P-ethyl, the abovementioned compounds B1) being known from
Pesticide Manual, 10th edition 1994, p. 439AA1 and 441-442,
B2) isoproturon ##STR8##
3-4-isopropylphenyl)-1,1-dimethylurea Pesticide Manual, 10th edition 1994, p. 611-612,
B3) diclofop ##STR9##
(RS)-@2 -[4-(2,4-dichlorophenoxy)phenoxy]propionic acid including, inter alia, as most important use
form the methyl ester diclofop-methyl Pesticide Manual, 10th edition 1994, p. 315-317;
B4) clodinafop ##STR10##
(R)-2-[4-(5-chloro-3-fluoro-2-pyridylox)phenoxy]propionic acid including in particular also the use
form as clodinafop-propagyl Pesticide Manual, 10th edition 1994, p. 216-217
B5) mixtures of B4) and cloquintocet ##STR11##
(5-chloroquinolin-8-yloxy)acetic acid, which is also employed as cloquintocet-mexyl and represents a
particularly preferred safener for B4), Pesticide Manual, 10th edition 1994, p. 226-227,
B6) chlortoluron ##STR12##
3(3-chloro-p-tolyl)-1-dimethylurea Pesticide Manual, 10th edition 1994, p. 194-196,
B7) methabenzthiazuron ##STR13##
1-(1,3-benzothiazol-2-yl)-1,3-dimethylurea Pesticide Manual, 10th edition 1994, p. 670-671,
B8) imazamethabenz, ##STR14##
a reaction product comprising (.+-.)-(4-isopropyl-4-ethyloxo-2-imidazolin-2-yl)-m-toluic acid and (.+.)-6-(4-isopropyl-4-methyl-4-oxo-2-imidazolin-2-yl)-p-toluic acid, it being in each case alternatively
possible to employ the methyl esters known as imazamethabenz-methyl Pesticide Manual, 10th edition
1994, p. 582-584,
B9) tralkoxydim ##STR15##
2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-enone Pesticide Manual, 10th edition
1994, p. 995-996
B10) difenzoquat ##STR16##
1,2-dimethyl-3,5-diphenylpyrazolium for example also as difenzoquat-metilsulfate Pesticide Manual,
10th edition 1994, p. 330-331
160/2194
B11) flamprop, flamprop-M, ##STR17##
N-benzoyl-N-(3-chloro-4-fuorophenyl)-DL-alanine N-benzoyl-N-3-chloron-A4luorophenyl)-Dalanine including, inter alia, flamprop-methyl, flamprop-M-methyl, flamprop-M-isopropyl Pesticide
Manual, 10th edition 1994, p. 464-465 and 466-468
and
B12) pendimethalin ##STR18##
N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine Pesticide Manual, 10th edition 1994, p. 779-780.
The compounds B1) to B12) are herbicides known, for example, from the reference given for the
respective compound, which have specific selective activity against grasses in cereals. In addition to
the parent compound, whose formula is generally also given for reasons of clarity, reference is also
made to derivatives of the parent compounds which are usually employed. Thus, for example, B4)
(clodinafop) is usually employed in the form of the propargyl ester and diclofop (B3)) is employed as
methyl ester, etc. When optically active forms of the type B compounds are customary, these forms are
also referred to (for example fenoxaprop-ethyl and fenoxaprop-P-ethyl, etc.).
The compounds B1), B3) and B4) belong to the class of chemical substances of the 2-(4aryloxyphenoxy)propionic acids or to the ester derivatives. B2), B6) and B7) are ureas, whereas B8) is
a representative of the imidazolinones, B9) is a cyclohexanedione oxime, B11) is an arylalanine and
812) is a 2,6-dinitroaniline. Thus, although the representatives of this group have relatively differing
chemical structures, they do nevertheless, owing to their activity spectrum and to the fact that they are
synergists of the compounds of the formula 1, form a coherent subgroup.
Particularly advantageous mixtures in the context of the invention result when the combination
according to the invention comprises the type B compounds diclofop-methyl, fenoxaprop-P-ethyl,
isoproturon, mixtures of clodinafop-propargyl with cloquintocet-mexyl (known under the protected
name Topik.RTM.) and/or imazamethabenz-methyl.
The invention furthermore provides compositions which comprise the herbicides of type B from
subgroup Bb). Particular preference is given to employing one or more herbicides which have selective
activity against dicotyledons in cereals and which are selected from the group comprising
aryloxyalkylcarboxylic acids, hydroxybenzonitriles, diphenyl ethers, azoles and pyrazoles, diflufenican
and bentazone.
From among the possible aryloxyalkylcarboxylic acids, preference is given in turn to those herbicides
which are selected from the group comprising
B13) mecoprop, mecoprop-P ##STR19##
(RS)-2-(4-chloro-o-tolyloxy)propionic acid (R)-2-(4-chloro-o-tolyloxy)propionic acid Pesticide
Manual, 10th edition 1994, p. 646-647 and 647-648,
B14) MCPA ##STR20##
(4-chloro-2-methylphenoxy)acetic acid, the forms which are predominantly employed are, inter alia,
MCPA-butotyl, MCPA-dimethylammonium, MCPA-isoctyl, MCPA-potassium, MCPA-sodium,
Pesticide Manual, 10th edition 1994, p. 638-640,
B15) dichlorprop, dichlorprop-P ##STR21##
(RS)-2-(2,4dichlorophenoxy)propionic acid (R)-2-(2,4-dichlorophenoxy)propionic acid commonly
used are, inter alia, also dichlorprop-butotyl, dichlorprop-ethylammonium, dichlorprop-isoctyl,
dichlorprop-potassium Pesticide Manual, 10th edition 1994, p. 309-311 and 311-312,
B16) 2,4-D ##STR22##
(2,4-dichlorophenoxy)acetic acid frequently used forms: 2,4-D-butotyl, 2,4-D-butyl, 2,4-Ddimethylammonium, 2,4-D-diolamine, 2,4D-:isoctyl, 2,4-D-isopropyl, 2,4-D-trolamine, Pesticide
Manual, 10th edition 1994, p. 271-273,
B17) dicamba ##STR23##
161/2194
3,6-dichloro-o-anisic acid used inter alia as dicamba-dimethylammonium, dicamba-potassium,
dicamba-sodium, dicamba-trolamine, Pesticide Manual, 10th edition 1994, p. 298-300 and
B18) fluroxypyr ##STR24##
4-amino-3,5-dichloro-6-fluoro-2-pyridyloxyacetic acid, further use forms: fluoroxypyr-meptyl and
particularly preferably: fluroxypyr-butoxypropylester Pesticide Manual, 10th edition 1994, p. 505-507.
Of particular interest are furthermore herbicidal compositions with hydroxybenzonitriles which have
selective activity against dicotyledons in cereals. These preferably include
B19) ioxynil ##STR25##
4-hydroxy-3,5-diiodobenzonitrile, common use forms: ioxynil octanoate, ioxynil-sodium, Pesticide
Manual, 10th edition 1994, p. 598-600 and
B20) bromoxynil ##STR26##
3,5-dibromo-4-hydroxybenzonitrile frequently employed as bromoxynil-octanoate, bromoxynilpotassium, Pesticide Manual, 10th edition 1994, p. 121-123.
Further advantageous compositions according to the invention comprise as herbicides of type B) one
or more diphenyl ethers which have selective activity against dicotyledons in cereals and which are
selected from the herbicides
B21) bifenox ##STR27##
methyl 5(2,4-dichlorophenoxy)-2-nitrobenzoate Pesticide Manual, 10th edition 1994, p. 94-96,
B22) fluoroglycofen ##STR28##
O-[5-(2-chloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-2-nitrobenzoy l]glycolic acid, further use
form: fluoroglycofen-ethyl, Pesticide Manual, 10th edition 1994, p. 492-494,
B23) lactofen ##STR29##
ethyl O-[5-(2chloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-2-nitrobenzoyl ]-DL-lactate Pesticide
Manual, 10th edition 1994, p. 623,
B24) fomesafen ##STR30##
5-(2-chloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-N-methylsulfonyl -2-nitrobenzamide, also used
as formesafen-sodium, Pesticide Manual, 10th edition 1994, p. 520-521 and
B25) oxyfluorfen ##STR31##
2-chloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl-ethoxy-4-nitrophenyl ether Pesticide Manual, 10th
edition 1994, p. 764-765.
Also of particular interest are herbicidal compositions which comprise, as compound of type B, one or
more azoles or pyrazoles which have selective activity against dicotyledons in cereals and which are
selected from the group consisting of the herbicides
B26) ET 751 ##STR32##
ethyl 2-chloro-5-(4-chloro-5-difluoromethoxy-1-methylpyrazol-3-yl)-4-fluoropheno xyacetate
Pesticide Manual, 10th edition 1994, p. 400;
B27) azoles of the formula II ##STR33##
in which
R@1 is (C1 -C4)-alkyl
R@2 is (C1 -C4)-alkyl, (C1 -C4)-alkylthio or (C1 -C4)-alkoxy, each of which may be substituted by
one or more halogen atoms, or
R@1 and R@2 together form the group (CH2)m where m=3 or 4,
R@3 is hydrogen or halogen
R@4 is hydrogen or (C1 -C4)-alkyl,
162/2194
R@5 is hydrogen, nitro, cyano or one of the groups --COOR@7, --C(.dbd.X)NR@7 R@8 or -C(.dbd.X)R@10, wherein X.dbd.O or S,
R@6 is hydrogen, halogen, cyano, (C1 -C4)-alkyl, (C1 -C4)-alkylthio or --NR@11 R@12,
R@7 and R@8 are identical or different and each is hydrogen or (C1 -C4)-alkyl, or
R@7 and R@8 join with the nitrogen to which they are attached to form a saturated 5- or 6-membered
carbocyclic ring,
R@10 is hydrogen or (C1 -C4)-alkyl, the latter optionally being substituted by one or more halogen
atoms, and
R@11 and R@12 are identical or different and each is hydrogen, (C1 -C4)-alkyl or (C1 -C4)alkoxycarbonyl, where
R@11 and R@12 may join with the nitrogen to which they are attached to form a 3-, 5- or 6membered carbocyclic or aromatic ring in which one carbon atom may be replaced by an oxygen atom;
the azoles of the formula II being known, inter alia, from WO 94/08999; and
B28) F 8426 ##STR34##
ethyl 2-chloro-3-2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3methyl-5-oxo -1H-1,2,4-triazol1-ylphenyl)propionate Pesticide Manual, 10th edition 1994, p. 421.
A preferred type B compound is also
B29) diflufenican ##STR35##
2',4'-difluoro-2-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyloxy)nicotinanil ide Pesticide Manual, 10th
edition 1994, p. 335-336.
A further advantageous embodiment of the invention is characterized by a herbicidal composition
which comprises as herbicide of type B
B30) bentazone ##STR36##
3-isopropyl-1H-2,1,3-benzothiadiazine-4(3M-one 2,2-dioxide Pesticide Manual, 10th edition 1994, p.
90-91.
From among the type B compounds having selective activity against dicotyledons in cereals {subgroup
Bb)comprising the herbicidally active compounds B13)-B30) and frequently used derivatives thereof},
MCPA, mecoprop, dicamba, fluroxypyr, diflufenican, ioxynil and/or fluoroglycofen are very
particularly suitable components of a herbicidal composition according to the invention.
A third subgroup of compounds, whose addition to compounds of type A makes it possible to obtain
herbicidal compositions having outstanding properties, is the subgroup Bc) of the herbicides which
have selective activity against grasses and dicotyledons in cereals. Type B substances having this
activity profile are preferably found in the chemical substance classes of the triazine derivatives,
chloroacetanilides and those sulfonylureas which differ from the sulfonylureas mentioned in formula 1.
Further substance classes are, inter alia, triazoles, (thio)carbamates and furanones.
Preferred representatives include, inter alia, the herbicidally active triazine derivative
B31) metribuzin ##STR37##
4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one Pesticide Manual, 10th edition
1994, p. 699-700.
Useful triazoles and thiocarbamates are, inter alia
B32) metosulam ##STR38##
2',6'-dichloro-5,7-dimethoxy-3'-methyl[1,2,4]triazolo[1,5-.alpha.]pyrimidin e-2-sulfoanilide Pesticide
Manual, 10th edition 1994, p. 696-697;
B32a) flupoxam ##STR39##
1-[4-chloro-3-(2,2,3,3,3-pentafluoropropoxymethyl)phenyl]-5-phenyl-1H-1,2, 4-triazol-3-carboxamide
Pesticide Manual, 10th edition 1994, p. 495-496; and/or
163/2194
B33) prosulfocarb ##STR40##
S-benzyl dipropylthiocarbamate Pesticide Manual, 10th edition 1994, p. 863-864.
Preferred representatives furthermore include the herbicidally active furanone derivative
B34) flurtamone ##STR41##
(RS)-5-methylamino-2-phenyl(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)fura n-3(2H)-one Pesticide
Manual, 10th edition 1994, p. 509.
Advantageous embodiments of the herbicidal compositions according to the invention furthermore
comprise, as component of type B, one or more sulfonylureas having selective activity against grasses
and dicotyledons in cereals and differing from the type A compounds. Particularly preferred
sulfonylureas of this kind are, inter alia
B35) amidosulfuron ##STR42##
1-(4,6-dimethoxypyrimidin-2-yl)-3-mesyl(methyl)sulfamoylurea Pesticide Manual, 10th edition 1994,
p. 34-35,
B36) metsulfuron ##STR43##
2-(4-methoxy-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)benzoic acid, usually employed as
metsulfuron-methyl, Pesticide Manual, 10th edition 1994, p. 701-702,
B37) tribenuron ##STR44##
2-[4-methoxy-6-methyl-1,3,5triazin-2-yl(methyl)carbamoylsulfamoyl]benzoic acid, usually employed
as tribenuron-methyl Pesticide Manual, 10th edition 1994, p. 1010-1011,
B38) thifensulfuron ##STR45##
3(4-methoxysmethyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)thiophene-2-carbox ylic acid, usually
employed as thifensulfuron-methyl Pesticide Manual, 10th edition 1994, p. 976-978,
B39) triasulfuron ##STR46##
1-[2-(2chloroethoxy)phenylsulfonyl]3(4-methoxy-6-methyl-1, 3, 5-triazin-2-yl)urea Pesticide Manual,
10th edition 1994, p. 1005-1006,
B40) chlorsulfuron ##STR47##
1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea Pesticide Manual, 10th
edition 1994, p. 203-205,
B41) sulfonylureas of the formula III ##STR48##
in which
R@1 is (C1 -C4)-alkyl, (C2 -C4)-alkenyl or (C2 -C4)-alkynyl, preferably (C1 -C4) alkyl, allyl or
propargyl,
R@2 is CO--R@5, COOR@6, CO--NR@8 R@9, CS--NR@10 R@11, SO2 R@14 or SO2 NR@15
R@16,
R@3 is COR@17, COOR@18, CONR@19 R@20 or CO--ON.dbd.CR@22 R@23, preferably
COOR@18,
R@4 is hydrogen or (C1 -C4)-alkyl, preferably hydrogen or methyl,
R@5 is hydrogen, (C1 -C6)-alkyl which is unsubstituted or substituted by one or more radicals
selected from the group consisting of halogen, (C1 -C4)-alkoxy, (C1 -C4)-alkylthio or NR@31 R@32,
or is (C3 -C6)-cycloalkyl, phenyl with or without substitution, benzyl with or without substitution or
heteroaryl with or without substitution, preferably H, (C1 -C6)-alkyl, (C1 -C4)-haloalkyl, cyclopropyl,
cyclopentyl, cyclohexyl, phenyl or heteroaryl, the last two radicals being unsubstituted or substituted
by one or more radicals selected from the group consisting of (C1 -C4)-alkyl, (C1 -C4)-alkoxy and
halogen,
R@6 is (C1 -C6)-alkyl, (C2 -C6)-alkenyl, (C2 -C6)-alkynyl, (C1 -C6)-haloalkyl or (C3 -C6)cycloalkyl, preferably (C1 -C4)alkyl, (C1 -C4)-haloalkyl, allyl, propargyl or (C3 -C6)-cycloalkyl,
R@7 is (C1 -C4)-alkyl,
164/2194
R@8 is hydrogen, (C1 -C6)-alkyl, (C1 -C4)-haloalkyl or (C1 -C4)-alkoxy or (C1 -C4 -alkoxy)carbonyl,
R@9 is hydrogen, (C1 -C6)-alkyl which is unsubstituted or substituted by one or more radicals
selected from the group consisting of halogen, (C1 -C4)-alkoxy and NR@31 R@32 or is CO--R@33,
CO--OR@34 or NR@35 R@36 or
R@8 and R@9 together form a bivalent radical of the formula --(CH2)4 --, --(CH2)5 -- or --CH2 CH2
-O-CH2 CH2 --,
R@10 is analogous to R@8,
R@11 is analogous to R@9,
R@12 is analogous to R@6,
R@13 is analogous to R@6,
R@14 is (C1 -C6)alkyl, (C1 -C6)haloalkyl, preferably (C1 -C4)-alkyl or (C1 -C4)-haloalkyl,
R@15 and R@16 are independently of one another identical or different and are each hydrogen or (C1
-C4)alkyl,
R@17 is hydrogen, (C1 -C4)-alkyl, (C1 -C4)-haloalkyl, (C3 -C6)-cycloalkyl, phenyl or heteroaryl, the
last two radicals being unsubstituted or substituted,
R@18 is hydrogen (C1 -C4)-alkyl, (C2 -C6)-alkenyl or (C2 -C6)-alkynyl, the last three radicals being
unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1
-C4)-alkoxy, (C1 -C4)-alkylthio and NR@31 R@32, or is (C3 -C6)-cycloalkyl or (C3 -C6)-cycloalkyl(C1 -C3)-alkyl,
R@19 is analogous to R@8,
R@20 is analogous to R@9,
R@22 and R@23 are independently of one another identical or different and are each hydrogen or (C1
-C2)-alkyl,
R@29 is hydrogen, hydroxyl, amino, NHCH3, N(CH3)2, (C1 -C4)-alkyl or (C1 -C4)-alkoxy,
R@30 is hydrogen or (C1 -C4)-alkyl,
R@31 and R@32 are independently of one another identical or different and are each hydrogen or (C1
-C4)alkyl,
R@33 is hydrogen, (C1 -C4)-alkyl, (C1 -C4 haloalkyl, (C3 -C6)-cycloalkyl or phenyl which is
unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1
-C4)-alkyl and (C1 -C4)-alkoxy,
R@34 is (C1 -C4)-alkyl, allyl, propargyl or cycloalkyl,
R@35 and R@36 are independently of one another identical or different and are each hydrogen or (C1
-C4)-alkyl,
W is oxygen or sulfur,
X is (C1 -C4)-alkyl, (C1 -C4)-alkoxy, (C1 -C4)-haloalkyl, (C1 -C4)-alkylthio halogen or mono- or diC1 -C2 -alkyl)-amino, preferably methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, chlorine,
NHCH3 or N(CH3)2,
Y is (C1 -C4)-alkyl, (C1 -C4)-alkoxy, (C1 -C4)haloalkyl or (C1 -C4)-alkylthio, preferably methyl,
ethyl, methoxy, ethoxy and
Z is CH or N,
the sulfonylureas of the formula III being known from WO 94/10154, a particularly interesting
combination partner B) being compounds of the formula III in which
R@1 is methyl, ethyl, n-propyl, isopropyl or allyl,
R@2 is CO-R@5, COOR@6, CO--NR@8 R@9, CS--NR@10 R@11, SO2 R@14 or SO2 NR@15
R@16,
R@3 is COR@17, COOR@18, CONR@19 R@20 or CO--ON.dbd.CR@22 R@23,
R@4 is hydrogen or (C1 -C4)-alkyl,
R@5 is hydrogen, (C1 -C4)-alkyl, (C1 -C2)-haloalkyl, cyclopropyl, phenyl, benzyl or heteroaryl
having 5 or 6 ring atoms, the last 3 radicals being unsubstituted or substituted by one or more halogen
atoms,
R@6 is (C1 -C4)-alkyl, allyl, propargyl or cyclopropyl,
R@8 is hydrogen, (C1 -C4)-alkyl, (C1 -C4)-haloalkyl or (C1 -C4 -alkoxy)-carbonyl,
R@9 -R@11 are independently of one another identical or different H or (C1 -C4)-alkyl,
R@14 is (C1 -C4)-alkyl,
R@15 and R@16 are independently of one another identical or different hydrogen or (C1 -C4)-alkyl,
R@17 is hydrogen, (C1 -C4)alkyl, (C1 -C4)-haloalkyl, (C3 -C6)-cycloalkyl, phenyl or heteroaryl, the
last two radicals being unsubstituted or substituted,
165/2194
R@18 is hydrogen, (C1 C4)-alkyl, (C2 -C6)-alkenyl or (C2 -C6)-alkynyl, the last three radicals being
unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1
-C4)-alkoxy, (C1 -C4)-alkylthio and NR@31 R@32, or (C3 -C6)-cycloalkyl or (C3 -C6)-cycloalkyl(C1 -C3)-alkyl,
R@19 is analogous to R@8,
R@20 is analogous to R@9,
R@22 and R@23 are independently of one another identical or different hydrogen or (C1 -C2)-alkyl,
R@31 and R@32 are independently of one another identical or different hydrogen or (C1 -C4)-alkyl,
W is oxygen or sulfur,
X is (C1 -C4)-alkyl, (C1 -C4)-alkoxy, (C1 -C4)haloalkyl, (C1 -C4)-alkylthio, halogen or mono- or di(C1 -C2 -alkyl)amino,
Y is (C1 -C4)-alkyl, (C1 -C4)-alkoxy, (C1 -C4)haloalkyl or (C1 -C4)-alkylthio, and
Z is CH or N,
very particularly interesting combination partners B) also being those compounds of the formula III in
which
R@1 is methyl, ethyl, n-propyl, i-propyl or allyl,
R@2 is CO--R@5, COOR@6, CO--NR@8 R@9, CS--NR@10 R@11, SO2 R@14 or SO2 NR@15
R@16,
R@5 is hydrogen, (C1 -C4)-alkyl, (C1 -C2)-haloalkyl, cyclopropyl, phenyl, benzyl or heteroaryl
having 5 or 6 ring atoms, the last 3 radicals being unsubstituted or substituted by one or more halogen
atoms,
R@6 is (C1 -C4)-alkyl, allyl, propargyl or cyclopropyl,
R@8 is hydrogen, (C1 -C4)-alkyl, (C1 -C4)-haloalkyl or (C1 -C4 -alkoxy)-carbonyl,
R@9 -R@11 are independently of one another identical or different H or (C1 -C4)-alkyl,
R@14 is (C1 -C4)-alkyl and
R@15 and R@16 are independently of one another identical or different hydrogen or (C1 -C4)-alkyl,
most particularly advantageous combination partners B) being those compounds of the formula III in
which
R@5 is H, CH3, C2 H5, n- or i-C3 H7, n-, i-, t- or 2-butyl, n-pentyl, CF3, CH2 Cl, CCl3, CH2 Br,
CH2 CCl3, cyclopropyl, phenyl, thienyl, furyl or pyridyl, where the last four radicals may be
substituted by 1 to 3 halogen atoms,
B42) sulfonylureas of the formula IV and agriculturally tolerable and acceptable salts thereof
##STR49##
in which
R@1 is (C1 -C8)-alkyl, (C3 -C4)-alkenyl, (C3 -C4)-alkynyl or (C1 -C4)-alkyl which is mono- to
tetrasubstituted by radicals selected from the group consisting of halogen and (C1 -C2)-alkoxy, where
in the herbicide of the formula (IV) or the salt thereof particularly preferably R@1 is methyl;
and where likewise those salts have particularly favorable activity where the salt of the herbicide of the
formula (IV) is formed by replacing the hydrogen of the --O2 --NHCO-- group by a cation selected
from the group of the alkali metals, alkaline earth metals and ammonium, preferably sodium, the
compounds of the formula IV being known, for example, from WO 92/13845,
B43) flupyrsulfuron (DPX-KE459) ##STR50##
preferably as sodium salt, introduced at the Brighton Crop Protection Conference Weeds 1995,
B44) MON 48500 preferably as sodium salt, introduced at the Brighton Crop Protection Conference
Weeds 1995,
and/or
B45) sulfosulfuron (MON37500) ##STR51##
introduced at the Brighton Crop Protection Conference Weeds 1995.
From among the type B compounds having selective activity against grasses and dicotyledons in
cereals {subgroup Bc) comprising the herbicidally active compounds B31)-B45) and commonly used
derivatives thereof}, metsulfurone-methyl, tribenurone-methyl, sulfonylureas of the formula IV (B42))
166/2194
and/or amidosulfurone are very particularly suitable components of a herbicidal composition according
to the invention.
A fourth subgroup of compounds, whose addition to compounds of type A makes it possible to obtain
herbicidal compositions having superadditive activity, is the subgroup Bd) of the herbicides which
have activity against weed grasses and broad-leaved weeds and which are nonselective in non-crop
areas and/or selective in transgenic crops. Type B substances which answer this description include,
inter alia,
B46) glufosinate, glufosinate-P ##STR52##
4-[hydroxy(methyl)phosphinoyl]-DL-homoalanine,
4-[hydroxy(methyl)phosphinoyl]-L-homoalanine, each of which is preferably employed as
glufosinate-ammonium or glufosinate-P-ammonium, Pesticide Manual, 10th edition 1994, p. 541-542
and/or
B47) Glyphosate ##STR53##
N-(phosphonomethyl)glycine, which is preferably employed as glyphosate-isopropylammonium,
glyphosate-sesquinatrium, glyphosate-trimesium, Pesticide Manual, 10th edition 1994, p. 542-544.
Combinations of the active compounds A+B show superadditive effects, i.e. with the same level of
control of harmful plants, the herbicidal compositions according to the invention permit reduction of
the application rate, make it possible to control some species at all and/or allow the safety margin,
especially in cereal crops, to be increased. Both are advantageous, economically as well as
ecologically. Here, the selection of the amounts of components A+B to be employed, the ratio of the
components A: B and the application sequence as well as, for example, the formulation to be selected,
depend on a large number of factors. Not insignificant in this context are, inter alia, the kind of cocomponents, the development stage of the weed grasses or broad-leaved weeds, the range of weeds to
be controlled, environmental factors, climatic conditions, soil properties, etc.
In a very particularly preferred embodiment of the invention, herbicidal compositions according to the
invention have a synergistically effective content of a combination of the compounds of the formula I
or salts thereof (type A compounds) with compounds from group B. It has to be emphasized that even
in combinations having application rates or weight ratios of A:B where a synergism is not in each case
immediately evident--for example because the individual compounds are usually present in the
combination in very different application rates or else because the control of the harmful plants by the
individual compounds is already very good--the herbicidal compositions of the invention generally
have an inherent synergistic activity.
The application rates of herbicide A are generally between 0.1 and 100 g of ai/ha (ai =active
ingredients, i.e. the application rate based on the active compound), preferably between 2 and 40 9 of
ai/ha.
The application rates of compounds of type B are usually:
>;t
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
Application rates g of ai/ha
Type B compounds
standard preferred
Ba)
10 to 4000 50 to 1000
grass herbicides in cereals
{e.g. B1)-B12)}
Bb)
50 to 3000 100 to 2000
dicotyledon herbicides in
cereals
{e.g. B13)-B16)}
Bb)
50 to 1000 100 to 500
dicotyledon herbicides in
cereals
{e.g. B17)}
Bb)
50 to 300 50 to 200
dicotyledon herbicides in
167/2194
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>;tb;
>;tb;
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>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
cereals
{e.g. B18)}
Bb)
50 to 1000 100 to 500
dicotyledon herbicides in
cereals
{e.g. B19) and B20)}
Bb)
5 to 1000 20 to 500
dicotyledon herbicides in
cereals
{e.g. B21) to B25)}
Bb)
10 to 60 20 to 50
dicotyledon herbicides in
cereals
{e.g. B26) to B28)}
Bb)
50 to 500 100 to 300
dicotyledon herbicides in
cereals
{e.g. B29)}
Bb)
500 to 2500 1000 to 2000
dicotyledon herbicides in
cereals
{e.g. B30)}
Bc)
100 to 5000 250 to 2500
grass and dicotyledon
herbicides in cereals
{e.g. B31)-B34)}
Bc)
2 to 80
5 to 50
grass and dicotyledon
herbicides in cereals
{e.g. B35)-B45)}
Bd)
100 to 3000 100 to 1000
broad band herbicides
which are nonselective or
selective only in transgenic
crops
{e.g. B46) and B47)}
In the combinations of the invention, the application rates of compounds of type A+compounds of type
B are usually:
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>;tb;
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>;tb;
>;tb;
Application rates g of ai/ha
Type B compounds
A
+B
Ba)
2 to 40
50 to 1000
grass herbicides in cereals
{e.g. B1)-B12)}
Bb)
2 to 40
100 to 3000
dicotyledon herbicides in
cereals
{e.g. B13)-B16)}
Bb)
2 to 40
50 to 1000
dicotyledon herbicides in
cereals
{e.g. B17)}
Bb)
2 to 40
50 to 2500
dicotyledon herbicides in
cereals
{e.g. B18)}
Bb)
2 to 40
50 to 1000
168/2194
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>;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;
dicotyledon herbicides in
cereals
{e.g. B19) and B20)}
Bb)
2 to 40
5 to 1000
dicotyledon herbicides in
cereals
{e.g. B21) to B25)}
Bb)
2 to 40
3 to 25
dicotyledon herbicides in
cereals
{e.g. B26) to B28)}
Bb)
2 to 40
50 to 500
dicotyledon herbicides in
cereals
{e.g. B29)}
Bb)
2 to 40
50 to 2500
dicotyledon herbicides in
cereals
{e.g. B30)}
Bc)
2 to 40
100 to 5000
grass and dicotyledon
herbicides in cereals
{e.g. B31)-B34)}
Bc)
2 to 40
2 to 80
grass and dicotyledon
herbicides in cereals
{e.g. B35)-B45)}
Bd)
broad band herbicides 2 to 40
100 to 3000
which are nonselective or
selective only in transgenic
crops
{e.g. B46) and B47)}
As mentioned above, both the weight ratios A:B of the combined herbicides and their application rates
can vary within wide limits. In the context of the invention, preference is given to compositions which
comprise compounds of the formula I or salts thereof (type A compounds) and compounds of group B
in a weight ratio of 1:2500 to 20:1.
The following weight ratios are preferably employed:
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>;tb;
>;tb;
>;tb;
Mixing ratio A:B
Type B compounds
preferred partic. preferred
Ba)
1:500 to 1:1 1:200 to 1:2
grass herbicides in cereals
{e.g. B1)-B12)}
Bb)
1:1500 to 1:1 1:500 to 1:10
dicotyledon herbicides in
cereals
{e.g. B13)-B16)}
Bb)
1:500 to 1:1 1:300 to 1:3
dicotyledon herbicides in
cereals
{e.g. B17)}
Bb)
1:1200 to 1:1 1:600 to 1:3
dicotyledon herbicides in
cereals
{e.g. B18)}
169/2194
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
Bb)
1:500 to 1:1 1:200 to 1:3
dicotyledon herbicides in
cereals
{e.g. B19) and B20)}
Bb)
1:500 to 8:1 1:300 to 2:1
dicotyledon herbicides in
cereals
{e.g. B21) to B25)}
Bb)
1:20 to 20:1 1:10 to 10:1
dicotyledon herbicides in
cereals
{e.g. B26) to B28)}
Bb)
1:250 to 1:1 1:100 to 1:3
dicotyledon herbicides in
cereals
{e.g. B29)}
Bb)
1:1200 to 1:1 1:600 to 1:3
dicotyledon herbicides in
cereals
{e.g. B30)}
Bc)
1:2500 to 1:2 1:2000 to 1:4
grass and dicotyledon
herbicides in cereals
{e.g. B31)-B34)}
The active compound combinations according to the invention can be present both as mixed
formulations of the components which are then applied in a customary manner diluted with water, or as
tank mixes which are prepared by jointly diluting the individually formulated components with water.
The active compounds of types A and B can be formulated in various ways, depending on the
prevailing biological and/or chemico-physical parameters. The following are examples of suitable
formulations: wettable powders (WP), emulsifiable concentrates (EC), water-soluble powders (SP),
water-soluble concentrates (SL), concentrated emulsions (BW), such as oil-in-water and water-in-oil
emulsions, sprayable solutions or emulsions, capsule suspensions (CS), oil- or water-based dispersions
(SC), suspoemulsions, suspension concentrates, dusts (DP), oil-miscible solutions (OL), seed-dressing
products, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption
granules, granules for broadcasting or soil application, water-soluble granules (SG), water-dispersible
granules (WG), ULV formulations, microcapsules and waxes.
Among these, water-soluble wettable powders (WP), water-dispersible granules (WG), wateremulsifiable granules (EC), suspoemulsions (SE) and oil-suspension concentrates (SC) are preferred.
These individual types of formulation are known in principle and are described, for example, in:
Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag
Munich, 4th Ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973;
K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
The formulation auxiliaries required, such as inert materials, surfactants, solvents and other additives
are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents
and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H. v. Olphen, "Introduction to Clay Colloid
Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; Marsden, "Solvents Guide"; 2nd Ed., lnterscience, N.Y.
1963; =McCutcheon's "Detergents and Emulsifiers Annual", MC PubI. Corp., Ridgewood N.J.; Sisley
and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt,
"Grenzflachenaktive Athylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss.
Verlagsgesellschaft, Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie" [Chemical
Technology], Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986.
170/2194
Based on these formulations, it is also possible to prepare combinations with other pesticidally active
compounds, herbicides, insecticides, fungicides, and also antidotes, safeners, fertilizers and/or growth
regulators, for example in the form of a ready mix or a tank mix.
The herbicide combinations of the invention are prepared particularly advantageously by formulating
the compounds of the formula I or salts thereof (type A compounds) with one or more compounds of
type B similar to a conventional crop protection formulation from the group consisting of water-soluble
wettable powders (WP), water-dispersible granules (WDG), water-emulsifiable granules (WEG),
suspoemulsions (SE) and oil suspension concentrates (SC).
Wettable powders are preparations which are uniformly dispersible in water and which, besides the
active compounds, also comprise ionic and/or nonionic surfactants (wetting agents, dispersants), for
example polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines,
fatty alcohol polyglycol ether sulfates, alkanesulfonates or alkylarylsulfonates, sodium lignosulfonate,
sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutyinaphthalene-sulfonate or else sodium
oleoylmethyltaurinate, in addition to a diluent or inert substance.
Emulsifiable concentrates are prepared by dissolving the active compound or active compounds in an
organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or else higherboiling aromatics or hydrocarbons with the addition of one or more ionic and/or nonionic surfactants
(emulsifiers). Examples of emulsifiers which can be used are: calcium salts of alkylarylsulfdnic acids,
such as calcium dodecylbensulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters,
alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, -propylene oxide/ethylene oxide
condensates (for example block copolymers), alkyl polyethers, sorbitan fatty acid esters,
polyoxyethylene sorbitan fatty acid esters or other polyoxyethylene sorbitan esters.
Dusts are obtained by grinding the active compound or the active compounds with finely divided
substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous
earth.
Granules can be prepared either by spraying the active compound or the active compounds onto
adsorptive granulated inert material or by applying active compound concentrates to the surface of
carriers such as sand, kaolinites or of granulated inert material by means of binders, for example
polyvinyl alcohol, sodium polyacrylate or else mineral oils.
Water-dispersible granules are generally prepared by the customary processes such as spray drying,
fluidized-bed granulation, disk granulation, mixing with high-speed mixers and extrusion without solid
inert material. It is also possible to granulate suitable active compounds in the manner customarily used
for preparing fertilizer granules--if appropriate in a mixture with fertilizers.
Generally, the agrochemical preparations according to the invention comprise 0.1 to 99% by weight, in
particular 2 to 95% by weight, of active compounds of types A and B, in addition to customary
formulation auxiliaries.
The concentrations of the active compounds A+B in the formulations may vary. In wettable powders,
the active compound concentration is, for example, approximately 10 to 95% by weight, the remainder
to 100% by weight being composed of customary formulation components. In the case of emulsifiable
concentrates, the active compound concentration may amount to approximately 1 to 85% by weight,
preferably 5 to 80% by weight. Formulations in the form of dusts comprise approximately 1 to 25% by
weight, in most cases 5 to 20% by weight, of active compounds, and sprayable solutions comprise
approximately 0.2 to 25% by weight, preferably 2 to 20% by weight, of active compounds. The active
compound content of granules such as dispersible granules depends partly on whether the active
compound is in liquid or solid form and on which granulation auxiliaries and fillers are being used. In
general, the content of the water-dispersible granules amounts to between 10 and 90% by weight.
In addition, the abovementioned active compound formulations comprise, if appropriate, the tackifiers,
wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers,
colorants, carriers, antifoams, evaporation inhibitors and pH and viscosity regulators which are
customary in each case.
171/2194
Owing to the relatively low application rate of the combinations of A+B according to the invention,
they are generally already very well tolerated. In particular, the combinations according to the
invention permit a reduction of the absolute application rate, compared with the individual application
of a herbicidally active compound. However, to increase the tolerability and/or selectivity of the
herbicide combinations according to the invention, if desired, even more, it is advantageous to apply
these jointly in a mixture or successively at different times together with safeners or antidotes. Suitable
safeners or antidotes for the combinations according to the invention are the compounds known, for
example, from EP-A33 131 (ZA-89/1960), EP-A-269 806, (U.S. Pat. No. 4,891,057), EP-A-346 620
(AU-A-89/34951) and the international patent applications PCT/EP 90/01966 (WO-91/08202) and
PCT/EP 90/02020 (WO-91/078474) and the literature cited therein, or they can be prepared by the
methods described therein. Further suitable safeners are known from EP-A-94 349 (U.S. Pat. No.
4,902,304), EP-A-191 736 (U.S. Pat. No. 4,881,966) and EP-A0 492 366 and the literature cited
therein.
In the most favorable case, the herbicidal mixtures or use combinations of the invention additionally
comprise
C) one or more compounds of the formulae C1 and C2, ##STR54##
in which
X is hydrogen, halogen, (C1 -C4)alkyl, (C1 -C4)-alkoxy, nitro or (C1 -C4)-haloalkyl,
X is OR@1, SR@1, NR@1 R, where R is hydrogen, (C1 -C6)-alkyl, (C1 -C6)-alkoxy or phenyl with
or without substitution, or is a saturated or unsaturated 3- to 7-membered heterocycle having at least
one nitrogen atom and up to three hetero atoms which is linked to the carbonyl group via the nitrogen
atom and which is unsubstituted or substituted by radicals selected from the group consisting of (C1 C4)-alkyl, (C1 -C4)-alkoxy and phenyl with or without substitution, preferably a radical of the formula
OR@1, NHR@1 or N(CH3)2, in particular OR@1,
R* is a (C1 -C2)-alkylene chain (=(C1 -C2)-alkanediyl chain) which may additionally be substituted
by one or two (C1 -C4)-alkyl radicals or by [(C1 -C3)-alkoxy]carbonyl, preferably --CH2 --,
R@1 is hydrogen, (C1 -C18)-alkyl, (C3 -C12)-cycoalkyl, (C2 -C8)-alkenyl or (C2 -C8)-alkynyl,
where the abovementioned carbon-containing radicals are unsubstituted or mono- or polysubstituted,
preferably up to trisubstituted, by identical or different radicals selected from the group consisting of
halogen, hydroxyl, (C1 -C8)-alkoxy, (C1 -C8)-alkylthio, (C2 -C8)-alkenylthio, (C2 -C8)-alkynylthio,
(C2 -C8)-alkenyloxy, (C2 -C8)-alkynyloxy, (C3 -C7)-cycloalkyl, (C3 -C7)cycloalkyl, cyano, monoand di- (C1 -C8)alkylamino, carboxy, (C1 -C8)-alkoxy-carbonyl, (C2 -C8)-alkenyloxy-carbonyl, (C1 C8)-alkylthio-carbonyl, (C2 -C8)-alkynyloxy-carbonyl, (C1 -C8)-alkyl carbonyl, (C2 -C8)-alkenylcarbonyl, (C2 -C8)-alkynyl-carbonyl, 1-(hydroxyimino)-C1 -C6)-alkyl, 1-[(C1 -C4)-alkylimino)]-(C1 C4)-alkyl, 1-[(C1 -C4)-alkoxyimino)]-(C1 -C6)-alkyl, [(C1 -C8)-alkyl-carbonylamino, (C2 -C8)alkenyl-carbonylamino, (C2 -C8)-alkynyl-carbonylamino, aminocarbonyl, (C1 -C8)alkylaminocarbonyl, di-C1 -C6)alkyl-aminocarbonyl, (C2 -C6)-alkenyl-aminocarbonyl, (C2 -C6)alkynyl-aminocarbonyl, (C1 -C8)-alkoxycarbonylamino, (C1 -C8)-alkylaminocarbonylamino, (C1 C6)-alkylcarbonyloxy which is unsubstituted or substituted by halogen, NO2, (C1 -C4)-alkoxy or
phenyl with or without substitution, (C2 -C6)-alkenyl-carbonyloxy, (C2 -C6)-alkynyl-mrbonyloxy, (C1
-C8)-alkylsulfonyl, phenyl, phenyl-(C1 -C6)-alkoxy, phenyl-(C2 -C6)-alkoxy-carbonyl, phenoxy,
phenoxy-(C1 -C6)-alkoxy, phenoxy-(C1 -C6)-alkoxy-carbonyl, phenylcarbonyloxy,
phenylcarbonylamino, phenyl-(C1 -C6)-alkyl-carbonylamino, where the last nine radicals are
unsubstituted in the phenyl ring or mono- or polysubstituted, preferably up to trisubstituted, by
identical or different radicals selected from the group consisting of halogen, (C1 -C4)-alkyl, (C1 -C4)alkoxy, (C1 -C4)-haloalkyl, (C1 -C4)-haloalkoxy and nitro, and radicals of the formulae SiR'3, --O-SiR'3, R'3 Si-(C1 -C8)-alkoxy, --CO--O--NR'2, --O--N.dbd.CR'2, --N.dbd.CR'2, --O--NR'2, CH(OR')2
and --O--CH2)m --CH(OR'2)2, where the R' in the abovementioned formulae independently of one
another are each hydrogen, (C1 -C4 -alkyl, phenyl which is unsubstituted or mono- or polysubstituted,
preferably up to trisubstituted, by identical or different radicals selected from the group consisting of
halogen, (C1 -C4)-alkyl, (C1 -C4)-alkoxy, (C1 -C4)-haloalkyl, (C1 -C4)-haloalkoxy and nitro, or, as a
pair, are a (C2 C6)-alkylene chain, and m=0 to 6, and a radical of the formula R"O-CHR'" (OR)-(C1 C6)-alkoxy, where the radicals R" independently of one another are each (C1 -C4)-alkyl or together a
(C16)-alkylene radical and R'" is hydrogen or (C1 -C4)-alkyl,
R is hydrogen, (C1 -C6 alkyl, (C1 -C6)-alkoxy or phenyl with or without substitution,
n is an integer from 1 to 5, preferably 1 to 3,
172/2194
W is a bivalent heterocyclic radical having 5 ring atoms of the formulae W1 to W4 ##STR55##
in which
R@2 is hydrogen, (C1 -C8)-alkyl, (C1 -C8)-haloalkyl, (C3 -C12)-cycloalkyl or phenyl with or without
substitution and
R@3 is hydrogen, (C1 -C8)-alkyl, (C1 -C8)-haloalkyl, (C1 -C4)-alkoxy-(C1 -C4)-alkyl, (C1 -C6)hydroxyalkyl, (C3 -C12)-cycloalkyl or tri-((C1 -C4)-alkyl)silyl,
or the salts of the abovementioned compounds.
Unless specifically defined otherwise, the following definitions apply to the radicals in the formulae
used in this description:
alkyl, alkenyl and alkynyl are straight-chain or branched, and have up to 8, preferably up to 4, carbon
atoms;
this applies correspondingly to the aliphatic moiety of substituted alkyl, alkenyl and alkynyl radicals or
radicals derived therefrom such as haloalkyl, hydroxyalkyl, alkoxycarbonyl, alkoxy, alkanoyl,
haloalkoxy, etc.;
alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl and 2-butyl, pentyls,
in particular n-pentyl and neo-pentyl, hexyls such as n-hexyl and i-hexyl and 1,3-dimethylbutyl,
heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl, alkenyl is, for example, inter alia allyl,
1-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-ene and 1-methylbut-2ene;
alkynyl is, inter alia, propargyl, but-2-in-1-yl, but-in-1-yl, 1-methylbut-3-ine;
cycloalkyl preferably has 3 to 8 carbon atoms and is, for example, cyclobutyl, cyclopentyl, cyclohexyl
or cycloheptyl. Cycloalkyl may carry up to two (C1 -C4)-alkyl radicals as substituents.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular
fluorine or chlorine; haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl and alkynyl, respectively, which
are mono-, di- or polysubstituted by halogen, for example CF3, CHF2, CH2 F, CF3 CF2, CH2 FCHCl,
CCl3, CHCl2, CH2 CH2 Cl; haloalkoxy is, for example, inter alia OCF3, OCHF2, OCH2 F, CF3 CF2
O, CF3 CH2 O;
aryl preferably has 6 to 12 carbon atoms and is, for example, phenyl, naphthyl or biphenyl, preferably
phenyl.
This applies correspondingly to radicals derived therefrom such as aryloxy, aroyl or aroylalkyl;
phenyl with or without substitution is, for example, phenyl which is unsubstituted or mono- or
polysubstituted, preferably mono-, di- or trisubstituted, by identical or different radicals selected from
the group consisting of halogen, (C1 -C4)alkyl, (C1 -C4)-alkoxy, (C1 -C4)-haloalkyl, (C1 -C4)haloalkoxy, (C1 -C4)-alkylthio, (C2 -C5)-alkoxycarbonyl, (C2 -C5)-alkylcarbonyloxy, carbonamide,
(C2 -C5)-alkylcarbonylamino, di[(C1 -C4)-alkyl]aminocarbonyl and nitro, for example o-, m- and ptolyl, dimethylphenyls, 2-, 3 and 4-chlorophenyl, 2-, 3 and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,S,
2,5 and 2,3-dichlorophenyl or o-, m- and p-methoxyphenyl. This applies correspondingly to aryl with
or without substitution.
Of particular interest are herbicidal compositions according to the invention where in the compounds
of the formula C1 and C2
R@1 is hydrogen, (C1 -C8)-alkyl, (C3 -C7)-cycloalkyl, (C2 -C8)-alkenyl or (C2 -C8)-alkynyl, where
the abovementioned carbon-containing radicals are unsubstituted or mono- or polysubstituted by
halogen or mono- or disubstituted, preferably monosubstituted, radicals selected from the group
consisting of hydroxyl, (C1 -C4)-alkoxy, (C1 -C4)-alkylthio, (C2 -C4)-alkenyloxy, (C2 -C6)alkynyloxy, mono- and di- ((C1 -C2)-alkyl)amino, (C1 -C4)-alkoxy-carbonyl, (C2 -C4)alkenyloxycarbonyl, (C1 -C4)-alkynyloxy-carbonyl, (C2 -C4)alkyl-carbonyl, (C2 -C4)-alkenylcarbonyl, (C2 -C4)-alkynyl-carbonyl, (C1 -C4)-alkylsulfonyl, phenyl, phenyl-(C1 -C4)-alkoxycarbonyl, phenoxy, phenoxy-C1 -C4)-alkoxy, phenoxy-(C1 -C4)-alkoxy-carbonyl, where the last six
173/2194
radicals are unsubstituted in the phenyl ring or mono- or polysubstituted by radicals selected from the
group consisting of halogen, (C1 -C2)-alkyl, (C1 -C2)-alkoxy, (C1 -C2)-haloalkyl, (C1 -C2)haloalkoxy and nitro, and radicals of the formulae SiR'3, --O--N.dbd.CR'2, --N.dbd.CR'2 and --O-NR'2 --CH(OR')2, where the R' in the abovementioned formulae independently of one another are each
halogen, (C1 -C2)alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals selected
from the group consisting of halogen, (C1 -C2)-alkyl, (C1 -C2)-alkoxy, (C1 -C2)-haloalkyl, (C1 -C2)haloalkoxy and nitro, or as a pair are a (C4 -C5)-alkanediyl chain,
R@2 is hydrogen, (C1 -C8 -alkyl, (C1 -C6)-haloalkyl, (C3 -C7)-cycloalkyl or phenyl and
R@3 is hydrogen, (C1 -C8)alkyl, (C1 -C8)-haloalkyl, ((C1 -C4)-alkoxy)-C1 -C4)-alkyl, (C1 -C6)hydroxyalkyl, (C3 -C7)-cycloalkyl or tri-(C1 -C4)-alkyl)silyl.
Also of particular interest are herbicidal compositions according to the invention where in the
compounds of the formulae C1 and C2
X is hydrogen, halogen, methyl, elthyl, methoxy, ethoxy, (C1 -C2)-haloalkyl, preferably hydrogen,
halogen or (C1 -C2)-haloalkyl.
Preference is given to herbicidal compositions according to the invention where in the compounds of
the formula C1
X is hydrogen, halogen, nitro or (C1 -C4)-haloalkyl,
Z is a radical of the formula OR@1,
n is an integer from 1 to 3,
R@1 is hydrogen, (C1 -C8)alkyl, (C3 -C7)-cycloalkyl, where the abovementioned carbon-containing
radicals are unsubstituted or mono- or polysubstituted by radicals from the group consisting of halogen
or mono- or disubstituted, preferably unsubstituted or monosubstituted by radicals selected from the
group consisting of hydroxyl, (C1 -C4)-alkoxy, ((C1 -C4 -alkoxy)carbonyl, (C2 -C6)-alkenyloxycarbonyl, ((C2 -C6)-alkynyloxy)carbonyl and radicals of the formulae SiR'3, --O--N.dbd.CR'2, -N.dbd.CR'2, --O--N R'2, where the radicals R' in the abovementioned formulae independently of one
another are each hydrogen or (C1 -C4)-alkyl or as a pair are a (C4 -C5)-alkylene chain,
R@2 is hydrogen, (C1 -C8)-alkyl, (C1 -C6)haloalkyl, (C3 -C7)-cycloalkyl or phenyl and
R@3 is hydrogen, (C1 -C8)-alkyl, (C1 -C8)-haloalkyl, ((C1 -C4)-alkoxy)C1 -C4)-alkyl, (C1 -C6)hydroxyalkyl, (C3 -C7)-cycloalkyl or tri-(C1 -C4)-alkyl)silyl.
Preference is also given to herbicidal compositions according to the invention where in the compounds
of the formula C2
X is hydrogen, halogen, or (C1 -C4)-haloalkyl and n is an integer from 1 to 3, preferably (X)n =5C1,
Z is a radical of the formula OR@1,
R* is CH2 and
R@1 is hydrogen, (C1 -C8)-alkyl, (C1 -C8)-haloalkyl, ((C1 -C4)-alkoxy)-(C1 -C4)-alkyl or ((C1 -C4)alkenyloxy)-(C1 -C4)-alkyl, preferably (C1 -C8)-alkyl.
Particular preference is given to herbicidal compositions according to the invention comprising
compounds of the formula C1 in which
W is W1
X is hydrogen, halogen or (C1 -C2)-haloalkyl and n=1-3, in particular (X)n =2,4Cl2,
Z is a radical of the formula OR@1,
R@1 is hydrogen, (C1 -C8)-alkyl, (C1 -C4)-haloalkyl, (C1 -C4)-hydroxyalkyl, (C3 -C7)-cycloalkyl,
((C1 -C4)-alkoxy)-(C1 -C4)-alkyl, tri-((C1 -C2)-alkyl)silyl, preferably (C1 -C4)-alkyl,
R@2 is hydrogen, (C1 -C8)-alkyl, (C1 -C4)-haloalkyl or (C3 -C7)-cycloalkyl, preferably hydrogen or
(C1 -C4)-alkyl and
R@3 is hydrogen, (C1 -C8)-alkyl, (C1 -C4)-haloalkyl, (C1 -C4)-hydroxyalkyl, (C3 -C7)-cycloalkyl,
((C1 -C4)-alkoxy-(C1 -C4)-alkyl or tri-((C1 -C2)-alkyl)silyl, preferably H or (C1 -C4)-alkyl.
Particular preference is also given to herbicidal compositions according to the invention comprising
compounds of the formula C1 in which
W is W2
X is hydrogen, halogen or (C1 -C2)-haloalkyl and n=1-3, in particular (X)n =2,4Cl2,
Z is a radical of the formula OR@1,
R@1 is hydrogen, (C1 -C8)-alkyl, (C1 -C4)-haloalkyl, (C1 -C4)-hydroxyalkyl, (C3 -C7)-cyloalkyl,
((C1 -C4)-alkoxy)-(C1 -C4)-alkyl, tri-((C1 -C2)-alkyl)silyl, preferably (C1 -C4)-alkyl, and
174/2194
R@2 is hydrogen, (C1 -C8)-alkyl, (C1 -C4)-haloalkyl, (C3 -C7)-cycloalkyl or phenyl, preferably
hydrogen or (C1 -C4)alkyl.
Particular preference is also given to herbicidal compositions according to the invention comprising
compounds of the formula Cl in which
W is W3
X is hydrogen, halogen or (C1 -C2)haloalkyl and n=1-3, in particular (X)n =2,4-Cl2,
Z is a radical of the formula OR@1,
R@1 is hydrogen, (C1 -C8)-alkyl, (C1 -C4)-haloalkyl, (C1 -C4)-hydroxyalkyl, (C3 -C7)-cycloalkyl,
((C1 -C4)-alkoxy)(C1 -C4)-alkyl, tri-((C1 -C2)-alkyl)silyl, preferably (C1 -C4)-alkyl, and
R@2 is (C1 -C8)-alkyl or (C1 -C4)-haloalkyl, preferably C1 -haloalkyl.
Particular preference is also given to herbicidal compositions according to the invention comprising
compounds of the formula C1 in which
W is W4
X is hydrogen, halogen, nitro, (C1 -C4)-alkyl, (C1 -C4)-alkoxy or (C1 -C2)-haloalkyl and n=1-3,
preferably CF3 or (C1 -C4)-alkoxy,
Z is a radical of the formula OR@1 and
R@1 is hydrogen, (C1 -C4)-alkyl or ((C1 -C4)-alkoxy)-carbonyl-((C1 -C4)-alkyl, preferably ((C1 C4)-alkoxy)-CO--CH2 --, ((C1 -C4)-alkoxy)-CO--C(CH3)H--, HO--CO--CH2 -- or HO--CO-C(CH3)H--.
The compounds of the formula C1 are known from EP-A-0 333 131, EP-A-0 269 806, EP-A-0 346
620, International Patent Application PCT/EP 90/01966 and International Patent Application PCTIEP
90/02020 and the literature cited therein, or they can be prepared by or similar to the methods described
therein. The compounds of the formula C2 are known from EP-A0 086 750, EP-A0 094 349 and EP-A0 191 736 and the literature cited therein, or they can be prepared by or similar to the methods
described therein. Furthermore, they are proposed in DE-A-40 41 121.4.
Particularly preferred antidotes or safeners or groups of compounds which have proved themselves
suitable as safeners or antidotes for the product combinations of the invention described above are,
inter alia:
a) Compounds of the type of the dichlorophenylpyrazolin-3-carboxylic acid (i.e. the formula C1 where
W.dbd.W1 and (X)n =2,4Cl2), preferably compounds such as ethyl 1-(2,4dichlorophenyl)5(ethoxycarbonyl)-5-methyl-2-pyrazolin-3-carboxylate (compound C1--1) and related compounds as
described in the International Application WO 91/07874 (PCT/EP 90/02020);
b) Derivatives of dichlorophenylpyrazolecarboxylic acid (i.e. the formula C1 where W.dbd.W2 and
(X)n =2,4-Cl2), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3carboxylate (compound C1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazol-3-carboxylate
(compound C1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate
(compound C1-4), ethyl 1-(2,4dichlorophenyl)-5-phenylpyrazole-3-carboxylate (compound C1-5) and
related compounds as described in EP-A0 333 131 and EP-A40 269 806;
c) Compounds of the type of the triazolecarboxylic acids (i.e. the formula C1 where W.dbd.W3 and
(X)n =2,4-Cl2), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-(trichloromethyl-1H)1,2,4-triazole-3-carboxylate (compound C1-6, fenchlorazole) and related compounds (see EP-A0 174
562 and EP-A-0 436 620);
d) Compounds of the type of the dichlorobenzyl-2-isoxazolin-3-carboxylic acid, (i.e. the formula C1
where W=W4 and (X)n =2,4-Cl2), compounds of the type of the 5-benzyl- or 5-phenyl-2-isoxazolin-3carboxylic acid, preferably compounds such as ethyl 5-(2,4dichlorobenzyl)-2-isoxazolin-3-carboxylate
(compound C1-7) or ethyl 5-phenyl-2-isoxazolin-3-carboxylate (compound (C1-8) and related
compounds as described in the International Patent Application WO 91/08202 (PCT/EP 90/01966);
e) Compounds of the type of the 8-quinolinoxyacetic acid (i.e. of the formula C2 where (X)n =5-Cl,
hydrogen, Z=OR@1, R*=CH2) preferably compounds such as 1-methylhex-1-yl (5-chloro-8quinolinoxy)acetate (C2-1), 1,3-dimethylbut-1-yl (5-chloro~quinolinoxy)acetate (C2--2), 4allyloxybutyl (5-chloro-8-quinolinoxy)acetate (C2-3), 1-allyloxyprop-2-yl (5-chloro-8quinolinoxy)acetate (C2-4), ethyl (5-chloro-8-quinolinoxy)acetate (C2-5), methyl (5-chloro-8quinolinoxy)acetate (C2-6), allyl (5-chloro-8-quinolinoxy)acetate (C2-7), 2-(2-propylideneiminoxy)-1ethyl 5-chloro-8-quinolinoxy)acetate (C2-8), 2-oxoprop-1-yl (5-chloro-8-quinolinoxy)acetate (C2-9)
175/2194
and related compounds as described in EP-A0 086 750, EP-A-0 094 349; and EP-A-0 191 736 or EPA-0 492 366;
f) Compounds of the type of the (5-chloro-8-quinolinoxy)malonic acid, i.e. the formula C2 where (X)n
=5Cl, hydrogen, Z.dbd.OR@1, R*.dbd.--CH(COO-alkyl)-, preferably compounds such as diethyl (5chloro-8-quinolinoxy)malonate, diallyl (5chloro-8-quinolinoxy)malonate, methyl ethyl (5-chloro-8quinolinoxy)malonate and related compounds as described and proposed in the German Patent
Application P 40 41 121.4;
g) and active compounds of the type of the phenoxyacetic or phenoxypropionic acid derivatives or of
the aromatic carboxylic acids such as, for example, 2,4-dichlorophenoxyacetic acid(ester) (2,4-D),
4chloro-2-methylphenoxypropionic ester (mecoprop), MCPA or 3,6-dichloro-2-methoxybenzoic
acid(ester) (dicamba).
At least some of the compounds mentioned are additionally described in EP-A0 640 587, to which
reference is made herewith for purposes of disclosure.
The safeners (antidotes) of the above groups a) to g) (in particular compounds of the formulae C1 and
C2) reduce or neutralize phytotoxic effects which can occur when using the product combinations
according to the invention in crops of useful plants, without adversely affecting the activity of the
herbicides against harmful plants. Thus, it is possible to increase the area of use of the herbicide
mixtures according to the invention considerably. In particular, the use of safeners permits the use of
combinations which hitherto could be used only with limitations or without sufficient success, i.e. of
combinations which, without safener, at low application rates with a narrow spectrum of activity did
not provide sufficient control of the harmful plants.
The herbicidal mixtures according to the invention and said safeners can be applied together (in the
form of a finished formulation or by the tank mix method) or in any desired sequence one after the
other. The weight ratio safener: herbicide (group A, i.e. compounds of the formula 1) can vary within
wide limits and is preferably in the range from 1:10 to 10:1, in particular from 1:10 to 5:1. The amounts
of herbicides (type A and type B compounds) and safener which are optimal in each case depend on the
type of herbicide mixture used and/or on the safener used and on the nature of the plant stand to be
treated and can be determined in each individual case by suitable preliminary trials.
Depending on their properties, the safeners of type C) can be used for pretreating the seed of the crop
plant (seed dressing) or be incorporated into the seed furrows before seeding or used together with the
herbicide mixture before or after the plants have emerged. Preemergence treatment includes treatment
of the area under cultivation before seeding and also treatment of those areas under cultivation which
have been seeded but where growth has not yet taken place. Application together with the herbicide
mixture is preferred. Tank mixes or finish formulations can be used for this purpose.
The required application rates of safeners can vary within wide limits, depending on the indication and
the herbicide used, and are generally in the range from 0.001 to 1 kg, preferably 0.005 to 0.2 kg, of
active compound per hectare.
For use, the formulations, which are in commercially available form, are, if appropriate, diluted in the
customary manner, for example using water in the case of wettable powders, emulsifiable concentrates,
dispersions and water-dispersible granules. Preparations in the form of dusts, granules for soil
application or for broadcasting and sprayable solutions are usually not diluted further with additional
inert substances prior to use.
The invention also relates to a method for controlling undesirable plants which comprises applying a
herbicidally effective amount of a combination of active compounds A+B according to the invention to
these plants or to the area under cultivation. The active compounds can be applied to the plants, to parts
of plants, plant seeds or to the area under cultivation. In a preferred variant of the method, the
compounds of the formula (i) or salts thereof (type A compounds) are applied at application rates of
from 0.1 to 100 g of ai/ha, preferably from 2 to 40 g of ai/ha, while the application rates for the
compounds of type B are from 1 to 5000 g of ai/ha. Preference is given to applying the active
compounds of types A and B simultaneously or at different times at a weight ratio of 1:2500 to 20:1.
Furthermore, particular preference is given to the joint application of the active compounds in the form
176/2194
of tank mixes, the optimally formulated concentrated formulations of the individual active compounds
being mixed together in the tank with water and the resulting spray liquor being applied.
Since the combinations according to the invention provide extremely good crop safety and at the same
time very efficient control of harmful plants, they can be considered to be selective. In a preferred
variation of the method, herbicidal compositions comprising the active compound combinations
according to the invention are therefore employed for selective control of undesirable plants.
The method for the selective control of harmful plants using the combination partners of type B) from
subgroups Ba) to Bc) is particularly advantageous when the herbicidal compositions of the invention
are employed in crops of useful cereal plants, in plantations and on meadows or pasture land. However,
the use in maize or other crops of useful plants such as, for example, rice, is not precluded a priori.
The combination partners of type A, applied on their own by the pre-emergence and post-emergence
method in cereals, on non-crop areas and in plantations, already control a relatively wide range of
annual and perennial broad-leaved weeds, weed grasses and Cyperaceae.
Combination with the type B partners mentioned in the invention improve the activity spectrum of the
type A compounds even further.
Thus, the compounds B1) to B12) complement and enhance, inter alia, the activity in the control of
grass weeds in cereals and, to some extent, also the activity against broad-leaved weeds in cereals, in
each case both by the pre-emergence and by the post-emergence method.
The growth-regulating herbicides from the subgroup Bb) (compounds B13) to B16)), i.e. in particular
the derivatives of dichlorophenoxyacetic acid, dichlorophenoxypropionic acid,
chloromethylphenoxyacetic acid and chloromethylphenoxypropionic acid and the analogous dicamba
(B17)) and fluroxypyr (B18)), which is also related, serve, in the context of the invention, primarily for
the more efficient control of annual and perennial broad-leaved weeds, in particular by the postemergence method in cereals.
The compounds B19) and B20) (HBNs or bipyridilium derivatives) are herbicidally active compounds
which, above all, improve the effectiveness of weed control in cereals. They are mainly employed by
the post-emergence method. The nitrodiphenyl ethers B21) to B25) are employed both pre-emergence
and post-emergence. They serve to enhance the activity in cereals.
The azoles and pyrazoles of the subgroup Bb) (for example B26) to B28)) can be employed
particularly advantageously at comparatively low application rates by the post-emergence method for
the control of dicotyledonous weeds in cereals.
B29) improves the activity spectrum of the combinations according to the invention used pre- and
post-emergence in the control of weeds in cereals and other crop types, whereas B30) is a herbicidally
active compound which is employed in a large number of agricultural crop plants by the postemergence method for controlling weeds.
The triazines, triazoles, (thio)carbamates and furanones of the subgroup Bc) (for example B31) to
B34)) are common active compounds which can be employed both by the pre-emergence and by the
post-emergence method to increase the activity of the type A compounds in the control of weed grasses
and broad-leaved weeds in cereals, in non-crop areas or in plantations.
Finally, the compounds B35) to B45) (subgroup Bc)) preferably serve in the invention for controlling
broad-leaved weeds--to some extent also weed grasses--in cereals and in potatoes, in meadows or in
non-crop areas, and, if appropriate, in plantations or perennial crops, by the post-emergence method,
though in some instances also by the pre-emergence method.
Depending on the nature of the combination partner B, the herbicidal combinations according to the
invention can also be used advantageously for controlling undesirable plants in non-crop a nd/or in
transgenic crops, for example maize, rice, soya, cereals, inter alia. Particularly suitable for this purpose
are the partners from group Bd) (compounds B46) and B47)).
177/2194
Here, the term non-crop area does not only include paths, open spaces, industrial terrain and railways
which regularly have to be kept free from weeds, but, in the context of the invention, plantation crops
are also included in this generic term, even if they are not mentioned separately. Thus, the
combinations according to the invention (especially those comprising combination partners from
subgroup Bd)) which cover a wide spectrum of weeds extending from annual and perennial broadleaved weeds such as, for example, Agropyron, Paspalum, Cynodon, Imperata over Pennisetum,
Convolvulus and Cirsium to Rumex and others, can be employed for the selective control of harmful
plants in plantation crops such as oil palm, coconut palm, rubber tree (Hevea brasiliensis), citrus,
pineapples, cotton, sugar cane, coffee, cocoa and the like, and also in fruit production and viticulture.
Equally, the combinations according to the invention can be employed in arable crop production using
the no-till or zero-till methods. Alternatively, as already mentioned they can be used in proper non-crop
areas, i.e. nonselectively on paths, in open spaces, etc. to keep these areas free of undesirable
vegetation. However, the combination partners of group Bd), which are nonselective per se, do not only
become selective herbicides when the crop plants have the appropriate resistance, but combinations
according to the invention are also selective when used in transgenic crops. Transgenic crops are tho se
in which the plants are made resistant to nonselective herbicides by genetic manipulation or selection.
Crop plants which have been modified in such a way, for example maize, cereals or soya, then permit
the selective use of combinations comprising B46) and/or B47).
In summary, it may be stated that superadditive (=synergistic) effects are achieved when N-[(4,6dimethoxypyrimidin-2-yl)aminocarbonyl]-5-methylsulfonamidomethyl-2 alkoxycarbonylbenzenesulfonamides, and/or salts thereof are used together with one or more active
compounds of group B, optionally and particularly preferably additionally with one or more safeners of
group C. The activity in the combination s is more pronounced than that of the individual products used
employed alone. These effects permit
the application rate to be reduced,
a broader spectrum of broad-leaved weeds and weed grasses to be controlled,
a more rapid and safer action,
a more prolonged action,
complete control of harmful plants with only one or few applications and
a widening of the period of time when the active compounds in the combination can be applied.
The abovementioned properties are required in weed control practice to keep agricultural crops free
from undesirable competing plants and thus to ensure and/or increase yields from a qualitative and
quantitative point of view. The combinations according to the invention markedly surpass the prior art
with a view to the above-described properties.
Additionally, the combinations according to the invention permit the outstanding control of otherwise
resistant harmful plants.
The following examples serve to illustrate the invention:
1. Formulation examples
a) A dust is obtained by mixing 10 parts by weight of an active compound combination according to
the invention and 90 parts by weight of talc as inert substance and comminuting the mixture in a
hammer mill.
b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of
active compounds A+B, 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by
weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurate as wetting
agent and dispersant, and grinding the mixture in a pinned-disk mill.
c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by
weight of active compounds A+B with 6 parts by weight of alkylphenol polyglycol ether (.RTM.Triton
X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic
mineral oil (boiling range for example approximately 255 to 277 DEG C.), and grinding the mixture in
a ball mill to a fineness of below 5 microns.
d) An emulsifiable concentrate is obtained from 15 parts by weight of cyclohexanone as solvent and
10 parts by weight of ethoxylated nonylphenol as emulsifier.
178/2194
e) Water-dispersible granules are obtained by mixing 75 parts by weight of active compounds A+B, 10
parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight
of polyvinyl alcohol and 7 parts by weight of kaolin, grinding the mixture in a pinned-disk mill and
granulating the powder in a fluidized bed by spraying on water as granulation liquid.
f) Water-ispersible granules are also obtained by homogenizing, in a colloid mill, 25 parts by weight of
active compounds A+B, 5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, 2 parts
by weight of sodium oleoylmethyltaurate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of
calcium carbonate and 50 parts by weight of water, precomminuting the mixture, subsequently grinding
it in a bead mill and atomizing and drying the resulting suspension in a spray tower by means of a
single-substance nozzle.
g) Extruder granules are obtained by mixing and grinding 20 parts by weight of active compounds
A+B, 3 parts by weight of sodium lignosulfonate, 1 part by weight of carboxymethylcellulose and 76
parts by weight of kaolin and moistening the mixture with water. This mixture is extruded and
subsequently dried in a stream of air.
2. Biological examples
The examples mentioned below were carried out in the greenhouse, and in some instances, in field
trials.
Field trials
After the natural emergence of the weeds in the cereals, the herbicides or the combinations were
applied using plot sprayers. After the application, the effects, such as damage to the crop plants and the
effect on broad-leaved weeds/weed grasses, were assessed by visual scoring. The herbicidal activity
was assessed qualitatively and quantitatively (0-100%) by comparing untreated and treated plots with
respect to the influence on plant growth and chlorotic and necrotic effects up to the total eradication of
the weeds. Application was carried out at the 2-4 leaf stage of the crop plants and weeds. Evaluation
was carried out approximately 4 weeks after the application.
Greenhouse trials
In the greenhouse trials, the crop plants and broad-leaved weeds/weed grasses were grown in size 13
pots and treated at the 2-4 leaf stage. The pots were subsequently stood in the greenhouse under good
conditions for growth (temperature, air humidity, water supply).
Evaluation was carried out similar to the field trials, i.e. by visually scoring the treated plants in
comparison to untreated control variants. These evaluations were carried out 3 weeks after the
application of the preparations to be tested and combinations thereof. The experiments were carried out
in duplicate.
* Evaluation of the combination effects in the examples
For the assessment of the combination effects, the activity of the individual components was added
and compared to the effect of mixtures of the same dosage. In many cases, it became evident that the
combinations had higher efficacies than the sum of the individual effects.
In cases of less pronounced effects, the expected value was calculated using COLBY'S formula and
compared to the empirical result. The calculated expected theoretical efficacy of a combination is
determined using the formula of S. R. Colby: "Calculation of synergistic and antagonistic responses of
herbicide combinations", Weeds 15 (1967), pages 20 to 22.
For combinations of two compounds, this formula is: ##EQU1##
and, correspondingly, for combinations of three herbicidally active compounds: ##EQU2##
where
X=% damage by herbicide A at an application rate of x kg of ai/ha;
Y=% damage by herbicide B at an application rate of y kg of ai/ha;
179/2194
Z=% damage by a further herbicide C at an application rate of z kg of ai/ha;
E=expected value, i.e. expected damage by herbicides A+B (or A+B+C) and x+y (or x+y+z) kg of
ai/ha
Synergistic effects were assumed to be present when the empirical value was greater than the expected
value. Combinations of individual components of the same active compounds could also be prepared
by using the sum formula.
However, in most cases the synergistic increase in activity is so high that the Colby criterion can be
dispensed with; in these cases, the activity of the combination considerably surpasses the formal
(calculated) sum of the activities of the individual compounds.
Particular attention has to be drawn to the fact that when the synergism between the active compounds
employed here is assessed, the highly different application rates of the individual active compounds
have to be taken into consideration. Thus, it is not expedient to compare the activities of the active
compound combinations and those of the individual active compounds in each case at identical
application rates. The amounts of active compounds that can be saved according to the invention
become evident only from the superadditive increase in activity when using the combined applicational
rates or by the reduction of the application rates of the two individual active compounds in the
combinations in comparison to the individual active compounds, the activity remaining the same in
each case.
>;tb; TABLE 1
>;tb; Active
LOLMU
TRZAW
>;tb; compound(s) g of ai/ha % control % damage
>;tb; A)*
5
8 0
>;tb;
10
73
0
>;tb;
20
97
0
>;tb;
40
98
0
>;tb;
80
99
0
>;tb; B1)
18
0 0
>;tb;
37
0 0
>;tb;
75
8 0
>;tb; A)* + B1) 5 + 18 75 (8 + 0) 0
>;tb;
5 + 37 85 (8 + 0) 0
>;tb;
10 + 18 95 (8 + 0) 0
>;tb;
10 + 37 96 (8 + 0) 0
>;tb;
20 + 18 99 (97 + 0) 0
>;tb;
20 + 37 100 (97 + 0) 0
>;tb;LOLMU = Lolium multiflorum
>;tb;TRZAW = Triticum aestivum
>;tb;A)* = Sodium salt of
>;tb;##STR56##
>;tb;B1) = Puma S .RTM. = mixture of fenoxaprop-P-ethyl and the safener
>;tb; fenchlorazole-ethyl = ethyl
>;tb; 1-(2,4-dichlorophenyl)-5-(trichloromethyl)-1H-1,2,4-triazole-3-carboxylate
>;tb; in a ratio of 2:1
>;tb;(+) = effect of the individual substances (additive method)
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
TABLE 2
Active
AVEFA
TRZAW
compound(s) g of ai/ha
% control % damage
A)
3.75
10
0
7.5
60
0
15
80
0
30
95
0
B2)
750
15
0
1500
60
0
3000
85
0
180/2194
>;tb; A) + B2) 3.75 + 750 88 (10 + 15) 0
>;tb;
7.5 + 750 85 (60 + 15) 0
>;tb;
15 + 750 95 (80 + 15) 0
>;tb;
3.75 + 1500 96 (10 + 60) 0
>;tb;
7.5 + 1500 99 (84)@E 0
>;tb;
15 + 1500 100 (92)@E 0
>;tb;AVEFA = Avena fabtua
>;tb;TRZAW = Triticum aestivum
>;tb;A) =
>;tb;##STR57##
>;tb;B2) = isoproturon (Arelon .RTM.)
>;tb;(+) = effect of the individual substances
>;tb;()@E = expected value calculated according to Colby
>;tb; TABLE 3
>;tb; Active
GALAP
TRZAW
>;tb; compound(s) g of ai/ha
% control % damage
>;tb; A)*
5
17
0
>;tb;
10
22
0
>;tb;
20
34
0
>;tb;
40
45
0
>;tb;
80
57
0
>;tb; B14)
250
0 0
>;tb;
500
0 0
>;tb;
1000
5 0
>;tb; A)* + B14) 5 + 1000 65 (17 + 5) 0
>;tb;
10 + 250 65 (22 + 0) 0
>;tb;
10 + 500 70 (22 + 0) 0
>;tb;
10 + 1000 80 (22 + 5) 0
>;tb;
20 + 250 75 (34 + 0) 0
>;tb;
20 + 500 80 (34 + 0) 0
>;tb;
20 + 1000 85 (34 + 5) 0
>;tb;GALAP = Galium aparine
>;tb;TRZAW = Triticum aestivum
>;tb;A)* = Sodium salt of
>;tb;##STR58##
>;tb;B14) = Sodium salt of MCPA
>;tb;(+) = effect of the individual substances
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
TABLE 4
Active
GALAP
TRZAW
compound(s) g of ai/ha % control % damage
A)*
5
17
0
10
22
0
20
34
0
40
45
0
80
57
0
B19)
63
0 0
125
3 0
250
10
0
500
18
0
A)* + B19) 10 + 500 75 (22 + 18) 0
20 + 125 70 (34 + 3) 0
20 + 250 77 (34 + 10) 0
20 + 500 83 (34 + 18) 0
40 + 63 70 (45 + 0) 0
40 + 125 75 (45 + 3) 0
40 + 250 82 (45 + 10) 0
40 + 500 87 (45 + 18) 0
181/2194
>;tb;
80 + 63 80 (57 + 0) 0
>;tb;
80 + 125 80 (57 + 3) 0
>;tb;
80 + 250 88 (57 + 10) 0
>;tb;
80 + 500 93 (57 + 18) 0
>;tb;GALAP = Galium aparine
>;tb;TRZAW = Triticum aestivum
>;tb;A)* = Sodium salt of
>;tb;##STR59##
>;tb;B19) = ioxynil
>;tb;(+) = effect of the individual substances
>;tb; TABLE 5
>;tb; Active
GALAP
TRZAW
>;tb; compound(s) g of ai/ha % control % damage
>;tb; A)*
5
17
0
>;tb;
10
22
0
>;tb;
20
34
0
>;tb;
40
45
0
>;tb;
80
57
0
>;tb; B22)
4
0 0
>;tb;
8
0 0
>;tb;
15
8 0
>;tb;
30
8 0
>;tb; A)* + B22) 5 + 30 45 (17 + 8) 0
>;tb;
10 + 15 68 (22 + 8) 0
>;tb;
10 + 30 65 (22 + 8) 0
>;tb;
20 + 4 48 (34 + 0) 0
>;tb;
20 + 8 65 (34 + 0) 0
>;tb;
20 + 15 73 (34 + 8) 0
>;tb;
20 + 30 78 (34 + 8) 0
>;tb;
40 + 4 55 (45 + 0) 0
>;tb;
40 + 8 65 (45 + 0) 0
>;tb;
40 + 15 75 (45 + 8) 0
>;tb;
40 + 30 80 (45 + 8) 0
>;tb;GALAP = Galium aparine
>;tb;TRZAW = Triticum aestivum
>;tb;A)* = Sodium salt of
>;tb;##STR60##
>;tb;B22) = fluoroglycofen-ethyl (Compete .RTM.)
>;tb;(+) = effect of the individual substances (additive method)
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
>;tb;
TABLE 6
Active
GALAP
TRZAW
compound(s) g of ai/ha % control % damage
A)*
5
17
0
10
22
0
20
34
0
40
45
0
80
57
0
B29)
13
0 0
25
0 0
50
5 0
100
5 0
A)* + B29) 5 + 100 60 (17 + 5) 0
10 + 100 65 (22 + 5) 0
20 + 50 68 (22 + 5) 0
20 + 100 70 (34 + 5) 0
40 + 25 68 (45 + 0) 0
40 + 50 75 (45 + 5) 0
182/2194
>;tb;
40 + 100 82 (45 + 5) 0
>;tb;
80 + 13 63 (57 + 0) 0
>;tb;
80 + 25 75 (57 + 0) 0
>;tb;
80 + 50 88 (57 + 5) 0
>;tb;
80 + 100 98 (57 + 5) 0
>;tb;GALAP = Galium aparine
>;tb;TRZAW = Triticum aestivum
>;tb;A)* = Sodium salt of
>;tb;##STR61##
>;tb;B29) = diflufenican
>;tb;(+) = effect of the individual substances (additive method)
>;tb; TABLE 7
>;tb; Active
OXAPC
TRZAW
>;tb; compound(s) g of ai/ha % control % damage
>;tb; A)*
5
0 0
>;tb;
10
7 0
>;tb;
20
20
0
>;tb; B42)
5
27
0
>;tb;
10
59
0
>;tb; A)* + B42) 5 + 5
93 (0 + 27) 0
>;tb;
5 + 10 94 (0 + 59) 0
>;tb;
10 + 5 100 (7 + 27) 0
>;tb;OXAPC = Oxalis pes-carprae
>;tb;TRZAW = Triticum aestivum (summer wheat)
>;tb;A)* = Sodium salt of
>;tb;##STR62##
>;tb;B42) = sodium salt of methyl
>;tb; 4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureidosulfonyl]benzoate
>;tb;(+) = effect of the individual substances (additive method)
>;tb;TABLE 7a
>;tb;Active
g of AVSSP LOLSP
TRZAW TRZD
>;tb;compound(s) ai/ha % control % control % damage % damage
>;tb;A)
10 70
29
4 3
>;tb;
20
87
69
11
6
>;tb;B42)
5 29
46
2 2
>;tb;
10
31
88
3 3
>;tb;A) + B42) 10 + 5 86 (78)@E 81 (29 + 27) 14
7
>;tb;AVSSP = Avena ssp.
>;tb;LOLSP = Lolium ssp.
>;tb;TRZAW = Triticum aestivum (summer wheat)
>;tb;TRZD = Triticum durum
>;tb;A) =
>;tb;##STR63##
>;tb;B42) = sodium salt of methyl
>;tb; 4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureidosulfonyl]benzoate
>;tb;(+) = effect of the individual substances (additive method)
>;tb;()@E = expected value calculated according to Colby
>;tb;TABLE 7b
>;tb;Active
g of APSV
GALAP TRZAW TRZD
>;tb;compound(s) ai/ha % control % control % damage % damage
>;tb;A)
10 68
10
4 3
>;tb;
20
78
13
11
6
>;tb;B42)
5 0 90
2 2
>;tb;
10
5 98
3 3
>;tb;A) + B42) 10 + 5 80 (68 + 0) 100 (91)@E 14
7
>;tb;APSV = Apera spica venti
183/2194
>;tb;GALAP = Galium aparine
>;tb;TRZAW = Triticum aestivum (summer wheat)
>;tb;TRZD = Triticum durum
>;tb;A) =
>;tb;##STR64##
>;tb;B42) = sodium salt of methyl
>;tb; 4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureidosulfonyl]benzoate
>;tb;(+) = effect of the individual substances (additive method)
>;tb;()@E = expected value calculated according to Colby
>;tb;TABLE 7c
>;tb;Active
g of POLGC
CHPA TRZAW TRZD
>;tb;compound(s) ai/ha % control % control % damage % damage
>;tb;A)
10 12
5 4 3
>;tb;
20
24
50
11
6
>;tb;B42)
5 65
0 2 2
>;tb;
10
83
65
3 3
>;tb;A) + B42) 10 + 5 90 (12 + 62) 94 (5 + 0) 14
7
>;tb;POLGC = Polygonum conv.
>;tb;CHPA = Chenopodium alb.
>;tb;TRZAW = Triticum aestivum (summer wheat)
>;tb;TRZD = Triticum durum
>;tb;A) =
>;tb;##STR65##
>;tb;B42) = sodium salt of methyl
>;tb; 4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureidosulfonyl]benzoate
>;tb;(+) = effect of the individual substances (additive method)
>;tb;()@E = expected value calculated according to Colby
>;tb;TABLE 7d
>;tb;Active
g of PAPRH
PHYAN TRZAW TRZD
>;tb;compound(s) ai/ha % control % control % damage % damage
>;tb;A)
10
0 38
4 3
>;tb;
20
50
50
11
6
>;tb;B42)
5 0
0 2 2
>;tb;
10
83
65
3 3
>;tb;A) + B42) 10 + 5 88 (0 + 0) 94 (5 + 0) 14
7
>;tb;PAPRH = Paphaver rhoeas
>;tb;PHYAN = Physalis angulata
>;tb;TRZAW = Triticum aestivum (summer wheat)
>;tb;TRZD = Triticum durum
>;tb;A) =
>;tb;##STR66##
>;tb;B42) = sodium salt of methyl
>;tb; 4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureidosulfonyl]benzoate
>;tb;(+) = effect of the individual substances (additive method)
>;tb;()@E = expected value calculated according to Colby
>;tb;TABLE 7e
>;tb;Active
g of BRASN
LAMPU TRZAW TRZD
>;tb;compound(s) ai/ha % control % control % damage % damage
>;tb;A)
10
5 47
4 3
>;tb;
20
50
48
11
6
>;tb;B42)
5 0 80
2 2
>;tb;
10
65
95
3 3
>;tb;A) + B42) 10 + 5 94 (5 + 0) 100 (90)@E 14
7
>;tb;Active
g of KOSC
STLMD TRZAW TRZD
>;tb;compound(s) ai/ha % control % control % damage % damage
>;tb;A)
10 58
80
4 3
184/2194
>;tb;
20
68
90
11
6
>;tb;B42)
5 94
98
2 2
>;tb;
10
98
100 3 3
>;tb;A) + B42) 10 + 5 98 (97)@E 100 (99)@E 14
7
>;tb;BRASN = Brassica napus
>;tb;LAMPU = Lamicum purpureum
>;tb;KOSC = Kochia scorpium
>;tb;STLMD = Stellaria media
>;tb;TRZAW = Triticum aestivum (summer wheat)
>;tb;TRZD = Triticum durum
>;tb;A) =
>;tb;##STR67##
>;tb;B42) = sodium salt of methyl
>;tb; 4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureidosulfonyl]benzoate
>;tb;(+) = effect of the individual substances (additive method)
>;tb;()@E = expected value calculated according to Colby
>;tb;TABLE 8
>;tb;Active
PHAMI
DESSO
CAPBP
>;tb;compound(s) g of ai/ha % control
% damage
>;tb;A)
10 30
80
0
>;tb;B46)
270
25
0 15
>;tb;
450
63
0 18
>;tb;A) + B46) 10 + 270 68 (30 + 25) 99 (80 + 0) 73 (0 + 15)
>;tb;PHAMI = Phalaris minor
>;tb;DESSO = Descurainia richardssonii
>;tb;CAPBP = Capsella bursa pastoris
>;tb;A) =
>;tb;##STR68##
>;tb;B46) = glufosinate-ammonium
>;tb;(+) = % effect of the individual active compounds (addition)
>;tb; TABLE 9
>;tb;
AVEFA % AVEFA %
>;tb; Active
effect
effect
>;tb; compound(s) g of ai/ha sensitive resistant
>;tb; A)
10
72
80
>;tb;
20
95
95
>;tb; B1)
100
90
35
>;tb; A) + B1) 10 + 100 98 (97)@E 97 (87)@E
>;tb;AVEFA = Avena Fatua
>;tb;sensitive = AVEFA populations which have not developed any resistance
>;tb;resistant = AVEFA populations which have already developed a resistance
>;tb;A) =
>;tb;##STR69##
>;tb;B1) = Puma S .RTM. = mixture of fenoxaprop-P-ethyl and the safener
>;tb; fenchlorazole-ethyl = ethyl
>;tb; 1-(2,4-dichlorophenyl)-5-(trichloromethyl)-1H-1,2,4-triazole-3-carboxylate
>;tb; in a ratio of 2:1
>;tb;()@E = expected value calculated according to Colby
The examples show that the individual active compounds allow efficient control of individual weeds
only in high dosages. If the combination partners are applied in low dosages, they generally only have
low activity, far less than required in practice. Good effects against all of the weed species examined
can only be obtained by joint application of the active compounds. Here, the additive effect of the
individual components was surpassed considerably, i.e. their required level of control is achieved by
significantly lower application rates. Owing to these effects, the activity spectrum is widened
significantly. Even populations of harmful plants which have already developed resistance against
185/2194
individual herbicides are more effectively controlled by the combinations according to the invention
(cf. Table 9).
The crop safety, assessed in the form of damage, is not affected negatively, i.e. the combinations can
be judged to be fully selective.
Further advantages and embodiments of the invention are evident from the patent claims below.Data
supplied from the esp@cenet database - Worldwide
Claims:
Claims of corresponding document: US6221809
What is claimed is:
1. A herbicidal composition, comprising
A) at least one compound from the group of the substituted phenylsulfonylureas of the formula I and
agriculturally acceptable salts thereof ##STR70##
in which
R@1 is (C1 -C8)-alkyl, (C3 -C4)alkenyl, or (C3 -C4)-alkynyl or (C1 -C4)-alkyl which is mono- to
tetrasubstituted by radicals selected from the group consisting of halogen and (C1 -C2)-alkoxy, and
B) at least one herbicidally active compound selected from the group of the compounds consisting of
Ba) herbicides which have selective activity against grasses in cereals,
Bb) herbicides which have selective activity against dicotyledons in cereals,
Bc) herbicides which have selective activity against grasses and dicotyledons in cereals and
Bd) herbicides which are active against weed grasses and broad-leaved weeds and which are
nonselective in non-cop areas or perennial crops (plantations) and/or selective in transgenic crops.
2. The composition as claimed in claim 1, wherein
in the herbicide of the formula (1) or the salt thereof
R@1 is methyl, ethyl,. n- or isopropyl, n-, tert-, 2-butyl or isobutyl, n-pentyl, isopentyl, n-exyl,
isohexyl, 1,3-dimethylbutyl, n-heptyl, 1 -methylhexyl or 1,4-dimethylpentyl.
3. The composition as claimed in claim 1, wherein
in the herbicide of the formula (I) or the salt thereof R@1 is methyl.
4. The composition as claimed in claim 1, wherein
the salt of the herbicide of the formula (I) is formed by replacing the hydrogen of the --SO2 --NHCO-group by a cation selected from the group of the alkali metals, alkaline earth metals and ammonium.
5. The composition as claimed in claim 1, which comprises
as herbicides of Ba which have selective activity against grasses in cereals and are selected from the
group comprising the 2(4aryloxyphenoxy)propionic acids, or esters sulfonylureas, cyclohexanedione
oximes, imidazolinones and difenzoquat.
6. The composition as claimed in claim 1, which comprises
as herbicides of Ba which have selective activity against grasses in cereals and are selected from the
group consisting of ##STR71## ##STR72##
7. The composition as claimed in claim 6, which comprises
as herbicides of fenoxaprop-P-ethyl, isoproturon and/or mixtures of clodinafop-propargyl with
cloquintocet-mexyl.
8. The composition as claimed in claim 1 which comprises
as herbicides of Bb which have selective activity against dicotyledons in cereals and are selected from
the group comprising aryloxyalkylcarboxylic acids, hydroxybenzonitriles, diphenyl ethers, azoles
pyrazoles, diflufenican and bentazone.
9. The composition as claimed in claim 1, which comprises
186/2194
as herbicides of Bb which have selective activity against dicotyledons in cereals and are selected from
the group consisting of ##STR73##
10. The composition as claimed in claim 1 which comprises
as herbicides of Bb which have selective activity against dicotyledons in cereals and are selected from
the group consisting of ##STR74##
11. The composition as claimed in claim 1, which comprises
as herbicides of Bb which have selective activity against dicotyledons in cereals and are selected from
the group consisting of ##STR75##
12. The composition as claimed in claim 1 which comprises
as herbicides Bb which have selective activity against dicotyledons in cereals and are selected from the
group consisting of ##STR76##
in which
R@1 is (C1 -C4)-alkyl
R@2 is (C1 -C4)alkyl, (C1 -C4)-alkylthio or (C1 -C4)-alkoxy, each of which may be substituted by
one or more halogen atoms, or
R@1 and R@2 together form the group (CH2)m where m =3 or 4,
R@3 is hydrogen or halogen
R@4 is hydrogen or (C1 -C4)-alkyl,
R@5 is hydrogen, nitro, cyano or one of the groups --COOR@7, --C(.dbd.X)NR@7 R@8 or -C(.dbd.X)R@10, X.dbd.O or S
R@6 is hydrogen, halogen, cyano, (C1 -C4)-alkyl, (C1 -C4)-alkylthio or --NR@11 R@12 ,
R@7 and R@8 are identical or different and each is hydrogen or (C1 -C4)-alkyl, or
R@7 and R@8 join with the nitrogen to which they are attached to form a saturated 5- or 6-membered
carbocyclic ring,
R@10 is hydrogen or (C1 -C4)-alkyl, the latter optionally being substituted by one or more halogen
atoms, and
R@11 and R@12 are identical or different and each is hydrogen, (C1 -C4)-alkyl or (C1 -C4)alkoxycarbonyl, where
R@11 and R@12 may join with the nitrogen to which they are attached to form a 3-, 5- or 6membered carbocyclic or aromatic ring in which one carbon atom may be replaced by an oxygen atom;
and ##STR77##
13. The composition as claimed in claim 1, which comprises.
as herbicide of Bb ##STR78##
which has selective activity against dicotyledons in cereals.
14. The composition as claimed in claim 1 which comprises
as herbicide Bb ##STR79##
which has selective activity against dicotyledons in cereals and/or maize.
15. The composition as claimed in claim 9, which comprises
herbicide MCPA diflufenican, ioxynil and/or fluoroglycofen.
16. The composition as claimed in claim 1, which comprises
as herbicides Bc which have selective activity against grasses and dicotyledons in cereals and are
selected from the group which -comprises triazine derivatives, (thio)carbamates, furanones and
sulfonylureas selected from the sulfonylureas of formula I.
17. The composition as claimed in claim 1, which comprises
herbicide selected from the group comprising ##STR80##
18. The composition as claimed in claim 1, which comprises
as herbicides group B selected from the group which includes ##STR81##
187/2194
in which
R@1 is methyl, ethyl, n-propyl, isopropyl or allyl,
R@2 is CO--R@5, COOR@6, CO--NR@8 R@9, CS--NR@10 R@11, SO2 R@14 or SO2 NR@15
R@16,
R@3 is COR@17, COOR@181 CONR@19 R@20 or CO--ON.dbd.CR@22 R@23,
R@4 is hydrogen or (C1 -C4)-alkyl,
R@5 is hydrogen, (C1 -C4)-alkyl, (C1 -C2)haloalkyl, cyclopropyl, phenyl, benzyl or heteroaryl having
5 or 6 ring atoms, the last 3 radicals being unsubstituted or substituted by one or more halogen atoms,
R@6 is (C1 -C4)-alkyl, allyl, propargyl or cyclopropyl,
R@8 is hydrogen, (C1 -C4)-alkyl, (C1 -C4)-haloalkyl or (C1 -C4 -alkoxy)-carbonyl,
R@9 -R@11 are independently of one another identical or different H or (C1 -C4)-alkyl,
R@14 is (C1 -C4)-alkyl,
R@15 and R@16 are independently of one another identical or different hydrogen or (C1 -C4)-alkyl,
R@17 is hydrogen, (C1 -C4)-alkyl, (C1 -C4)-haloalkyl, (C3 -C6)cycloalkyl, phenyl or heteroaryl, the
last two radicals being unsubstituted or substitutes
R@18 is hydrogen, (C1 -C4)-alkyl, (C2 -C6)-alkenyl or (C2 -C6)-alkynyl, the last three radicals being
unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1
-C4)-alkoxy, (C1 -C4)-alkylthio and NR@31 R@32, or (C3 -C6)-cycloalkyl or (C3 -C6)-cycloalkyl(C1
-C3)-alkyl,
R@19 is analogous to R@8,
R@20 is analogous to R@9,
R@22 and R@23 are independently of one another identical or different hydrogen or (C1 -C2)-alkyl,
R@31 and R@32 are independently of one another identical or different hydrogen or (C1 -C4)alkyl,
W is oxygen or sulfur,
X is (C1 -C4)alkyl, (C1 -C4)-alkoxy, (C1 -C4)-haloalkyl, (C1 -C4)-alkylthio, halogen or mono- or diC1 -C2 -alkyl)-amino,
Y is (C1 -C4)-alkyl, (C1 -C4)-alkoxy, (C1 -C4)-haloalkyl or (C1 -C4)-alkylthio, and
X is CH or N,
B42) sulfonylureas of the formula IV and agriculturally tolerable and acceptable salts thereof
##STR82##
which
R@1 is (C1 -C8)-alkyl, (C3 -C4)-alkenyl, or (C3 -C4)alkynyl or (C1 -C4)-alkyl which is mono- to
tetrasubstituted by radicals selected from the group consisting of halogen and (C1 -C2)-alkoxy, where
in the herbicide of the formula (IV) or the salt thereof.
and where those salts have favorable activity where the salt of the herbicide of the formula (IV) is
formed by replacing the hydrogen of the --SO2 --NHCO-- group by a cation selected from the group of
the alkali metals, alkaline earth metals and ammonium, ##STR83##
19. The composition as claimed in claim 17, which comprises
as herbicide of group B the sodium salt of methyl 4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2yl)ureidosulfonyl]benzoate .
20. The composition as claimed in claim 1, which comprises
as herbicides of Bd which are active against weed grasses and broad-leaved weeds and which are
nonselective in non-crop areas or perennial crops (plantations) and/or selected in transgenic crops and
which are selected from the group consisting of ##STR84##
21. The composition as claimed in claim 20, which comprises
as herbicide of group B glufosinate-ammonium.
22. The composition as claimed in claim 1, which comprises
a synergistically effective amount of a combination of the compounds of the formula I or salts thereof
(group A compound) with compounds selected from group B.
23. The composition as claimed in claim 1, which comprises the compounds of the formula I or salts
thereof (group A compounds) and the compounds selected from group B in a weight ratio of 1:2500 to
20:1.
188/2194
24. The composition as claimed in claim 1, which comprises
0.1 to 99% by weight of the active compounds A and B, in addition to customary formulation
auxiliaries.
25. A process for preparing a composition which comprises
mixing the compounds of the formula I or salts thereof (group A compounds) with one or more
compounds of group B and, if appropriate, with one or more compounds of group C using a customary
crop protection formulation selected from the group consisting of wettable powders, emulsifiable
concentrates, aqueous solutions, emulsions, sprayable solutions (tank-mix), oil- or water-based
dispersions, suspoemulsions, dusts, seed dressings, granules for soil application or application by
broadcasting, water-dispersible granules, ULV formulations, microcapsules and waxes.
26. A method for controlling undesirable plants, which comprises applying a herbicidally effective
amount of one of the combinations of active compounds A+B as claimed in claim 1 onto the plants or
the cultivated area.
27. The method as claimed in claim 26, wherein
the application rate for the compounds of the formula (I) or salts thereof (group A compounds) is from
0.1 to 100 g of ai/ha, and the application rates for the compounds of group B are from 1 to 5000 g of
ai/ha.
28. The method as claimed in claim 26, wherein
the active compounds of groups A and B are applied simultaneously or at different times in a weight
ratio of 1:2500 to 20:1.
29. The method as claimed in claim 26, wherein
the combinations are employed for the selective control of undesirable plants.
30. The method as claimed in claim 29, wherein
the combinations are employed in transgenic crops.
31. The method as claimed in claim 30, wherein
the combinations are employed in cereals, maize, rice, sugar cane, crop plantations, meadows or
pasture land.
32. The method as claimed in claim 26, wherein
the combinations are employed in crops of useful plants.
33. The method as claimed in claim 26, wherein
the combinations are employed in non-crop areas.
34. The method as claimed in claim 26, wherein
harmful plants which are usually resistant are controlled.
35. The composition as claimed in claim 4, wherein the alkali metal is sodium.
36. The composition of claim 18, wherein R@1 of the sulfonylurea of formula TV (B42) is methyl.
37. The composition of claim 18, wherein the alkali metal is sodium.
38. The composition of claim 27, wherein the application rate for the compounds of the formula (T) or
salts thereof is from 2 to 40 g of ai/ha.Data supplied from the esp@cenet database - Worldwide
189/2194
17. EP0377642
- 7/18/1990
HERBICIDES FOR WEED CONTROL IN RICE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=EP0377642
Inventor(s):
ACKERSON ROBERT CHARLES (--); YUYAMA TAJESHI (--)
Applicant(s):
DU PONT (US)
IP Class 4 Digits: A01N
IP Class:A01N47/36
E Class: A01N47/36
Application Number:
EP19880908091 (19880805)
Priority Number: US19870082697 (19870807); WO1988US02596 (19880805); US19880157548
(19880212); US19880194549 (19880516)
Family: EP0377642
Equivalent:
WO8901289; BR8807645; EP0377642
Abstract:
Abstract not available for EP0377642
Abstract of corresponding document: WO8901289
This invention relates to compositions comprising mixtures of compounds of formula (I), wherein X is
CH3 or OCH3; Y is OCH3; and Z is N or CH, provided that when Z is CH then X is OCH3 and when
Z is N then X is CH3, with compounds selected from 2,4-dichlorophenoxyacetic acid, bensulfuron
methyl, thiobencarb, dimepiperate, esprocarb or dymron. This invention also relates to a method for
controlling the growth of undesired vegetation in a rice crop by applying to the crop after
transplantation or emergence of the rice plants an effective amount of a compound of formula (I), alone
or in combination with other herbicides.Description:
Description of corresponding document: WO8901289
Title
HERBICIDES FOR WEED CONTROL IN RICE
RelatedApplication
This is a continuation-in-part of U.S. Serial
No. 194,549 filed May 16, 1988, which is a continuation-in-part of U.S. Serial No. 157,548 filed
February12,.1988 which is a continuation-in-part of
U.S. Serial No. 082,697 filed August 7, 1987.
Backaround of the Invention
This invention relates to novel compositions comprising mixtures of two herbicides and to a method of
controlling undesired vegetation in the growth of rice plants by the application of an effective amount
of one of-the herbicides that comprise the mixture, alone or the composition comprising the mixture.
New compounds effective for controlling the growth of. undesired vegetation are in constant demand.
In the most common situation, such compounds are sought to selectively control the growth of weeds
in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed growth
in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the
consumer. There is especially a need for finding compounds that selectively control the growth of
190/2194
undesired vegetation in growing rice. Rice is a staple crop for millions of people of the world whose
diet depends-on its availability. There are many products commercially available for such purposes, but
the search continues for products which are more effective, less costly and environmentally safe.
The "sulfonylurea" herbicides are an extremely potent class of herbicides discovered within the last
few years. A multitude of structural variations exist within this class of herbicides, but they generally
consist of a sulfonylurea bridge, -SO2NHCONH-, linking two aromatic or heteroaromatic rings.
U.S. Patent 4,394,506 discloses compounds within the scope of Formula I of the present invention.
U.S. Patent 4,383,113 also discloses compounds within the scope of Formula I of the present
invention.
U.S. Patent 4,645,527 discloses the use of certain sulfonamides to protect cereal crops from injury by
compounds within the scope of Formula I of the present invention where X is CH3, Y is OCH3 and
Z is N.
There is, however, no disclosure in any of the above references of the use of the compounds they
describe for control of vegetation in rice.
SUMARY OF THE INVENTION
This invention relates to compositions comprising mixtures of compounds of
EMI2.1
Formula I wherein
X is CH3 or OCH3;
Y is OCH3; and
Z is N or CH,
provided that when Z is CH then X is OCH3
and when Z is N then X is CH3, with compounds selected from 2,4-dichlorophenoxyacetic acid,
bensulfuron methyl, thiobencarb, dimepiperate, esprocarb ordymron.
The preferred mixtures of the invention are the compounds of Formula I wherein Z is N, X is CH3 and
Y is OCH3 with bensulfuron methyl.
This invention also relates to a method for controlling the growth of undesired vegetation in a rice crop
by applying to the crop after transplantation or emergence of the rice plants an effective amount of a
compound of Formula I, alone or in combination with other herbicides.
The preferred methods of the invention for reasons of either more effective weed control or better crop
tolerance are:
1. A method for controlling the growth of unde
sired vegetation in a rice crop. by applying
to the crop after transplantation or emer
gence of the rice plants an effective amount
of a compound of Formula I wherein Z is N, X
is CH3 and Y is OCH3.
2. A method for controlling the growth of unde
sired vegetation in a rice crop by applying
to the crop after transplantation or emer
gence of the rice plants an effective amount
of a compound of Formula I wherein Z is CH,
X and Y are OCH3.
3. A method of Preferred I in admixture with a
herbicidally effective amount of 2,4-dich
loro phenoxyacetic acid.
191/2194
4. A method of Preferred 1 in admixture with a
herbicidally effective amount of bensul
furon methyl.
5. A method of Preferred 1 in admixture with S-[(4-chlorophenyl)methylZdiethylcarbamothioate (Thiobencarb).
6 A method of Preferred 1 in admixture with
S-1-methyl-1-phenylethylpiperidine-1 carbothioate (Dimepiperate)r
7. A method of Preferred 1 in admixture with S-benzyl-N-ethyl-N-(1 , 2-dimethyl)-propylthiol carbamate (Esprocarb).
8. A method of Preferred 1 in admixture with 1-(;,;-dimethylbenzyl)-3-p-tolylurea
(Dymron).
9. A compound of Formula I wherein Z is N and X
is CH3 in admixture with benzsulfuron
methyl.
Undesired vegetation, especially broadleafed weeds, in a rice crop may be controlled by applying to
the crop after transplantation or emergence an effective amount of a compound of FormulaT.
Compounds of Formula I may be combined with other rice herbicides, such as 2,4dichlorophenoxyacetic acid, benzsulfuron methyl,S-((4-chloro- phenyl)methyladiethylcarbamothioate,
S-l-methyl1-phenylethylpiperidine-1-carbothioate, S-benzyl
N-ethyl-N-(1,2-dimethyl)propylthio carbamate or1-(;,;-dimethylbenzyl)-3-p-tolylurea to broaden the
spectrum of weed control.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of Formula I are known in the art. Their chemical names are
methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2
yl)amino]carbonyl)amino]sulfonyl]benzoate (X is
CH3, Y is OCH3 and Z is N.)
methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]
carbonyl]aminoasulfonyl]benzoate (X is OCH3, Y
is OCH3 and Z is CH.)
In addition, methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2yl)amino)carbonyl]amino]sulfonyl]benzoate is known under the common name of metsulfuron methyl.
The compounds of Formula I wherein X isOCH3,
Y is OCH3, and Z is CH and wherein X is CH3, Y is
OCH3 and Z is N can be prepared by the processes specifically taught in Examples 1, 3, 4, 5, 6, 12 and
13 of U.S. Patents 4,394,506 and 4,383,113.
As discussed in the Utility section, the compounds of the instant invention are particularly effective in
controlling broadleafed weeds and sedges when combined with 2,4-dichlorophenoxyacetic acid (2,4D), its agriculturally suitable esters or salts, or with benzsulfuron methyl, or with Thiobencarb, or with
Dimepiperate, or with Esprocarb, or with Dymron.
2,4-D, its esters and salts are well known in the art of weed control. Some of its more frequently used
esters are prepared from 2-propanol, n-butanol, 2-butoxyethanol and 6-methyl-l-heptanol. Some of its
more frequently used salts are sodium, diethanolamine, diethylamine, dimethylamine, ethanolamine,
methylamine and triethanolamine. Neither the list of esters nor the list of salts is intended to be
limiting.
The complete chemical name of benzsulfuronmethyl is methyl 2-[ [ t[[(4,6-dimethoxy-2pyrimidinyl)amino]carbonyl]amino]sulfonyl]methyl]benzoate. It is sold under the tradename
ofLondaxs
192/2194
Herbicide by E. I. du Pont de Nemours and Company for weed control in rice. It is specifically
disclosed in
U.S. Patent 4,420,325 and can be prepared by the general processes described therein.
Formulations
Useful formulations of the compounds of Formula
I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions,
emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied
directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a
few liters to several hundred liters per hectare. High strength compositions are primarily used as
intermediates for further formulation.The formulations, broadly, contain about 1% to 99% by weight of
active ingredient(s) and at least one of (a) about0.18 to 20% surfactants) and b) about 5% to 99% solid
or liquiddiluen(s). More specifically, they will contain these ingredients in the following approximate
proportions:
Percent by Weight
Active
Ingredient(s) Diluent(s) Surfactant(s)
Wettable powders 20-90 0-74 1-10
Oil Suspensions, 5-5040 95 0-15
Emulsions, Solutions, (including Emulsifiable
Concentrates)
Aqueous Suspensions 10-50 40-841 20
Dusts 1-25 70-99 0-5
Granules and Pellets 1-95 5-99 0-15
High Strength 90-99 0-10 0-2
Compositions
Lower or higher levels of active ingredient can, of course, be present depending on the intended use
and the physical properties of the compound.Higher ratios of surfactant to active ingredient are
sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and
Carriers", 2ndEd., Dorland Books, Caldwell, New
Jersey, but other solids, either mined or manufactered, may be used. The more absorptive diluents are
preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents
aredescribed-in Marsden, "Solvents Guide,"2nd Ed.,
Interscience, New York, 1985.Solubility under0.18 is preferred for suspension concentrates; solution
concentrates are preferably stable against phase separation at0 C. "McCutcheon's Detergents and
Emulsifiers
Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia
of Surface
Active Agents", Chemical Publishing Co.,Inc., New
York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of
additives to reduce foaming, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing
the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or
fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent
3,060,084).
Granules and pellets may be made by spraying the active material upon preformed granular carriers or
by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, December
4, 1967, pp. 147ff. and "Perry's Chemical Engineer's
Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp.
8-57ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Patent 3,235,361, February 15, 1966,Col. 6, line 16 throughCol. 7, line 19 and
Examples 10 through 41;
193/2194
R. W. Luckenbaugh, U.S. Patent 3,309,192,
March 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132,
138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Patent 2,891,855,
June 23, 1959,Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;
G. C. Klingman, "Weed Control as a Science",
John Wiley and Sons,Inc., New York, 1961, pp. 81-96; and
J. D. Fryer and S.A Evans, "Weed Control
Handbook", 5th Ed., Blackwell Scientific Publications,
Oxford, 1968, pp. 101-103.
Example 1
Wettable Powder 2,4-dichlorophenoxyacetic acid, sodium salt 60% methyl 2-[[[[(4-methoxy-6-methyl1% 1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate
dodecylphenol polyethylene glycol ether 2%
sodium ligninsulfonate 4%
sodium silicoaluminate 6%
sodium carbonate 2%
montmorillonite (calcined) 25%
The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid
ingredients in the blender. After grinding in a hammermill to produce particles essentially all below
100 microns,the materlal is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and
packaged.
Example S
Wettable Powder methyl2-1[[[(4-methoxy-6-methyl-1,3,5-triazin- 40% 2yl)amino]carbonyl]amino]sulfonyl]benzoate
dioctyl sodium sulfosuccinate 1.5%
sodium ligninsulfonate 3%
low viscosity methyl cellulose 1.5%
attapulgite 54%
The ingredients are thoroughly blended,-passed through an air mill, to produce an average particle size
under 15 microns, reblended, and sifted through a
U.S.S. No. 50 sieve(0.3 mm opening) before packaging.
Examle3
Granule
wettable powder of Example 2 25%
gypsum 64%
potassium sulfate11%
The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When
most of the material has reached the desired range of 1.0 toQ.42 mm, (U.S.S. ;18 to 40 sieves), the
granules are removed,dried, and screened. Oversize material is crushed to produce additional material
in the desired range. These granules contain 10% active ingredient.
Example 4
Oil Suspension methyl 2-[[[[(4-methoxy-6-methyl-2- 25%
pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate
polyoxyethylene sorbitol hexaoleate 5%
highly aliphatic hydrocarbon oil 70%
The ingredients are ground together in a sand mill until the solid particles have been reduced to under
about 5 microns. The resulting thick suspension may be applied directly, but preferably after being
extended with oils or emulsified in water.
Example 5
Aqueous Suspension methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin2yl)aminoicarbonyl]aminojsulfonyljbenzoate 25%
hydrated attapulgite 3%
crude calcium ligninsulfonate 10%
194/2194
sodium dihydrogen phosphate 0.5%
water 61.5%
The ingredients are ground together in abal or roller mill until the solid particles have been reduced to
diameters under 10 microns.
Example 6
Wettable Powder methyl2-[[[t(4,6-dimethoxy-2-pyrimidinyl)- 95%
amino]carbonyl]amino]sulfonyl]benzoate
dioctyl sodium sulfosuccinate0.5%
sodium ligninsuifonate 1.5%
synthetic fine silica 3.0%
The ingredients are blended and ground in a hammermill to produce particles, almost all of which are
below 100 microns in size. Thismaterial- is sifted through a U.S.S. No. 50 (0.3 mm) screen and then
packaged.
Example 7
Granule
wettable powder of Example 6 8%
wettable powder of Example 2 2%
attapulgite granules 90%
(U.S.S. No. 20-40 mesh)
A slurry of the wettable powders is sprayed onto the surface of the granules, which are being mixed in
a blender After the slurry has been added, the granules are removed from the blender, dried and
packaged.
Example 8
Oil Suspension 2,4-dichlorophenoxyacetic acid, butoxyethyl 24.6% ester methyl 2-[[[[(4-methoxy-6methyl- 0.4% 1,3,5-triazin-2-yl)amino]carbonyl]amino] sulfonylj benzoate
polyoxyethylene sorbitol hexazolate 5%
highly aliphatic hydrocarbon oil 70%
Theingredient are ground together in a sand mill until thesolid particles have been reduced to under
about 5microns The resulting thick suspension may be applied directly, but preferably after being
extended with oils or emulsifiedwater.
Example 9
Extruded Pellet methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino9- 25%
carbonyl]amino]sulfonyl]benzoate
anhydrous sodium sulfate 10%
crudecalc==m liXninsulfonate 5%
sodium alkylnaphthalenesulfonate 1%
calcium/magnesium bentonite 59%
The ingredients are blended, hammermilled and then moistened witDUt 12% water. The mixture is
extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These
may be used directly after drying, Dr the dried pellets may be crushed to pass a U.S.S. No. 20 sieve
(0.84 mm openings). Thegranules held on aU.S.S. No. 40 sieve (0.42 mm openings) may be packaged
for use and the fines recycled.
Example 10
Granule methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin- 10% 2-yl]carbonyl]amino]sulfonyl]benzoate
methyl2- ([([((4, 6-dimethoxy-2- 50% pyrimidinyl)amino]carbonyl]aminosulfonyl)methyl] benzoate
wetting agent 1%
dispersing agent 2%
crude ligninsulfonate salt (containing 10%
5-20% of the natural sugars)
attapulgite clay 27%
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added
to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of
water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules
of the desired size range are made.
195/2194
The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is
reduced to the desired level, generally less than 1%. The material is then discharged, screened to the
desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
Example 11
Wettable Powder methyl2-[[[[(4,6-dimethoxy-2-pyrimidinyl)80%amino]carbonyllamino]sulfonyl]benzoate
sodium alkylnaphthalenesulfonate 2%
sodium ligninsulfonate 2%
synthetic amorphous silica 3%
kaolinite 13%
The ingredients are blended and then ground in a hammermill to produce particles with an average
particle size less than 25 microns in diameter. The material is reblended and sifted through a U.S.S. No.
50 sieve (0.3 mm opening) before being packaged.
Example lZ
Wettable Powder methyl2-[[[ [(4-methoxy-6-methyl-l,3,5 4% triazin-2yl)amino]carbonyl]amino]sulfonyl] benzoate methyl 2-[[[[(4,6-dimethoxy-6-methyl-2pyrimidinyl)amino]carbonyl]amino]sulfonyl]methyl]benzoate 36%
dioctyl sodium sulfosuccinate 1.5%
sodium ligninsulfonate 3%
low viscosity methyl cellulose 1.5%
attapulgite 54%
The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size
under 15 microns, reblended, and sifted through a
U.S.S. No. 50 sieve (0.3 mm opening) before packaging.
All compounds of the invention may be formulated in the same manner.
Example 13
Extruded Pellet methyl2-lelC(4-methoxy-6-methyl- 1% 1,3,5-triazin-2yl)amino]carbonyl]amino]sulfonyl]benzoate methyl 2-[[[[[(4,6-dimethoxy-2- 24%
pyrimidinyl)amino]carbonyl] amino- sulfonyl]methylgbenzoate
anhydrous sodium sulfate10%
crude calcium ligninsulfonate 5%
sodium alkylnaphthalenesulfonate 1%
calcium/magnesium bentonite 59%
The ingredients are blended, hammermilled and then moistened with about 12% water. The mixture is
extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These
may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve
(0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged
for use and the fines recycled.
Examolel4
Wettable Powder methyl2-[[[((4-methoxy-'6-methyl-l13,5-triazin- 2ylamino]carbonyl]amino]sulfonyl]benzoate 65%
dodecylphenol polyethylene glycol ether 2%
sodium ligninsulfonate 4%
sodium silicoaluminate 6%
montmorillonite (calcined) 23%
The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid
ingredients in the blender. After grinding in a hammermill to produce particles essentially all below
100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and
packaged.
ExamPle 15
196/2194
Wettable Powder 2,4-dichlorophenoxyacetic acid, 49.5% sodium salt methyl 2-[[[[(4-methoxy-6methyl-1,3,5-triazin- 0.5% 2-ylamino]carbonyl]amino]sulfonyl]benzoate
sodium alkylnaphthalenesulfonate 2%
low viscosity methylcellulose 2%
diatomaceous earth 46%
The ingredients are blended, coarsely hammermilled and then air milled to produce particles of active
essentially all below 10 microns in diameter. The product is reblended before packaging.
Example 16
Wettable Powder
S-[(4-chlorophenyl)methyl]diethylcarbamothioate 60% methyl 2-[[[[(4-methoxy-6-methyl- 1% 1,3,5triazin-2-yl)amino]carbonyl]amino3sulfonyl3benzoate
dodecylphenol polyethylene glycol ether 2%
sodium ligninsulfonate 4%
sodium silicoaluminate 6%
sodium carbonate 2%
montmorillonite (calcined) 25%
The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid
ingredients in the blender. After grinding in a hammermill to produce particles essentially all below
100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and
packaged.
Examolel7
Wettable Powder
S-l-methyl-1-phenylethylpiperidine-l-carbothioate 60% methyl2- ((F ((4-methoxy-6-methyl- 1% 1,3,5triazin-2-yl)amino]carbonyl]amino] sulfonyl)benzoate
dodecylphenol polyethylene glycol ether 2%
sodium ligninsulfonate48
sodium silicoaluminate 6%
sodium carbonate 2%
montmorillonite (calcined) 25%
The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid
ingredients in the blender. After grinding in a hammermill to produce particles essentially all below
100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and
packaged.
Example 18
Wettable Powder
S-benzyl-N-ethyl-N-(1,2-dimethyl)-propylthiol
carbamate 60% methyl 2-[[[[(4-methoxy-6-methyl- 1% 1,3,5-triazin-2yl)amino]carbonyl]amino]sulfonylZbenzoate
dodecylphenol polyethylene glycol ether 2%
sodium ligninsulfonate 4%
sodium silicoaluminate 6%
sodium carbonate 2%
montmorillonite (calcined) 25%
The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid
ingredients in the blender. After grinding in a hammermill to produce particles essentially all below
100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and
packaged.
Example 19
Wettable Powder1-(;,;-dimethylbenzyl)-3-p-tolylurea 60% methyl2-tttt(4-methoxy-6-methyl- 1%
1,3,5-triazin-2-yl)amino]carbonyl]aminolsulfonyl]benzoate
dodecylphenol polyethylene glycol ether 2%
sodium ligninsulfonate 4%
sodium silicoaluminate 6%
sodium carbonate 2%
montmorillonite (calcined)25
197/2194
The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid
ingredients in the blender. After grinding in a hammermill to produce particles essentially all below
100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve(0X3 mm opening) and
packaged.
Utility
The compounds of this invention are useful for the control of weeds in rice and may be used in both
transplanted and direct seeded rice. They are applied postemergence to the crop and may be applied
from 7 days after transplanting or emergence to the time the rice crop has closed and no longer needs
chemical weed control. They may be applied as a foliar spray in sufficient water to evenly distribute
the treatment.
Additives may be included in the spray to aid in penetration of the treatment.
The chemicals are particularly effective in controlling broadleafed weeds and may be combined with
other rice herbicides to broaden the spectrum of weed control. They are particularly effective on
broadleafed weeds and sedges when combined with 2,4dichlorophenoxyacetic acid (2,4-D), its
agriculturally suitable esters of salts, or with benzsulfuron methyl.
Particularly useful combinations with2,4wD comprise ratios of instant compound to 2,4-D of 4:125 to
1:625. Particularly useful combinations with benzsulfuron methyl comprise ratios of instant compound
to benzsulfuron methyl of 1:2 to 1:50. The compounds of this invention may also be mixed with other
rice herbicides including thiobencarb, esprocarb, dymron, dimepiperate, butachlor, molinate, ethyl 5[[[[4,6-dimethoxy-2-pyrimidinyl)amino]carbonyli amino)sulfonyl-l-methyl-lH-pyrazole-4carboxylate, naproanilide, bentazon, cinmethylin,chlormethoxnyl, quinchlorac,pretilachior, MCPA,
propanil, diflufenican,oxadiazon, and pyrazolate.
The application rates of the compounds of this invention may vary from 0.5 to 10 g/ha (preferably 1 to
5 g/ha) depending on weeds to be controlled, stage of growth of the crop and weeds, crop variety and
environmental conditions at the time of application.
One with ordinary skill in the art can select the rate to be used in each situation.
The examples below clearly demonstrate the utility of the compounds of this invention both alone and
in mixtures.
ExamPles
Methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin2-yl)amino]carbonyl]amino]sulfonyl]benzoate
(Compound 1) and mixtures thereof with other compounds were applied as a spray (using a hand
sprayer) to rice (either transplanted or direct seeded) in several rice growing areas in Southeast Asia
and in the U.S.
Tables 1-26 contain the results of these tests and clearly exemplify the utility of this invention. The
details of each application are included in the appropriate table.
EMI23.1
Compound 1
EMI23.2
Compound 2
Table 1
Herbicidal efficacy of Compound 1 in Thailand
TREATMENT RATE SZ5 CY5 SZ5 SZ5
(GAI/HA) 2WAA4 2WAA4 4WAA 6WAA4
Trial 1 2 100 33 100 100
3 99 67 100 100
4100 67 100 100
6 100 67 100 100
198/2194
Trial 2 2 97 0 99 99
3 100 67 100 100
4 99 33 99 100
6 100 67 100 100 1. 100 denotes complete control, and 0 denotes no
control.
2. Application rate in grams active ingredient per
hectare.
3. Treatments applied at 36 days after seeding.
4. WAA = weeks after application (evaluation).
5. Abbreviations: SZ = Sphenoclea zeylanica
CY = Cyperus species
Table 2
Effects of Compound 1 on rice growth in Thailand
based on an average of three results
TREATMENT PHYTOTOXICITY
GAI/HA1 7 DAS3 14 DAS3 21 DAS3 28 DAS3
Compound 1 3 1.67 1.0 0 0
Compound 1 6 1.331.0 0 0 2.4-D (SODIUM 600 2.33 1.33 0 0
SALT) 2,4-D (BUTYL 600 2.0 1.67 0 0
ESTER)
Compound 1+ 3+600 2.33 1.0 0.67 0
2,4-D (SODIUM
SALT)
Compound 1 + 3+600 2.67 1.33 0 0
2,4-D (BUTYL
ESTER)
Compound 1 + 3+600 2.0 1.0 0 0
PROPANIL 1. Application rate in grams active ingredient per
hectare.
2. Phytotoxicity scale is: O = no effect
3 = unacceptable
10 = 100% plant death 3. DAS = days after seeding (application time).
Table3
Herbicidal efficacy of Compound 1 and
combinations with 2,4-D in Thailand
based on an average of three results
TREATMENT RATE FIMBRISTYLIS MILIACEA CONTROL
(GAI/
HA) 7 DAS3 14 DAS3 14 DAS321 DAS328 DAS3
Compound 1 3 53 200 0
Compound 1 6 73 40 0 0 2,4-D (SODIUM 60096 95 93 98
SALT) 2,4-D (BUTYL 600 94 98 60 43
ESTER)
Compound 1 + 3+60097 90 92 100
2,4-D (SODIUM
SALT)
Compound 1 + 3+600 70 47 27 43
2,4-D (BUTYL
ESTER) 1. Application rate in grams active ingredient per
hectare.
2. % Control evaluated at 6 weeks after application.
199/2194
3. DAS = days after seeding (application time).
Table 4
Effects ofCompound 1 on rice growth in Thailand
based on an average oftee results
TREATMENTS
GAI/HA1 7 DAS3 14 DAS321 DAS328 DAS3
Compound 1 3 1.671.0 0.67 0
Compound 1 6 1.671.0 1.0 0 2,4-D (SODIUM 6005.O 3.67 3.0 1
SALT) 2,4-D (BUTYL 600 3.67 2.33 2.67 3
ESTER)
Compound 1 + 3+600 4.67 2.67 6.33 1.67
2,4-D (SODIUM
SALT)
Compound 1 + 3+600 3.33 2.33 4.0 2.0
2,4-D (BUTYL
ESTER) 1. Application rate in grams active ingredient per
hectare.
2. Phytotoxicity scale is: O = no effect
3 = unacceptable
10 = 100% plant death 3. DAS = days after seeding (application time).
Table5
Herbicidal efficacy of Compound 1 in
relation to application timing in Indonesia
TREATMENT1 RATES
MV3 CI3 PS3 RICE
GAI/HA 1 2 3 1 2 3 1 2 3 1 2 3
----% CONTROL--Compound 1 2 80 80 100 0 0 0 0 0 0 0 0 0 (3 WAT)5
3 80 100 100 20 0 0 0 0 0 0 0 0
4 100 100 100 20 0 0 0 0 0 0 0 0
6 80 100 100 20 0 0 0 0 0 0 0 0
8 100 100 100 20 0 0 0 0 0 0 0 0
Compound 1 2 80 100 100 0 0 0 0 0 0 0 0 0 (4 WAT)
3 80 100 100 0 0 0 0 0 0 0 0 0
4 80 100 100 20 20 0 0 0 0 . 20 20 0
6 80 100 100 20 20 0 0 0 0 20 20 0
8 100 100 100 20 20 0 0 0 0 20 20 0
Compound 1 2 80 80 80 0 0 0 0 0 0 10 0 0 (5 WAT)
3 80 10010Q 50 20 0 0 0 0 10 0 0
4 80 100 100 60 30 0 0 0 0 30 0 0
6 80 100 100 60 40 0 0 0 0 0 0 0
8 100 100 100 60 60 30 0 0 0 30 10 0
1. Plots drained prior to application and reflooded
3 days later.
2. Application rate in grams active ingredient per
hectare.
3. Abbreviations: MV = Monochoria vaginalis
CI = Cyperus iria
PS = Pistia stratioides
4. Weeks after application (evaluation).
5. WAT = weeks after transplanting (application).
Table 6
200/2194
Herbicidal efficacy of Compound 1 in Indonesia
TREATMENT1 RATES SM3 SJ MV EC RICE
GAI/HA 24 5 7 2 5 7 2 5 7 2 5 7 2
----% CONTROL-Compound 1 3 30 70 80 60 90 70 100 100 100 20 30 0 10
4 40 70 80 60 100 7090 100 100 20 300 10
6 30 90 90 90 100 80 100 100 100 20 300 10
8 40 80 90 80 100 80 100 100 100 20 300 10
Compound 1 3+515 20 70 80 90 100 100 100 100 100 20 300 10 + HERBA
ZOL5 4+515 30 90 80 80 90100 90 100 100 20 300 10
6+515 30 70 90 80 100 80 100 100 100 20 40 0 10
HERBAZOL 515 10 50 30 80 100 90 80 50 50 20 300 10
10330 50 30 100100 90 500 50 50 20 30 0 10
1. Application was at 2 weeks after transplanting.
Plots were drained prior to application and
reflooded 3 days after application.
2. Application rate in grams active ingredient per
hectare.
3. Abbreviations: SM = Salvinia molesta
MV = Monochoria vaginal is
SJ = Scirpus juncoides
EC = Echinochloa crus-galli
4. Weeks after application (evaluation).
5. 2,4-D amine salt.
Table 7
Effects of herbicide treatments on the
crop tolerance of transplanted rice
TREATMENTS CROP TOLERANCE
GAI/HA 1 WAA3 2WAA 4WAA 6WAA
Compoundl
30000
40000
6 1 0 00
8 11 0 0
Compound 1 + HERBAZOL4
3+515 0 0 0 0
4+515l 0 0 0
6+515 2 1 0 0
HERBAZOL 515 1 1 0 0
1,020 2 2 0 0
1. Crop tolerance rating:0 = no effect; 10 =
completely killed
2. Application rate in grams active ingredient per
hectare.
3. WAA = weeks after application (evaluation).
4. 2,4-D amine salt.
Table 8
Herbicidal efficacy of Compound 1 and
combinations with 2,4-D in Malaysia
TREATMENT1 RATESSG MV SZ CD FM MC
GAI/HA ----%CONTROL---
201/2194
Compound 1 1 80 95 0 0 0 20
2 100 95 100 100 100 95
3 95 100 100 95 50 100
4 95 100 100 100 50 95
5 100 100 100 100 20 100 2,4-D4 500 50 90 100 95 1000
1000 75 100 100 100 100 0
Compound 1 +2,4-D 1+500 90 95 100 67 100 95
2+500 95 100 100 95 100 100
3+500 100 100 100 100 100 100
4+500 100 100 100 100 100 100
5+500 100 100 100 95 95 100
1. Applications at 30 days after seeding.
Evaluation at 22 days after treatment.
2. Application rate in grams active ingredient per
hectare.
3. Abbreviations: SG = Scirous grossus
MV = Monochoria vaginalis
Sz = Sphenocleszevlanica
CD = Cyperusdifformis
FM = Fimbristylis miliacea
MC = Marsilea crenata
4. 2,4-D was dimethylamine salt.
Table 9
Broadleaf weed control with a late-post
application of Compound 1 in Beaumont, Texas
RATE RICE EC SEAl CC COMEA SEDGE
G/HA% INJURY OR CONTROL
3 3 26 68 68 11 13 13 43
6 5 30 62 62 19 24 23 56 12 6 24 46 46 18 23 15 56 1. Compoundl applied with 0.25% AG-98
wetting
agent.
2. Application rate is stated in units of grams
active ingredient per hectare.
3. Treated 30 days after seeding (24 days after
emergence) to wet soil; flooded 24 days after
emergence (6 days after application); evaluated
at 70 days after seeding.
4.Abbreviations: EC = Echinochloa colonum
SE = Sesbania exaltata
Al = Aeschynomene indica
CC = Caperonia casteniifolia
COM = Commelina communis
EA = Eclipta alba
SEDGE = Annual sedge (?)
Table 10
Field Test Results of Compound 1 + Bensulfuron
methyl for weed control in direct seeded rice
TREATMENTS MEEDS CONTROL at 4 WAA YIELD
TONS/
GAI/HA1 SZ CI4 MC5 HA
COMPOUND 1 - 2 7.93 010 3.62
COMPOUND 1 4 9.33 0 10 3.62
202/2194
BENSULFURON 10 0 2 0 3.04
METHYL
BENSULFURON 20 6 8 3.33 3.34
METHYL
COMPOUND 1 + 2+10 9.1 6.33 10 3.64
BENSULFURON
METHYL
COMPOUND 1 + 4+10 9.93 5.0 10 3.79
BENSULFURON
METHYL
COMPOUND 1 + 2+20 8.33 5.67 10 3.50
BENSULFURON
METHYL
COMPOUND 1 + 4+20 10 9.0 10 3.72
BENSULFURON
METHYL
UNTREATED -0 0 0 2.75 1.Application rate is stated in units of grams
active ingredient per hectare.
2. 10 is complete control, and 0 is no control, WAA
= weeks after application (evaluation).
3.SZ =Sphenoclea zeylanica 4.Cl = Cvperus iria 5. MC = Marsilea crenata
Table 11
Field Test Results of Compound 1 +
Bensulfuron methyl applied
at 7 DAS1 for weed control in direct seeded rice
TREATMENTS GM.A.I. PHYTO WEED CONTROL4
at at 6 WAA YIELD
TONS/
/HA 2WAA SZ5 CD6 HA
COMPOUND 1 40 10 10 4.90
BENSULFURON 10 0 1010 4.92
- METHYL 150 10 10 4.99
20 0 10 10 5.01
30 0 10 10 4.67
COMPOUND 1+ 4+10 010 10 5.35
BENSULFURON4+15 0 10 10 4.56
METHYL4+20 0 10 10 4.73
COMPOUND 1+ 4+750 0 10 10 4.81
2,4-D (NA)7
2,4-D (NA) 1,500 0 6.6 10 4.13
UNTREATED - 0 0 0 3.55
1. DAS = Days after seeding
2. Application rate is stated in units of grams
active ingredient per hectare.
3. Phytotoxicity is rated on a scale of:
o = no effect
3 = unacceptable
10 = 100% plant death
4. Control is rated on a scale of:
0 = no control
10 = complete control
WAA = weeks after application
5. SZ = Sphenoclea zeylanica
6. CD = Cyperus difformis
7. Sodium salt of 2,4-D.
203/2194
Table 12
Field Test Results of Compound 1 +
Bensulfuron methyl applied at 18 DAS1
for weed control in direct seeded rice
TREATMENTS GM.A.I. PHYTO WEED CONTROL
at at 6 WAA YIELD
/HA 2WAA SZ5 CI6 FM7 JL8 HA
COMPOUND 1 4 0 6.33 0.33 0 7.67 4.65
BENSULFURON 10 0 5.67 6.67 10 8.0 4.61
METHYL 15 0 6.67 9.0 9.67 7.67 4.49
20 0 5.67 9.33 10 9.50 4.61
30 0 9.67 9.67 10 8.67 5.17
COMPOUND 1+ 4+10 0 10 8.83 10 9.50 5.40
BENSULFURON 4+15 0 10 10 10 10 5.40
METHYL 4+20 0 10 9.63 9.67 10 5.06
COMPOUND 1+ 4+750 0 9.0 9.67 9.0 10 5.04 2,4-D (NA)9 2,4-D (NA) 1,500 0 4.67 9.33 9.33 10
4.59
UNTREATED O 0 0 0 0 0 4.31
1. DAS = Days after seeding
2. Application rate is stated in units of grams
active ingredient per hectare.
3. Phytotoxicity is rated on a scale of:
0 = no effect
3 = unacceptable
10 =100% plant death
WAA = weeks after application
4. Control is rated on a scale of:
0 = no control
10 = complete control
WAA = weeks after application
5.SZ =Sphenoclea zevlanica
6. CI = Cyperus iria
7. FM = Fimbristylismiliacea
8. JL = Jussiaea linifolia
9. Sodium salt of 2,4-D.
Table 13
Field Test Results of Compound 1 +
Bensulfuron methyl applied at 25 DAS1
for weed control in direct seeded rice
TREATMENTS GM.A.I. PHYTO WEED CONTROL4
at at 6 WAA YIELD
TONS/
/HA 2WAA SZ5Cl6 HA
COMPOUND 1 4 09e53 0 5.04
BENSULFURON 10 0 9.17 9.67 4.77
METHYL 150 9.80 9.83 4.85
20 0 9.50 10 5.40
30 0 9.93 10 5.51
COMPOUND 1 +4+10 0 10 9.5 5.57
BENSULFURON4+15 0 10in 5.51
METHYL4+20 0 9.83 10 5.34
COMPOUND 1+ 4+750 0 10 10 4.83 2,4-D (NA)7 2,4-D (NA) 1,500 0 6.67 10 4.59
UNTREATED - 0 0 0 4.27
1. DAS = Days after seeding
2. Application rate is stated in units of grams
active ingredient per hectare.
204/2194
3. Phytotoxicity is rated on a scale of:
0 = no effect
3 = unacceptable
10 = 100% plant death
WAA = weeks after application
4. Control is rated on a scale of:
0 = no control
10 = complete control
WAA = weeks after application
5. SZ = Spenocles zeylanica
6. CI = Cyperus iria
7. Sodium salt of 2,4-D
Field Test Results of Compound 1 +
Bensulfuron Methyl, Applied 7 DAS1,
for weed control in direct seeded rice in the
Philippines, average of 3 repetitions
PHYTO % WEED %BYG4 s SEDGE
TREATMENTS(1-9) COVER COVER COVER
G AI/HA 30 DAA 47 DAA 47 DAA 47 DAA
COMPOUND 1 1.65 + 1.7 20 18 5
BENSULFURON
METHYL 8.25
COMPOUND 1 2.40 + 2.3 28 17 3
BENSULFURON
METHYL 12.0
COMPOUND 1 3.33+ 4.3 3 3 0.5
BENSULFURON
METHYL 16.5
COMPOUND 1 1.65 2 29 26 5
COMPOUND 1 2.40 2.3 35 35 6
COMPOUND 1 3.33 3.3 35 35 4
COMPOUND 1 8.25 1.3 29 29 4
COMPOUND 1 12.0 1 20 17 2
COMPOUND 1 16.501.7 28 28 2
Untreated Check 1 46 27 18
1. DAS = Days after seeding
2. Application rate is stated in units of grams
active ingredient per hectare.
3. Phytotoxicity is rated on a scale of:
1 = no effect
9 = 100% plant death
DAA = days after application
4. Barnyardgrass(Echinochloa crus-palli)
Table 15
Effects of Compound 1 in Combination
With Thiobencarb, Dimepiperate,Esprocarb
and Dymron on Rice Growth
TREATMENT RATE CROP TOLERANCE5 (Nihonbere)
GAI/HA1 VA PH DW4
Compound 1 4 0 103 107
Compound 1 and Thiobencarb 4 + 21000 102 110
Comppund 1 and Dimepiperate 4+ 30000 104 110
Compound 1 and Esprocarb 4 + 21000 101 106
Compound 1 and Dymron 4 + 2100 0 102 101
Compound 1 8 3 95 83
Compound I and Thiobencarb 8+ 21000 101 108
Compound 1 and Dimepiperate 8+ 3000 0 103 103
Compound 1 and Esprocarb 8 + 2100 0.5 99 98
205/2194
Compound 1 and Dymron 8+ 2100 1.0 100 96
Thiobencarb 21000 102 112Dimepiperate 30000 102 106
Esprocarb 2100 0 92 94
Dymron 2100 0 102 107
Untreated - 0 100 100
1. Application rate in grams active ingredient per hectare.
2. Visual crop injury (relative to untreated check) scale of:
o to 100%
0 = no injury
100 =100% plant death.
3. Plant Height (relative to untreated check) on scale
of:
0 to100s.
4. Dry Weight (relative to untreated check) on scale
of:
0 to 100%.
5. Crop tolerance - Compounds were applied to transplanted rice
5 days after transplanting (var. Nihonbare) 2.0 to 2.2 leaf
stage. Ratings were taken 15 days after application. Results
are the average of three replications.
TABLE 16
Herbicidal Efficacy of Compound 1
in United States
RATE % CONTROL OF INJURY1
GAI/HA3 EA SE RICE
797 97 3
1498 98 10
21 9898 5 1. Evaluations made 57 days after application.
2. Abbreviations: EA = Eclipta alba
SE = Sesbania exaltata 3. Application rate in grams active ingredient
per hectare.
TABLE 17
Herbicidal Efficacy of Compound 1
and 2,4-D in Thailand
% CONTROL OF INJURY1
TREATMENT GAI/HA3 CD LL MC SZ RICE
Compound 1 4 100 87 100 100 16.6
Compound 1+ 4 100 100 100 100 24.42,4 D 750
1. Evaluations made 14 days after treatment.
2. Abbreviations: CD = Cyperus difformis
LL = Ludwigia linifolia
MV = Monochoria vaginalis
SZ =Sphenoclea zeylanica
3. Application rate in grams active ingredient
per hectare.
TABLE 18
Herbicidal Efficacy of Compound 1,
Benzsulfuron methyl and
2,4-D in Thailand
RATE % CONTROL OR INJURY1
206/2194
RATE 3
TREATMENT GAI/HA CD LL SZ RICE
Compound 1 4 100 100 98U
Bensulfuron 10 100 10099 0
methyl 15 100 100 1000
20 100 100 100 0
Compound 1 + 4 100 100 100 0
Hensulforen 10
methyl
Compound 1 + 4 100 100 100 0
Bensulfuron 15
methyl
Compound 1 + 4 100 100 1000
Bensulfuron 20
methyl 2,4-D 1500 100 100 90 0
Compound 1 + 4 100 100 1000 2,4-D 750
1. Evaluation made 13 days after treatment.
2. Abbreviations: CD = Cyperus difformis
LL - Ludwigia linifolia
SZ = Spenoclen Zevlanica
3. Application rate in grams active ingredient
per hectare.
TABLE 19
Herbicidal Efficacy of Compound 1
Benzsulfuron Methyl and 2,4-D in Thailand
RATE % CONTROL OR INJURY1
TREATMENT GAI/HA CD LL SZ RICE
Compound 1 4 10093 93 0
Bensulfuron 10 100100 88 Q
methyl 15 100 100 100 0
20 100 100 1000
Compound 1 + 4100 100 1000
Bensulfuron 10
methyl
Compound 1 + 4 100 100 1000
Bensulfuron 15
methyl
Compound 1+ 4 100 100 1000
Bensulfuron 20
methyl 2,4-D 1500 100 97 86 0
Compound 1+ 4 100100 100 0 2,4-D 750
1. Evaluation made 13 days after treatment.
2. Abbreviations: CD = Cuperus difformis
LL = Ludwigia linifolia
SZ = Sphenoclea zeylanica
3. Application rate in grams active ingredient
per hectare
TABLE 20
Herbicidal Efficacy of Compound 1,
benzsulfuron methyl and 2,4-D in Thailand
RATE % CONTROL OF INJURY1
TREATMENT GAI/HA CI FM LL SZ RICE
Compound 1 4 0 0 67 60 0
Bensulfuron 10 77 80 80 23 0
methyl 15 90 100 80 600
20 95 100 87 53 0
207/2194
Compound 1+ 4 95 100 98 97 0
Bensulfuron 10
methyl
Compound 1 + 4 100 100 100 100 0
Bensulfuron 15
methyl
Compound 1 + 4 98 90 100 97 0
Bensulfuron 20
methyl
Compound 1 4 95 90 100 88 0 2,4-D 750 2,4-D 1500 100 100 100 33.3 0
1. Evaluations made 14 days after treatment.
2. Abbreviations: CI = Cuperusiria
FM =Fimbristylis miliacea
LL = Ludwigialinifalia
SZ =Sohenoclea zevlanica
3. Application rate in grams active ingredient
per hectare.
TABLE 21
Herbicidal Efficacy of Compound1,
and 2,4-D in Malaysia
RATE % CONTROL OR INJURY
TREATMENT GAI/HA FM LA MC MV SG SS
Compound 1 4+ 330 28 89 78 100 100 63 +2,4-D
Compound 1 4 + 500 28 88 98 100 100 62 +2,4-D 2,4-D 1000 73 93 56100 74 55
1. Evaluations made 42 days after treatment.
2. Abbreviations: FM = Fimbristylis miliacea
LA = Ludwigia adscendens
MC = Masilea crenata
MV = Monochoria vaginalis
SG = Saggittaria guayanensis
SS = Scirpusspp.
3. Application rate in grams active ingredient
per hectare.
Table 22
Effects of Compound 1 in Combination
With Thiobencarb and Bensulfuron Methyl
on Rice Growth
TREATMENT RATE CROP TOLERANCE5
GAI/HA1 VA PH3 DW4
Compound 1 8 0.5 99 92
Compound5 and Thiobencarb 8 +2100 1.5 93 87
Compound 1 and Bensulfuron 8+ 75 3.5 62 65
methyl
Compound 1 and Thiobencarb, 8 + 21001.5 94 88
and Bensulfuron methyl+ 75
Bensulfuron 75 3.5 84 76
Bensulfuron methyl and 75 + 2100 1.5 94 83
Thiobencarb
Thiobencarb 21000 99 99
Untreated# 0 100 100
1. Application rate in grams active ingredient per hectare.
2. Visual crop injury (relative to untreated check) on scale of:
0 to 100%
208/2194
0 = no injury
100 = 100% plant death.
3. Plant height (relative to untreated check) on scale of:
0 to 100%.
4. Dry weight (relative to untreated check) on scale of:
0 to100%.
5. Crop tolerance - compounds were applied to transplanted rice
7 days after transplanting (var.Koshihikari) at the 2.0 to
2.2 leafstage. Ratings were made 21 days after application.
Results are the average of three replications.
Table 23
Effects of Compound 1 in Combination
With Bensulfuron Methyl and Thiobencarb
or Pretilachlor on Rice Growth
TREATMENT RATE CROPTOLERANCE
GAl/HA1 V PH3 DW4
Compound 1 2 3 86 73
Bensulfuron Methyl 25 2.5 89 79
Compound 1 and Bensulfuron 2 +25 3.5 86 69
methyl
Compound 1 Bensulfuron 8 + 252.5 87 73
methyl and Thiobencarb+ 2100
Compound 1 and Bensulfuron 2+ 25 2.5 90 72
methyl andPretilachior + 600
Thiobencarb 2100 2 93 81
Pretilachlor 600 3 87 71
Untreated -0 100 100
1. Application rate in grams active ingredient per hectare.
2. Visual crop injury (relative to untreated check) on scale of:
0 to100%
0 = no injury
100 = 100% plant death.
3. Plant height (relative to untreated check) on scale of:
0 to 100%.
4. Dry weight (relative to untreated check) on scale of:
0 to 100%.
5. Crop tolerance - compounds were applied to transplanted rice
7 days after transplanting (var.Koshihikari) at the 2.0
to2.2 leaf stage. Ratings were made 21 days after applica
tion. Results are the average of three replications.
Table 24
Effects of Compound 1 in Combination
With Bensulfuron Methyl and Thiobencarb
or Pretilachlor on Weed Control
TREATMENTS RATE WEED CONTROL RATINGS
GAI/HA1 EO CD4 MV5 BL6 SJ7 SP8 CS9
COMPOUND 1 2 1 10 10 10 7 8
BENSULFURON 25 1 1 10 10 5 8.5 6
METHYL
209/2194
COMPOUND 1 AND 2+ 4 10 10 10 9 8.5 8
BENSULFURON 25
METHYL
COMPOUND 1, 2 + 8 10 10 10 9 8.5 9
BENSULFURON 25 + 2100
METHYL AND THIOBENCARB
COMPOUND 1, 2 + 10 10 10 10 9 9 8
BENSULFURON 25 + 600
METHYL AND
PRETILACHLOR
THIOBENCARB 2100 10 10 10 9 7 0 9
PRETILACHLOR 600 1010 5 10 5 3 3
UNTREATED -0 O 00 0 0 0 0
1. Application rate in grams active ingredient per
hectare.
2. Visual weed control (relative to untreated check)
on scale of:
0 to 10
0 = no injury
10 = complete control.
3. EO = Echinochloa oryzicola
4. CD = Cyperus difformis
5. MV = Monochoria vaginalis
6. BL = Linderniapvxidaria
7. SJ = Scirpusjuncoides
8. SP = Sagittaria pygmea
9. CS = Cyperus serotinus
10. Weeds were treated at the 1.0 leaf stage and
evaluated four weeks later. Results are the
average of two replications.
Table 25
Effects of Compound 1 in Combination
With Bensulfuron Methyl and Thiobencarb
or Pretilachlor on Weed Control
WEED CONTROL RATINGS
TREATMENTS RATE
GM.A.I.1 EO CD4 MV5 BL6 SJ7 SP8 CS9
COMPOUND 1 2 1 710 10 6 8 0
BENSULFURON 25 1 10 9 9 5 8 2
METHYL
COMPOUND 1 AND 2+ 3 10 10 10 8.5 8.5 3
BENSULFURON 25
METHYL
COMPOUND 1, 2 + 5 10 10 10 9 8 6
BENSULFURON 25 + 2100
METHYL AND THIOBENCARB
COMPOUND 1, 2+ 6 10 10 10 9 8 3
BENSULFURON 25 + 600
METHYL AND
PRETILACHLOR
THIOBENCARS 2100 6 10 10 9.5 8.5 0 2
PRETILACHLOR 600 7 10 3 7 2 6 3UNTREATED - 0 0 0 O 0 0 O 0
1. Application rate in grams active ingredient per
hectare.
2. Visual weed control (relative to untreated check)
210/2194
on scale of:
0 to1O
0 = no injury
10 = complete control.
3. EO = Echinochloa oryzicola
4. CD = Cyperus difformis
5. MV = Monochoria vaginalis
6. BL =Lindernia pyxidaria
7. SJ = Scirpus juncoides
8. SP =Sagittaria pygmaea.
9. CS = Cyperusserotinus
10. Weeds were treated at the 2.0 leaf stage and
evaluated four weeks later. Results are the
average of two replications.
TABLE 26
Herbicidal Efficacy and Crop Tolerance of
Compound 1 and Compound 2 in a Greenhouse Test
RATE % CONTROL OR INJURY
TREATMENT GAI/HA1 M1013 LEMONT4 CD5 AT7 SR8
Compound 1 1 0 10 60 0 80 90
2 10 20 60 0 95 95
4 10 40 80 60 95 95
8 35 50 100 70 95 95
Compound 2 1 0 30 70 0 950
2 0 40 80 0 95 0
4 30 70lQ0 20 95 80
8 50 80 100 30 95 80
Untreated - 0 0 0 0 0 0
1. Application rate in grams active ingredient per
hectare.
2. Visual weed control or crop injury (relative
to untreated check) on scale of:
0 to 100%
0 = no injury
100 = 100% plant death.
3. M101 = japonica rice variety M101.
4. LEMONT = indica rice variety Lemont.
5. CD = Cyperus difformis
6. AP = Alternanthera philoxeroides
7. AT = Alisma triviale
8. SR -Sagittaria riida
9. Rice was transplanted at the 2.0 to 2.5 leaf stage
and treated 12 days later. Crop injury and weed
control ratings were made 24 days after treatment.
TABLE 27
Expected1 and Observed Activity of Combinations
of Compound 1 and Benzsulfuron Methyl on Weeds
Table/
Compound# Rate, Species Expected Observed 1+ Benzsulfuron 2 + 10 10/SZ 7.9 9.1
Methyl 2 + 10 10/CI 2.0 6.33
4 + 10 10/SZ 9.3 9.93
211/2194
4+ 10 10/CI 2.0 5.0
4+ 20 10/SZ 9.7 10
4+ 20 10/CI8.6 91 + Benzsulfuron 4+ 10 12/SZ 8.4 10
Methyl 4+ 15 12/SZ 8.8 10
4 + 20 12/SZ 8.4 10 1 + Benzsulfuron 4 + 10 12/C1 6.8 8.33
Methyl 4 + 15 12/CI 9.0 10
4 + 20 13/CI 9.4 9.63 1+ Benzsulfuron 4 + 15 12/JL 9.46 10
Methyl 4 + 20 12/JL 9.88 10 1 + Benzusulfuron 4 +15 20/CI 9.83 10
Methyl
I+ Benzsulfuron 4 + 10 20/CI 77 95
Methyl 4 + 10 20/FM8Q 100
4 + 10 20/LL 93.4 98
4 + 10 20/SZ 69.2 97 1 + Benzsulfuron 4 + 15 20/CL 90 100
Methyl 4 + 15 20/CL 93.4 100
4 + 15 20/S2 84100 1 + Benzsulfuron 4 + 20 20/CI 95 98
Methyl 4 + 20 20/LL 95.7 100
4 + 20 20/SZ 81.2 97 1 + Benzsulfuron 2 + 25 24/EO 1.9 4
Methyl 2 + 25 24/SJ 8.5 9 1 + Benzsulfuron 2 + 25 25/EO 1.9 3
Methyl 2 + 25 25/SJ 8.0 8.5
2 + 25 25/CS 2.0 3 1.Solby2 equation for calculating symergism.
E= A + B - A x B
100
E = expected value
A = observed value for Compound 1
B= observed value for benzsulfuron
if the observed value minus the expected value
is positive, the combination is considered
synergistic.
For example:
Table 20 A = 60 on SZ at 4 g/ha
B= 23 on SZ at 10 g/ha E = 60 + 23 - #####
E = 69.2
The observed value of Compound 1 in combination with
benzsulfuron methyl on sphenocleaieylanica
at the 4 and 10 g raterespectively is 97.
Observed - Expected
97 - 69.2 =+ 27.8 2. Kolby, S.R., Weeds 15:20-22, 1967.
TABLE 28
Expected and Observed Activity of Combinations
of Compound 1 and Benzsulfuron Methyl on Rice
Table
Compound Rate Species Expected Observed 1+ Benzsulfuron 2+ 25 23/Va 4.75 3.5
The expected injury to rice (as calculated by the
Kolby equation) is reduced by the combination of Compound No. 1 with benzsulfuron methyl This
constitutes a substantial safening of the rice crop.Data supplied from the esp@cenet database Worldwide
Claims:
Claims of corresponding document: WO8901289
CLAIMS
What is claimed is:
1. Compositions comprising mixtures of compounds of the formula
EMI53.1
wherein
212/2194
X is CH3 or OCH3;
Y is OCH3; and
Z is N or CH,
provided that when Z is CH then X is OCH3 and
when Z is N then X is CH3,
with compounds selected from 2,4-dichlorophenoxy
acetic acid, bensulfuron methyl, thiobencarb,
dimepiperate, esprocarb or dymron.
2 The compositions of Claim 1 comprising a compound of Formula I wherein Z is N with
bensulfuronmethyl
3. A method for controlling the growth of undesired vegetation in a rice crop by applying to the crop
after transplantation or emergence an effective amount of a compound of Claim 1 of Formula I
EMI53.2
wherein
X is CH3 or OCH3;
Y is OCH3; and
Z is N or CH,
provided that when Z is CH then X is OCH3 and
when Z is N then X is CH3.
4. The method of Claim 3 wherein Z is N, X is CH3 and Y is OCH3.
5. The method of Claim 3 wherein Z isGH, X and Y are OCH3.
6. The method of' Claim 4 wherein a herbicidally effective amount of 2,4-dichloro phenoxyacetic acid
is applied in admixture with the compound of Formula I.
7. The method of Claim 4 wherein a herbicidally effective amount of bensulfuron methyl is applied in
admixture with the compound of Formula
I.
8. The method of Claim 4 wherein a herbicidally effective amount ofS-F(4-chlorophenyl)methyl]diethylcarbamothioate (Thiobencarb) is applied in admixture with the compound of
FormulaI.
9. The method of Claim 4 wherein a herbicidally effective amount of S-1-methyll-phenylethylpiperidine-l-carbothioate (Dimepiperate) is applied in admixture with the compound of Formula I.
10. The method of Claim 4 wherein a herbicidally effective amount ofS-benzyl-N- ethyl-N-(1,2dimethyl)propylthiol carbamate (Esprocarb) is applied inadmixtuze with the compound of Formula I.
11. The method of Claim 4 wherein a herbicidally effective amount of1-(a,a-dimethyl- benzyl)-3-ptolylurea (Dymron) is applied in admixture with the compound of Formula I.Data supplied from the
esp@cenet database - Worldwide
213/2194
18. EP0493925
- 7/8/1992
PYRAZOLE DERIVATIVES HAVING HERBICIDAL ACTIVITY, THEIR
PREPARATION AND THEIR USE
URL EPO =
http://v3.espacenet.com/textdoc?F=3&CY=ep&LG=en&IDX=EP0493925
Inventor(s):
SUGAI SOJI (JP); MIO SHIGERU (JP); HONMA TOYOKUNI (JP); SAKAMOTO
TAKASHI (JP)
Applicant(s):
SANKYO CO (JP)
IP Class 4 Digits: A01N; C07D
IP Class:A01N43/56; C07D231/18
E Class: A01N47/38; C07D231/18; C07D231/28; C07D401/12; C07D403/12
Application Number:
EP19910311679 (19911216)
Priority Number: JP19910039784 (19910306); JP19910219620 (19910830); JP19900402675
(19901217)
Family: EP0493925
Equivalent:
JP5112532; EP0493925
Cited Document(s):
EP0014810
Abstract:
Abstract of EP0493925
Compounds of formula (I): >;CHEM; (in which: R>;1; and R>;2; are each hydrogen, optionally
substituted alkyl, optionally substituted alkenyl, alkynyl, alkoxy, aryl or pyridyl, or R>;1; and R>;2;
together represent alkylene; A and B are each hydrogen, halogen, optionally substituted alkyl,
optionally substituted alkenyl, optionally substituted alkoxy, alkylthio, alkylsulphonyl,
dialkylsulphamoyl, aliphatic carboxylic acyl, carboxy, -CONR>;a;R>;b; where R>;a; and R>;b; are
each hydrogen or alkyl, formyl or cyano groups; D represents optionally substituted phenyl, benzyl,
pyridyl or pyrimidinyl; and n is 0, 1 or 2; and salts and esters thereof) have valuable herbicidal
properties, and, since they are totally innocuous to rice plants, are especially useful for the treatment of
paddy fields.Description:
Description of EP0493925
The present invention relates to a series of new pyrazole derivatives having valuable herbicidal activity
and provides methods and compositions using these compounds, as well as processes for preparing
them.
The purpose of herbicides in agriculture and horticulture is to kill unwanted plants (weeds), whilst
leaving untouched plants which are wanted (crops). A herbicide is of restricted practical use if it is
lethal to all plants. Accordingly, for maximum practical effect, it is desirable to target not only specific
weeds, but also the desired crop, to ensure that the herbicide is lethal to the weeds and inactive against
the crops. We have now discovered a series of pyrazole derivatives which have this effect.
A number of pyrazole derivatives have previously been described and said to have herbicidal activity.
For example, UK Patent Specification No. 1 488 285 and US Patent Specification No. 4 008 249
214/2194
disclose compounds of this general type which are said to be useful as herbicides, whilst European
Patent Specification No. 14 810 discloses such compounds for the protection of plants from "pests",
primarily insects, i.e. the compounds are presented as insecticides. However, the closest prior art to the
present invention is believed to be European Patent Specification No. 7 990 (equivalent to US Patent
Specifications No. 4 316 040 and 4 298 749), which discloses a wide class of compounds (embracing
some of those of the present invention) which are said to have herbicidal activity.
In accordance with the present invention, we have now discovered that a limited class of pyrazole
compounds has excellent herbicidal activity against a wide range of weeds (significantly better than
that of the prior art) whilst exhibiting no harmful effects on crop plants, notably rice.
The compounds of the present invention are those compounds of formula (I): EMI2.1 in which:
R>;1; and R>;2; are the same or different and each represents:
a hydrogen atom,
an unsubstituted alkyl group which has from 1 to 6 carbon atoms,
a substituted alkyl group which has from 1 to 6 carbon atoms and which is substituted by at least one
of substituents (a), defined below,
an unsubstituted alkenyl group having from 2 to 6 carbon atoms,
a substituted alkenyl group which has from 2 to 6 carbon atoms and which is substituted by at least
one halogen substituent,
an alkynyl group which has from 2 to 6 carbon atoms,
an alkoxy group which has from 1 to 6 carbon atoms,
a carbocyclic aryl group which has from 6 to 14 ring carbon atoms and which is unsubstituted or is
substituted by at least one of substituents (b), defined below, or
a pyridyl group which is unsubstituted or is substituted by at least one of substituents (b), defined
below,
or R>;1; and R>;2; together represent an alkylene group having from 4 to 7 carbon atoms;
A and B are the same or different and each represents:
a hydrogen atom,
a halogen atom,
an unsubstituted alkyl group which has from 1 to 6 carbon atoms,
a substituted alkyl group which has from 1 to 6 carbon atoms and which is substituted by at least one
of substituents (c), defined below,
an unsubstituted alkenyl group which has from 2 to 6 carbon atoms,
a substituted alkenyl group which has from 2 to 6 carbon atoms and which is substituted by at least
one halogen substituent,
an alkoxy group which has from 1 to 6 carbon atoms,
a substituted alkoxy group which has from 1 to 6 carbon atoms and which is substituted by at least
one of substituents (a), defined below,
an alkylthio group which has from 1 to 6 carbon atoms,
an alkylsulphonyl group which has from 1 to 6 carbon atoms,
a dialkylsulphamoyl group in which the alkyl parts are the same or different and each represents an
alkyl group having from 1 to 4 carbon atoms,
an aliphatic carboxylic acyl group which has from 2 to 7 carbon atoms and which is unsubstituted or
is substituted by at least one of substituents (a), defined below,
a carboxy group,
a group of formula -CONR>;a;R>;b;, in which R>;a; and R>;b; are the same or different and each
represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms,
a formyl group, or
a cyano group;
D represents a group of formula (II), (III) or (IV): EMI4.1 EMI4.2 EMI4.3 in which:
X, Y and Z are the same or different and each represents
a halogen atom,
an unsubstituted alkyl group which has from 1 to 6 carbon atoms,
a substituted alkyl group which has from 1 to 6 carbon atoms and which is substituted by at least one
of substituents (a), defined below,
an alkoxy group which has from 1 to 6 carbon atoms,
a substituted alkoxy group which has from 1 to 6 carbon atoms and which is substituted by at least
one halogen substituent,
215/2194
an alkylthio group which has from 1 to 6 carbon atoms,
a substituted alkylthio group which has from 1 to 6 carbon atoms and which is substituted by at least
one halogen substituent,
an alkylsulphonyl group which has from 1 to 6 carbon atoms,
a substituted alkylsulphonyl group which has from 1 to 6 carbon atoms and which is substituted by at
least one halogen substituent,
an aryloxy group in which the aryl part is a carbocyclic aryl group which has from 6 to 14 ring
carbon atoms and is unsubstituted or is substituted by at least one of substituents (b), defined below,
an aralkyl group in which the alkyl part has from 1 to 4 carbon atoms and the aryl part is a
carbocyclic aryl group which has from 6 to 14 ring carbon atoms and which is unsubstituted or are
substituted by at least one of substituents (b), defined below,
a carboxy group,
a nitro group, or
a cyano group;
m is 0 or 1;
k is 0 or an integer from 1 to 5, and, where k is an integer from 2 to 5, the groups and atoms
represented by X may be the same or different;
j is 0 or an integer from 1 to 4, and, where j is an integer from 2 to 4, the groups and atoms represented
by Y may be the same or different;
i is 0 or an integer from 1 to 3, and, where i is an integer from 2 to 3, the groups and atoms represented
by Z may be the same or different;
n is 0, 1 or 2;
substituents (a) are halogen atoms and/or alkoxy groups having from 1 to 6 carbon atoms; ;
substituents (b) are halogen atoms and/or alkyl groups having from 1 to 6 carbon atoms and/or alkoxy
groups having from 1 to 6 carbon atoms; and
substituents (c) are selected from:
halogen atoms,
hydroxy groups,
alkoxy groups which have from 1 to 6 carbon atoms,
aliphatic acyl groups having from 2 to 7 carbon atoms,
halogenated aliphatic acyl groups having from 2 to 7 carbon atoms,
aromatic acyl groups in which the aryl part is a carbocyclic aryl group which has from 6 to 14 ring
carbon atoms and is unsubstituted or is substituted by at least one of substituents (b), defined above,
alkoxycarbonyl groups in which the alkoxy part has from 1 to 4 carbon atoms,
alkenyloxycarbonyl groups in which the alkenyl part has from 2 to 4 carbon atoms, and
aralkyloxycarbonyl groups in which the alkyl part has from 1 to 4 carbon atoms and the aryl part is a
carbocyclic aryl group which has from 6 to 14 ring carbon atoms and which is unsubstituted or are
substituted by at least one of substituents (b), defined above;
and salts and esters thereof.
The invention also provides a herbicidal composition comprising an effective amount of a herbicidal
agent in admixture with an agriculturally or horticulturally acceptable carrier or diluent, wherein the
herbicidal agent is at least one compound selected from compounds of formula (I) and salts and esters
thereof.
The invention still further provides a method of destroying weeds by administering a herbicidal agent
to a locus including said weeds, wherein the herbicidal agent is at least one compound of formula (I) or
a salt or ester thereof.
The invention still further provides the use of a compound of formula (I) or a salt or ester thereof for
destroying weeds.
The invention also provides processes for preparing the compounds of the present invention which are
described in more detail hereafter.
In the compounds of the present invention, where R>;1;, R>;2;, X, Y or Z represents an alkyl group
having from 1 to 6 carbon atoms, this may be a straight or branched chain group having from 1 to 6,
preferably from 1 to 5, carbon atoms, and examples include the methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1-ethylpropyl, 4-methylpentyl,
216/2194
3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, hexyl and
isohexyl groups. Of these, we prefer those alkyl groups having from 1 to 4 carbon atoms, preferably the
methyl, ethyl, propyl, isopropyl, butyl and isobutyl groups, and most preferably the methyl, ethyl and
propyl groups.In the case of Y and Z, we particularly prefer those alkyl groups having 1 or 2 carbon
atoms, the methyl and ethyl groups, and most prefer the methyl group.
In the case of A and B, where they represent an alkyl group having from 1 to 6 carbon atoms, this may
be a straight or branched chain group, for example the methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl, t-butyl, pentyl, isopentyl, 2-methylbutyl, neopentyl and 1-ethylpropyl groups, preferably a
straight or branched chain alkyl group having from 1 to 3 carbon atoms, more preferably 1 or 2 carbon
atoms.
Such alkyl groups included in the definitions of R>;1;, R>;2;, A, B, X, Y or Z may be unsubstituted or
they may be substituted by one or more substituents, selected, in the case of R>;1;, R>;2;, X, Y and Z,
from substituents (a), or, in the case of A and B, from substituents (c), both of which are as defined
above, and examples of which include::
halogen atoms, such as the fluorine, chlorine, bromine and iodine atoms, preferably the fluorine,
chlorine or bromine atoms, and most preferably the fluorine or chlorine atoms;
alkoxy groups, which may be straight or branched chain groups, having from 1 to 6, preferably from 1
to 4, carbon atoms, such as the methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy
and t-butoxy groups, of which we prefer those straight or branched chain alkoxy groups having from 1
to 3 carbon atoms, most preferably the methoxy group;
and, in the case of substituents (c), hydroxy groups.
The aliphatic acyl groups, halogenated aliphatic acyl groups, aromatic acyl groups, alkoxycarbonyl
groups, alkenyloxycarbonyl groups, and aralkyloxycarbonyl groups which are included in substituents
(c) are all as exemplified hereafter in relation to the groups which may be represented by R>;8;.
Where these alkyl groups are substituted, there is no specific limitation upon the number of
substituents, except such as may be imposed by the number of substitutable positions or possibly by
steric constraints. However, in general, we prefer from 1 to 3 substituents. The same applies likewise to
other substituted groups referred to herein where the number of substituents is not otherwise specified.
Where there are two or more such substituents, these may be the same or different.
Where R>;1;, R>;2;, A or B represents an alkenyl group, this may be a straight or branched chain
group having from 2 to 6, preferably from 3 to 6, more preferably from 3 to 5 and most preferably 3 or
4, carbon atoms, and examples include the vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl,
3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,
2-ethyl-2-propenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,
1-hexenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-pentenyl,
1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 4-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 2hexenyl, 3-hexenyl, 4-hexenyl and 5-hexenyl groups, of which the vinyl, allyl, methallyl, 1-propenyl,
isopropenyl and butenyl groups are preferred, the allyl (2-propenyl) group being most preferred.
Such groups may be unsubstituted or they may be substituted by one or more halogen atoms, for
example as exemplified in relation to substituents (a) and (c). Where they are substituted, there is no
specific limitation upon the number of substituents, except such as may be imposed by the number of
substitutable positions or possibly by steric constraints. However, in general, we prefer from 1 to 3
substituents. An example of a preferred substituted group is the 2-chloroallyl group.
Where R>;1; or R>;2; represents an alkynyl group having from 2 to 6 carbon atoms, this may be a
straight or branched chain group having from 2 to 6, preferably from 3 to 6, more preferably from 3 to
5 and most preferably 3 or 4, carbon atoms, and examples include the ethynyl, propargyl (2-propynyl),
1-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-2-propynyl, 1-pentynyl,
2-pentynyl, 3-pentynyl, 4-pentynyl, 2-ethyl-2-propynyl, 1-methyl-2-butynyl, 2-methyl-2-butynyl, 1ethyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-ethyl-3-butynyl, 2-hexynyl, 3-hexynyl, 4hexynyl, 5-hexynyl 1-methyl-2-pentynyl, 2-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-
217/2194
pentynyl, 1-methyl-4-pentynyl and 2-methyl-4-pentynyl groups, of which the propynyl and butynyl
groups are preferred, the propargyl and 2-butynyl groups being most preferred.
Where R>;1;, R>;2;, A, B, X, Y or Z represents an alkoxy group having from 1 to 6 carbon atoms, this
may be a straight or branched chain group having from 1 to 6, preferably from 1 to 4, carbon atoms,
and examples include the methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tbutoxy, pentyloxy, isopentyloxy, 2-methylbutyloxy, neopentyloxy, hexyloxy, 4-methylpentyloxy, 3methylpentyloxy, 2-methylpentyloxy, 3,3-dimethylbutyloxy, 2,2-dimethylbutyloxy, 1,1dimethylbutyloxy, 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy and 2,3-dimethylbutyloxy groups, of
which those straight or branched chain alkoxy groups containing 1 to 4 carbon atoms are preferred, the
methoxy and isopropoxy groups being most preferred.In the case of A and B, where they represent one
of these groups, the group may be unsubstituted or it may be substituted by one or more (preferably
from 1 to 3) of substituents (a), defined and exemplified above. In the case of X, Y and Z, where they
represent one of these groups, the group may be unsubstituted or it may be substituted by one or more
(preferably from 1 to 3) halogen substituents, e.g. as defined and exemplified above.
Where R>;1; or R>;2; represents a carbocyclic aryl group, this has from 6 to 14, preferably from 6 to
10, ring carbon atoms and is unsubstituted or is substituted by at least one of substituents (b), defined
and exemplified above. Examples of the unsubstituted aryl groups are those aromatic hydrocarbon
groups containing from 6 to 14 carbon atoms, for example the phenyl, indenyl, naphthyl, phenanthrenyl
and anthracenyl groups, preferably the phenyl or naphthyl groups (1- or 2- naphthyl), and more
preferably the phenyl group. Such groups may also, if desired be substituted by one or more of
substituents (b), defined above.Examples of these substituents include the halogen atoms and alkoxy
groups exemplified in relation to substituents (a) and (c), and alkyl groups having from 1 to 6 carbon
atoms, such as the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl,
2-methylbutyl, neopentyl and 1-ethylpropyl groups, preferably a straight or branched chain alkyl group
having from 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms. There is no specific limitation
on the number of substituents, except such as may be imposed by the number of substitutable positions
(e.g. 5 in the case of the phenyl group or 7 in the case of the naphthyl group) or possibly by steric
constraints. However, in general, from 1 to 3 substituents are preferred. If there are two or more
substituents, these may be the same or different.Specific examples of preferred substituted groups
include the 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl,
2,4,5-trichlorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dichloro-3-methylphenyl,
4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl and 3-chloro-4-methoxyphenyl groups.
Where R>;1; or R>;2; represents a pyridyl group, this may be the 2-pyridyl, 3-pyridyl or 4-pyridyl
group and may be substituted or unsubstituted. If substituted, the substituents are selected from
substituents (b), as defined and exemplified above. There is no specific limitation on the number of
substituents, except such as may be imposed by the number of substitutable positions (i.e. 4) or
possibly by steric constraints. However, in general, from 1 to 3 substituents are preferred. If there are
two or more substituents, these may be the same or different. Specific examples of preferred substituted
groups include the 3,5-dichloro-2-pyridyl, 4-chloro-5-methyl-2-pyridyl, 4-methoxy-2-pyridyl and 5chloro-2-pyridyl groups.
Alternatively, R>;1; and R>;2; together may represent a straight or branched chain alkylene group
having from 4 to 7 carbon atoms, so as to form with the nitrogen atom to which they are attached a
nitrogen-containing heterocyclic ring having from 5 to 8 ring atoms and optionally having fewer ring
atoms but substituted by one or more lower alkyl groups. Examples of such alkylene groups include the
tetramethylene, 1-methyltetramethylene, 2-methyltetramethylene, 3-methyltetramethylene,
pentamethylene, 1,4-dimethylpentamethylene, hexamethylene, 1-methylhexamethylene and
heptamethylene groups, of which we prefer the straight chain alkylene groups containing 4 or 5 carbon
atom, most preferably the tetramethylene group.
Where A, B, X, Y or Z represents an alkylthio group, this has from 1 to 6 carbon atoms and may be a
straight or branched chain group. Examples of such groups include the methylthio, ethylthio,
propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, t-butylthio, pentylthio, isopentylthio, 2methylbutylthio, neopentylthio, 1-ethylpropylthio, hexylthio, 4-methylpentylthio, 3-methylpentylthio,
2-methylpentylthio, 1-methylpentylthio, 3,3-dimethylbutylthio, 2,2-dimethylbutylthio, 1,1dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,3-dimethylbutylthio and 2-
218/2194
ethylbutylthio groups, of which we prefer the straight and branched chain alkylthio groups containing
from 1 to 3 carbon atoms, and most prefer the methylthio or ethylthio group.
Where A, B, X, Y or Z represents an alkylsulphonyl group, this has from 1 to 6 carbon atoms and may
be a straight or branched chain group. Examples of such groups include the methylsulphonyl,
ethylsulphonyl, propylsulphonyl, isopropylsulphonyl, butylsulphonyl, isobutylsulphonyl, secbutylsulphonyl, t-butylsulphonyl, pentylsulphonyl, isopentylsulphonyl, 2-methylbutylsulphonyl,
neopentylsulphonyl, 1-ethylpropylsulphonyl, hexylsulphonyl, 4-methylpentylsulphonyl, 3methylpentylsulphonyl, 2-methylpentylsulphonyl, 1-methylpentylsulphonyl, 3,3dimethylbutylsulphonyl, 2,2-dimethylbutylsulphonyl, 1,1-dimethylbutylsulphonyl, 1,2dimethylbutylsulphonyl, 1,3-dimethylbutylsulphonyl, 2,3-dimethylbutylsulphonyl and 2ethylbutylsulphonyl groups, of which we prefer the straight or branched chain alkylsulphonyl groups
having from 1 to 3 carbon atoms, and most prefer the methylsulphonyl or ethylsulphonyl group.
In the case of X, Y and Z, the above alkylthio and alkylsulphonyl groups may be unsubstituted or they
may have one or more (preferably from 1 to 3) halogen substituents, e.g. as exemplified above,
preferably fluorine atoms. Examples of such substituted groups include the trifluoromethylthio and
trifluoromethylsulphonyl groups.
Where A or B represents a dialkylsulphamoyl group, this is a group of formula -SO2NR>;c;R>;d;, in
which R>;c; and R>;d;, which may be the same or different (although they are preferably the same),
each represents an alkyl group having from 1 to 4 carbon atoms. Examples of such groups include the
dimethylsulphamoyl, diethylsulphamoyl, N-ethyl-N-propylsulphamoyl, dipropylsulphamoyl,
diisopropylsulphamoyl, N-methylpropyl-N-sulphamoyl and N-methyl-N-butylsulphamoyl groups, of
which we prefer those groups in which R>;c; and R>;d; both represent alkyl groups having from 1 to 3
carbon atoms, and most prefer the dimethylsulphamoyl group.
Where A or B represents an aliphatic carboxylic acyl group, this has, in total, from 2 to 7 carbon atoms
and may be a saturated or unsaturated (referring to carbon-carbon bonds) group; it is preferably an
alkylcarbonyl group, in which the alkyl part has from 1 to 6 carbon atoms, more preferably from 1 to 4
carbon atoms. Examples of such groups include the acetyl, propionyl, butyryl, isobutyryl, valeryl,
isovaleryl, 2-methylbutyryl and pivaloyl groups, of which we prefer those groups having, in total, from
1 to 3 carbon atoms, and most prefer the acetyl group.
Where A, B, X, Y or Z represents a carboxy group, the resulting compound can form esters. There is,
in principle, no limitation upon the nature of such esters, provided that, where the compound as such is
to be used in agricultural or horticultural treatment, the ester group does not increase the toxicity of the
compounds to useful plants or does not do so to an unacceptable extent. Examples of preferred esters
include the lower alkyl esters having from 1 to 6, preferably from 1 to 4 carbon atoms, for example, the
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and t-butyl esters, of which we prefer alkyl
esters having from 1 to 3 carbon atoms, and most prefer the ethyl esters. However, as is well known in
the art, a wide range of esters may be formed using a variety of ester groups which form part of the
common general knowledge.
Where A or B represents a group of formula -CONR>;a;R>;b;, R>;a; and R>;b;, which may be the
same or different, each represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms,
preferably an alkyl group. These groups are the carbamoyl, alkylcarbamoyl and dialkylcarbamoyl
groups, for example the methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyl,
dimethylcarbamoyl, diethylcarbamoyl, N-ethyl-N-Propylcarbamoyl, dipropylcarbamoyl,
diisopropylcarbamoyl, N-methyl-N-propylcarbamoyl and N-methyl-N-butylcarbamoyl groups, of
which we prefer the dialkylcarbamoyl groups, especially those having two alkyl groups, which may be
the same or different, which each have from 1 to 3 carbon atoms, and most prefer the
dimethylcarbamoyl group.
Where X, Y or Z represents an aryloxy group, the aryl part of this may be as defined and exemplified
above in relation to the aryl groups which may be represented by R>;1; or R>;2;, and examples of the
unsubstituted groups include the phenoxy, indenyloxy, naphthyloxy (1- or 2- naphthyloxy),
phenanthrenyloxy and anthracenyloxy groups, of which we prefer the phenoxy and naphthyloxy
groups, and most prefer the phenoxy group. Examples of substituted groups include the aryloxy
219/2194
equivalents of the substituted aryl groups exemplified above in relation to the aryl groups which may
be represented by R>;1; or R>;2;.
Where X, Y or Z represents an aralkyl group, the alkyl part of this group has from 1 to 4 carbon atoms,
and the aryl part may be as defined and exemplified above in relation to the aryl groups which may be
represented by R>;1; or R>;2;. Examples of the unsubstituted groups include the benzyl, 2-phenylethyl,
1-phenylethyl, 3-phenylpropyl, 2-phenylpropyl, 1-phenylpropyl, 4-phenylbutyl, 3-phenylbutyl, 2phenylbutyl, 1-phenylbutyl, alpha -naphthylmethyl and beta -naphthylmethyl groups, of which we
prefer those groups in which the alkyl part has from 1 to 3 carbon atoms and the aryl part is a phenyl or
naphthyl (preferably phenyl) group, and most prefer the benzyl group, or substituted equivalents as
exemplified above in relation to the aryl groups which may be represented by R>;1; or R>;2;.
When D represents a group of formula (II) and m is 1, this is an optionally substituted benzyl group;
and, where m is 0, this is an optionally substituted phenyl group. These groups may be substituted by
the groups or atoms represented by X at any free position, for example, at the 2-, 3-, 4-, 2,3-, 2,4-, 2,5-,
2,6-, 3,4-, 3,5-, 2,4,6-, 3,4,6-, 3,4,5-, 2,3,5-, 2,3,4-, 2,3,5,6-, 2,3,4,6- or 2,3,4,5,6- positions. k may be 0
or an integer from 1 to 5, but is preferably 0 or an integer from 1 to 3. Where k is greater than 1, the
groups or atoms represented by X may be the same or different.
Where D represents a group of formula (III), this is an optionally substituted pyridyl group, which may
be attached to the remainder of the molecule via any of its carbon atoms, i.e. it may be a 2-pyridyl, 3pyridyl or 4-pyridyl group, preferably a 2-pyridyl or 4-pyridyl group. Where j is an integer of from 1 to
4, the group is substituted by one or more of the groups and atoms defined by Y, and may be
substituted at any free position, for example the 3-, 5-, 6- or 3,5- positions. j may be 0 or an integer
from 1 to 4, but is preferably 0, 1 or 2. Where j is greater than 1, the groups or atoms represented by Y
may be the same or different.
Where D represents a group of formula (IV), this is an optionally substituted pyrimidin-2-yl group.
Where i is an integer of from 1 to 3, the group is substituted by one or more of the groups and atoms
defined by Z, and may be substituted at any free position, for example the 4-, 5- or 4,6- positions. i may
be 0 or an integer from 1 to 3, but is preferably 0, 1 or 2. Where i is greater than 1, the groups or atoms
represented by Z may be the same or different.
Of the compounds of the present invention, we prefer those in which each of R>;1; and R>;2;, which
may be the same or different, represents:
an alkyl group having from 1 to 6 carbon atoms;
an alkenyl group having from 3 to 6 carbon atoms;
an alkynyl group having from 3 to 6 carbon atoms; or
an aryl group which has from 6 to 10 carbon atoms and is unsubstituted or is substituted by at least
one of substituents (b), defined above;
or R>;1; and R>;2; together represent an alkylene group having from 4 to 6 carbon atoms.
More preferably, each of R>;1; and R>;2;, which may be the same or different, represents:
an alkyl group having from 1 to 4 carbon atoms;
an alkenyl group having 3 or 4 carbon atoms; or
an alkynyl group having 3 or 4 carbon atoms;
or R>;1; and R>;2; together represent an alkylene group having from 4 to 6 carbon atoms.
Most preferably, each of R>;1; and R>;2;, which may be the same or different, represents:
an alkyl group having from 1 to 4 carbon atoms;
an alkenyl group having 3 or 4 carbon atoms; or
or R>;1; and R>;2; together represent an alkylene group having from 4 to 6 carbon atoms.
We also particularly prefer those compounds of the present invention in which A represents:
a hydrogen atom;
a halogen atom;
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by at
least one of substituents (c), defined above;
an alkenyl group having from 3 to 6 carbon atoms; or
220/2194
a cyano group.
More preferably, A represents:
a hydrogen atom;
a halogen atom;
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by
from 1 to 3 of substituents (a), defined above; or
a cyano group.
Most preferably, A represents a hydrogen atom, a halogen atom or a cyano group.
We also particularly prefer those compounds of the present invention in which B represents:
a hydrogen atom;
a halogen atom;
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by at
least one of substituents (c), defined above;
an alkoxy group which has from 1 to 6 carbon atoms; or
a cyano group.
More preferably, B represents:
a hydrogen atom;
a halogen atom;
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by at
least one of substituents (c), defined above; or
a cyano group.
Most preferably, B represents a hydrogen atom, a halogen atom or a cyano group, in particular a
fluorine atom.
Of the groups of formulae (II), (III) and (IV), we prefer that D should represent a group of formula (II)
or (III), more preferably a group of formula (II) in which m is 0 or a group of formula (III), and most
preferably a group of formula (II) in which m is 0.
In the compounds of formula (I), n can be: 0, in which case the compound is a thio compound; 1, in
which case the compound is a sulphinyl compound; or 2, in which case the compound is a sulphonyl
compound. We prefer that n should be 0 or 2, most preferably 2.
In the case of the compounds of formula (I) in which D represents a group of formula (II), we prefer
that X should represent:
a halogen atom;
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by at
least one of substituents (a), defined above;
an alkoxy group which has from 1 to 6 carbon atoms;
an alkoxycarbonyl group which has from 2 to 5 carbon atoms; or
a cyano group.
More preferably, X represents:
a halogen atom;
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by
from 1 to 3 substituents selected from substituents (a), defined above;
an alkoxy group which has from 1 to 6 carbon atoms; or
a cyano group.
Most preferably, X represents:
a halogen atom;
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by
from 1 to 3 of substituents (a), defined above; or
an alkoxy group which has from 1 to 6 carbon atoms.
221/2194
In the case of the compounds of formula (I) in which D represents a group of formula (III), we prefer
that Y should represent:
a halogen atom;
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by at
least one of substituents (a), defined above; or
an alkoxy group which has from 1 to 6 carbon atoms.
More preferably Y represents a halogen atom or an alkyl group which has from 1 to 6 carbon atoms
and which is unsubstituted or is substituted by from 1 to 3 of substituents (a), defined above.
In the case of the compounds of formula (I) in which D represents a group of formula (IV), we prefer
that Z should represent: a halogen atom; an alkyl group which has from 1 to 6 carbon atoms; or an
alkoxy group which has from 1 to 6 carbon atoms. More preferably Z represents a halogen atom or an
alkyl group which has from 1 to 6 carbon atoms, and most preferably Z represents an alkyl group
which has from 1 to 6 carbon atoms.
Substituents (a) preferably comprise halogen atoms.
Substituents (b) preferably comprise a halogen atom and/or an alkyl group which has from 1 to 6
carbon atoms, more preferably a halogen atom.
Substituents (c) preferably comprise a halogen atom or a hydroxy group, more preferably a halogen
atom.
The preferred compounds of the present invention are those compounds of formula (I), in which:
R>;1; and R>;2; are the same or different and each represents:
an alkyl group which has from 1 to 6 carbon atoms,
an alkenyl group which has from 3 to 5 carbon atoms,
an alkynyl group which has from 3 to 5 carbon atoms, or
an aryl group which has from 6 to 10 ring atoms and which is unsubstituted or is substituted by from
1 to 3 substituents selected from halogen atoms and alkyl groups which have from 1 to 4 carbon atoms,
or R>;1; and R>;2; together represent an alkylene group which has from 4 to 7 carbon atoms;
A represents::
a hydrogen atom,
a halogen atom,
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by
from 1 to 3 substituents selected from halogen atoms and hydroxy groups,
an alkenyl group which has from 3 to 5 carbon atoms, or
a cyano group;
B represents:
a hydrogen atom,
a halogen atom,
an alkyl group which has from 1 to 6 carbon atoms and which is unsubstituted or is substituted by
from 1 to 3 substituents selected from halogen atoms and hydroxy groups,
an alkoxy group which has from 1 to 6 carbon atoms, or
a cyano group;
D represents a group of formula (II): EMI24.1 in which:
X represents
a halogen atom,
an unsubstituted alkyl group which has from 1 to 6 carbon atoms,
a substituted alkyl group which has from 1 to 6 carbon atoms and which is substituted by from 1 to 3
of substituents (a), defined above, an alkoxy group which has from 1 to 6 carbon atoms,
an alkoxycarbonyl group which has from 2 to 7 carbon atoms, or
a cyano group;
m is 0 or 1; and
k is as defined above;
or
D represents a group of formula (III): EMI24.2 in which:
Y represents
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a halogen atom,
an unsubstituted alkyl group which has from 1 to 6 carbon atoms,
a substituted alkyl group which has from 1 to 6 carbon atoms and which is substituted by from 1 to 3
of substituents (a), defined above,
an alkoxy group which has from 1 to 6 carbon atoms, and
j is as defined above; and
n is 0 or 2;
and salts and esters thereof.
More preferred compounds of the present invention are those compounds of formula (I) in which:
R>;1; and R>;2; are the same or different and each represents an alkyl group which has from 1 to 6
carbon atoms, an alkenyl group which has from 3 to 5 carbon atoms or an alkynyl group which has
from 3 to 5 carbon atoms, or R>;1; and R>;2; together represent an alkylene group which has from 4 to
7 carbon atoms;
A represents a hydrogen atom or a halogen atom;
B represents a hydrogen atom, a halogen atom or a cyano group;
n is 2; and
D represents a group of formula (II): EMI26.1 in which:
X represents
a halogen atom,
an unsubstituted alkyl group which has from 1 to 6 carbon atoms,
a substituted alkyl group which has from 1 to 6 carbon atoms and which is substituted by from 1 to 3
halogen substituents,
an alkoxy group which has from 1 to 6 carbon atoms, or
a cyano group;
m is 0; and
k is as defined above;
or
D represents a group of formula (III): EMI26.2 in which:
Y represents
a halogen atom,
an unsubstituted alkyl group which has from 1 to 6 carbon atoms, or
a substituted alkyl group which has from 1 to 6 carbon atoms and which is substituted by from 1 to 3
halogen substituents, and
j is as defined above;
and salts and esters thereof.
The most preferred compounds of the present invention are those compounds of formula (I) in which:
R>;1; and R>;2; are the same or different and each represents an alkyl group having from 1 to 6
carbon atoms;
A represents a hydrogen atom;
B represents a hydrogen atom or a halogen atom;
n is 2; and
D represents a group of formula (II): EMI27.1 in which:
X represents
a halogen atom,
an unsubstituted alkyl group which has from 1 to 6 carbon atoms,
a substituted alkyl group which has from 1 to 6 carbon atoms and which is substituted by from 1 to 3
halogen substituents, or
an alkoxy group which has from 1 to 6 carbon atoms,;
m is 0; and
k is as defined above;
and salts and esters thereof.
In all of the compounds of the present invention, including the preferred, more preferred and most
preferred classes of compounds described above, it is considered especially advantageous that B should
represent a fluorine atom, i.e. the 4-fluoropyrazole derivatives are most preferred.
223/2194
Those compounds of the present invention which contain a carboxy group or a pyridyl or pyrimidinyl
group can form salts. There is no particular restriction on the nature of these salts, provided that, where
they are intended for agricultural or horticultural use, they are agriculturally or horticulturally
acceptable. Where they are intended for non-agricultural or horticultural uses, e.g. as intermediates in
the preparation of other, and possibly more active, compounds, even this restriction does not apply. The
compounds of the present invention can form salts with bases.Examples of such salts which may be
formed by compounds containing a carboxy group include: salts with an alkali metal, such as sodium,
potassium or lithium; salts with an alkaline earth metal, such as barium or calcium; salts with another
metal, such as magnesium and aluminium; organic base salts, such as a salt with dicyclohexylamine;
and salts with a basic amino acid, such as lysine or arginine. Where the compound of the present
invention contains a basic group in its molecule, i.e. compounds containing a pyridyl or pyrimidinyl
group, it can form acid addition salts.Examples of such acid addition salts include: salts with mineral
acids, especially hydrohalic acids (such as hydrofluoric acid, hydrobromic acid, hydroiodic acid or
hydrochloric acid), nitric acid, carbonic acid, sulphuric acid or phosphoric acid; salts with lower
alkylsulphonic acids, such as methanesulphonic acid, trifluoromethane- sulphonic acid or
ethanesulphonic acid; salts with arylsulphonic acids, such as benzenesulphonic acid or ptoluenesulphonic acid; salts with organic carboxylic acids, such as acetic acid, fumaric acid, tartaric
acid, oxalic acid, maleic acid, malic acid, succinic acid or citric acid; and salts with amino acids, such
as glutamic acid or aspartic acid.
Specific examples of individual compounds of the present invention are shown in the following
formulae (I-1), (I-2) and (I-3): EMI30.1 EMI30.2 EMI30.3
In these formulae, the meanings of R>;1;, R>;2;, n, m, X, k, Y, j, Z and i are as given in the following
Tables 1 to 12, in which Tables 1 through 10 relate to formula (I-1), Table 11 relates to formula (I-2)
and Table 12 relates to formula (I-3). In the Tables, the following abbreviations are used:
All allyl
Bu butyl
sBu sec-butyl
tBu t-butyl
Bz benzyl
Et ethyl
Me methyl
Ph phenyl
Pr propyl
iPr isopropyl
Prg propargyl (= 2-propynyl)
Pyr pyridyl
In Compounds No. 4.36 to 4.41, 6.48 to 6.55, 7.60 to 7.74, 9.37 to 9.39 and 10.45, R>;1; and R>;2;
together represent the alkylene group indicated under their respective columns. In Table 11, the
heading "subst. posn." refers to the position on the pyridyl group in formula (I-2) by which it is
attached to the group of formula -S(O)n-. EMI32.1 EMI33.1 EMI34.1 EMI35.1 EMI36.1 EMI37.1
EMI38.1 EMI39.1 EMI40.1 EMI41.1 EMI42.1 EMI43.1 EMI44.1 EMI45.1 EMI46.1 EMI47.1
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
EMI68.1 EMI69.1 EMI70.1 EMI71.1 EMI72.1 EMI73.1 EMI74.1 EMI75.1 EMI76.1 EMI77.1
EMI78.1 EMI79.1 EMI80.1 EMI81.1 EMI82.1 EMI83.1 EMI84.1 EMI85.1 EMI86.1
Of the compounds listed above, preferred compounds are Compounds No. 1.1, 1.4, 1.6, 1.7, 1.8, 1.10,
1.15, 1.16, 1.19, 1.21, 1.23, 1.57, 1.81, 2.1, 2.4, 2.6, 2.7, 2.10, 2.12, 2.13, 2.16, 2.42, 2.45, 2.50, 2.52,
2.56, 2.59, 2.64, 2.65, 2.68, 2.83, 2.105, 3.1, 3.3, 3.6, 3.9, 3.11, 3.12, 3.15, 3.16, 3.18, 3.20, 4.1, 4.3,
4.5, 4.7, 4.43, 4.45, 4.46, 4.48, 4.50, 4.52, ,4.56, 4.58, 4.64, 4.65, 4.66, 4.67, 4.69, 4.134, 5.1, 5.3, 5.5,
5.6, 5.8, 5.9, 5.11, 5.13, 5.15, 5.17, 5.19, 5.26, 5.28, 5.30, 5.32, 5.34, 5.36, 5.38, 5.39, 5.40, 5.42, 5.70,
5.72, 5.74, 5.75, 5.76, 6.1, 6.3, 6.6, 6.8, 6.10, 6.11, 6.14, 6.16, 6.17, 6.19, 6.62, 6.63, 6.66, 6.101, 6.102,
6.104, 6.106, 6.109, 6.111, 6.112, 6.115, 6.119, 6.145, 6.148, 6.160, 7.1, 7.2, 7.4, 7.6, 7.7, 7.10, 7.12,
7.15, 7.17, 7.20, 7.22, 7.24, 7.75, 7.76, 7.91, 7.93, 7.95, 7.96, 7.100, 7.103, 7.112, 7.113, 7.114, 7.115,
7.120, 7.126, 7.142, 7.167, 7.168, 7.169, 7.173, 7.175, 7.177, 7.179, 7.182, 7.188, 7.190, 7.191, 7.213,
7.215, 7.216, 7.218, 7.220, 7.221, 7.222, 7.223, 7.252, 7.257, 7.259, 8.1, 8.4, 8.5, 8.7, 8.9, 8.12, 8.17,
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8.21, 8.23, 8.24, 8.27, 8.31, 8.32, 8.35, 9.1, 9.4, 9.6, 9.8, 9.11, 9.18, 9.22, 9.26, 9.27, 9.34, 9.49, 9.56,
9.77, 9.84, 9.85, 9.88, 9.123, 9.126, 10.1, 10.4, 10.6, 10.14, 10.23, 10.25, 10.41, 10.46, 10.47, 10.50,
10.53, 10.54, 10.56, 10.57, 10.58, 10.59, 10.62, 10.66, 10.67, 10.68, 10.70, 10.77, 10.83, 10.84, 10.85,
10.86, 10.87, 10.90, 10.117, 10.118, 10.119, 10.141, 10.160, 11.1, 11.10, 11.14, 11.61, 11.19, 11.21,
11.23, 11.25, 11.27, 11.31 and 12.2.
More preferred compounds are Compounds No. 1.4, 1.6, 1.10, 1.15, 1.23, 1.57, 1.81, 2.1, 2.4, 2.16,
2.42, 2.56, 2.59, 2.64, 2.65, 2.68, 2.83, 2.105, 3.1, 3.3, 3.12, 3.15, 3.16, 4.1, 4.3, 4.5, 4.7, 4.43, 4.45,
4.46, 4.48, 4.50, 4.52, 4.56, 4.58, 4.65, 4.66, 4.67, 4.69, 4.134, 5.3, 5.6, 5.8, 5.11, 5.13, 5.15, 5.28, 5.30,
5.32, 5.34, 5.38, 5.40, 5.72, 5.74, 5.75, 5.76, 6.3, 6.6, 6.8, 6.19, 6.62, 6.63, 6.66, 6.101, 6.104, 6.106,
6.109, 6.111, 6.115, 6.145, 6.148, 7.1, 7.2, 7.4, 7.6, 7.7, 7.10, 7.17, 7.20, 7.22, 7.24, 7.112, 7.113,
7.114, 7.115, 7.120, 7.126, 7.142, 7.165, 7.167, 7.168, 7.173, 7.175, 7.177, 7.179, 7.188, 7.190, 7.191,
7.220, 7.221, 7.257, 7.259, 8.1, 8.5, 8.12, 8.24, 8.32, 8.35, 9.1, 9.4, 9.8, 9.11, 9.18, 9.22, 9.34, 9.49,
9.56, 9.77, 9.84, 9.85, 9.88, 9.126, 10.1, 10.6, 10.23, 10.41, 10.46, 10.50, 10.53, 10.54, 10.56, 10.57,
10.58, 10.59, 10.66, 10.77, 10.83, 10.84, 10.85, 10.86, 10.87, 10.90, 10.160, 11.1, 11.10, 11.14, 11.16
and 11.25.
Still more preferred compounds are Compounds No. 1.81, 2.42, 2.64, 2.65, 2.68, 4.69, 5.76, 6.66,
7.112, 7.113, 7.120, 7.126, 7.142, 7.173, 7.188, 7.190, 8.35, 9.1, 9.56, 10.46 and 10.85.
The most preferred compounds are Compounds No.:
7.112. 1-(diethylcarbamoyl)-3-(2,6-dimethylphenylsulphonyl)-4-fluoropyrazole;
7.126. 1-(dimethylcarbamoyl)-3-(2,6-dimethylphenylsulphonyl)-4-fluoropyrazole;
7.173. 4-chloro-3-(2-chloro-6-methylphenylsulphonyl)-1-(diethylcarbamoyl)pyrazole;
9.1. 3-(3,5-dichlorophenylsulphonyl)-1-(diethylcarbamoyl)pyrazole;
10.46. 1-(dipropylcarbamoyl)-3-(2,4,6-trimethylphenylsulphonyl)pyrazole;
10.85. 1-(diethylcarbamoyl)-3-(2,4,6-trimethylphenylsulphonyl)-4-fluoropyrazole.
The compounds of the present invention can be prepared by a variety of methods well known in the art
for the preparation of compounds of this type. For example, in general terms, the compounds may be
prepared by reacting a compound of formula (V): EMI89.1 (in which: A min and B min represent any
of the groups or atoms represented by A and B, respectively, as defined above, or such a group or atom
in which any reactive group is protected, and D and n are as defined above) with a compound of
formula (VI): EMI89.2 (in which R>;1 min ; and R>;2 min ; represent any of the groups or atoms
represented by R>;1; and R>;2;, respectively, as defined above, or such a group or atom in which any
reactive group is protected, and W represents a halogen atom);
optionally, where n is 0, oxidising the product to prepare a compound in which n is 1 or 2;
optionally, where R>;1 min ; , R>;2 min ; , A min and/or B min represents a hydrogen atom,
converting it to another group or atom represented by R>;1;, R>;2;, A or B;
and optionally removing any protecting group.
Where the compound contains a carboxy group, it may, if desired, then be salified or esterified. Where
the compound contains a pyridyl or pyrimidinyl group, it may be salified. Where the compound
contains an esterified carboxy group, e.g. an alkoxycarbonyl group, it may be de-esterified.
More specifically, the compounds may be prepared as illustrated in the following Reaction Scheme A:
EMI91.1
In the above formulae, R>;1 min ;, R>;2 min ; , A min , B min and D are as defined above, R>;3;
represents an amino-protecting group, r is 1 or 2, W represents a halogen atom and R>;4; represents a
leaving group.
Suitable halogen atoms which may be represented by W include the fluorine, chlorine, bromine and
iodine atoms, of which the chlorine and bromine atoms are preferred.
The nature of the amino-protecting group represented by R>;3; is not particularly critical, provided that
it can be removed under appropriate conditions and without harming the rest of the molecule. Preferred
examples of such protecting groups include: aliphatic acyl groups, such as alkylcarbonyl groups (e.g.
the acetyl and propionyl groups) and halogenated alkylcarbonyl groups (e.g. the chloroacetyl,
225/2194
dichloroacetyl, trichloroacetyl and trifluoroacetyl groups); aromatic acyl groups, such as the benzoyl
group; lower alkoxycarbonyl groups, in which the alkoxy part preferably has from 1 to 4 carbon atoms,
such as the methoxycarbonyl group; lower alkenyloxycarbonyl groups, in which the alkenyl part
preferably has from 2 to 4 carbon atoms, such as the vinyloxycarbonyl and allyloxycarbonyl groups;
aralkyloxycarbonyl groups, such as the benzyloxycarbonyl group; tri(lower alkyl)silyl groups, in which
each alkyl part preferably has from 1 to 4 carbon atoms, such as the trimethylsilyl and tbutyldimethylsilyl groups; di(lower alkyl)sulphamoyl groups, in which each alkyl part preferably has
from 1 to 4 carbon atoms, such as the dimethylsulphamoyl group; and (lower alkoxy)-substituted lower
alkyl groups, in which the alkyl and alkoxy parts each preferably have from 1 to 4 carbon atoms, such
as the methoxymethyl and methoxyethyl groups. Of these, we prefer the aliphatic acyl groups, the
lower alkoxycarbonyl groups, the tri(lower alkyl)-silyl groups, the di(lower alkyl)sulphamoyl groups
and the (lower alkoxy)-substituted lower alkyl groups.
The nature of the leaving group which may be represented by R>;4; is not particularly critical,
provided that it can be eliminated as a nucleophilic residue, and any group commonly used in known
reactions of this type may equally be used here. Preferred examples of such groups include: halogen
atoms, such as the chlorine, bromine and iodine atoms; dicarboximide groups, such as the succinimide
and maleimide groups; and groups of formula D-S- or D-SO2- (in which D is as defined above). Of
these, we prefer the succinimide group and groups of formula D-S-.
This reaction scheme is particularly useful for the preparation of compounds in which A min and B
min are both hydrogen atoms.
In step A1 of this reaction scheme, a compound of formula (IX) is prepared by replacing a hydrogen
atom at the 5-position of a pyrazole ring in the compound of formula (VII) with a thioether group using
a compound of formula (VIII).
The reaction is carried out in the presence of a base. The nature of the base to be used is not
particularly critical, provided that it has the basicity necessary to dissociate a proton at the 5-position of
the pyrazole ring, and examples of such bases are well known to those skilled in the art. Examples of
preferred bases include organic metal bases, such as butyllithium, sec-butyllithium, lithium
diisopropylamide and lithium bis(trimethylsilyl)amide, of which butyllithium and sec-butyllithium are
most preferred.
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include ethers, such as diethyl ether or tetrahydrofuran.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from -90 DEG C to 50 DEG C, more preferably from -78 DEG C to 20 DEG C. The time required
for the reaction may also vary widely, depending on many factors, notably the reaction temperature and
the nature of the reagents. However, provided that the reaction is effected under the preferred
conditions outlined above, a period of from 5 minutes to 4 hours, more preferably from 15 minutes to
1.5 hours, will usually suffice.
In Step A2 a compound of formula (X) is prepared by removing the protecting group represented by
R>;3; from the 1-position of the pyrazole ring in the compound of formula (IX). The nature of the
reaction employed to achieve this will depend upon the nature of the protecting group to be removed.
Thus, where the protecting group represented by R>;3; is a silyl group, such as a tri(lower alkyl)silyl
group (in which each alkyl part preferably has from 1 to 4 carbon atoms), or an equivalent group in
which one or two of the alkyl groups have been replaced by an aryl (e.g. phenyl) group, it can be
removed by treating the compound of formula (IX) with a compound capable of forming a fluoride
anion.
There is no particular limitation upon the nature of the compound capable of forming a fluoride anion,
provided that it contains a fluorine atom and can give rise to a fluoride anion. Preferred examples of
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such compounds include: inorganic fluorides, such as inorganic metal fluorides (e.g. lithium fluoride,
sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, magnesium fluoride or
calcium fluoride) and organic fluorides, such as quaternary ammonium fluorides (e.g.
tetrabutylammonium fluoride); we prefer the quaternary ammonium fluorides, especially
tetrabutylammonium fluoride.
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include ethers, such as tetrahydrofuran and dioxane.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from 0 DEG C to 100 DEG C, preferably at room temperature. The time required for the reaction
may also vary widely, depending on many factors, notably the reaction temperature and the nature of
the reagents. However, provided that the reaction is effected under the preferred conditions outlined
above, a period of from 1 to 24 hours, more preferably from 2 to 8 hours, will usually suffice.
Where the protecting group represented by R>;3; is an aliphatic acyl group, an aromatic acyl group, a
lower alkoxycarbonyl group, a di(lower alkyl)sulphamoyl group or a (lower alkoxy)-substituted lower
alkyl group, it can be removed by treating the compound of formula (IX) with an acid or base in the
presence or absence of an aqueous medium.
The nature of the acid to be used is not particularly critical, and any acid commonly used for this type
of reaction may equally be used here. Examples of preferred acids include: inorganic acids, such as
hydrochloric acid, sulphuric acid, phosphoric acid or hydrobromic acid; organic acids, such as
trifluoroacetic acid; and Lewis acids, such as aluminium chloride, zinc chloride or titanium chloride. Of
these, we prefer hydrochloric acid, sulphuric acid or trifluoroacetic acid.
The nature of the base to be used is likewise not particularly critical, provided that it has no adverse
effect upon other parts of the compound of formula (IX). Examples of preferred bases include: metal,
especially alkali metal, alkoxides such as sodium methoxide; alkali metal carbonates, such as sodium
carbonate or potassium carbonate; alkali metal hydroxides, such as sodium hydroxide or potassium
hydroxide; and amines, such as aqueous ammonia, concentrated methanolic ammonia or hydrazine. Of
these, we prefer sodium carbonate, potassium carbonate or hydrazine.
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent, and
any solvent capable of use in a conventional hydrolysis reaction can equally be used here. Examples of
suitable solvents include: water; organic solvents, such as alcohols (e.g. methanol, ethanol, propanol or
isopropanol), ethers (e.g. tetrahydrofuran or dioxane) and halogenated hydrocarbons, especially
halogenated aliphatic hydrocarbons (e.g. methylene chloride, chloroform or dichloroethane); and
mixtures of water with any one or more of the above organic solvents.Of these, we prefer methanol,
tetrahydrofuran, methylene chloride, chloroform, dichloroethane or a mixture of methanol and water.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from 0 DEG C to 150 DEG C, more preferably from 30 DEG C to 80 DEG C, in order to suppress
side reactions. The time required for the reaction may also vary widely, depending on many factors,
notably the reaction temperature and the nature of the reagents. However, the reaction is normally
completed within a period of from 30 minutes to 15 hours, more preferably from 1 to 8 hours, in order
to reduce side reactions.
Where the protecting group represented by R>;3; is a lower alkenyloxycarbonyl group, it can generally
be removed by treating the compound of formula (IX) with a base in a similar manner to that described
above for the removal of an amino-protecting group when that group is an aliphatic acyl, aromatic acyl
or alkoxycarbonyl group. Where the protecting group represented by R>;3; is an aralkyloxycarbonyl
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group, it can simply be removed by hydrogenation using palladium and triphenyl phosphine or nickel
tetracarbonyl without accompanying side reactions.
At the end of this Step, the compound of formula (X) can, if desired, be subjected to the subsequent
reactions without intermediate isolation.
In Step A3, a compound of formula (XII) [a compound of formula (I), in which A and B are A min
and B min , and preferably each represents a hydrogen atom, and n is 0] is prepared by introducing a
carbamoyl group at the 1-position of the pyrazole ring in the compound of formula (X), using a
compound of formula (XI). The reaction is carried out in the presence of a base.
The nature of the base used is not particularly critical, and any base commonly used in condensation
reactions of this type may equally be used here. Examples of preferred bases include: alkali metal
hydroxides, such as sodium hydroxide or potassium hydroxide; alkali metal carbonates, such as sodium
carbonate or potassium carbonate; alkali metal hydrides, such as lithium hydride, sodium hydride or
potassium hydride; alkali metal alkoxides, such as potassium t-butoxide; organic amines, such as
triethylamine, tributylamine, diisopropylethylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4diazabicyclo[2.2.2]octane (DABCO) or 1,8-diazabicyclo[5.4.0]undec7-ene (DBU); and organic metal
bases, such as butyllithium, sec-butyllithium, lithium diisopropylamide, sodium
bis(trimethylsilyl)amide and lithium bis(trimethylsilyl)amide.Of these, we prefer triethylamine,
pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include: aromatic hydrocarbons, such as benzene, toluene or xylene;
halogenated hydrocarbons, especially halogenated aliphatic or aromatic hydrocarbons, such as
methylene chloride, chloroform, carbon tetrachloride, chlorobenzene or dichlorobenzene; esters, such
as ethyl acetate; ethers, such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane,
dimethoxyethane or diethylene glycol dimethyl ether; alcohols, such as t-butanol; nitriles, such as
acetonitrile; and ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone.Of these, we
prefer toluene, methylene chloride, dichloroethane, tetrahydrofuran or acetonitrile.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from 0 DEG C to 150 DEG C, more preferably from 30 DEG C to 80 DEG C. The time required for
the reaction may also vary widely, depending on many factors, notably the reaction temperature and the
nature of the reagents. However, provided that the reaction is effected under the preferred conditions
outlined above, a period of from 30 minutes to 12 hours, more preferably from 1 to 4 hours, will
usually suffice.
An alternative method of converting a compound of formula (X) to a compound of formula (XII),
which may be employed in place of Step A3, involves the chlorocarbonylation of the compound of
formula (X) followed by reacting the product with the corresponding secondary amine of formula
HNR>;1 min ;R>;2 min ;.
Examples of reagents which may be employed for chlorocarbonylation include phosgene,
trichloromethyl chloroformate and oxalyl chloride.
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include: aromatic hydrocarbons, such as benzene, toluene or xylene;
halogenated hydrocarbons, especially halogenated aliphatic hydrocarbons, such as methylene chloride,
chloroform, carbon tetrachloride or dichloroethane; and ethers, such as diethyl ether, tetrahydrofuran or
dioxane. Of these, we prefer toluene, chloroform or dichloroethane.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
228/2194
of from 0 DEG C to 150 DEG C, more preferably from 20 DEG C to 80 DEG C. The time required for
the reaction may also vary widely, depending on many factors, notably the reaction temperature and the
nature of the reagents and solvent employed. However, provided that the reaction is effected under the
preferred conditions outlined above, a period of from 30 minutes to 24 hours, more preferably from 1
to 5 hours will usually suffice.
The chlorocarbonyl compound prepared in this reaction can be used in the subsequent reaction without
isolation.
The reaction of this chlorocarbonyl compound with a secondary amine is preferably carried out in the
presence of a base. The nature of the base used is not particularly critical provided that it has no
adverse effects on the reagents, and any base commonly used in reactions of this type may equally be
used here. Examples of suitable bases include organic bases, such as triethylamine, tributylamine,
diisopropylethylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane
(DABCO) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Of these, we prefer triethylamine or
pyridine.
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include: aromatic hydrocarbons, such as benzene, toluene or xylene;
halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride,
dichloroethane, chlorobenzene and dichlorobenzene; esters, such as ethyl acetate; ethers, such as
diethyl ether, tetrahydrofuran, dioxane or dimethoxyethane; and nitriles, such as acetonitrile. Of these,
we prefer toluene, methylene chloride or tetrahydrofuran.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from 0 DEG C to 150 DEG C, more preferably from 5 DEG C to 60 DEG C. The time required for
the reaction may also vary widely, depending on many factors, notably the reaction temperature and the
nature of the reagents and solvent employed. However, provided that the reaction is effected under the
preferred conditions outlined above, a period of from 5 minutes to 24 hours, more preferably from 20
minutes to 4 hours will usually suffice.
In Step A4, the sulphoxide or sulphone compound of formula (XIII) [i.e. a compound of formula (I),
wherein both A and B are A min and B min , and preferably each represents a hydrogen atom, and n is
1 or 2] may, if desired, be prepared by oxidizing the thioether compound of formula (XII) with an
appropriate oxidizing agent in the presence of a solvent.
The nature of oxidizing agent used is not particularly critical, and any compound capable of being used
in conventional oxidation reactions of this type may be used, provided that it does not adversely affect
the desired compound. Examples of preferred oxidizing agents include: manganese oxides, such as
potassium permanganate, sodium permanganate or manganese dioxide; chromic acids, such as
potassium chromate, chromic acid/sulphuric acid complex or chromic acid/pyridine complex; a
hydrogen peroxide solution; organic peroxides, such as t-butyl hydroperoxide; and organic peracids,
such as peracetic acid or 3-chloroperoxybenzoic acid. Of these, we prefer a hydrogen peroxide solution
or 3-chloroperoxybenzoic acid.
The amount or nature of the oxidizing agent and the reaction conditions, including reaction time and
temperature, may be varied in a manner known per se, in order to produce selectively the sulphone (n =
1) or the sulphoxide (n = 2).
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include: halogenated hydrocarbons, such as methylene chloride,
chloroform or dichloroethane; alcohols, such as t-butanol; ketones, such as acetone or methyl ethyl
ketone; nitriles, such as acetonitrile; and acetic acid. Of these, we prefer methylene chloride,
dichloroethane or acetic acid.
229/2194
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from 20 DEG C to 150 DEG C, more preferably from 20 DEG C to 80 DEG C. The time required
for the reaction may also vary widely, depending on many factors, notably the reaction temperature and
the nature of the reagents and solvent employed. However, provided that the reaction is effected under
the preferred conditions outlined above, a period of from 1 to 24 hours, more preferably from 1to 4
hours, will usually suffice.
Alternatively, as illustrated in Reaction Scheme B, Steps A3 and A4 may be carried out in the reverse
order. EMI104.1
In the above formulae, R>;1;, R>;2;, A min , B min D, W and r are as defined above.
In this scheme, a compound of formula (XIII) [i.e., the compound of formula (I), wherein A and B are
A min and B min , and preferably each represents a hydrogen atom, and n is 1 or 2] is prepared by first
oxidizing the compound of formula (X), prepared as described in Reaction Scheme A, as shown in Step
B1, followed by carbamoylation in Step B2.
Steps B1 and B2 are essentially the same as Steps A4 and A3, respectively, and may be carried out in
the same manner and using the same reagents as in those Steps.
A compound of formula (I) having a halogen substituent at the 4-position of the pyrazole ring may be
prepared as shown in Reaction Scheme C: EMI106.1
In the above formulae, R>;1 min ; , R>;2 min ; , R>;3;, R>;4;, D, W and r are as defined above and
R>;5; represents a halogen, e.g. fluorine, chlorine, bromine or iodine, atom.
Reaction Scheme C involves the preparation of a compound of formula (XVIII) [i.e. a compound of
formula (I), wherein A represents a hydrogen atom, B represents a halogen, e.g. fluorine, chlorine,
bromine or iodine, atom, and n is 0] or a compound of formula (XIX) [i.e. a compound of formula (I),
wherein A represents a hydrogen atom, B represents a halogen, e.g. fluorine, chlorine, bromine or
iodine, atom, and n is 1 or 2] by introducing a halogen atom at the 4-position of the pyrazole ring in the
compound of formula (VII) and then conducting similar reactions to those described in Reaction
Scheme A.
In Step C1, a compound of formula (XV) is prepared by introducing a halogen, e.g. fluorine, chlorine,
bromine or iodine, atom at the 4-position of the compound of formula (VII).
The reaction is carried out by reacting the compound of formula (VII) with a halogenating agent in the
presence of a solvent. Examples of suitable halogenating agents include: N-halosuccinimides, such as
N-chlorosuccinimide, N-bromosuccinimide or N-iodosuccinimide; and halogen molecules, such as
fluorine, chlorine, bromine or iodine.
There is no particular restriction on the nature of the solvent to be employed, provided that it has no
adverse effect on the reaction or on the reagents involved and that it can dissolve the reagents, at least
to some extent. Examples of suitable solvents include: halogenated hydrocarbons, such as methylene
chloride, chloroform, dichloroethane or trifluorochloromethane; amides, especially fatty acid amides,
such as dimethylformamide or diethylformamide; nitriles, such as acetonitrile; acetic acid; and
mixtures of any two or more of the above solvents.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from -70 DEG C to 150 DEG C, more preferably from -40 DEG C to 110 DEG C. The time required
for the reaction may also vary widely, depending on many factors, notably the reaction temperature and
the nature of the reagents. However, provided that the reaction is effected under the preferred
conditions outlined above, a period of from 1 to 24 hours, more preferably from 1 to 10 hours, will
usually suffice.
230/2194
Steps C2, C3, C4 and C5 can be conducted in a similar manner to that described above in respect of
Steps A1, A2, A3 and A4, respectively.
An alternative method of preparing a compound of formula (XVI) (prepared in Step C2 of Reaction
Scheme C) is shown in Reaction Scheme D: EMI109.1
In the above formulae, R>;3;, R>;5; and D are as defined above.
The reaction consists of the halogenation of the compound of formula (IX min ), which may be
prepared as shown in Step A1 [formula (IX), A min and B min are both hydrogen]; the reaction may
be conducted in a similar manner to that described in Step C1.
Reaction Scheme E shows an alternative method of preparing a compound of formula (XVII)
(otherwise prepared in Step C3 of Reaction Scheme C): EMI110.1
In the above formulae, R>;5; and D are as defined above.
Reaction Scheme E consists of preparing the compound of formula (XVII) by halogenating the
compound of formula (X min ), which is a compound of formula (X), in which A min and B min are
both hydrogen, prepared as shown in Step A2 of Reaction Scheme A. Step E1 can be carried out in a
similar manner to that described in step C1.
Other compounds having a substituent on the 4-position of the pyrazole ring may be prepared as shown
in Reaction Scheme F: EMI111.1
In the above formulae, R>;1 min ; , R>;2 min ; , R>;3;, R>;5;, D, W and r are as defined above and
R>;6; represents:
a hydroxy group,
a fluorine atom,
an unsubstituted alkyl group having from 1 to 6 carbon atoms,
a substituted alkyl group having from 1 to 6 carbon atoms and having at least one, and preferably
from 1 to 3, of substituents (c), defined above,
an unsubstituted alkenyl group having from 2 to 6 carbon atoms,
a substituted alkenyl group which has from 2 to 6 carbon atoms and which is substituted by at least
one halogen substituent,
an alkylthio group having from 1 to 6 carbon atoms, a dialkylsulphamoyl group, in which each alkyl
part has from 1 to 4 carbon atoms,
an aliphatic acyl, preferably alkylcarbonyl, group which has from 2 to 7 carbon atoms and which is
unsubstituted or is substituted by at least one of substituents (a), defined above,
an alkoxycarbonyl group having from 2 to 7 carbon atoms,
a group of formula -CONR>;a;R>;b;, in which R>;a; and
R>;b; are the same or different and each represents a hydrogen atom or an alkyl group having from 1
to 4 carbon atoms,
a formyl group or
a cyano group.
All of the above groups which may be represented by R>;6; may be as defined and exemplified above
in relation to the corresponding groups which may be represented by B.
In Reaction Scheme F, we prepare a compound of formula (XXII) [i.e. a compound of formula (I),
wherein A represents a hydrogen atom; B represents any of the groups and atoms defined above for
R>;6;; and n is 0] and a compound of formula (XXIII) [i.e. a compound of formula (I), wherein A
represents a hydrogen atom; B represents any of the groups and atoms defined above for R>;6;; and n
is 1 or 2] by introducing a substituent represented by R>;6; at the 4-position of the pyrazole ring in the
compound of formula (XVI), which may have been prepared as described in Reaction Scheme C, and
then treating the product in a similar manner to that described in Reaction Scheme A.
Step F1 involves the preparation of the compound of formula (XX) from a compound of formula (XVI)
prepared as described in Step C2 of Reaction Scheme C, either by directly replacing a halogen atom
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represented by R>;5; (preferably a chlorine, bromine or iodine atom) at the 4-position of the pyrazole
ring by a group or atom R>;6;, or by replacing this halogen atom by a metal atom, and then replacing
the metal atom by a group or atom R>;6;. The conditions under which we prefer to carry out this
reaction will vary, depending upon the nature of the group or atom R>;6; which it is wished to
introduce.
Thus, where R>;6; represents a trifluoromethyl group, the desired compound can be prepared by
reacting the compound of formula (XVI) with a trifluoromethylating agent, with heating. Examples of
trifluoromethylating agents which may be used include: trifluoromethyl metal salts, such as
trifluoromethyl silver or trifluoromethyl copper (I); and fluorosulphonyldifluoroacetates, such as
methyl fluorosulphonyldifluoroacetate, in the presence of cuprous iodide.
The reaction is normally and preferably carried out in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include: halogenated hydrocarbons, such as dichloroethane,
tetrachloroethane, chlorobenzene or dichlorobenzene; ketones, such as methyl ethyl ketone or methyl
isobutyl ketone; amides, especially fatty acid amides, such as dimethylformamide or
dimethylacetamide; and sulphoxides, such as dimethyl sulphoxide.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from 50 DEG C to 200 DEG C, more preferably from 80 DEG C to 150 DEG C. The time required
for the reaction may also vary widely, depending on many factors, notably the reaction temperature and
the nature of the reagents and solvent employed. However, provided that the reaction is effected under
the preferred conditions outlined above, a period of from 1 to 10 hours, more preferably from 1 to 6
hours, will usually suffice.
Where R>;6; represents a hydroxy group, a fluorine atom, an alkyl group which is unsubstituted or
substituted by one or more of substituents (c), an alkenyl group, a haloalkenyl group, an alkylthio
group, a dialkylsulphamoyl group, an aliphatic acyl group, an alkoxycarbonyl group, a carbamoyl
group, an alkylcarbamoyl group, a dialkylcarbamoyl group, a formyl group or a cyano group, the
reaction is preferably initiated by replacing the halogen, preferably chlorine, bromine or iodine, atom at
the 4-position of the pyrazole ring in the compound of formula (XVI) with a metal atom. Examples of
the reagents which may be used for replacing the halogen atom by a metal atom include organic lithium
bases, such as butyllithium, sec-butyllithium or t-butyllithium, and lithium metal.
The reaction is normally and preferably carried out in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include ethers, such as diethyl ether or tetrahydrofuran.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a relatively
low temperature of from -90 DEG C to 10 DEG C, more preferably from -78 DEG C to 0 DEG C. The
time required for the reaction may also vary widely, depending on many factors, notably the reaction
temperature and the nature of the reagents and solvent employed. However, provided that the reaction
is effected under the preferred conditions outlined above, a period of from 5 minutes to 1 hour, more
preferably from 10 minutes to 1 hour, will usually suffice.
The metal salt prepared in this exchange reaction of a halogen atom with a metal atom can be used in
the subsequent reaction with a nucleophilic reagent to introduce the desired group or atom R>;6;
without intermediate isolation. The nature of the nucleophilic agent used will, of course, depend upon
the nature of the group or atom R>;6; which it is desired to introduce.
Thus, for example, when R>;6; is a hydroxy group, the nucleophilic reagent used is a peroxide, such as
trimethylsilyl peroxide.
232/2194
Where R>;6; represents a fluorine atom, examples of nucleophilic reagents include N-fluoropyridinium
salts, such as N-fluoropyridinium triflate; and N-fluorosulphonimides, such as Nfluorobenzenesulphonimide or N-fluoro-o-benzenedisulphonimide.
Where R>;6; represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a
dialkylsulphamoyl group, an optionally substituted aliphatic acyl group, an alkoxycarbonyl group or a
group of formula -CONR>;a;R>;b;, examples of nucleophilic reagents are the corresponding halides
(i.e. the compounds represented by the formula R>;6;X min , wherein R>;6; is as defined above and X
min represents a halogen atom).
Where R>;6; represents an alkylthio group, examples of nucleophilic reagents include the disulphide or
monosulphone compounds equivalent to the corresponding thiol compounds (R>;6;-SH).
Where R>;6; represents a formyl group, examples of nucleophilic reagents include: formamides, such
as dimethylformamide or diethylformamide; formates, such as ethyl formate or t-butyl formate; and
mixed formic acid anhydrides, such as formic pivalic anhydride.
Where R>;6; represents a cyano group, examples of nucleophilic reagents are cyanides, such as
trimethylsilyl cyanide or p-toluenesulphonyl cyanide.
The reaction with a nucleophilic reagent can take place over a wide range of temperatures, and the
precise reaction temperature is not critical to the invention. In general, we find it convenient to carry
out the reaction at a relatively low temperature of from -90 DEG C to 50 DEG C, more preferably from
-78 DEG C to 20 DEG C. The time required for the reaction may also vary widely, depending on many
factors, notably the reaction temperature and the nature of the reagents and solvent employed.
However, provided that the reaction is effected under the preferred conditions outlined above, a period
of from 10 minutes to 10 hours, more preferably from 10 minutes to 2 hours, will usually suffice.
Steps F2, F3 and F4 involve essentially the same reactions as do Steps A2, A3 and A4, respectively,
and can be carried out using the same reagents and reaction conditions.
Those compounds of formulae (XX), (XXI), (XXII) and (XXIII) in which R>;6; represents a formyl
group, prepared as described in Reaction Scheme F, can be reduced to the corresponding compounds
having a hydroxymethyl group to produce the corresponding compounds of formulae (XX), (XXI),
(XXII) and (XXIII) in which R>;6; represents a methyl group substituted with a hydroxy group.
Examples of the reducing agents which may be used to effect this reduction include: alkali metal
aluminium hydrides, such as lithium aluminium hydride, sodium aluminium hydride or sodium
aluminium triethoxyhydride; and metal borohydrides, such as sodium borohydride, sodium
cyanoborohydride or lithium borohydride.
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include: aromatic hydrocarbons, such as benzene, toluene or xylene;
halogenated hydrocarbons, especially halogenated aliphatic hydrocarbons, such as methylene chloride,
chloroform or dichloroethane; ethers, such as diethyl ether, tetrahydrofuran, dimethoxyethane or
dioxane; and alcohols, such as methanol, ethanol, propanol or isopropanol.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from -30 DEG C to 150 DEG C, more preferably from 0 DEG C to 60 DEG C. The time required for
the reaction may also vary widely, depending on many factors, notably the reaction temperature and the
nature of the reagents and solvent employed. However, provided that the reaction is effected under the
preferred conditions outlined above, a period of from 10 minutes to 15 hours, more preferably from 30
minutes to 2 hours, will usually suffice.
Ester compounds [i.e. B in the compound of formula (I) represents an acyloxymethyl group] can be
prepared by reacting a compound in which R>;6; represents a hydroxymethyl group with a carboxylic
acid compound of formula R>;8;OH or reactive derivative thereof, in which R>;8; represents: an
233/2194
aliphatic acyl group, such as an alkylcarbonyl group (e.g. an acetyl or propionyl group) or a
halogenated alkylcarbonyl group (e.g. a chloroacetyl, dichloroacetyl, trichloroacetyl or trifluoroacetyl
group); an aromatic acyl group, such as a benzoyl group; a lower alkoxycarbonyl group, in which the
alkoxy part preferably has from 1 to 4 carbon atoms, such as a methoxycarbonyl group; a lower
alkenyloxycarbonyl group, in which the alkenyl part preferably has from 2 to 4 carbon atoms, such as a
vinyloxycarbonyl or allyloxycarbonyl group; or an aralkyloxycarbonyl group, such as a
benzyloxycarbonyl group.The reaction preferably takes place in the presence of a condensing agent,
such as dicyclohexylcarbodiimide (DCC) or carbonyldiimidazole. Alternatively, esters may be
prepared by reacting a compound in which R>;6; represents a hydroxymethyl group with an activated
acylating agent of formula R>;8;Z [in which R>;8; is as defined above and Z represents a leaving
group, such as a group of formula OR>;8;, a halogen atom (e.g. a chlorine, bromine or iodine atom), a
lower alkylcarbonyloxy group, preferably having from 1 to 6 carbon atoms in the alkyl part (e.g. a
pivalyloxy group), a lower alkoxycarbonyloxy group, preferably having from 1 to 6 carbon atoms in
the alkoxy part (e.g. a methoxycarbonyloxy or ethoxycarbonyloxy group), a lower alkylthio group,
preferably having from 1 to 6 carbon atoms in the alkyl part (e.g. a methylthio or ethylthio group), a
pyridylthio group (e.g. a 2-pyridylthio group), or a lower alkylsulphonyloxy group, preferably having
from 1 to 6 carbon atoms in the alkyl part (e.g. a methanesulphonyloxy or ethanesulphonyloxy group)].
These reactions are preferably carried out in a solvent in the presence of a base.
There is no particular restriction on the nature of the solvent to be employed, provided that it has no
adverse effect on the reaction or on the reagents involved and that it can dissolve the reagents, at least
to some extent. Examples of suitable solvents include: aromatic hydrocarbons, such as benzene,
toluene or xylene; halogenated hydrocarbons, such as methylene chloride, chloroform or carbon
tetrachloride; ethers, such as diethyl ether, tetrahydrofuran or dioxane; and esters, such as ethyl acetate.
The nature of the base used is likewise not particularly critical, and any base conventionally used in
reactions of this type can equally be used here. Examples of preferred bases include: organic bases,
such as triethylamine, tributylamine, diisopropylethylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5ene, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); and organic
metal bases, such as butyllithium, sec-butyllithium, lithium diisopropylamide, sodium
bis(trimethylsilyl)amide or lithium bis(trimethylsilyl)amide. Of these, we prefer triethylamine,
pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from 0 DEG C to 100 DEG C, more preferably from 20 DEG C to 50 DEG C. The time required for
the reaction may also vary widely, depending on many factors, notably the reaction temperature and the
nature of the reagents and solvent employed. However, provided that the reaction is effected under the
preferred conditions outlined above, a period of from 10 minutes to 24 hours, more preferably from 30
minutes to 2 hours, will usually suffice.
If desired, the resulting ester can be converted to the free carboxylic acid by conventional means.
Alternatively, where R>;6; represents a hydroxymethyl group, it can be converted to a halogenated
methyl group, such as a fluoromethyl, chloromethyl, bromomethyl or iodomethyl group, by treating the
compound with a halogenating agent.
Any halogenating agent capable of converting a general hydroxy group to halogen atom may be used
in this reaction. Examples of preferred halogenating agents include: diethylaminosulphur trifluoride
(DAST) for fluorination; thionyl chloride, phosphorus oxychloride or phosphorus pentachloride for
chlorination; phosphorus tribromide or phosphorus pentabromide for bromination; and
methyltriphenylphosphonium iodide for iodination.
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include: aromatic hydrocarbons, such as benzene, toluene or xylene;
halogenated hydrocarbons, especially halogenated aliphatic hydrocarbons, such as methylene chloride,
chloroform or carbon tetrachloride; ethers, such as diethyl ether, tetrahydrofuran, dioxane or
234/2194
dimethoxyethane; esters, such as ethyl acetate; amides, such as dimethylformamide or
hexamethylphosphoric triamide; sulphoxides, such as dimethyl sulphoxide; and ketones, such as
acetone or methyl ethyl ketone.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from -20 DEG C to 150 DEG C, more preferably from 0 DEG C to 60 DEG C. The time required for
the reaction may also vary widely, depending on many factors, notably the reaction temperature and the
nature of the reagents and solvent employed. However, provided that the reaction is effected under the
preferred conditions outlined above, a period of from 30 minutes to 20 hours, more preferably from 1
to 4 hours, will usually suffice.
The compounds of formula (XX), (XXI), (XXII) and (XXIII), in which R>;6; represents a formyl
group, and which may have been prepared as described in Reaction Scheme F, can be converted to the
corresponding compounds in which B represents a difluoromethyl group by using a fluorinating agent
such as diethylaminosulphur trifluoride (DAST).
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include: aromatic hydrocarbons, such as benzene, toluene or xylene;
halogenated hydrocarbons, such as methylene chloride, chloroform, dichloroethane or chlorobenzene;
ethers, such as diethyl ether, tetrahydrofuran, dioxane or dimethoxyethane; esters, such as ethyl acetate;
and nitriles, such as acetonitrile.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from -20 DEG C to 150 DEG C, more preferably from 0 DEG C to 60 DEG C. The time required for
the reaction may also vary widely, depending on many factors, notably the reaction temperature and the
nature of the reagents and solvent employed. However, provided that the reaction is effected under the
preferred conditions outlined above, a period of from 1 to 36 hours, more preferably from 1 to 20
hours, will usually suffice.
Compounds, in which R>;6; represents a lower alkoxy group which may optionally be substituted with
at least one, and preferably from 1 to 3, substituents, which may be the same or different, selected from
substituents (a), defined and exemplified above, can be prepared by reacting the corresponding
compound of formula (XX), (XXI), (XXII) or (XXIII), in which R>;6; represents a hydroxy group, and
which may have been prepared as described in Reaction Scheme F, with various alkylating agents in
the presence of a base.
Examples of alkylating agents which may be used in this reaction include: lower alkyl halides, such as
iodomethane, iodoethane, iodopropane, 2-iodopropane, bromomethane, bromoethane, bromopropane
and 2-bromopropane.
The nature of the base used is not particularly critical, and any base commonly used in conventional
reactions of this type may equally be used here. Examples of preferred bases include: alkali metal
hydroxides, such as sodium hydroxide or potassium hydroxide; alkali metal carbonates, such as sodium
carbonate or potassium carbonate; alkali metal hydrides, such as lithium hydride, sodium hydride or
potassium hydride; alkali metal alkoxides, such as potassium t-butoxide; organic bases, such as
triethylamine, tributylamine, diisopropylethylamine, pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4diazabicyclo[2.2.2]octane (DABCO) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); and organic metal
bases, such as butyllithium, sec-butyllithium, lithium diisopropylamide, sodium
bis(trimethylsilyl)amide and lithium bis(trimethylsilyl)amide.Of these, we prefer triethylamine,
pyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)
The reaction is normally and preferably effected in the presence of a solvent. There is no particular
restriction on the nature of the solvent to be employed, provided that it has no adverse effect on the
reaction or on the reagents involved and that it can dissolve the reagents, at least to some
extent.Examples of suitable solvents include: aromatic hydrocarbons, such as benzene, toluene or
235/2194
xylene; halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride,
dichloroethane, chlorobenzene or dichlorobenzene; esters, such as ethyl acetate; ethers, such as diethyl
ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl
ether; alcohols, such as methanol, ethanol or isopropyl alcohol; nitriles, such as acetonitrile;
formamides, such as dimethylformamide or diethylformamide; sulphoxides, such as dimethyl
sulphoxide; and mixtures of water with one or more of the above solvents.
The reaction can take place over a wide range of temperatures, and the precise reaction temperature is
not critical to the invention. In general, we find it convenient to carry out the reaction at a temperature
of from -90 DEG C to 150 DEG C, more preferably from -78 DEG C to 60 DEG C. The time required
for the reaction may also vary widely, depending on many factors, notably the reaction temperature and
the nature of the reagents and solvent employed. However, provided that the reaction is effected under
the preferred conditions outlined above, a period of from 10 minutes to 24 hours, more preferably from
30 minutes to 4 hours, will usually suffice.
Compounds in which R>;6; represents a lower alkylsulphonyl group can be prepared by oxidizing the
corresponding compound of formula (XX), (XXI), (XXII) or (XXIII), in which R>;6; represents a
lower alkylthio group, and which may have been prepared as described in Reaction Scheme F, with
various kinds of oxidizing agents.
The reaction is essentially the same as and may be carried out using the same reagents and reaction
conditions as described above in relation to Step A4. EMI125.1
In the above formulae, R>;3;, R>;4;, R>;5;, R>;6; and D are as defined above.
Reaction Scheme G provides an alternative method of preparation of the compound of formula (XX),
which is also prepared as shown in Step F1 of Reaction Scheme F, by exchanging a halogen atom at
the 4-position of the pyrazole ring in a compound of formula (XV) (prepared as shown in Step C1 of
Reaction Scheme C) with a nucleophilic agent, and then subjecting the resulting compound of formula
(XXIV) to thioetherification.
Steps G1 and G2 involve essentially the same reactions as those described in Steps F1 and A1,
respectively, and may be carried out using the same reagents and reaction conditions. EMI126.1
In the above formulae, R>;1 min ; , R>;2 min ; , B min , D and r are as defined above and R>;7;
represents:
a hydroxy group,
a halogen atom,
an unsubstituted alkyl group having from 1 to 6 carbon atom,
a substituted alkyl group having from 1 to 6 carbon atoms and having at least one, and preferably
from 1 to 3, of substituents (c), defined above,
an unsubstituted alkenyl group having from 2 to 6 carbon atoms,
a substituted alkenyl group which has from 2 to 6 carbon atoms and which is substituted by at least
one halogen substituent,
an alkylthio group having from 1 to 6 carbon atoms, a dialkylsulphamoyl group, in which each alkyl
part has from 1 to 4 carbon atoms,
an aliphatic acyl, preferably alkylcarbonyl, group which has from 2 to 7 carbon atoms and which is
unsubstituted or is substituted by at least one of substituents (a), defined above,
an alkoxycarbonyl group having from 2 to 7 carbon atoms,
a group of formula -CONR>;a;R>;b;, in which R>;a; and
R>;b; are the same or different and each represents a hydrogen atom or an alkyl group having from 1
to 4 carbon atoms,
a formyl group or
a cyano group.
All of the above groups which may be represented by R>;7; may be as defined and exemplified above
in relation to the corresponding groups which may be represented by A.
236/2194
In Reaction Scheme H, a compound of formula (XXVI) [i.e. a compound of formula (I), wherein A
represents any one of the groups and atoms defined above in relation to R>;7;, B is B min and n is 0]
and a compound of formula (XXVII) [i.e., the compound of formula (I), wherein A represents any one
of the groups and atoms defined above in relation to R>;7;, B is B min and n is 1 or 2] may be
prepared by introducing a nucleophilic substituent, R>;7;, at the 5-position of the pyrazole ring in a
compound of formula (XXV), which may have been prepared as described in any of Reaction Schemes
A, C and F.
In Step H1 a compound of formula (XXVI) is prepared by introducing a nucleophilic substituent,
R>;7;, at the 5-position of the pyrazole ring in the compound of formula (XXV) [which may be the
compound of formula (XII) prepared in Reaction Scheme A, the compound of formula (XVIII)
prepared in Reaction Scheme C or the compound of formula (XXII) prepared in Reaction Scheme F].
The substitution reaction of the compound of formula (XXV) can be carried out by deprotonating the
hydrogen atom at the 5-position of the pyrazole ring, and then introducing a substituent, R>;7;, using a
nucleophilic reagent.
The nature of the deprotonating agent used in the first reaction of this Step is not particularly critical,
provided that it has sufficient basicity to dissociate a proton at the 5-position of a pyrazole ring.
Examples of suitable deprotonating agents include organic bases, such as butyllithium, secbutyllithium, t-butyllithium, lithium diisopropylamide or lithium bis(trimethylsilyl)amide, and more
preferably butyllithium or sec-butyllithium.
The deprotonation reaction is normally and preferably effected in the presence of a solvent. There is no
particular restriction on the nature of the solvent to be employed, provided that it has no adverse effect
on the reaction or on the reagents involved and that it can dissolve the reagents, at least to some extent.
Examples of suitable solvents include ethers, such as diethyl ether or tetrahydrofuran.
The deprotonation reaction can take place over a wide range of temperatures, and the precise reaction
temperature is not critical to the invention. In general, we find it convenient to carry out the reaction at
a temperature of from -90 DEG C to 50 DEG C, more preferably from -78 DEG C to 20 DEG C. The
time required for the reaction may also vary widely, depending on many factors, notably the reaction
temperature and the nature of the reagents and solvent employed. However, provided that the reaction
is effected under the preferred conditions outlined above, a period of from 5 minutes to 4 hours, more
preferably from 15 minutes to 1.5 hours will usually suffice.
The nature of the nucleophilic reagent used will, of course, depend on the nature of the group which it
is desired to introduce.
Thus, for example, where R>;7; represents a hydroxy group, preferred examples of the nucleophilic
reagent used for the nucleophilic reaction are peroxides, such as trimethylsilyl peroxide.
Where R>;7; represents a halogen atom, examples of nucleophilic reagents include: Nhalosuccinimides, such as N-chlorosuccinimide or N-bromosuccinimide; halogenated alkanes, such as
1,2-dibromoethane or hexachloroethane; hypochlorites, such as t-butyl hypochlorite; halogen
molecules, such as bromine or iodine; N-fluoropyridinium salts, such as N-fluoropyridinium triflate;
and N-fluorosulphonimides, such as N-fluoro-o-benzenedisulphonimide.
Where R>;7; represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a
dialkylsulphamoyl group, an optionally substituted aliphatic acyl group, an alkoxycarbonyl group or a
group of formula -CONR>;a;R>;b;, examples of nucleophilic reagents are the corresponding halides
(i.e. the compounds represented by the formula R>;7;X min , wherein R>;7; is as defined above and X
min represents a halogen atom).
Where R>;7; represents an alkylthio group, examples of nucleophilic reagents include the disulphide or
monosulphone compounds equivalent to the corresponding thiol compounds (R>;7;-SH).
237/2194
Where R>;7; represents a formyl group, examples of nucleophilic reagents include: formamides, such
as dimethylformamide or diethylformamide; formates, such as ethyl formate or t-butyl formate; and
mixed formic acid anhydrides, such as formic pivalic anhydride.
Where R>;7; represents a cyano group, examples of nucleophilic reagents are cyanides, such as
trimethylsilyl cyanide or p-toluenesulphonyl cyanide.
The reaction with the nucleophilic reagent can take place over a wide range of temperatures, and the
precise reaction temperature is not critical to the invention. In general, we find it convenient to carry
out the reaction at a relatively low temperature of from -90 DEG C to 50 DEG C, more preferably from
-78 DEG C to 20 DEG C. The time required for the reaction may also vary widely, depending on many
factors, notably the reaction temperature and the nature of the reagents and solvent employed.
However, provided that the reaction is effected under the preferred conditions outlined above, a period
of from 10 minutes to 10 hours, more preferably from 10 minutes to 2 hours, will usually suffice.
Step H2 involves essentially the same reaction as Step A4 and can be carried out using the same
reagents and reaction conditions.
In the compounds of formulae (XXVI) and (XXVII), which may be prepared as described in Reaction
Scheme H, a compound having a formyl group represented by R>;7; can be reduced to a corresponding
compound having a hydroxymethyl group. The hydroxymethyl compound thus obtained by reduction
can be reacted with various kinds of carboxylic acid compounds to produce the corresponding ester
compounds.
Further, the hydroxymethyl group prepared by reduction can be converted to a halogenated methyl
group, such as a fluoromethyl, chloromethyl or bromomethyl group, by reaction with a halogenating
agents.
Also, in the compounds of formulae (XXVI) and (XXVII), which may have been prepared as described
in Reaction Scheme H, a compound having a formyl group represented by R>;7; can be converted to a
corresponding compound having a difluoromethyl group.
A compound in which R>;7; represents an optionally substituted alkoxy group can be prepared by
reacting the compound of formula (XXVI) or (XXVII), wherein R>;7; represents a hydroxy group,
prepared as described in Reaction Scheme H, with various kinds of alkylating agents by conventional
means.
All of the above reactions involving the group or atom R>;7; in the compounds of formulae (XXVI)
and (XXVII) prepared as described in Reaction Scheme H can be carried out in a similar manner to
those described in relation to R>;6; in Reaction Scheme F.
A compound having an alkylsulphonyl group represented by R>;7; can also be prepared by oxidizing
the corresponding compound having a lower alkylthio group represented by R>;7; in the compounds of
formulae (XXVI) and (XXVII) with various oxidizing agents by conventional means. This reaction can
be conducted in a similar manner to that described in Step A4. EMI132.1
In the above formulae, R>;1 min ; , R>;2 min ; , R>;7;, B min , D and r are as defined above.
Reaction Scheme I provides an alternative method of preparing the compound of formula (XXVII) by
introducing a nucleophilic substituent represented by R>;7; at the 5-position of the pyrazole ring in the
compound of formula (XXVIII), which may have been prepared as described in Reaction Scheme A,
B, C or F.
The reaction of Step I1 involves essentially the same reaction as and may be carried out as described in
Step H1.
After completion of each reaction in the above Reaction Schemes A to I, the desired compound from
each of the steps can be recovered from the reaction mixture by conventional means. An example of
one such technique comprises: neutralizing appropriately the reaction mixture; if insoluble materials
238/2194
exist, filtering them off; adding a water-immiscible solvent; separating the organic phase and washing
it with water; and finally distilling off the organic solvent. The product thus obtained can further be
purified by conventional means, for example, recrystallization, reprecipitation, or the various
chromatography techniques, notably column chromatography or preparative thin layer
chromatography.
For use as a herbicide, the compounds of the invention may be applied in admixture with a carrier and,
if necessary, with other adjuvants, and may be used in the form of any preparation commonly used for
this purpose, for example, as dusts, coarse dusts, fine granules, granules, wettable powders, flowable
agents, emulsifiable concentrates, liquids and the like. The carrier with which it may be mixed may be
a synthetic or natural inorganic or organic substance, and is incorporated into a herbicide in order to
assist the active compound to reach the target plant or in order to facilitate storage, transport or
handling of the active compound.
Examples of suitable solid carriers include: clays, such as kaolinites, montmorillonites or attapulgites;
inorganic substances, such as talc, mica, agalmatolite, pumice, vermiculite, gypsum, dolomite,
diatomaceous earth, magnesium lime, apatite, zeolite, silicic acid anhydride, synthetic calcium silicate,
kaolin, bentonite or calcium carbonate; vegetable organic substances, such as soybean flour, tobacco
powder, walnut powder, wheat-meal, woodflour, starch or crystalline cellulose; synthetic or natural
high molecular weight compounds, such as coumarone resin, petroleum resin, alkyd resin, poly(vinyl
chloride), poly(alkylene glycol), ketone resin, ester gum, copal gum or dammar gum; waxes, such as
carnauba wax, paraffin wax or beeswax; and urea.
Examples of suitable liquid carriers include: paraffin or naphthene hydrocarbons, such as kerosene,
mineral oil, spindle oil or white oil; aromatic hydrocarbons, such as benzene, toluene, xylene,
ethylbenzene, cumene or methylnaphthalene; halogenated hydrocarbons, such as carbon tetrachloride,
chloroform, trichloroethylene, monochlorobenzene or o-chlorotoluene; ethers, such as dioxane or
tetrahydrofuran; ketones, such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone,
acetophenone or isophorone; esters, such as ethyl acetate, amyl acetate, ethylene glycol acetate,
diethylene glycol acetate, dibutyl maleate or diethyl succinate; alcohols, such as methanol, hexanol,
ethylene glycol, diethylene glycol, cyclohexanol or benzyl alcohol; ether alcohols, such as ethylene
glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether or diethylene glycol butyl
ether; polar solvents, such as dimethylformamide or dimethyl sulphoxide; and water.
In order to facilitate emulsification, dispersion, moisturizing, diffusion, spreading, bonding and control
of disintegration, to stabilize the active compound, to improve mobility and rust resistance and to
accelerate absorption in the plant, the compounds of the present invention may be used in admixture
with one or more surface active agents, which may be ionic or non-ionic agents.
Examples of suitable nonionic surface active agents include: for example, fatty acid sucrose esters,
addition polymers of ethylene oxide with higher alcohols, such as lauryl alcohol, stearyl alcohol or
oleyl alcohol; addition polymers of ethylene oxide with alkylphenols, such as isooctylphenol or
nonylphenol; addition polymers of ethylene oxide with alkylnaphthols, such as butylnaphthol or
octylnaphthol; addition polymers of ethylene oxide with higher fatty acids, such as palmitic acid,
stearic acid or oleic acid; addition polymers of ethylene oxide with mono- or di-alkyl phosphates, such
as stearyl phosphate or dilauryl phosphate; addition polymers of ethylene oxide with amines, such as
dodecylamine or stearamide; addition polymers of ethylene oxide with higher fatty acid esters of
polyhydric alcohols, such as sorbitan; and addition polymers of ethylene oxide with propylene oxide.
Examples of suitable anionic surface active agents include: for example, alkyl sulphates, such as
sodium lauryl sulphate or an amine salt of oleyl sulphate; salts of fatty acids, such as sodium dioctyl
sulphosuccinate, sodium oleate or sodium stearate; and alkyl arylsulphonates, such as sodium isopropyl
naphthalenesulphonate, sodium methylenebisnaphthalenesulphonate, sodium ligninsulphonate or
sodium dodecylbenzenesulphonate.
Examples of cationic surface active agents include, for example, higher aliphatic amines, quaternary
ammonium salts and alkyl pyridinium salts.
239/2194
Further, in order to improve the properties of the preparation and to enhance the biological effect, the
herbicides of the present invention may be used in combination with high molecular weight polymers,
such as gelatin, gum arabic, casein, albumin, glue, sodium alginate, poly(vinyl alcohol), carboxymethyl
cellulose, methyl cellulose, and hydroxymethyl cellulose; thixotropic agents, such as sodium
polyphosphate or bentonite; or other adjuvants.
These carriers and adjuvants can be used alone or in combination depending upon the purpose of the
preparation and the method of application.
The amount of the active compound in the preparation may vary over a wide range, and there is no
particular restriction on its concentration. However, the preferred concentration of active compound in
the preparation will depend primarily on the nature of the preparation, as well as upon the intended
manner of use and the nature of the weeds to be killed. If desired, the preparation may be supplied in a
concentrated form intended to be diluted by the user.
Thus, for example, dusts normally comprise from 2 to 10 parts by weight of the active compound, the
remainder being a solid carrier.
Wettable powders normally comprise from 10 to 80 parts by weight of the active compound, the
remainder being a solid carrier or a dispersing or moistening agent, and, if necessary, a protecting
colloidal agent, a thixotropic agent, a defoaming agent or the like.
Granules normally comprise from 0.1 to 10 parts by weight of the active compound, the remainder, for
the most part, being a solid carrier. The active compound may be homogeneously mixed with the solid
carrier, or adhered on or absorbed by a solid carrier. The particle diameter is preferably in the range of
from about 0.2 to 1.5 mm.
Emulsifiable concentrates normally comprise from 1 to 50 parts by weight of the active compound and
from 5 to 20 parts by weight of an emulsion, the remainder being a liquid carrier and also, if necessary,
a rust-resistant agent.
The herbicide of the present invention may be applied to soil, for example a paddy field or a farm,
before or after germination of weeds, preferably in an amount of from 1 to 1000 g, more preferably
from 10 to 300 g, of the active compound per 10 ares, in the various forms of preparation mentioned
above to eliminate weeds effectively. Furthermore, the compounds may be applied to non-farm areas,
such as a road, ground, a building site, a right-of-way or the like, preferably in an amount of from 200
to 1000 g per 10 ares to combat weeds effectively in those locations also.
If desired, the herbicide of the present invention may be used in combination with one or more other
herbicides in order to improve a weed-killing spectrum and, in some cases, a synergic effect may be
expected.
The herbicide of the invention may be applied in admixture with a plant growth regulator, a
bactericide, an insecticide, an acaricide, a nematocide or a fertilizer, if desired, in order to provide a
composition for agricultural or horticultural use have a wider field of use.
The compounds of the present invention have herbicidal activity and can be put to herbicidal use. The
activity is generally more efficacious against monocotyledons than against dicotyledons. For example,
the compounds of the invention can effectively control flourishing weeds in a paddy field, when
applied by soil application under flooded conditions to a paddy field before or after germination of the
weeds or forbs; in particular, they are effective against: gramineous weeds, such as Echinochloa
oryzicola Vasing, Echinochloa crus-galli (L.) Beauv. var. formosensis Ohwi and Echinochloa crus-galli
subsp. genuina var. echinata Honda; perennial weeds which are difficult to exterminate by conventional
herbicides, including, cyperaceous weeds, such as Eleocharis acicularis (L.) Roem. et Schult. var.
longiseta Sven., Scirpus juncoides Roxb. subsp. hotarui (Ohwi) T. Koyama, Eleocharis kuroguwai
Ohwi and Cyperus serotinus Rottb. and alismataceous weeds, such as Sagittaria pygmaea Miq. and
Sagittaria trifolia L.. Moreover, they can effectively control broadleaved weeds, including,
scrophulariaceous weeds, such as Lindernia pyxidaria L., lythraceous weeds, such as Rotala indica
(Willd.) Koehne var. ulginosa (Miq.) Koehne, Ammannia multiflora Roxb. and Rotala mexicana Cham
240/2194
et Schltdl. and pontederiaceous weeds, such as Monochoria vaginalis (Burm. f.) Presl var. plantaginea
(Roxb.) Solms-Laub and Monochoria korsakowii Regel et Maack.
On the other hand, it has been found that the compounds of the invention show a selective activity, in
that they do not harm many useful plants, such as rice, including paddy-rice plant, and have the
advantage of a wide range of application for treatment. In a farm, by treating the soil before
germination of weeds or forbs, the compounds of the invention can extensively exterminate flourishing
weeds or forbs, for example: amaranthaceous weeds, such as Amaranthus lividus L., Amaranthus
viridis L. and Achyranthes japonica (Miq.) Nakai; portulacaceous weeds, such as Portulaca oleracea L.;
chenopodiaceous weeds, such as Chenopodium album L. var. centrorubrum Makino, Chenopodium
album L. and Chenopodium serotinum L.; commelinaceous weeds, such as Commelina communis L .;
caryophyllaceous weeds, such as Stellaria media (L.) Villars, Stellaria alsine Grimm, Cerastium
holosteoides Fries var. angustifolium (Franch.) Mizushima and Sagina japonica (Sw.) Ohwi;
euphorbiaceous weeds, such as Acalypha australis L. and Euphorbia supina Raf.; especially,
gramineous weeds, such as Agropyron tskushiense (Honda) Ohwi var. transiens (Hack.), Digitaria
ciliaris (Retz.) Koeler, Digitaria timorensis (Kunth) Balansa, Echinochloa crus-galli (L.) Beauv. var.
crus-galli, Setaria viridis (L.) Beauv., Setaria faberi Herrm., Alopecurus aequalis Sobol. var. amurensis
(Komar.) Ohwi and Poa annua L. Furthermore, the compounds of the invention never cause damage to
farm products, such as sweet corn, sugar beet, soybean, cotton plant, radish, tomato, carrot, Chinese
cabbage, lettuce or the like.
Further, the compounds of the present invention can be used effectively on non-agricultral areas,
forests and the like as a herbicide.
The compounds of the present invention also have the ability to regulate the growth of plants and,
when plants are treated with these compounds at the appropriate season and at a proper concentration,
the growth of certain types of plants, especially grasses, can be controlled without withering. Thus the
compounds of the present invention can be used as a plant growth retardant towards certain plants.
Therefore, the term "herbicide" of the present invention covers a plant growth retardant.
In particular, the compounds of the present invention can be used as a lawn grass growth retardant by
inhibiting growth of: Japanese lawn grasses, such as lawn grass, sodded lawn grass, Korean lawn grass
or the like; and, in particular, American and European lawn grasses, such as Bermuda grass, bent grass,
blue grass, fescue grass, ryegrass or the like; they can, as a result, be used in a gardens, public areas of
greenery, golf courses and the like.
The preparation of the compounds of the present invention is further illustrated by the following
Examples, and the use of these compounds in agricultural and horticultural compositions is illustrated
in the subsequent Preparations. The activity of various of these compounds is then shown.
EXAMPLE 1
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)pyrazole (Compound No. 7.12)
and
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)pyrazole (Compound No. 7.10)
1(1) 1-(Dimethylsulphamoyl)pyrazole
241/2194
2.80 g of sodium hydride (as a 60% w/w dispersion in mineral oil), and then 10 ml of
dimethylsulphamoyl chloride, were added, in turn, to a solution of 4.76 g of pyrazole in 95 ml of
tetrahydrofuran, and the resulting mixture was stirred at room temperature for 3 hours. At the end of
this time, the reaction mixture was diluted with an excess of water and extracted with ethyl acetate. The
extract was washed with water and then dried over anhydrous sodium sulphate, after which it was
purified by distillation under reduced pressure.There were obtained 13.10 g (a quantitative yield) of the
title compound, boiling at 130 DEG C/0.1 mmHg (13.3 Pa).
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.98 (1H, doublet, J = 2.6 Hz);
7.74 (1H, doublet, J = 1.1 Hz);
6.39 (1H, doublet of doublets, J = 1.5 & 2.6 Hz);
2.81 (6H, singlet).
1(2) 1-(Dimethylsulphamoyl)-5-(2-ethyl-6-methylphenylthio)pyrazole
2.1 ml of a 1.49 M solution of butyllithium in hexane were added, at -78 DEG C and under an
atmosphere of nitrogen, to a solution of 547 mg of 1-(dimethylsulphamoyl)pyrazole [prepared as
described in step (1) above] in 16 ml of dry tetrahydrofuran, and the resulting mixture was allowed to
stand at the same temperature for 20 minutes. At the end of this time, a solution of 945 mg of 2-ethyl6-methylphenyl disulphide in 5 ml of tetrahydrofuran was added to the mixture, which was then stirred
at the same temperature for 40 minutes. The reaction mixture was then mixed with an aqueous solution
of ammonium chloride and extracted with ethyl acetate. The extract was washed with water and dried
over anhydrous sodium sulphate, after which it was concentrated by evaporation under reduced
pressure.The concentrate was purified by column chromatography through silica gel, eluted with a 10 :
1 by volume mixture of hexane and ethyl acetate, to give 701 mg (yield 69%) of the title compound as
an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.44 (1H, doublet, J = 1.7 Hz);
7.36 - 7.18 (3H, multiplet);
5.24 (1H, doublet, J = 1.7 Hz);
3.05 (6H, singlet);
2.85 (2H, quartet, J = 7.5 Hz);
2.44 (3H, singlet);
1.17 (3H, triplet, J = 7.5 Hz).
1(3) 3-(2-Ethyl-6-methylphenylthio)pyrazole
0.9 ml of trifluoroacetic acid was added to a solution of 640 mg of 1-(dimethylsulphamoyl)-5-(2-ethyl6-methylphenylthio)pyrazole [prepared as described in step (2) above] in 3 ml of methylene chloride,
and the resulting mixture was heated at 50 DEG C for 4 hours. At the end of this time, the reaction
mixture was poured into an aqueous solution of sodium hydrogencarbonate and extracted with
methylene chloride. The extract was washed with water and dried over anhydrous sodium sulphate.
The solvent was removed by distillation under reduced pressure, to give 628 mg (a quantitative yield)
of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.52 (1H, broad);
7.3 - 7.1 (4H, multiplet);
7.00 (1H, broad);
2.93 (2H, quartet, J = 7.5 Hz);
2.45 (3H, singlet);
1.19 (3H, triplet, J = 7.5 Hz).
1(4) 1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)pyrazole
242/2194
0.41 ml of 1,8-diazabicyclo[5.4.0]undec-7-ene and 0.21 ml of diethylcarbamoyl chloride were added,
in turn, to a solution of 299 mg of 3-(2-ethyl-6-methylphenylthio)pyrazole [prepared as described in
step (3) above] in 6 ml of acetonitrile, and the resulting mixture was stirred at room temperature for 3
hours. At the end of this time, the reaction mixture was mixed with water and extracted with ethyl
acetate. The extract was washed with water and dried over anhydrous sodium sulphate, after which the
solvent was removed by distillation under reduced pressure.The resulting residue was purified by
column chromatography through silica gel, eluted with a 6 : 1 by volume mixture of hexane and ethyl
acetate, to give 273 mg (yield 63%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.03 (1H, doublet, J = 2.9 Hz);
7.22 (1H, doublet, J = 7.0 Hz);
7.16 - 7.12 (2H, multiplet);
5.94 (1H, doublet, J = 2.9 Hz);
3.47 (4H, quartet, J = 7.0 Hz);
2.90 (2H, quartet, J = 7.5 Hz);
2.44 (3H, singlet);
1.18 (3H, triplet, J = 7.5 Hz);
1.09 (6H, broad triplet).
1(5) 1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)pyrazole
366 mg of 3-chloroperoxybenzoic acid were added to a solution of 245 mg of 1-(diethylcarbamoyl)-3(2-ethyl-6-methylphenylthio)pyrazole [prepared as described in step (4) above] in 4 ml of 1,2dichloroethane, and the resulting mixture was heated at 50 DEG C for 1 hour. At the end of this time,
the reaction mixture was mixed with an aqueous solution of sodium sulphite, after which it was
extracted with methylene chloride. The extract was washed with an aqueous solution of sodium
hydrogencarbonate and dried over anhydrous sodium sulphate, and then the solvent was removed by
distillation under reduced pressure.The resulting residue was purified by column chromatography
through silica gel, eluted with an 8 : 1 by volume mixture of hexane and ethyl acetate, to give 266 mg
(yield 99%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.20 (1H, doublet, J = 2.9 Hz);
7.37 (1H, triplet, J = 7.5 Hz);
7.20 (1H, broad doublet, J = 7.5 Hz);
7.13 (1H, broad doublet, J = 7.5 Hz);
6.89 (1H, doublet, J = 2.9 Hz);
3.44 (1H, quartet, J = 7.0 Hz);
3.11 (2H, quartet, J = 7.5 Hz);
2.67 (3H, singlet);
1.27 (3H, singlet);
1.3 - 0.9 (6H, broad).
EXAMPLE 2
1-(Dipropylcarbamoyl)-3-(2,4,6-trimethylphenylsulphonyl)pyrazole (Compound No. 10.46)
2(1) 3-(2,4,6-Trimethylphenylthio)pyrazole
243/2194
9.13 ml of trifluoroacetic acid were added to a solution of 11.59 g of 1-(dimethylsulphamoyl)-5-(2,4,6trimethylphenylthio)pyrazole [prepared in a similar manner to that described in Example 1(2)] in 58 ml
of chloroform, and the resulting mixture was heated at 60 DEG C for 4 hours. The reaction mixture
was then concentrated by evaporation under reduced pressure, and the concentrate was diluted with
water and made alkaline by the addition of an aqueous solution of sodium hydrogencarbonate; it was
then extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium
sulphate.The solvent was removed by distillation under reduced pressure, to give 7.77 g (a quantitative
yield) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.44 (1H, doublet, J = 2.1 Hz);
7.27 (2H, singlet);
5.95 (1H, doublet, J = 2.1 Hz);
2.45 (6H, singlet);
2.29 (3H, singlet).
2(2) 3-(2,4,6-Trimethylphenylsulphonyl)pyrazole
7.60 g of 3-chloroperoxybenzoic acid were added to a solution of 3.5 g of 3-(2,4,6trimethylphenylthio)pyrazole [prepared as described in step (1) above] in 70 ml of 1,2-dichloroethane,
and the resulting mixture was stirred at room temperature for 15 hours. At the end of this time, the
reaction mixture was washed with an aqueous solution of sodium hydrogencarbonate and with water, in
that order, after which it was dried over anhydrous sodium sulphate.The solvent was removed by
distillation under reduced pressure, and then the crystalline residue was recrystallized from a mixture of
methylene chloride and diisopropyl ether to give 3.70 g (yield 92%) of the title compound, melting at
185 - 186 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.85 (1H, doublet, J = 2.4 Hz);
6.96 (2H, singlet);
6.72 (1H, doublet, J = 2.4 Hz);
2.66 (6H, singlet);
2.30 (3H, singlet).
2(3) 1-(Dipropylcarbamoyl)-3-(2,4,6-trimethylphenylsulphonyl)pyrazole
2 ml of a 1.98 M solution of phosgene in toluene were added to a solution of 200 mg of 3-(2,4,6trimethylphenylsulphonyl)pyrazole [prepared as described in step (2) above] in 1 ml of toluene, and the
resulting solution was heated at 60 DEG C for 1 hour. The mixture was concentrated by evaporation
under reduced pressure, and then 97 mg of triethylamine and 89 mg of diisopropylamine were added,
in that order, to the oily residue. The reaction mixture was then stirred at ambient temperature for 20
minutes, after which it was diluted with diethyl ether. The ethereal solution was washed with 1N
aqueous hydrochloric acid, with an aqueous solution of sodium hydrogencarbonate and with water, in
that order, and was then dried over anhydrous sodium sulphate.The solvent was removed by distillation
under reduced pressure, and the resulting residue was purified by column chromatography through
silica gel, eluted with a 6 : 1 by volume mixture of hexane and ethyl acetate, to afford 268 mg (yield
89%) of the title compound, melting at 64 - 65 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.8 Hz);
6.94 (2H, singlet);
6.87 (1H, doublet, J = 2.8 Hz);
3.38 (4H, broad triplet, J = 7.2 Hz);
2.65 (6H, singlet);
2.29 (3H, singlet);
1.8 - 1.4 (4H, broad);
1.1 - 0.8 (3H, broad);
0.8 - 0.6 (3H, broad).
244/2194
EXAMPLE 3
1-(Diethylcarbamoyl)-4-chloro-3-(3,5-dichlorophenylthio)pyrazole (Compound No. 9.50)
and
1-(Diethylcarbamoyl)-4-chloro-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.49)
3(1) 1-(Dimethylsulphamoyl)-4-chloropyrazole
2.45 g of N-chlorosuccinimide were added to a solution of 2.14 g of 1-(dimethylsulphamoyl)pyrazole
[prepared as described in Example 1(1)] in 20 ml of chloroform, and the resulting mixture was heated
at 70 DEG C for 5 hours. At the end of this time, the reaction mixture was diluted with ethyl acetate,
and then the ethyl acetate solution was washed with water and dried over anhydrous sodium sulphate.
The solvent was then removed by distillation under reduced pressure. The resulting residue was
purified by column chromatography through silica gel, eluted with an 8 : 1 by volume mixture of
hexane and ethyl acetate, to give 2.00 g (yield 78%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
7.95 (1H, doublet, J = 0.8 Hz);
7.65 (1H, doublet, J = 0.8 Hz);
2.97 (6H, singlet).
Following the procedure described above, but using N-bromosuccinimide and N-iodosuccinimide, we
also produced:
1-(dimethylsulphamoyl)-4-bromopyrazole
as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
7.98 (1H, singlet);
7.68 (1H, singlet);
2.97 (6H, singlet).
1-(dimethylsulphamoyl)-4-iodopyrazole
as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.01 (1H, singlet);
7.71 (1H, singlet);
2.96 (6H, singlet.
3(2) 1-(Dimethylsulphamoyl)-4-chloro-5-(3,5-dichlorophenylthio)pyrazole
0.67 ml of a 1.49 M solution of butyllithium in hexane was added at -78 DEG C to a solution of 300
mg of 1-(dimethylsulphamoyl)-4-chloropyrazole [prepared as described in step (1) above] in 15 ml of
dry tetrahydrofuran. After 10 minutes, a solution of 449 mg of 3,5-dichlorophenyl disulphide in 7 ml of
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dry tetrahydrofuran was added to the mixture, which was then stirred at the same temperature for 1
hour. At the end of this time, the reaction mixture was mixed with an aqueous solution of ammonium
chloride and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous
sodium sulphate; the solvent was then removed by distillation under reduced pressure.The residue thus
obtained was purified by column chromatography through silica gel, eluted with a 6 : 1 by volume
mixture of hexane and ethyl acetate, to give 410 mg (yield 74%) of the title compound, melting at 32
DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.72 (1H, singlet);
7.21 (1H, triplet, J = 1.8 Hz);
7.11 (2H, doublet, J = 1.8 Hz);
3.08 (6H, singlet).
3(3) 1-(Diethylcarbamoyl)-4-chloro-3-(3,5-dichlorophenylthio)pyrazole
195 mg of trifluoroacetic acid were added to a solution of 200 mg of 1-(dimethylsulphamoyl)-4-chloro5-(3,5-dichlorophenylthio)pyrazole [prepared as described in step (2) above] in 5 ml of chloroform, and
the resulting mixture was heated at 50 DEG C for 2 hours. The mixture was allowed to cool, after
which it was diluted with water and neutralized with an aqueous solution of sodium
hydrogencarbonate. It was then extracted with ethyl acetate. The extract was washed with water and
dried over anhydrous sodium sulphate, and then the solvent was removed by distillation under reduced
pressure. The residue was dissolved in 5 ml of acetonitrile, and 89 mg of diethylcarbamoyl chloride
and 55 mg of 1,4-diazabicylo[2.2.2]octane were added to the resulting solution.The reaction mixture
was then heated at 50 DEG C for 2 hours, after which it was diluted with ethyl acetate and the solution
was washed with 2N aqueous hydrochloric acid, with a 5% w/v aqueous solution of sodium hydroxide
and with water, in that order. The organic layer was separated and dried over anhydrous sodium
sulphate, and then the solvent was removed by distillation under reduced pressure. There were obtained
163 mg (yield 83%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, singlet);
7.24 (3H, multiplet);
3.53 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
3(4) 1-(Diethylcarbamoyl)-4-chloro-3-(3,5-dichlorophenylsulphonyl)pyrazole
125 mg of 3-chloroperoxybenzoic acid were added to a solution of 125 mg of 1-(diethylcarbamoyl)-4chloro-3-(3,5-dichlorophenylthio)pyrazole [prepared as described in step (3) above] in 3 ml of 1,2dichloroethane, and the resulting mixture was heated at 50 DEG C for 2 hours. The reaction mixture
was then diluted with ethyl acetate, after which it was washed with an aqueous solution of sodium
sulphite, with an aqueous solution of sodium hydrogencarbonate and with water, in that order.The
mixture was then dried over anhydrous sodium sulphate, and the solvent was removed by distillation
under reduced pressure, after which the residue was purified by column chromatography through silica
gel, eluted with an 8 : 1 by volume mixture of hexane and ethyl acetate, to give 115 mg (yield 85%) of
the title compound, melting at 89 - 90 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
7.93 (2H, doublet, J = 1.9 Hz);
7.63 (1H, triplet, J = 1.9 Hz);
3.51 (4H, quartet, J = 7.0 Hz);
1.26 (6H, triplet, J = 7.0 Hz).
EXAMPLE 4
246/2194
1-(Diethylcarbamoyl)-4-bromo-5-(2,5-dimethylphenylthio)pyrazole (Compound No. 6.116)
and
1-(Diethylcarbamoyl)-4-bromo-3-(2,5-dimethylphenylsulphonyl)pyrazole (Compound No. 6.114)
4(1) 1-(Dimethylsulphamoyl)-4-bromo-5-(2,5-dimethylphenylthio)pyrazole
1.55 g of N-bromosuccinimide was added to a solution of 2.71 g of 1-(dimethylsulphamoyl)-5-(2,5dimethylphenylthio)pyrazole [prepared in a similar manner to that described in Example 1(2)] in 27 ml
of chloroform, and the resulting mixture was heated at 65 DEG C for 1.5 hours. At the end of this time,
the reaction mixture was poured into an aqueous solution of sodium sulphite and extracted with
methylene chloride. The extract was washed with water and dried over anhydrous sodium sulphate, and
the solvent was removed by distillation under reduced pressure.The residue was purified by column
chromatography through silica gel, eluted with an 8 : 1 by volume mixture of hexane and ethyl acetate,
to afford 2.44 g (yield 72%) of the title compound, melting at 83 - 84 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.72 (1H, singlet);
7.08 (1H, doublet, J = 7.7 Hz);
6.9 (1H, doublet, J = 7.7 Hz);
6.71 (1H, singlet);
3.05 (6H, singlet);
2.41 (3H, singlet);
2.21 (3H, singlet).
4(2) 1-(Diethylcarbamoyl)-4-bromo-5-(2,5-dimethylphenylthio)pyrazole
1.4 ml of trifluoroacetic acid was added to a solution of 2.39 g of 1-(dimethylsulphamoyl)-4-bromo-5(2,5-dimethylphenylthio)pyrazole [prepared as described in step (1) above] in 20 ml of methylene
chloride, and the resulting mixture was heated at 50 DEG C for 3 hours. At the end of this time, the
reaction mixture was diluted with water and extracted with methylene chloride. The extract was
washed with water and dried over anhydrous sodium sulphate; the solvent was then removed by
distillation under reduced pressure. The residue thus obtained was dissolved in 20 ml of acetonitrile,
and 1.15 g of 1,4-diazabicyclo[2.2.2]-octane, followed by 1.47 ml of diethylcarbamoyl chloride, were
added to the resulting solution. The resulting mixture was heated at 50 DEG C for 4 hours, poured into
water and then extracted with ethyl acetate.The extract was washed with a saturated aqueous solution
of sodium chloride and dried over anhydrous sodium sulphate; the solvent was then removed by
distillation under reduced pressure. The resulting residue was purified by column chromatography
through silica gel, eluted with a 6 : 1 by volume mixture of hexane and ethyl acetate, to afford 2.33 g (a
quantitative yield) of the title compound.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
7.23 - 7.01 (3H, multiplet);
3.44 (4H, quartet, J = 7.2 Hz);
2.40 (3H, singlet);
2.27 (3H, singlet);
1.20 - 0.95 (6H, broad).
247/2194
4(3) 1-(Diethylcarbamoyl)-4-bromo-5-(2,5-dimethylphenylsulphonyl)pyrazole
398 mg of 3-chloroperoxybenzoic acid were added to a solution of 315 mg of 1-(diethylcarbamoyl)-4bromo-5-(2,5-dimethylphenylthio)pyrazole [prepared as described in step (2) above] in 7 ml of 1,2dichloroethane, and the resulting mixture was heated at 50 DEG C for 2 hours. At the end of this time,
the reaction mixture was poured into an aqueous solution of sodium sulphite and extracted with
methylene chloride. The extract was washed with an aqueous solution of sodium hydrogencarbonate
and with water, in that order, after which it was dried over anhydrous sodium sulphate and the solvent
was removed by distillation under reduced pressure.The resulting residue was purified by column
chromatography through silica gel, eluted with a 10 : 1 by volume mixture of hexane and ethyl acetate,
to give 283 mg (yield 83%) of the title compound, melting at 82 - 83 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.24 (1H, singlet);
7.4 - 7.1 (3H, multiplet);
3.44 (4H, quartet, J = 7.0 Hz);
2.67 (6H, singlet);
1.35 - 0.9 (6H, broad).
EXAMPLE 5
1-(Diethylcarbamoyl)-4-chloro-3-(2,4,6-trimethylphenylthio)pyrazole (Compound No. 10.55)
and
1-(Diethylcarbamoyl)-4-chloro-3-(2,4,6-trimethylphenylsulphonyl)pyrazole (Compound No. 10.56)
5(1) 4-Chloro-3-(2,4,6-trimethylphenylthio)pyrazole
306 mg of N-chlorosuccinimide were added to a solution of 500 mg of 3-(2,4,6trimethylphenylthio)pyrazole [prepared as described in Example 2(1)] in 10 ml of chloroform, and the
resulting mixture was heated at 50 DEG C for 2 hours. The reaction mixture was then diluted with
water and extracted with methylene chloride. The extract was washed with water and dried over
anhydrous sodium sulphate, after which the solvent was removed by distillation under reduced
pressure.The resulting residue was purified by column chromatography through silica gel, eluted with a
5 : 1 by volume mixture of hexane and ethyl acetate, to afford 516 mg (yield 89%) of the title
compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.43 (1H, singlet);
6.98 (2H, singlet);
2.43 (6H, singlet);
2.29 (3H, singlet).
5(2) 1-(Diethylcarbamoyl)-4-chloro-3-(2,4,6-trimethylphenylthio)pyrazole
248/2194
453 mg of 1,4-diazabicyclo[2.2.2]octane and 356 mg of diethylcarbamoyl chloride were added, in that
order, to a solution of 510 mg of 4-chloro-3-(2,4,6-trimethylphenylthio)pyrazole [prepared as described
in step (1) above] in 5 ml of acetonitrile, and the resulting mixture was stirred at room temperature for
20 minutes. At the end of this time, the reaction mixture was diluted with water and extracted with
ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulphate, after
which the solvent was removed by distillation under reduced pressure.The residue was purified by
column chromatography through silica gel, eluted with a 6 : 1 by volume mixture of hexane and ethyl
acetate, to afford 561 mg (yield 79%) of the title compound, melting at 84 - 86 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.07 (1H, singlet);
6.95 (2H, singlet);
3.34 (4H, quartet, J = 7.0 Hz);
2.43 (6H, singlet);
2.28 (3H, singlet);
1.2 - 0.7 (6H, broad).
5(3) 1-(Diethylcarbamoyl)-4-chloro-3-(2,4,6-trimethylphenylsulphonyl)pyrazole
734 mg of 3-chloroperoxybenzoic acid were added to a solution of 536 mg of 1-(diethylcarbamoyl)-4chloro-3-(2,4,6-trimethylphenylthio)pyrazole [prepared as described in step (2) above] in 5 ml of 1,2dichloroethane, and the resulting mixture was heated at 50 DEG C for 1.5 hours. The reaction mixture
was then diluted with water and extracted with ethyl acetate. The extract was washed with an aqueous
solution of sodium hydrogencarbonate and with water, in that order, after which it was dried over
anhydrous sodium sulphate, and the solvent was removed by distillation under reduced pressure.The
resulting residue was purified by column chromatography through silica gel, eluted with an 8 : 1 by
volume mixture of hexane and ethyl acetate, to afford 504 mg (yield 86%) of the title compound,
melting at 123 - 126 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, singlet);
6.96 (2H, singlet);
3.47 (4H, quartet, J = 7.0 Hz);
2.63 (6H, singlet);
2.31 (3H, singlet);
1.3 - 0.9 (6H, broad).
EXAMPLE 6
4-Cyano-1-(diethylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)pyrazole (Compound No. 7.258)
and
4-Cyano-1-(diethylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)pyrazole (Compound No.
7.259)
6(1) 4-Cyano-1-(dimethylsulphamoyl)-5-(2-methoxy-6-methylphenylthio)pyrazole
249/2194
1.2 ml of a 1.48 M solution of t-butyllithium in pentane were added, at -78 DEG C and under an
atmosphere of nitrogen, to a solution of 561 mg of 4-iodo-1-(dimethylsulphamoyl)-5-(2-methoxy-6methylphenylthio)pyrazole [prepared in a similar manner to that described in Example 7(1)] in 25 ml of
dry diethyl ether, and the resulting mixture was stirred for 30 minutes. At the end of this time, a
solution of 314 mg of p-toluenesulphonyl cyanide in 3 ml of dry diethyl ether was added to the
mixture, and the resulting mixture was stirred for 30 minutes at -78 DEG C and then at 0 DEG C for a
further 30 minutes. The reaction mixture was then mixed with an aqueous solution of ammonium
chloride and extracted with diethyl ether.The extract was washed with wate r and dried over anhydrous
sodium sulphate over anhydrous sodium sulphate, after which the solvent was removed by distillation
under reduced pressure. The resulting residue was purified by column chromatography through silica
gel, eluted with an 8 : 1 by volume mixture of hexane and ethyl acetate, to afford 162 mg (yield 37%)
of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.70 (1H, singlet);
7.40 (1H, triplet, J = 8.0 Hz);
6.97 (1H, doublet, J = 8.0 Hz);
6.82 (1H, doublet, J = 8.0 Hz);
3.82 (3H, singlet);
3.12 (6H, singlet);
3.05 (3H, singlet).
6(2) 4-Cyano-1-(diethylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)pyrazole
0.10 ml of trifluoroacetic acid was added to a solution of 154 mg of 4-cyano-1-(dimethylsulphamoyl)5-(2-methoxy-6-methylphenylthio)pyrazole [prepared as described in step (1) above] in 2 ml of
chloroform, and the resulting mixture was heated at 60 DEG C for 2 hours. At the end of this time, the
reaction mixture was diluted with methylene chloride, and the organic layer was separated, washed
with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulphate. The
solvent was removed by distillation under reduced pressure, and then the oily residue thus obtained was
dissolved in 4 ml of acetonitrile. 59 mg of 1,4-diazabicyclo[2.2.2]octane and 60 mu l of
diethylcarbamoyl chloride were added, in that order, to the solution, and the resulting mixture was
stirred at room temperature for 2 hours.At the end of this time, the reaction mixture was diluted with
ethyl acetate, washed with water and then dried over anhydrous sodium sulphate. It was then
concentrated by evaporation under reduced pressure, and the resulting residue was purified by column
chromatography through silica gel, eluted with a 6 : 1 by volume mixture of hexane and ethyl acetate,
to afford 145 mg (yield 96%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.46 (1H, singlet);
7.31 (1H, triplet, J = 8.0 Hz);
6.92 (1H, doublet, J = 8.0 Hz);
6.80 (1H, doublet, J = 8.0 Hz);
3.82 (3H, singlet);
3.47 - 3.36 (4H, multiplet);
2.49 (3H, singlet);
1.4 - 0.9 (6H, broad).
6(3) 4-Cyano-1-(diethylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)pyrazole
175 mg of 3-chloroperoxybenzoic acid were added to a solution of 127 mg of 4-cyano-1(diethylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)pyrazole [prepared as described in step (2)
above] in 4 ml of 1,2-dichloroethane, and the resulting mixture was stirred at room temperature for 2
hours. At the end of this time, an aqueous solution of sodium sulphite was added to the reaction
mixture, after which it was extracted with methylene chloride. The extract was washed with an aqueous
solution of sodium hydrogencarbonate, dried over anhydrous sodium sulphate and concentrated by
evaporation under reduced pressure.The concentrate was purified by column chromatography through
250/2194
silica gel, eluted with a 10 : 1 by volume mixture of hexane and ethyl acetate, to afford 90 mg (yield
65%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.56 (1H, singlet);
7.44 (1H, doublet of doublets, J = 7.6 & 8.3 Hz);
6.92 (1H, doublet, J = 7.6 Hz);
6.83 (1H, doublet, J = 8.3 Hz);
3.85 (3H, singlet);
3.49 (4H, broad quartet, J = 7.2 Hz);
2.82 (3H, singlet);
1.3 - 1.1 (6H, broad).
EXAMPLE 7
1-(Diethylcarbamoyl)-3-(2,4,6-trimethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 10.85)
7(1) 1-(Dimethylsulphamoyl)-5-(2,4,6-trimethylphenylthio)-4-iodopyrazole
5.26 g of N-iodosuccinimide were added to a solution of 6.92 g of 1-(dimethylsulphamoyl)-5-(2,4,6trimethylphenylthio)pyrazole [prepared in a similar manner to that described in Example 1(2)] in 60 ml
of chloroform, and the resulting mixture was heated at 60 DEG C for 20 hours. At the end of this time,
the reaction mixture was diluted with an aqueous solution of sodium sulphite and extracted with
methylene chloride. The extract was washed with a saturated aqueous solution of sodium chloride and
dried over anhydrous sodium sulphate; the solvent was then removed by distillation under reduced
pressure.The resulting residue was purified by column chromatography through silica gel, eluted with
an 8 : 1 by volume mixture of hexane and ethyl acetate, to afford 8.34 g (yield 87%) of the title
compound, melting at 154 - 157 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.51 (1H, singlet);
6.91 (2H, singlet);
3.11 (6H, singlet);
2.33 (6H, singlet);
2.28 (3H, singlet).
7(2) 1-(Dimethylsulphamoyl)-5-(2,4,6-trimethylphenylthio)-4-fluoropyrazole
0.41 ml of a 1.64 M solution of butyllithium in tetrahydrofuran was added at -78 DEG C to a solution
of 277 mg of 1-(dimethylsulphamoyl)-5-(2,4,6-trimethylphenylthio)-4-iodopyrazole [prepared as
described in step (1) above] in 9 ml of dry tetrahydrofuran, and the resulting mixture was stirred for 50
minutes. At the end of this time, a solution of 193 mg of N-fluorobenzenesulphonimide in 10 ml of dry
tetrahydrofuran was added to the resulting mixture, which was then stirred for 30 minutes. The reaction
mixture was then poured into water and extracted with diethyl ether. The extract was washed with a
saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulphate and concentrated
by evaporation under reduced pressure. The concentrate was purified by column chromatography
through silica gel, eluted with a 5 : 1 by volume mixture of hexane and ethyl acetate, to afford 79 mg
(yield 37%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.42 (1H, doublet, J = 4.5 Hz);
6.94 (2H, singlet);
3.08 (6H, singlet);
2.44 (6H, singlet);
251/2194
2.28 (3H, singlet).
7(3) 1-(Diethylcarbamoyl)-3-(2,4,6-trimethylphenylsulphonyl)-4-fluoropyrazole
43 mu l of trifluoroacetic acid were added to a solution of 64 mg of 1-(dimethylsulphamoyl)-5-(2,4,6trimethylphenylthio)-4-fluoropyrazole [prepared as described in step (2) above] in 1.5 ml of
chloroform, and the resulting mixture was heated at 65 DEG C for 4 hours. At the end of this time, the
reaction mixture was poured into water and extracted with methylene chloride. The extract was washed
with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulphate; the
solvent was then removed by distillation under reduced pressure. The residue thus obtained was
dissolved in 3 ml of acetonitrile, and 32 mg of 1,4-diazabicyclo[2.2.2]octane, followed by 26 mu l of
diethylcarbamoyl chloride, were added to the resulting solution; the mixture was then stirred at room
temperature for 1 hour.After this, the reaction mixture was diluted with water and extracted with ethyl
acetate. The extract was washed with water and dried over anhydrous sodium sulphate, after which the
solvent was removed by distillation under reduced pressure. The residue was dissolved in 3 ml of 1,2dichloroethane, and 89 mg of 3-chloroperoxybenzoic acid were added to the resulting solution, after
which it was heated at 50 DEG C for 2 hours. The reaction mixture was then mixed with an aqueous
solution of sodium sulphite and extracted with methylene chloride. The extract was washed with an
aqueous solution of sodium hydrogencarbonate and dried over anhydrous sodium sulphate; the solvent
was then removed by distillation under reduced pressure.The resulting residue was purified by column
chromatography through silica gel, eluted with a 6 : 1 by volume mixture of hexane and ethyl acetate,
to afford 61 mg (yield 89%) of the title compound, melting at 109 - 111 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.00 (1H, doublet, J = 4.7 Hz);
6.96 (2H, singlet);
3.6 - 3.4 (4H, multiplet);
2.66 (6H, singlet);
2.30 (3H, singlet);
1.18 (6H, broad).
EXAMPLE 8
1-(Diethylcarbamoyl)-3-(2-methyl-6-ethylphenylthio)-4-methoxypyrazole (Compound No. 7.341)
and
1-(Diethylcarbamoyl)-3-(2-methyl-6-ethylphenylsulphonyl)-4-methoxypyrazole (Compound No.
7.286)
8(1) 1-(Dimethylsulphamoyl)-5-(2-methyl-6-ethylphenylthio)-4-iodopyrazole
5.53 g of N-iodosuccinimide were added to a solution of 8 g of 1-(dimethylsulphamoyl)-5-(2-methyl-6ethylphenylthio)pyrazole [prepared as described in Example 1(2)] in 80 ml of chloroform, and the
resulting mixture was heated at 60 DEG C for 8 hours. At the end of this time, the reaction mixture was
allowed to cool and was then mixed with 20 ml of an aqueous solution of sodium sulphite, stirred for 5
minutes and extracted with methylene chloride. The extract was washed with water and dried over
anhydrous sodium sulphate, after which the solvent was removed by distillation under reduced
252/2194
pressure.The crude product thus obtained was recrystallized from hexane, and further purified by
column chromatography through silica gel, eluted with a 10 : 1 by volume mixture of hexane and ethyl
acetate, to give 9.4 g (yield 85%) of the title compound, melting at 102 - 104 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.51 (1H, singlet);
7.24 (1H, doublet, J = 7.5 Hz);
7.11 (2H, triplet, J = 7.5 Hz);
3.11 (6H, singlet);
2.90 (2H, quartet, J = 7.5 Hz);
2.30 (3H, singlet);
1.20 (3H, triplet, J = 7.5 Hz).
8(2) 1-(Dimethylsulphamoyl)-5-(2-methyl-6-ethylphenylthio)-4-hydroxypyrazole
1.4 ml of a 1.59 M solution of butyllithium in tetrahydrofuran were added at -78 DEG C to a solution
of 826 mg of 1-(dimethylsulphamoyl)-5-(2-methyl-6-ethylphenylthio)-4-iodopyrazole [prepared as
described in step (1) above] in 30 ml of dry tetrahydrofuran, and the resulting mixture was allowed to
stand for 30 minutes. At the end of this time, a solution of 0.36 g of bistrimethylsilyl peroxide in 2 ml
of dry tetrahydrofuran was added to the mixture, which was then stirred at -78 DEG C for 30 minutes;
the temperature was then allowed to rise to 0 DEG C. The reaction mixture was then mixed with an
aqueous solution of ammonium chloride and extracted with diethyl ether. The extract was washed with
water and dried over anhydrous sodium sulphate; the solvent was then removed by distillation under
reduced pressure.The resulting residue was purified by column chromatography through silica gel,
eluted with a 5 : 1 by volume mixture of hexane and ethyl acetate, to afford 103 mg (yield 16%) of the
title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.35 (1H, singlet);
7.33 - 7.15 (3H, multiplet);
3.04 (6H, singlet);
2.97 (2H, quartet, J = 7.5 Hz);
2.42 (3H, singlet);
1.22 (3H, triplet, J = 7.5 Hz).
8(3) 1-(Dimethylsulphamoyl)-5-(2-methyl-6-ethylphenylthio)-4-methoxypyrazole
25 mg of sodium hydride (as a 50% w/w dispersion in mineral oil), followed by 36 mu l of
iodomethane, were added at 0 DEG C to a solution of 98 mg of 1-(dimethylsulphamoyl)-5-(2-methyl6-ethylphenylthio)-4-hydroxypyrazole [prepared as described in step (2) above] in a mixture of 1.5 ml
of dry tetrahydrofuran and 1 ml of dimethylformamide, and the resulting mixture was stirred for 2
hours. At the end of this time, the reaction mixture was poured into water and extracted with diethyl
ether. The extract was washed with water and dried over anhydrous sodium sulphate, after which the
solvent was removed by distillation under reduced pressure.The resulting residue was purified by
column chromatography through silica gel, eluted with an 8 : 1 by volume mixture of hexane and ethyl
acetate, to afford 74 mg (yield 73%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.41 (1H, singlet);
7.22 - 7.03 (3H, multiplet);
3.31 (3H, singlet);
3.05 (6H, singlet);
2.96 (2H, quartet, J = 7.5 Hz);
2.41 (3H, singlet);
1.17 (3H, triplet, J = 7.5 Hz).
8(4) 1-(Diethylcarbamoyl)-3-(2-methyl-6-ethylphenylthio)-4-methoxypyrazole
253/2194
45 mu l of trifluoroacetic acid were added to a solution of 70 mg of 1-(dimethylsulphamoyl)-5-(2methyl-6-ethylphenylthio)-4-methoxypyrazole [prepared as described in step (3) above] in 1 ml of
chloroform, and the resulting mixture was heated at 60 DEG C for 4 hours. At the end of this time, the
reaction mixture was poured into water and extracted with methylene chloride. The extract was washed
with a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulphate and
concentrated by evaporation under reduced pressure. The concentrate thus obtained was dissolved in
acetonitrile, and 27 mg of 1,4-diazabicyclo[2.2.2]octane and 30 mu l of diethylcarbamoyl chloride
were added, in that order, to the resulting solution, which was then stirred for 5 hours. After this, the
reaction mixture was diluted with water and extracted with ethyl acetate.The extract was washed with a
saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulphate and concentrated
by evaporation under reduced pressure. The crude product thus obtained was purified by column
chromatography through silica gel, eluted with a 6 : 1 by volume mixture of hexane and ethyl acetate,
to afford 66 mg (yield 96%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.68 (1H, singlet);
7.26 - 7.09 (3H, singlet);
3.81 (3H, singlet);
3.33 (4H, quartet, J = 7.0 Hz);
2.92 (2H, quartet; J = 7.6 Hz);
2.46 (3H, singlet);
1.18 (3H, triplet, J = 7.6 Hz);
1.08 - 0.8 (6H, broad).
8(5) 1-(Diethylcarbamoyl)-3-(2-methyl-6-ethylphenylsulphonyl)-4-methoxypyrazole
84 mg of 3-chloroperoxybenzoic acid were added to a solution of 62 mg of 1-(diethylcarbamoyl)-3-(2methyl-6-ethylphenylthio)-4-methoxypyrazole [prepared as described in step (4) above] in 2 ml of 1,2dichloroethane, and the resulting mixture was stirred at 50 DEG C for 2 hours. The reaction mixture
was then mixed with an aqueous solution of sodium sulphite and extracted with methylene chloride.
The extract was washed with an aqueous solution of sodium hydrogencarbonate and with a saturated
aqueous solution of sodium chloride, in that order, after which it was dried over anhydrous sodium
sulphate and concentrated by evaporation under reduced pressure.The concentrate was purified by
column chromatography through silica gel, eluted with a 7 : 1 by volume mixture of hexane and ethyl
acetate, to afford 34 mg (yield 51%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.76 (1H, singlet);
7.36 (1H, triplet, J = 7.6 Hz);
7.17 (1H, doublet, J = 7.6 Hz);
7.10 (1H, doublet, J = 7.6 Hz);
3.80 (3H, singlet);
3.10 (2H, quartet, J = 7.5 Hz);
3.43 (4H, quartet, J = 7.0 Hz);
2.67 (3H, singlet);
1.4 - 0.9 (6H, broad);
1.23 (3H, triplet, J = 7.5 Hz).
EXAMPLE 9
1-(Diethylcarbamoyl)-3-(2-methyl-3-chlorophenylthio)-4-formylpyrazole (Compound No. 4.138)
254/2194
and
1-(Diethylcarbamoyl)-3-(2-methyl-3-chlorophenylsulphonyl)-4-formylpyrazole (Compound No. 4.112)
9(1) 1-(Dimethylsulphamoyl)-5-(2-methyl-3-chlorophenylthio)-4-formylpyrazole
3.3 ml of a 1.59 M solution of butyllithium in tetrahydrofuran were added at -78 DEG C to a solution
of 2.0 g of 1-(dimethylsulphamoyl)-5-(2-methyl-3-chlorophenylthio)-4-iodopyrazole [prepared in a
similar manner to that described in Example 7(1)] in 70 ml of dry tetrahydrofuran, and the resulting
mixture was stirred at that temperature for 20 minutes, after which 0.51 ml of dimethylformamide was
added. The reaction mixture was stirred at the same temperature for 30 minutes, and then the reaction
temperature was allowed to rise to 0 DEG C. The reaction mixture was then mixed with an aqueous
solution of ammonium chloride and extracted with diethyl ether. The extract was washed with a
saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulphate and concentrated
by evaporation under reduced pressure.The concentrate was purified by column chromatography
through silica gel, eluted with a 10 : 1 by volume mixture of hexane and ethyl acetate, to afford 1.05 g
(yield 66%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
9.63 (1H, singlet);
8.10 (1H, singlet);
7.46 - 6.92 (3H, multiplet);
3.11 (6H, singlet);
2.56 (3H, singlet).
9(2) 1-(Diethylcarbamoyl)-3-(2-methyl-3-chlorophenylthio)-4-formylpyrazole
0.14 ml of trifluoroacetic acid was added to a solution of 224 mg of 1-(dimethylsulphamoyl)-5-(2methyl-3-chlorophenylthio)-4-formylpyrazole [prepared as described in step (1) above] in 2.5 ml of
chloroform, and the resulting mixture was stirred at 60 DEG C for 2 hours. At the end of this time, the
reaction mixture was diluted with water and extracted with methylene chloride. The extract was
washed with an aqueous solution of sodium hydrogencarbonate and with water, in that order, and dried
over anhydrous sodium sulphate, after which the solvent was removed by distillation under reduced
pressure. The residue was dissolved in 4 ml of acetonitrile, and 104 mg of 1,4diazabicyclo[2.2.2]octane and 117 mu l of diethylcarbamoyl chloride were added, in that order, to the
resulting solution. The resulting mixture was then stirred for 2 hours.At the end of this time, the
reaction mixture was diluted with water and extracted with ethyl acetate. The extract was washed with
water, dried over anhydrous sodium sulphate and concentrated by evaporation under reduced pressure.
The concentrate was purified by column chromatography through silica gel, eluted with a 6 : 1 by
volume mixture of hexane and ethyl acetate, to afford 96 mg (yield 44%) of the title compound as an
oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
9.99 (1H, singlet);
8.68 (1H, singlet);
7.52 (1H, doublet of doublets, J = 0.9 & 8.5 Hz);
7.42 (1H, doublet of doublets, J = 0.9 & 7.7 Hz);
7.13 (1H, doublet of doublets, J = 7.7 & 8.5 Hz);
3.36 (4H, quartet, J = 7.0 Hz);
2.52 (3H, singlet);
1.35 - 0.6 (6H, broad).
9(3) 1-(Diethylcarbamoyl)-3-(2-methyl-3-chlorophenylsulphonyl)-4-formylpyrazole
255/2194
0.77 g of 3-chloroperoxybenzoic acid was added to a solution of 0.57 g of 1-(diethylcarbamoyl)-3-(2methyl-3-chlorophenylthio)-4-formylpyrazole [prepared as described in step (2) above] in 15 ml of 1,2dichloroethane, and the resulting mixture was stirred at room temperature for 10 hours. The reaction
mixture was then mixed with an aqueous solution of sodium sulphite and extracted with methylene
chloride. The extract was washed with an aqueous solution of sodium hydrogencarbonate and with a
saturated aqueous solution of sodium chloride, in that order, after which it was dried over anhydrous
sodium sulphate and concentrated by evaporation under reduced pressure.The concentrate was purified
by column chromatography through silica gel, eluted with an 8 : 1 by volume mixture of hexane and
ethyl acetate, to afford 198 mg (yield 32%) of the title compound, melting at 95 - 97 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
10.31 (1H, singlet);
8.70 (1H, singlet);
8.20 (1H, doublet of doublets, J = 8.0 & 1.4 Hz);
7.40 (1H, triplet, J = 8.0 Hz);
3.44 (4H, quartet, J = 7.2 Hz);
2.64 (3H, singlet);
1.4 - 1.0 (6H, broad).
EXAMPLE 10
1-(Diethylcarbamoyl)-3-(2-methyl-3-chlorophenylsulphonyl)-4-hydroxymethylpyrazole (Compound
No. 4.102)
11 mg of sodium borohydride were added at 0 DEG C to a solution of 112 mg of 1-(diethylcarbamoyl)3-(2-methyl-3-chlorophenylsulphonyl)-4-formylpyrazole [prepared as described in Example 9(3)] in
3.5 ml of methanol, and the resulting mixture was stirred for 30 minutes. At the end of this time, the
reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with a
saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulphate and concentrated
by evaporation under reduced pressure.The concentrate was purified by column chromatography
through silica gel, eluted with a 5 : 1 by volume mixture of hexane and ethyl acetate, to afford 114 mg
(a quantitative yield) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
8.15 (1H, doublet of doublets, J = 8.0 & 1.4 Hz);
7.67 (1H, doublet of doublets, J = 8.0 & 1.4 Hz);
7.37 (1H, triplet, J = 8.0 Hz);
4.73 (2H, singlet);
3.93 (1H, singlet);
3.43 (4H, quartet, J = 7.0 Hz);
2.63 (3H, singlet);
1.4 - 0.9 (6H, broad).
EXAMPLE 11
1-(Diethylcarbamoyl)-3-(2-methyl-3-chlorophenylsulphonyl)-4-fluoromethylpyrazole (Compound No.
4.107)
20 mu l of diethylaminosulphur trifluoride were added at 0 DEG C to a solution of 54 mg of 1(diethylcarbamoyl)-3-(2-methyl-3-chlorophenylsulphonyl)-4-hydroxymethylpyrazole (prepared as
256/2194
described in Example 10) in 1.8 ml of methylene chloride, and the resulting mixture was stirred for 1
hour. At the end of this time, the reaction mixture was poured into water and extracted with methylene
chloride. The extract was washed with a saturated aqueous solution of sodium chloride, dried over
anhydrous sodium sulphate and concentrated by evaporation under reduced pressure.The concentrate
was purified by column chromatography through silica gel, eluted with an 8 : 1 by volume mixture of
hexane and ethyl acetate, to afford 51 mg (yield 95%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.27 (1H, doublet, J = 2.0 Hz);
8.14 (1H, doublet of doublets, J = 8.0 & 1.2 Hz);
7.66 (1H, doublet of doublets, J = 8.0 & 1.2 Hz);
7.36 (1H, triplet, J = 8.0 Hz);
5.57 (2H, doublet, J = 47.3 Hz);
3.46 (4H, quartet, J = 7.0 Hz);
2.64 (3H, singlet);;
1.4 - 1.0 (6H, broad).
EXAMPLE 12
1-(Diethylcarbamoyl)-3-(2-methyl-6-ethylphenylthio)-4-trifluoromethylpyrazole (Compound No.
7.246)
and
1-(Diethylcarbamoyl)-3-(2-methyl-6-ethylphenylsulphonyl)-4-trifluoromethylpyrazole (Compound No.
7.247)
12(1) 1-(Dimethylsulphamoyl)-5-(2-methyl-6-ethylphenylthio)-4-trifluoromethylpyrazole
0.22 ml of methyl fluorosulphonyl(difluoro)acetate and 73 mg of cuprous iodide were added to a
solution of 346 mg of 1-(dimethylsulphamoyl)-5-(2-methyl-6-ethylphenylthio)-4-iodopyrazole
[prepared as described in Example 8(1)] in 5 ml of dimethylformamide, and the resulting mixture was
heated at 120 DEG C for 4 hours. At the end of this time, the reaction mixture was poured into water
and extracted with diethyl ether. The extract was washed with water, dried over anhydrous sodium
sulphate and concentrated by evaporation under reduced pressure.The concentrate was purified by
column chromatography through silica gel, eluted with a 10 : 1 by volume mixture of hexane and ethyl
acetate, to afford 270 mg (yield 90%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.70 (1H, singlet);
7.28 - 7.06 (3H, multiplet);
3.16 (6H, singlet);
2.87 (2H, quartet, J = 7.6 Hz);
2.30 (3H, singlet);
1.17 (3H, triplet, J = 7.6 Hz).
12(2) 1-(Diethylcarbamoyl)-3-(2-methyl-6-ethylphenylthio)-4-trifluoromethylpyrazole
257/2194
0.12 ml of trifluoroacetic acid was added to a solution of 210 mg of 1-(dimethylsulphamoyl)-5-(2methyl-6-ethylphenylthio)-4-trifluoromethylpyrazole [prepared as described in step (1) above] in 2 ml
of chloroform, and the resulting mixture was heated at 60 DEG C for 1.5 hours. At the end of this time,
the reaction mixture was poured into water and extracted with methylene chloride. The extract was
washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium
sulphate; the solvent was then removed by distillation under reduced pressure. The residue was
dissolved in 4 ml of acetonitrile, and 72 mg of 1,4-diazabicyclo[2.2.2]octane and 81 mu l of
diethylcarbamoyl chloride were added, in that order, to the resulting solution. The resulting mixture
was then heated at 50 DEG C for 2 hours.After this, the reaction mixture was diluted with water and
extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium
chloride, dried over anhydrous sodium sulphate and concentrated by evaporation under reduced
pressure. The concentrate was purified by column chromatography through silica gel, eluted with a 6 :
1 by volume mixture of hexane and ethyl acetate, to afford 203 mg (yield 99%) of the title compound
as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.40 (1H, quartet, J = 1.0 Hz);
7.28 - 7.11 (3H, multiplet);
3.4 - 3.2 (4H, multiplet);
2.88 (2H, quartet, J = 7.5 Hz);
2.43 (3H, singlet);
1.17 (3H, triplet, J = 7.5 Hz);
1.35 - 0.50 (6H, broad).
12(3) 1-(Diethylcarbamoyl)-3-(2-methyl-6-ethylphenylsulphonyl)-4-trifluoromethylpyrazole
189 mg of 3-chloroperoxybenzoic acid were added to a solution of 154 mg of 1-(diethylcarbamoyl)-3(2-methyl-6-ethylphenylthio)-4-trifluoromethylpyrazole [prepared as described in step (2) above] in 5.0
ml of 1,2-dichloroethane, and the resulting mixture was stirred at room temperature for 10 hours. At the
end of this time, the reaction mixture was poured into an aqueous solution of sodium sulphite and
extracted with methylene chloride. The extract was washed with an aqueous solution of sodium
hydrogencarbonate and with a saturated aqueous solution of sodium chloride, in that order, after which
it was dried over anhydrous sodium sulphate and concentrated by evaporation under reduced
pressure.The concentrate was purified by column chromatography through silica gel, eluted with an 8 :
1 by volume mixture of hexane and ethyl acetate, to afford 154 mg (yield 93%) of the title compound
as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.53 (1H, multiplet);
7.46 - 7.12 (3H, multiplet);
3.5 - 3.2 (4H, broad);
3.05 (2H, quartet, J = 7.4 Hz);
2.60 (3H, singlet);
1.24 (3H, triplet, J = 7.4 Hz);
1.4 - 0.6 (6H, broad).
EXAMPLE 13
1-(Diethylcarbamoyl)-3-(3-chlorophenylthio)-4-difluoromethylpyrazole (Compound No. 2.97)
and
258/2194
1-(Diethylcarbamoyl)-3-(3-chlorophenylsulphonyl)-4-difluoromethylpyrazole (Compound No. 2.98)
13(1) 1-(Dimethylsulphamoyl)-4-formylpyrazole
1.26 ml of a 1.4 M solution of t-butyllithium in pentane was added at -78 DEG C to a solution of 299
mg of 1-(dimethylsulphamoyl)-4-bromopyrazole [prepared as described in Example 3(1)] in 7 ml of
dry diethyl ether, and the resulting mixture was stirred for 20 minutes, after which 0.27 ml of
dimethylformamide was added to it. After it had been stirred for 50 minutes, the reaction mixture was
poured into an aqueous solution of ammonium chloride and extracted with ethyl acetate. The extract
was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous sodium
sulphate and concentrated by evaporation under reduced pressure.The concentrate was purified by
column chromatography through silica gel, eluted with an 8 : 1 by volume mixture of hexane and ethyl
acetate, to afford 128 mg (yield 53%) of the title compound, melting at 86 - 88 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
9.96 (1H, singlet);
8.47 (1H, singlet);
8.15 (1H, singlet);
3.01 (6H, singlet).
13(2) 1-(Dimethylsulphamoyl)-4-difluoromethylpyrazole
0.83 ml of diethylaminosulphur trifluoride was added to a solution of 847 mg of 1(dimethylsulphamoyl)-4-formylpyrazole [prepared as described in step (1) above] in 8 ml of methylene
chloride, and the resulting mixture was stirred at room temperature for 19 hours. At the end of this
time, the reaction mixture was diluted with water and extracted with methylene chloride. The extract
was washed with water, dried over anhydrous sodium sulphate and concentrated by evaporation under
reduced pressure.The resulting concentrate was purified by column chromatography through silica gel,
eluted with a 10 : 1 by volume mixture of hexane and ethyl acetate, to afford 777 mg (yield 83%) of the
title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, singlet);
7.86 (1H, singlet);
6.73 (1H, triplet, J = 55.6 Hz);
2.98 (6H, singlet).
13(3) 1-(Dimethylsulphamoyl)-5-(3-chlorophenylthio)-4-difluoromethylpyrazole
0.66 ml of a 1.5 M solution of butyllithium in hexane was added at -78 DEG C to a solution of 203 mg
of 1-(dimethylsulphamoyl)-4-difluoromethylpyrazole [prepared as described in step (2) above] in 5 ml
of tetrahydrofuran, and the resulting mixture was stirred for 30 minutes, after which a solution of 311
mg of 3-chlorophenyl disulphide in 2 ml of dry tetrahydrofuran was added to the mixture. After it had
been stirred for 40 minutes, the reaction mixture was poured into an aqueous solution of ammonium
chloride and extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of
sodium chloride, dried over anhydrous sodium sulphate and concentrated by evaporation under reduced
pressure.The concentrate was purified by column chromatography through silica gel, eluted with a 10 :
1 by volume mixture of hexane and ethyl acetate, to afford 280 mg (yield 84%) of the title compound
as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.93 (1H, singlet);
7.23 - 7.21 (3H, multiplet);
7.15 - 7.07 (1H, multiplet);
6.65 (1H, triplet, J = 54.5 Hz);
259/2194
3.07 (6H, singlet).
13(4) 1-(Diethylcarbamoyl)-3-(3-chlorophenylthio)-4-difluoromethylpyrazole
0.16 ml of trifluoroacetic acid was added to a solution of 253 mg of 1-(dimethylsulphamoyl)-5-(3chlorophenylthio)-4-difluoromethylpyrazole [prepared as described in step (3) above] in 5 ml of 1,2dichloroethane, and the resulting mixture was heated at 50 DEG C for 2 hours. At the end of this time,
the reaction mixture was poured into an aqueous solution of sodium hydrogencarbonate and extracted
with methylene chloride. The extract was dried over anhydrous sodium sulphate, and the solvent was
removed by distillation under reduced pressure. The residue was dissolved in 4 ml of acetonitrile, and
155 mg of 1,4-diazabicyclo[2.2.2]-octane, followed by 0.11 ml of diethylcarbamoyl chloride, were then
added to the resulting solution. The reaction mixture was then heated at 50 DEG C for 1.5 hours, after
which it was diluted with water and extracted with ethyl acetate.The extract was washed with water,
dried over anhydrous sodium sulphate and concentrated by evaporation under reduced pressure. The
concentrate was purified by column chromatography through silica gel, eluted with a 6 : 1 by volume
mixture of hexane and ethyl acetate, to afford 207 mg (yield 83%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.38 (1H, triplet, J = 1.6 Hz);
7.42 - 7.40 (1H, multiplet);
7.32 - 7.22 (3H, multiplet);
6.61 (1H, triplet, J = 55.1 Hz);
3.53 (4H, quartet, J = 6.6 Hz);
1.19 (6H, triplet, J = 6.6 Hz).
13(5) 1-(Diethylcarbamoyl)-3-(3-chlorophenylsulphonyl)-4-difluoromethylpyrazole
250 mg of 3-chloroperoxybenzoic acid were added to a solution of 179 mg of 1-(diethylcarbamoyl)-3(3-chlorophenylthio)-4-difluoromethylpyrazole [prepared as described in step (4) above] in 4 ml of 1,2dichloroethane, and the resulting mixture was heated at 50 DEG C for 1.5 hours. At the end of this
time, the reaction mixture was poured into an aqueous solution of sodium sulphite and extracted with
methylene chloride. The extract was washed with an aqueous solution of sodium hydrogencarbonate
and with a saturated aqueous solution of sodium chloride, in that order, after which it was dried over
anhydrous sodium sulphate and concentrated by evaporation under reduced pressure.The concentrate
was purified by column chromatography through silica gel, eluted with an 8 : 1 by volume mixture of
hexane and ethyl acetate, to afford 170 mg (yield 87%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.38 (1H, doublet, J = 1.6 Hz);
8.02 (1H, triplet, J = 1.6 Hz);
7.91 (1H, triplet of doublets, J = 1.6 & 7.9 Hz);
7.61 (1H, triplet of doublets, J = 1.6 & 7.9 Hz);
7.50 (1H, triplet, J = 7.9 Hz);
7.16 (1H, triplet, J = 54.9 Hz);
3.48 (4H, quartet, J = 7.0 Hz);
1.25 (6H, triplet, J = 7.0 Hz).
EXAMPLE 14
4-Cyano-1-(diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)pyrazole (Compound No. 7.252)
and
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4-Cyano-1-(diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)pyrazole (Compound No. 7.253)
14(1) 4-Cyano-1-(dimethylsulphamoyl)pyrazole
2.03 ml of a 1.48 M solution of t-butyllithium in pentane were added, at -78 DEG C and under an
atmosphere of nitrogen, to a solution of 500 mg of 4-bromo-1-(dimethylsulphamoyl)pyrazole prepared
as described in Example 3(1)] in 20 ml of dry diethyl ether, and the resulting mixture was stirred for 20
minutes, after which 710 mg of p-toluenesulphonyl cyanide were added. The reaction mixture was then
stirred at 0 DEG C for 1 hour, after which it was poured into ice-water and extracted with ethyl acetate.
The extract was dried over anhydrous sodium sulphate and concentrated by evaporation under reduced
pressure.The concentrate was then purified by column chromatography through silica gel, eluted with a
10 : 1 by volume mixture of hexane and ethyl acetate, to afford 245 mg (yield 62%) of the title
compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.37 (1H, singlet);
7.96 (1H, singlet);
3.07 (6H, singlet).
14(2) 4-Cyano-1-(dimethylsulphamoyl)-5-(2-ethyl-6-methylphenylthio)pyrazole
0.47 ml of a 1.49 M solution of butyllithium in hexane was added, at -78 DEG C and under an
atmosphere of nitrogen, to a solution of 138 mg of 4-cyano-1-(dimethylsulphamoyl)pyrazole [prepared
as described in step (1) above] in dry tetrahydrofuran, and after 20 minutes, 200 mg of 2-ethyl-6methylphenyl disulphide were added to the resulting mixture. The reaction mixture was stirred at 0
DEG C for 15 minutes, after which it was mixed with an aqueous solution of ammonium chloride and
extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulphate
over anhydrous sodium sulphate and concentrated by evaporation under reduced pressure.The
concentrate was purified by column chromatography through silica gel, eluted with a 10 : 1 by volume
mixture of hexane and ethyl acetate, to afford 120 mg (yield 50%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.70 (1H, singlet);
7.39 (1H, doublet, J = 7.6 Hz);
7.25 - 7.20 (2H, multiplet);
3.13 (6H, singlet);
2.88 (2H, quartet, J = 7.6 Hz);
2.46 (3H, singlet);
1.23 (3H, triplet, J = 7.6 Hz).
14(3) 4-Cyano-1-(diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)pyrazole
0.13 ml of trifluoroacetic acid was added to a solution of 200 mg of 4-cyano-1-(dimethylsulphamoyl)5-(2-ethyl-6-methylphenylthio)pyrazole [prepared as described in step (2) above] in 5 ml of 1,2dichloroethane, and the resulting mixture was stirred at 50 DEG C for 40 minutes. At the end of this
time, the reaction mixture was poured into ice-water and extracted with methylene chloride. The
extract was dried over anhydrous sodium sulphate and concentrated by evaporation under reduced
pressure. The resulting oily residue was dissolved in 4 ml of acetonitrile, and 90 mu l of
diethylcarbamoyl chloride and 132 mg of 1,4-diaza-bicyclo[2.2.2]octane were added, in that order, to
the resulting solution. The reaction mixture was then stirred at 50 DEG C for 50 minutes, after which it
was poured into ice-water and extracted with ethyl acetate.The extract was washed with water, dried
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over anhydrous sodium sulphate and concentrated by evaporation under reduced pressure. The
concentrate was purified by column chromatography through silica gel, eluted with a 5 : 1 by volume
mixture of hexane and ethyl acetate, to afford 170 mg (yield 87%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.48 (1H, singlet);
7.31 - 7.14 (3H, multiplet);
3.33 (4H, quartet, J = 7.0 Hz);
2.88 (2H, quartet, J = 7.5 Hz);
2.44 (3H, singlet);
1.88 (3H, triplet, J = 7.5 Hz);
1.13 - 0.74 (6H, broad).
14(4) 4-Cyano-1-(diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)pyrazole
200 mg of 3-chloroperoxybenzoic acid were added to a solution of 150 mg of 4-cyano-1(diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)pyrazole [prepared as described in step (3) above]
in 5 ml of 1,2-dichloroethane, and the resulting mixture was heated at 50 DEG C for 2 hours. At the
end of this time, the reaction mixture was poured into an aqueous solution of sodium sulphite and
extracted with methylene chloride. The extract was washed with an aqueous solution of sodium
hydrogencarbonate, dried over anhydrous sodium sulphate and concentrated by evaporation under
reduced pressure.The concentrate was purified by column chromatography through silica gel, eluted
with a 6 : 1 by volume mixture of hexane and ethyl acetate, to afford 153 mg (yield 95%) of the title
compound, melting at 101 - 102 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.59 (1H, singlet);
7.43 (1H, triplet, J = 7.5 Hz);
7.22 - 7.16 (2H, multiplet);
3.46 (4H, quartet, J = 7.1 Hz);
3.12 (2H, quartet, J = 7.4 Hz);
2.70 (3H, singlet);
1.26 (3H, triplet, J = 7.4 Hz);
1.27 - 1.08 (6H, broad).
EXAMPLE 15
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)-5-methylpyrazole (Compound No. 7.342)
and
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-5-methylpyrazole (Compound No. 7.90)
15(1) 1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)-5-methylpyrazole
0.45 ml of a 1.59 M solution of butyllithium in hexane was added at -78 DEG C to a solution of 211
mg of 1-(diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)pyrazole (prepared as described in
Example 17) in 7 ml of dry tetrahydrofuran, and the resulting mixture was allowed to stand for 45
minutes, after which 0.20 ml of iodomethane was added. The mixture was stirred at the same
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temperature for 1.5 hours, and then the temperature of the reaction mixture was allowed to rise to 0
DEG C, upon which it was stirred for a further 15 minutes. The reaction mixture was then mixed with
an aqueous solution of ammonium chloride and extracted with ethyl acetate. The extract was washed
with water, dried over anhydrous sodium sulphate and concentrated by evaporation under reduced
pressure.The concentrate was purified by column chromatography through silica gel, eluted with a 6 : 1
by volume mixture of hexane and ethyl acetate, to afford 190 mg (yield 86%) of the title compound as
an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.37 - 7.32 (1H, multiplet);
7.25 - 7.19 (2H, multiplet);
5.80 (1H, singlet);
3.36 (4H, quartet, J = 7.0 Hz);
2.52 (3H, singlet);
2.35 (3H, singlet);
1.15 (6H, broad).
15(2) 1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-5-methylpyrazole
252 mg of 3-chloroperoxybenzoic acid were added to a solution of 180 mg of 1-(diethylcarbamoyl)-3(2-chloro-6-methylphenylthio)-5-methylpyrazole [prepared as described in step (1) above] in 4 ml of
1,2-dichloroethane, and the resulting mixture was heated at 50 DEG C for 45 minutes. At the end of
this time, the reaction mixture was poured into an aqueous solution of sodium sulphite and extracted
with methylene chloride. The extract was washed with an aqueous solution of sodium
hydrogencarbonate and with water, in that order, after which it was dried over anhydrous sodium
sulphate and the solvent was removed by distillation under reduced pressure.The residue was purified
by column chromatography through silica gel, eluted with an 8 : 1 by volume mixture of hexane and
ethyl acetate, to afford 195 mg (a quantitative yield) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
7.35 - 7.33 (2H, multiplet);
7.25 - 7.21 (1H, multiplet);
6.71 (1H, singlet);
3.43 (2H, quartet, J = 7.0 Hz);
3.13 (2H, quartet, J = 7.0 Hz);
2.84 (3H, singlet);
2.46 (3H, singlet);
1.24 (3H, broad);
0.97 (3H, broad).
EXAMPLE 16
4-Chloro-1-(diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-5-methylthiopyrazole
(Compound No. 7.329)
0.11 ml of a 1.49 M solution of butyllithium in hexane was added, at -78 DEG C and under an
atmosphere of nitrogen, to a solution of 59 mg of 4-chloro-1-(diethylcarbamoyl)-3-(2-ethyl-6methylphenylsulphonyl)pyrazole (prepared as described in Example 18) in 2 ml of dry tetrahydrofuran,
and the resulting mixture was stirred for 30 minutes, after which 15 mu l of methyl disulphide were
added. The resulting reaction mixture was stirred for 30 minutes, and then mixed with an aqueous
solution of ammonium chloride and extracted with diethyl ether. The extract was washed with water,
dried over anhydrous sodium sulphate and concentrated by evaporation under reduced pressure.The
concentrate was purified by column chromatography through silica gel, eluted with a 10 : 1 by volume
mixture of hexane and ethyl acetate, to afford 28 mg (yield 35%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
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7.43 (1H, triplet, J = 7.6 Hz);
7.20 (1H, broad doublet, J = 7.6 Hz);
7.14 (1H, broad doublet, J = 7.6 Hz);
3.50 (1H, quartet, J = 7.2 Hz);
3.16 - 3.02 (4H, multiplet);
2.68 (3H, singlet);
2.45 (3H, singlet);
1.33 - 1.19 (6H, multiplet);
1.04 (3H, triplet, J = 7.0 Hz).
EXAMPLE 17
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)pyrazole (Compound No. 7.19)
17(1) 1-(Dimethylsulphamoyl)-5-(2-chloro-6-methylphenylthio)pyrazole
32.3 ml of a 1.59 M solution of butyllithium in hexane were added, at -78 DEG C and under an
atmosphere of nitrogen, to a solution of 8.18 g of 1-(dimethylsulphamoyl)pyrazole [prepared as
described in Example 1(1)] in 250 ml of dry tetrahydrofuran, and the resulting mixture was allowed to
stand at the same temperature for 40 minutes. At the end of this time, a solution of 14.73 g of 2-chloro6-methylphenyl disulphide in 100 ml of tetrahydrofuran was added to the mixture, which was then
stirred at the same temperature for 1 hour. The reaction mixture was then mixed with an aqueous
solution of ammonium chloride and extracted with ethyl acetate. The extract was washed with water
and dried over anhydrous sodium sulphate, after which it was concentrated by evaporation under
reduced pressure.The concentrate was purified by column chromatography through silica gel, eluted
with a 10 : 1 by volume mixture of hexane and ethyl acetate, to give 13.70 g (yield 88%) of the title
compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.48 (1H, doublet, J = 1.6 Hz);
7.45 - 7.27 (3H, multiplet);
5.32 (1H, doublet, J = 1.6 Hz);
3.05 (6H, singlet);
2.53 (3H, singlet).
17(2) 1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)pyrazole
9.8 ml of trifluoroacetic acid were added to a solution of 12.70 mg of 1-(dimethylsulphamoyl)-5-(2chloro-6-methylphenylthio)pyrazole [prepared as described in step (1) above] in 60 ml of chloroform,
and the resulting mixture was heated at 50 DEG C for 6 hours. The mixture was allowed to cool, after
which it was diluted with water and neutralized with an aqueous solution of sodium
hydrogencarbonate. It was then extracted with ethyl acetate. The extract was washed with water and
dried over anhydrous sodium sulphate, and then the solvent was removed by distillation under reduced
pressure. The residue was dissolved in 110 ml of acetonitrile, and 8.18 ml of diethylcarbamoyl chloride
and 9.02 g of 1,4-diazabicyclo[2.2.2]octane were added to the resulting solution. The reaction mixture
was then stirred at room temperature for 6 hours, after which it was diluted with ethyl acetate; the
resulting solution was washed with 2N aqueous hydrochloric acid, with a 5% w/v aqueous solution of
sodium hydroxide and with water, in that order. The organic layer was separated and dried over
anhydrous sodium sulphate, and then the solvent was removed by distillation under reduced
pressure.The residue thus obtained was purified by column chromatography through silica gel, eluted
with a 3 : 1 by volume mixture of hexane and ethyl acetate, to give 10.29 g (yield 83%) of the title
compound melting at 57 - 58 DEG C.
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Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.06 (1H, doublet, J = 2.5 Hz);
7.38 - 7.32 (1H, multiplet);
7.26 - 7.18 (2H, multiplet);
6.11 (1H, doublet, J = 2.5 Hz);
3.46 (4H, quartet, J = 7.0 Hz);
1.09 (6H, broad).
EXAMPLE 18
1-(Diethylcarbamoyl)-4-chloro-3-(2-ethyl-6-methylphenylthio)pyrazole (Compound No. 7.169)
and
1-(Diethylcarbamoyl)-4-chloro-3-(2-ethyl-6-methylphenylsulphonyl)pyrazole (Compound No. 7.168)
18(1) 1-(Dimethylsulphamoyl)-4-chloro-5-(2-ethyl-6-methylphenylthio)pyrazole
2.6 ml of a 1.49 M solution of butyllithium in hexane were added at -78 DEG C to a solution of 747 mg
of 1-(dimethylsulphamoyl)-4-chloropyrazole [prepared as described in Example 3(1)] in 20 ml of dry
tetrahydrofuran. After 20 minutes, a solution of 1.08 g of 2-ethyl-6-methylphenyl disulphide in 12 ml
of dry tetrahydrofuran was added to the mixture, which was then stirred at the same temperature for 30
minutes. At the end of this time, the reaction mixture was mixed with an aqueous solution of
ammonium chloride and extracted with ethyl acetate. The extract was washed with water and dried
over anhydrous sodium sulphate; the solvent was then removed by distillation under reduced
pressure.The residue thus obtained was purified by column chromatography through silica gel, eluted
with a 4 : 1 by volume mixture of hexane and ethyl acetate, to give 1.19 g (yield 93%) of the title
compound, melting at 68 - 72 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.45 (1H, singlet);
7.21 (1H, doublet, J = 7.3 Hz);
7.14 - 7.06 (2H, multiplet);
3.11 (6H, singlet);
2.92 (2H, quartet, J = 7.5 Hz);
2.36 (3H, singlet);
1.19 (3H, triplet, J = 7.5 Hz).
18(2) 1-(Diethylcarbamoyl)-4-chloro-3-(2-ethyl-6-methylphenylthio)pyrazole
0.76 ml of trifluoroacetic acid was added to a solution of 1.08 g of 1-(dimethylsulphamoyl)-4-chloro-5(2-ethyl-6-methylphenylthio)pyrazole [prepared as described in step (1) above] in 5 ml of methylene
chloride, and the resulting mixture was stirred for 2 hours. The mixture was then diluted with water and
neutralized with an aqueous solution of sodium hydrogencarbonate. It was then extracted with ethyl
acetate. The extract was washed with water and dried over anhydrous sodium sulphate, and then the
solvent was removed by distillation under reduced pressure. The resulting residue was dissolved in 8
ml of acetonitrile, and 0.19 ml of diethylcarbamoyl chloride and 0.31 ml of 1,8diazabicylo[5,4,0]undec-7-ene were added to the resulting solution.The reaction mixture was then
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heated at 50 DEG C for 2 hours, after which it was diluted with ethyl acetate, and the solution thus
obtained was washed with 2N aqueous hydrochloric acid, with a 5% w/v aqueous solution of sodium
hydroxide and with water, in that order. The organic layer was separated and dried over anhydrous
sodium sulphate, and then the solvent was removed by distillation under reduced pressure.The residue
thus obtained was purified by column chromatography through silica gel, eluted with a 6 : 1 by volume
mixture of hexane and ethyl acetate, to give 915 mg (yield 79%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.08 (1H, singlet);
7.23 - 7.10 (3H, singlet);
3.30 (4H, quartet, J = 7.0 Hz);
2.89 (2H, quartet, J = 7.6 Hz);
2.44 (3H, singlet);
1.27 - 1.14 (9H, multiplet).
18(3) 1-(Diethylcarbamoyl)-4-chloro-3-(2-ethyl-6-methylphenylsulphonyl)pyrazole
0.44 g of 3-chloroperoxybenzoic acid were added to a solution of 288 mg of 1-(diethylcarbamoyl)-4chloro-3-(2-ethyl-6-methylphenylthio)pyrazole [prepared as described in step (2) above] in 6 ml of 1,2dichloroethane, and the resulting mixture was heated at 50 DEG C for 2 hours. The reaction mixture
was then diluted with ethyl acetate, after which it was washed with an aqueous solution of sodium
sulphite, with an aqueous solution of sodium hydrogencarbonate and with water, in that order.The
mixture was then dried over anhydrous sodium sulphate, and the solvent was removed by distillation
under reduced pressure, after which the residue was purified by column chromatography through silica
gel, eluted with an 8 : 1 by volume mixture of hexane and ethyl acetate, to give 168 mg (yield 53%) of
the title compound as a gum.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm::
8.16 (1H, singlet);
7.41 (1H, triplet, J = 7.6 Hz);
7.21 (1H, broad doublet, J = 7.3 Hz);
7.15 (1H, broad doublet, J = 7.3 Hz);
3.44 (4H, quartet, J = 7.0 Hz);
3.10 (2H, quartet, J = 7.4 Hz);
2.67 (3H, singlet);
1.24 (3H, triplet, J = 7.4 Hz);
1.5 - 0.9 (6H, broad).
EXAMPLE 19
1-(Diethylcarbamoyl)-4-fluoro-3-(2,4,6-trichlorophenylthio)pyrazole (Compound No. 10.161)
and
1-(Diethylcarbamoyl)-4-fluoro-3-(2,4,6-trichlorophenylsulphonyl)pyrazole (Compound No. 10.92)
19(1) 1-(Dimethylsulphamoyl)-4-fluoropyrazole
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2.1 litres of fluorine gas (10% in N2) were bubbled, at 0 - 5 DEG C, into a solution of 11.1 g of 1(dimethylsulphamoyl)pyrazole [prepared as described in Example 1(1)] and 25.9 g of sodium acetate in
500 ml of a 9 : 1 by volume mixture of chloroform and acetic acid. The mixture was stirred for 2 hours,
after which it was diluted with water. The organic layer was separated, washed with water and dried
over anhydrous sodium sulphate. The solvent was then removed by distillation under reduced pressure.
The resulting residue was purified by column chromatography through silica gel, eluted with a 5 : 1 by
volume mixture of hexane and ethyl acetate, to give 1.77 g (yield 14%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
7.84 (1H, doublet, J = 4.8 Hz);
7.63 (1H, doublet, J = 4.8 Hz);
2.96 (6H, singlet).
19(2) 1-(Dimethylsulphamoyl)-4-fluoro-5-(2,4,6-trichlorophenylthio)pyrazole
0.30 ml of a 1.64 M solution of butyllithium in hexane was added at -78 DEG C to a solution of 76 mg
of 1-(dimethylsulphamoyl)-4-fluoropyrazole [prepared as described in step (1) above] in 3 ml of dry
tetrahydrofuran. After 40 minutes, a solution of 201 mg of 2,4,6-trichlorophenyl disulphide in 2.5 ml of
dry tetrahydrofuran was added to the mixture, which was then stirred at the same temperature for 1
hour. At the end of this time, the reaction mixture was mixed with an aqueous solution of ammonium
chloride and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous
sodium sulphate; the solvent was then removed by distillation under reduced pressure.The residue thus
obtained was purified by column chromatography through silica gel, eluted with an 8 : 1 by volume
mixture of hexane and ethyl acetate, to give 104 mg (yield 65%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.50 (1H, doublet, J = 4.8 Hz);
7.42 (2H, singlet);
3.07 (6H, singlet).
19(3) 1-(Diethylcarbamoyl)-4-fluoro-3-(2,4,6-trichlorophenylthio)pyrazole
0.06 ml of trifluoroacetic acid were added to a solution of 97 mg of 1-(dimethylsulphamoyl)-4-fluoro5-(2,4,6-dichlorophenylthio)pyrazole [prepared as described in step (2) above] in 2 ml of chloro form,
and the resulting mixture was heated at 50 DEG C for 2 hours. The mixture was then allowed to cool,
after which it was diluted with water and neutralized with an aqueous solution of sodium
hydrogencarbonate. It was then extracted with ethyl acetate. The extract was washed with water and
dried over anhydrous sodium sulphate, and then the solvent was removed by distillation under reduced
pressure. The residue was dissolved in 3 ml of acetonitrile, and 34 mu l of diethylcarbamoyl chloride
and 51 mg of 1,4-diazabicyclo[2.2.2]octane were added to the resulting solution.The reaction mixture
was then heated at 50 DEG C for 2 hours, after which it was diluted with ethyl acetate and the solution
was washed with 2N aqueous hydrochloric acid, with a 5% w/v aqueous solution of sodium hydroxide
and with water, in that order. The organic layer was separated and dried over anhydrous sodium
sulphate, and then the solvent was removed by distillation under reduced pressure. The residue thus
obtained was purified by column chromatography, eluted with a 10 : 1 by volume mixture of hexane
and ethyl acetate, to give 73 mg (yield 77%) of the title compound as an oil.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.95 (1H, doublet, J = 4.8Hz);
7.44 (2H, singlet);
3.43 (2H, quartet, J = 7.0 Hz);
1.10 (3H, triplet, J = 7.0 Hz).
19(4) 1-(Diethylcarbamoyl)-4-fluoro-3-(2,4,6-trichlorophenylsulphonyl)pyrazole
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83 mg of 3-chloroperoxybenzoic acid were added to a solution of 69 mg of 1-(diethylcarbamoyl)-4fluoro-3-(2,4,6-trichlorophenylthio)pyrazole [prepared as described in step (3) above] in 2 ml of 1,2dichloroethane, and the resulting mixture was heated at 50 DEG C for 4 hours. The reaction mixture
was then diluted with ethyl acetate, after which it was washed with an aqueous solution of sodium
sulphite, with an aqueous solution of sodium hydrogencarbonate and with water, in that order.The
mixture was then dried over anhydrous sodium sulphate, and the solvent was removed by distillation
under reduced pressure, after which the residue was purified by column chromatography through silica
gel, eluted with a 6 : 1 by volume mixture of hexane and ethyl acetate, to give 65 mg (yield 88%) of the
title compound, melting at 89 - 90 DEG C.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.06 (1H, doublet, J = 5.0 Hz);
7.49 (2H, singlet);
3.46 (4H, broad quartet, J = 7.0 Hz);
1.40 - 0.95 (6H, broad).
By using the procedures described in Examples 1 to 19, the following compounds were also prepared.
1-(Diethylcarbamoyl)-3-phenylsulphonylpyrazole (Compound No. 1.1)
Following the procedure of Example 1, there were obtained 194 mg (yield 59.7%) of the title
compound, melting at 65 - 66.5 DEG C.
1-(Diethylcarbamoyl)-3-phenylthiopyrazole (Compound No. 1.2)
Following the procedure of Example 1, there were obtained 463 mg (yield 60.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.11 (1H, doublet, J = 2.6 Hz);
7.44 (2H, doublet of doublets, J = 1.4 & 7.8 Hz);
7.34 - 7.28 (3H, multiplet);
6.25 (1H, doublet, J = 2.6 Hz);
3.57 (4H, broad quartet, J = 7.0 Hz);
1.21 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-fluorophenylsulphonyl)pyrazole (Compound No. 1.4)
Following the procedure of Example 1, there were obtained 185 mg (yield 65.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.19 (1H, doublet, J = 2.9 Hz);
8.16 (1H, doublet of triplets, J = 1.7 & 8.0 Hz);
7.68 - 7.60 (1H, multiplet);
7.35 (1H, triplet, J = 7.5 Hz);
7.17 (1H, triplet, J = 8.0 Hz);
6.96 (1H, doublet, J = 2.9 Hz);
3.48 (4H, broad quartet, J = 7.0 Hz);
1.18 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-fluorophenylthio)pyrazole (Compound No. 1.5)
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Following the procedure of Example 1, there were obtained 627 mg (yield 70.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.12 (1H, doublet, J = 2.6 Hz);
7.45 - 7.10 (4H, multiplet);
6.27 (1H, doublet, J = 2.6 Hz);
3.53 (4H, broad quartet, J = 7.0 Hz);
1.17 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-chlorophenylsulphonyl)pyrazole (Compound No. 1.6)
Following the procedure of Example 1, there were obtained 154 mg (yield 57.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.37 - 8.32 (1H, multiplet);
8.12 (1H, doublet, J = 2.8 Hz);
7.59 - 7.46 (4H, multiplet);
6.99 (1H, doublet, J = 2.8 Hz);
3.42 (4H, quartet, J = 7.0 Hz);
1.4 - 0.8 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chlorophenylsulphinyl)pyrazole (Compound No. 1.7)
Following the procedure of Example 1, there were obtained 172 mg (yield 61.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.8 Hz);
8.12 (1H, doublet of doublets, J = 2.0 & 7.6 Hz);
7.61 - 7.43 (4H, multiplet);
6.51 (1H, doublet, J = 2.8 Hz);
3.56 - 3.44 (4H, multiplet);
1.3 - 1.1 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-bromophenylsulphonyl)pyrazole (Compound No. 1.8)
Following the procedure of Example 1, there were obtained 203 mg (yield 36.3%) of the title
compound, melting at 54 - 56 DEG C.
1-(Diethylcarbamoyl)-3-(2-bromophenylthio)pyrazole (Compound No. 1.9)
Following the procedure of Example 1, there were obtained 712 mg (yield 39.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.7 Hz);
7.57 (1H, doublet of doublets, J = 7.7 & 1.1 Hz);
7.26 - 7.08 (3H, multiplet);
6.39 (1H, doublet, J = 2.7 Hz);
3.57 (4H, quartet, J = 7.0 Hz);
1.20 (6H, triplet, J = 7.0 Hz).
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1-(Diethylcarbamoyl)-3-(2-methylphenylsulphonyl)pyrazole (Compound No. 1.10)
Following the procedure of Example 1, there were obtained 179 mg (yield 59.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.20 - 8.17 (1H, multiplet);
8.18 (1H, doublet, J = 2.6 Hz);
7.51 (1H, doublet of triplets, J = 7.5 & 1.2 Hz);
7.41 - 7.36 (1H, multiplet);
7.29 - 7.26 (1H, multiplet);
6.87 (1H, doublet, J = 2.6 Hz);
3.45 (4H, broad quartet, J = 7.0 Hz);
2.58 (3H, singlet);
1.15 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-methylphenylthio)pyrazole (Compound No. 1.11)
Following the procedure of Example 1, there were obtained 605 mg (yield 69.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.10 (1H, doublet, J = 2.9 Hz);
7.41 (1H, broad doublet, J = 7.0 Hz);
7.24 - 7.11 (3H, multiplet);
6.16 (1H, doublet, J = 2.9 Hz);
3.54 (4H, broad quartet, J = 7.0 Hz);
2.42 (3H, singlet);
1.17 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-methylbenzylsulphonyl)pyrazole (Compound No. 1.12)
Following the procedure of Example 1, there were obtained 151 mg (yield 48.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.9 Hz);
7.26 - 7.12 (4H, multiplet);
6.64 (1H, doublet, J = 2.9 Hz);
4.57 (2H, singlet);
3.54 (4H, quartet, J = 7.0 Hz);
2.34 (3H, singlet);
1.29 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-methylbenzylthio)pyrazole (Compound No. 1.13)
Following the procedure of Example 1, there were obtained 574 mg (yield 56.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.10 (1H, doublet, J = 2.9 Hz);
7.29 - 7.11 (4H, multiplet);
6.22 (1H, doublet, J = 2.9 Hz);
4.29 (2H, singlet);
3.60 (4H, quartet, J = 7.0 Hz);
2.42 (3H, singlet);
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1.28 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-ethylphenylthio)pyrazole (Compound No. 1.14)
Following the procedure of Example 1, there were obtained 1.53 g (yield 39.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, doublet, J = 2.0 Hz);
7.41 (1H, doublet, J = 7.5 Hz);
7.26 (2H, doublet of doublets, J = 2.4 & 1.1 Hz);
7.24 - 7.11 (1H, multiplet);
6.15 (1H, doublet, J = 2.0 Hz);
3.54 (4H, quartet, J = 7.0 Hz);
2.84 (2H, quartet, J = 7.4 Hz);
1.22 (6H, triplet, J = 7.0 Hz);
1.18 (3H, triplet, J = 7.4 Hz).
1-(Diethylcarbamoyl)-3-(2-ethylphenylsulphonyl)pyrazole (Compound No. 1.15)
Following the procedure of Example 2, there were obtained 228 mg (yield 39.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.6 Hz);
7.57 (1H, triplet of doublets, J = 7.4 & 1.5 Hz);
7.38 (2H, multiplet);
6.86 (1H, doublet, J = 2.6 Hz);
3.45 (4H, quartet, J = 7.4 Hz);
2.99 (2H, quartet, J = 7.4 Hz);
1.19 (9H, triplet, J = 7.4 Hz).
1-(Diethylcarbamoyl)-3-(2-isopropylphenylsulphonyl)pyrazole (Compound No. 1.16)
Following the procedure of Example 1, there were obtained 161 mg (yield 17.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.7 Hz);
7.63 - 7.32 (4H, multiplet);
6.85 (1H, doublet, J = 2.7 Hz);
3.88 (1H, septet, J = 6.8 Hz);
3.45 (4H, quartet, J = 7.0 Hz);
1.35 - 0.98 (6H, broad);
1.11 (6H, doublet, J = 6.8 Hz).
1-(Diethylcarbamoyl)-3-(2-benzylphenylsulphonyl)pyrazole (Compound No. 1.17)
Following the procedure of Example 1, there were obtained 226 mg (yield 37.0%) of the title
compound, melting at 72 - 73 DEG C.
1-(Diethylcarbamoyl)-3-(2-benzylphenylthio)pyrazole (Compound No. 1.18)
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Following the procedure of Example 1, there were obtained 497 mg (yield 37.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.08 (1H, doublet, J = 2.9 Hz);
7.48 - 7.43 (1H, multiplet);
7.31 - 7.12 (8H, multiplet);
6.12 (1H, doublet, J = 2.9 Hz);
4.20 (2H, singlet);
3.53 (4H, quartet, J = 7.0 Hz);
1.17 (4H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-methoxyphenylsulphonyl)pyrazole (Compound No. 1.19)
Following the procedure of Example 1, there were obtained 193 mg (yield 69.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.15 (1H, doublet, J = 2.9 Hz);
7.59 (1H, doublet of triplets, J = 1.7 & 8.7 Hz);
7.12 (1H, triplet, J = 7.2 Hz);
6.97 - 6.94 (1H, multiplet);
6.94 (1H, doublet, J = 2.9 Hz);
3.80 (3H, singlet);
3.40 (4H, broad quartet, J = 7.0 Hz);
1.15 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-methoxyphenylthio)pyrazole (Compound No. 1.20)
Following the procedure of Example 1, there were obtained 619 mg (yield 69.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.12 (1H, doublet, J = 2.6 Hz);
7.29 - 7.23 (2H, multiplet);
6.90 (2H, doublet, J = 8.0 Hz);
6.26 (1H, doublet, J = 2.6 Hz);
3.87 (3H, singlet);
3.57 (4H, broad quartet, J = 7.0 Hz);
1.20 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-phenoxyphenylsulphonyl)pyrazole (Compound No. 1.21)
Following the procedure of Example 1, there were obtained 330 mg (yield 67.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.24 (1H, doublet, J = 8.1 Hz);
8.11 (1H, doublet, J = 2.6 Hz);
7.51 (1H, triplet, J = 8.1 Hz);
7.36 - 7.12 (5H, multiplet);
6.93 (1H, doublet, J = 2.6 Hz);
6.87-6.81 (2H, multiplet);
3.47 (4H, quartet, J = 6.8 Hz);
1.16 - 1.08 (6H, multiplet).
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1-(Diethylcarbamoyl)-3-(2-phenoxyphenylthio)pyrazole (Compound No. 1.22)
Following the procedure of Example 1, there were obtained 1.06 g (yield 67.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.6 Hz);
7.37 - 6.89 (9H, multiplet);
6.34 (1H, doublet, J = 2.6 Hz);
3.57 (4H, quartet, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-trifluoromethylphenylsulphonyl)pyrazole (Compound No. 1.23)
Following the procedure of Example 1, there were obtained 214 mg (yield 46.8%) of the title
compound, melting at 67 - 68 DEG C.
1-(Diethylcarbamoyl)-3-(2-trifluoromethylphenylthio)pyrazole (Compound No. 1.24)
Following the procedure of Example 1, there were obtained 864 mg (yield 47.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.6 Hz);
7.69 (1H, doublet of doublets, J = 2.2 & 7.0 Hz);
7.44 - 7.30 (3H, multiplet);
6.31 (1H, doublet, J = 2.6 Hz);
3.60 (4H, quartet, J = 6.9 Hz);
1.37 (3H, triplet, J = 6.9 Hz).
Ethyl 2-(1-diethylcarbamoyl-3-pyrazolylthio)benzoate (Compound No. 1.26)
Following the procedure of Example 1, there were obtained 203 mg (yield 55.2%) of the title
compound, melting at 47 - 49 DEG C.
Ethyl 2-(1-diethylcarbamoyl-3-pyrazolylsulphonyl)benzoate (Compound No. 1.27)
Following the procedure of Example 1, there were obtained 154 mg (yield 55.2%) of the title
compound, melting at 59 - 61 DEG C.
1-(Diethylcarbamoyl)-3-(2-benzylphenylthio)-5-formylpyrazole (Compound No. 1.30)
Following the procedure of Example 15, there were obtained 76 mg (yield 23.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
10.0 (1H, singlet);
7.49 (1H, doublet, J = 6.7 Hz);
7.30 - 7.10 (8H, multiplet);
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6.58 (1H, singlet);
4.20 (2H, singlet);
3.52 - 3.33 (4H, multiplet);
1.34 - 1.10 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(2-chlorophenylsulphonyl)-4-fluoropyrazole (Compound No. 1.37)
Following the procedure of Example 19, there were obtained 82 mg (yield 8.5%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.36 - 8.31 (1H, multiplet);
8.01 (1H, doublet, J = 4.8 Hz);
7.61 - 7.47 (3H, multiplet);
3.46 (4H, quartet, J = 7.0 Hz);
1.29 - 1.08 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-ethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 1.38)
Following the procedure of Example 19, there were obtained 74 mg (yield 7.8%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, doublet, J = 7.5 Hz);
8.00 (1H, doublet J = 4.8 Hz);
7.59 (1H, triplet of doublets, J = 7.5 & 1.4 Hz);
7.40 (2H, triplet of doublets, J = 7.5 & 1.4 Hz);
3.49 (4H, broad quartet, J = 6.3 Hz);
3.03 (2H, quartet, J = 7.4 Hz);
1.22 (6H, triplet, J = 6.3 Hz).
1.20 (3H, triplet, J = 7.4 Hz).
1-(Diethylcarbamoyl)-3-(2-trifluoromethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 1.40)
Following the procedure of Example 19, there were obtained 26 mg (yield 2.9%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200,MHz), delta ppm:
8.55 - 8.51 (1H, multiplet);
7.94 (1H, doublet, J = 5.7 Hz);
7.88 - 7.66 (3H, multiplet);
3.43 (4H, quartet, J = 7.0 Hz);
1.27 - 1.05 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chlorophenylthio)-4-chloropyrazole (Compound No. 1.56)
Following the procedure of Example 3, there were obtained 216 mg (yield 44.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, singlet);
7.44 - 7.39 (1H, multiplet);
7.20 - 7.17 (3H, multiplet);
3.52 (4H, quartet, J = 7.0 Hz);
1.66 (6H, triplet, J = 7.0 Hz).
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1-(Diethylcarbamoyl)-3-(2-chlorophenylsulphonyl)-4-chloropyrazole (Compound No. 1.57)
Following the procedure of Example 3, there were obtained 146 mg (yield 33.1%) of the title
compound, melting at 84 - 86 DEG C.
1-(Diethylcarbamoyl)-3-(2-ethylphenylsulphonyl)-4-chloropyrazole (Compound No. 1.58)
Following the procedure of Example 5, there were obtained 128 mg (yield 9.8%) of the title compound,
melting at 68 - 69 DEG C.
Ethyl 2-(1-diethylcarbamoyl-4-chloro-3-pyrazolylthio)benzoate (Compound No. 1.59)
Following the procedure of Example 5, there were obtained 150 mg (yield 44.0%) of the title
compound, melting at 113 - 117 DEG C.
Ethyl 2-(1-diethylcarbamoyl-4-chloro-3-pyrazolylsulphonyl)benzoate (Compound No. 1.60)
Following the procedure of Example 5, there were obtained 112 mg (yield 40.7%) of the title
compound, melting at 54 - 58 DEG C.
1-(Diethylcarbamoyl)-3-(2-ethylphenylsulphonyl)-4-bromopyrazole (Compound No. 1.79)
Following the procedure of Example 4, there were obtained 89 mg (yield 10.0%) of the title compound,
melting at 65 - 67 DEG C.
1-(Diethylcarbamoyl)-3-(2-trifluoromethylphenylthio)-4-fluoropyrazole (Compound No. 1.80)
Following the procedure of Example 19, there were obtained 33 mg (yield 3.9%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.02 (1H, doublet, J = 5.1 Hz);
7.69 (1H, doublet, J = 7.2 Hz);
7.43 - 7.35 (3H, multiplet);
3.54 (4H, quartet, J = 7.0 Hz);
1.20 (6H, triplet J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-methylphenylsulphonyl)-4-fluoropyrazole (Compound No. 1.81)
Following the procedure of Example 7, there were obtained 12 mg (yield 1.5%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, doublet of doublets, J = 7.9 & 1.4 Hz);
8.00 (1H, doublet, J = 4.8 Hz);
7.54 (1H, triplet of doublets, J = 7.9 & 1.4 Hz);
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7.40 (1H, triplet, J = 7.9 Hz);
7.30 (1H, doublet, J = 7.9 Hz);
3.49 (4H, quartet, J = 6.9 Hz);
2.61 (3H, singlet);
1.20 (6H, triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(3-fluorophenylsulphonyl)pyrazole (Compound No. 2.1)
Following the procedure of Example 1, there were obtained 219 mg (yield 50.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.7 Hz);
7.83 (1H, multiplet);
7.74 (1H, multiplet);
7.53 (1H, multiplet);
7.33 (1H, multiplet);
6.88 (1H, doublet, J = 2.7 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-fluorophenylthio)pyrazole (Compound No. 2.2)
Following the procedure of Example 1, there were obtained 567 mg (yield 51.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.4 Hz);
7.32 - 7.11 (3H, multiplet);
6.98 (1H, multiplet);
6.33 (1H, triplet, J = 2.4 Hz);
3.58 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chlorophenylthio)pyrazole (Compound No. 2.3)
Following the procedure of Example 1, there were obtained 585 mg (yield 72.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.6 Hz);
7.39 - 7.20 (4H, multiplet);
6.33 (1H, doublet, J = 2.6 Hz);
3.57 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chlorophenylsulphonyl)pyrazole (Compound No. 2.4)
Following the procedure of Example 1, there were obtained 217 mg (yield 63.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, doublet, J = 2.9 Hz);
8.03 (1H, triplet, J = 1.7 Hz);
7.94 - 7.89 (1H, multiplet);
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7.62 - 7.57 (1H, multiplet);
7.48 (1H, triplet, J = 7.7 Hz);
6.88 (1H, doublet, J = 2.9 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-bromophenylthio)pyrazole (Compound No. 2.5)
Following the procedure of Example 1, there were obtained 747 mg (yield 63.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.7 Hz);
7.55 (1H, triplet, J = 1.7 Hz);
7.40 - 7.30 (2H, multiplet);
7.16 (1H, triplet, J = 8.0 Hz);
6.33 (1H, doublet, J = 2.7 Hz);
3.57 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-bromophenylsulphonyl)pyrazole (Compound No. 2.6)
Following the procedure of Example 1, there were obtained 229 mg (yield 55.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.10 - 8.16 (2H, multiplet);
7.99 - 7.93 (1H, multiplet);
7.78 - 7.72 (1H, multiplet);
7.42 (1H, triplet, J = 7.9 Hz);
6.88 (1H, doublet, J = 2.7 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-methylphenylsulphonyl)pyrazole (Compound No. 2.7)
Following the procedure of Example 1, there were obtained 367 mg (yield 49.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.8 Hz);
7.85 - 7.82 (1H, multiplet);
7.44 - 7.41 (1H, multiplet);
6.86 (1H, doublet, J = 2.8 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
2.43 (3H, singlet);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-methylphenylthio)pyrazole (Compound No. 2.8)
Following the procedure of Example 1, there were obtained 2.18 g (yield 49.4%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.11 (1H, doublet, J = 2.7 Hz);
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7.23 - 7.06 (4H, multiplet);
6.25 (1H, doublet, J = 2.7 Hz);
3.68 (4H, quartet, J = 7.0 Hz);
2.32 (3H, singlet);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-isopropylphenylthio)pyrazole (Compound No. 2.9)
Following the procedure of Example 1, there were obtained 706 mg (yield 54.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.11 (1H, doublet, J = 2.5 Hz);
7.32 - 7.11 (4H, multiplet);
6.23 (1H, doublet, J = 2.5 Hz);
3.57 (4H, quartet, J = 7.0 Hz);
2.87 (1H, septet, J = 7.0 Hz);
1.23 (6H, doublet, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-isopropylphenylsulphonyl)pyrazole (Compound No. 2.10)
Following the procedure of Example 1, there were obtained 147 mg (yield 48.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.8 Hz);
7.89 - 7.81 (2H, multiplet);
7.48 - 7.40 (2H, multiplet);
6.86 (1H, doublet, J = 2.8 Hz);
3.49 (4H, quartet, J = 6.9 Hz);
2.99 (1H, septet, J = 6.9 Hz);
1.27 (6H, doublet, J = 6.9 Hz);
1.21 (6H, triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(3-methoxyphenylthio)pyrazole (Compound No. 2.11)
Following the procedure of Example 1, there were obtained 615 mg (yield 73.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.11 (1H, doublet, J = 2.6 Hz);
7.21 (1H, triplet, J = 7.9 Hz);
7.01 - 6.95 (2H, multiplet);
6.83 - 6.77 (1H, multiplet);
6.28 (1H, doublet, J = 2.6 Hz);
3.76 (3H, singlet);
3.58 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-methoxyphenylsulphonyl)pyrazole (Compound No. 2.12)
Following the procedure of Example 1, there were obtained 169 mg (yield 69.4%) of the title
compound, as an oily substance.
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Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.7 Hz);
7.63 - 7.58 (1H, multiplet);
7.52 (1H, triplet, J = 2.3 Hz);
7.43 (1H, triplet, J = 7.9 Hz);
7.17 - 7.11 (1H, multiplet);
6.85 (1H, doublet, J = 2.7 Hz);
3.85 (3H, singlet);
3.48 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-cyanophenylsulphonyl)pyrazole (Compound No. 2.13)
Following the procedure of Example 1, there were obtained 304 mg (yield 48.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.35 - 8.23 (2H, multiplet);
8.19 (1H, doublet, J = 2.8 Hz);
7.91 (1H, doublet of triplets, J = 7.9 & 1.4 Hz);
7.70 (1H, triplet, J = 7.9 Hz);
6.91 (1H, doublet, J = 2.8 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-cyanophenylthio)pyrazole (Compound No. 2.14)
Following the procedure of Example 1, there were obtained 808 mg (yield 52.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.21 (1H, doublet, J = 2.7 Hz);
7.66 - 7.40 (4H, multiplet);
6.38 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-trifluoromethylphenylthio)pyrazole (Compound No. 2.15)
Following the procedure of Example 1, there were obtained 633 mg (yield 47.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.8 Hz);
7.67 - 7.41 (4H, multiplet);
6.35 (1H, doublet, J = 2.8 Hz);
3.55 (4H, quartet, J = 7.0 Hz);
1.19 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-trifluoromethylphenylsulphonyl)pyrazole (Compound No. 2.16)
Following the procedure of Example 1, there were obtained 232 mg (yield 43.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.33 - 8.19 (2H, multiplet);
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8.18 (1H, doublet, J = 2.6 Hz);
7.91 - 7.88 (1H, multiplet);
7.70 (1H, triplet, J = 8.0 Hz);
6.91 (1H, doublet, J = 2.6 Hz);
3.48 (4H, quartet, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
Ethyl 3-(1-diethylcarbamoyl-3-pyrazolylthio)benzoate (Compound No. 2.18)
Following the procedure of Example 1, there were obtained 279 mg (yield 80.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.7 Hz);
8.13 - 8.11 (1H, multiplet);
7.96 - 7.91 (1H, multiplet);
7.62 - 7.57 (1H, multiplet);
7.40 (1H, triplet, J = 7.7 Hz);
6.30 (1H, doublet, J = 2.7 Hz);
4.37 (2H, quartet, J = 7.1 Hz);
3.56 (4H, broad quartet, J = 7.0 Hz);
1,38 (3H, triplet, J = 7.0 Hz);
1.20 (6H, triplet, J = 7.0 Hz).
Ethyl 3-(1-diethylcarbamoyl-3-pyrazolylsulphonyl)benzoate (Compound No. 2.19)
Following the procedure of Example 1, there were obtained 262 mg (yield 80.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.68 (1H, triplet, J = 1.7 Hz);
8.33 - 8.19 (2H, multiplet);
8.17 (1H, doublet, J = 2.7 Hz);
7.64 (1H, triplet, J = 7.8 Hz);
6.90 (1H, doublet, J = 2.7 Hz);
4.41 (2H, quartet, J = 7.1 Hz);
3.48 (4H, broad quartet, J = 7.0 Hz);
1.41 (3H, triplet, J = 7.1 Hz);
1.21 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-methylthiophenylthio)pyrazole (Compound No. 2.21)
Following the procedure of Example 1, there were obtained 737 mg (yield 60.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.13 (1H, doublet, J = 2.3 Hz);
7.30 - 7.11 (4H, multiplet);
6.29 (1H, doublet, J = 2.3 Hz);
3.58 (4H, quartet, J = 7.0 Hz);
2.45 (3H, singlet);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-methylsulphonylphenylsulphonyl)pyrazole (Compound No. 2.22)
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Following the procedure of Example 1, there were obtained 334 mg (yield 60.0%) of the title
compound, melting at 133 - 135 DEG C.
1-(Diethylcarbamoyl)-3-(3-fluorophenylthio)-4-chloropyrazole (Compound No. 2.41)
Following the procedure of Example 3, there were obtained 242 mg (yield 53.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
7.33 - 7.22 (1H, multiplet);
7.18 - 7.00 (2H, multiplet);
7.00 - 6.90 (1H, multiplet);
3.54 (4H, quartet, J = 6.9 Hz);
1.20 (6H, triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(3-fluorophenylsulphonyl)-4-chloropyrazole (Compound No. 2.42)
Following the procedure of Example 3, there were obtained 216 mg (yield 49.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.13 (1H, singlet);
7.87 (1H, doubled doublet of doublets, J = 7.8, 2.0 & 1.1 Hz);
7.76 (1H, triplet of doublets, J = 2.0 & 8.1 Hz);
7.56 (1H, triplet of doublets, J = 8.1 & 5.1 Hz);
7.36 (1H, tripled doublet of doublets, J = 8.1, 2.0 & 1.1 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chlorophenylthio)-4-chloropyrazole (Compound No. 2.43)
Following the procedure of Example 3, there were obtained 398 mg (yield 33.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
7.40 - 7.22 (4H, multiplet);
3.54 (4H, quartet, J = 7.0 Hz);
1.19 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chlorophenylsulphonyl)-4-chloropyrazole (Compound No. 2.44)
Following the procedure of Example 3, there were obtained 354 mg (yield 31.4%) of the title
compound, melting at 77 - 79 DEG C.
1-(Diethylcarbamoyl)-3-(3-bromophenylsulphonyl)-4-chloropyrazole (Compound No. 2.45)
Following the procedure of Example 4, there were obtained 220 mg (yield 42.0%) of the title
compound, as an oily substance.
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Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, triplet, J = 1.1 Hz);
8.13 (1H, singlet);
8.00 (1H, doublet of triplets, J = 8.0 & 1.1 Hz);
7.78 (1H, doublet of triplets, J = 8.0 & 1.1 Hz);
7.45 (1H, triplet, J = 8.0 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-methylthiophenylthio)-4-chloropyrazole (Compound No. 2.46)
Following the procedure of Example 3, there were obtained 834 mg (yield 47.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, singlet);
7.30 - 7.12 (4H, multiplet);
3.52 (4H, quartet, J = 6.9 Hz);
2.45 (3H, singlet);
1.18 (6H, triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(3-methylsulphonylphenylsulphonyl)-4-chloropyrazole (Compound No. 2.50)
Following the procedure of Example 3, there were obtained 331 mg (yield 44.9%) of the title
compound, melting at 127 - 130 DEG C.
1-(Diethylcarbamoyl)-3-(3-trifluoromethylphenylthio)-4-chloropyrazole (Compound No. 2.51)
Following the procedure of Example 3, there were obtained 186 mg (yield 45.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.70 (1H, singlet);
7.70 - 7.40 (4H, multiplet);
3.08 (6H, singlet).
1-(Diethylcarbamoyl)-3-(3-trifluoromethylphenylsulphonyl)-4-chloropyrazole (Compound No. 2.52)
Following the procedure of Example 3, there were obtained 146 mg (yield 36.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.34 (1H, singlet);
8.27 (1H, doublet, J = 8.0 Hz);
8.15 (1H, singlet);
7.93 (1H, doublet, J = 8.0 Hz);
7.74 (1H, doublet, J = 8.0 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
Ethyl 3-(1-diethylcarbamoyl-4-chloro-3-pyrazolylthio)benzoate (Compound No. 2.53)
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Following the procedure of Example 4, there were obtained 346 mg (yield 60.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
8.13 - 8.11 (1H, multiplet);
7.95 (1H, doublet of triplets, J = 8.0 & 1.5 Hz);
7.58 (1H, doublet of triplets, J = 8.0 & 1.5 Hz);
7.39 (1H, triplet, J = 8.0 Hz);
4.37 (2H, quartet, J = 7.0 Hz);
3.51 (4H, broad quartet, J = 7.0 Hz);
1.39 (3H, triplet, J = 7.0 Hz);
1.16 (6H, broad triplet, J = 7.0 Hz).
Ethyl 3-(1-diethylcarbamoyl-4-chloro-3-pyrazolylsulphonyl)benzoate (Compound No. 2.54)
Following the procedure of Example 4, there were obtained 318 mg (yield 60.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.70 (1H, triplet, J = 1.6 Hz);
8.33 (1H, doublet of triplets, J = 7.8 & 1.6 Hz);
8.25 (1H, doublet of triplets, J = 7.8 & 1.6 Hz);
8.13 (1H, singlet);
7.66 (1H, triplet, J = 7.8 Hz);
4.42 (2H, quartet, J = 7.1 Hz);
3.49 (4H, broad quartet, J = 7.0 Hz);
1.41 (3H, triplet, J = 7.1 Hz);
1.22 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-methoxyphenylsulphonyl)-4-chloropyrazole (Compound No. 2.56)
Following the procedure of Example 3, there were obtained 118 mg (yield 14.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.12 (1H, singlet);
7.64 (1H, doublet of doublets, J = 8.0 & 1.2 Hz);
7.56 (1H, doublet, J = 1.2 Hz);
7.45 (1H, triplet, J = 8.0 Hz);
7.17 (1H, doublet of doublets, J = 8.0 & 0.9 Hz);
3.86 (3H, singlet);
3.50 (4H, broad quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-fluorophenylthio)-4-bromopyrazole (Compound No. 2.58)
Following the procedure of Example 4, there were obtained 203 mg (yield 47.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, singlet);
7.29 (1H, triplet of doublets, J = 8.2 & 5.6 Hz);
7.19 - 7.06 (2H, multiplet);
6.96 (1H, tripled doublet of doublets, J = 8.2, 2.4 & 1.1 Hz);
3.53 (4H, quartet, J = 7.1 Hz);
1.19 (6H, triplet, J = 7.1 Hz).
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1-(Diethylcarbamoyl)-3-(3-fluorophenylsulphonyl)-4-bromopyrazole (Compound No. 2.59)
Following the procedure of Example 4, there were obtained 194 mg (yield 46.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
7.88 (1H, doubled doublet of doublets, J = 7.8, 2.0 & 1.0 Hz);
7.77 (1H, triplet of doublets, J = 2.0 & 8.1 Hz);
7.56 (1H, triplet of doublets, J = 8.1 & 5.2 Hz);
7.36 (1H, tripled doublet of doublets, J = 8.1, 2.0 & 1.0 Hz);
3.49 (4H, quartet, J = 6.9 Hz);
1.23 (6H, triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(3-bromophenylthio)-4-bromopyrazole (Compound No. 2.60)
Following the procedure of Example 4, there were obtained 170 mg (yield 46.7%) of the title
compound, melting at 65 - 65.5 DEG C.
1-(Diethylcarbamoyl)-3-(3-bromophenylsulphonyl)-4-bromopyrazole (Compound No. 2.61)
Following the procedure of Example 4, there were obtained 78 mg (yield 21.0%) of the title compound,
melting at 104 - 105 DEG C.
1-(Diethylcarbamoyl)-3-(3-fluorophenylsulphonyl)-4-fluoropyrazole (Compound No. 2.64)
Following the procedure of Example 19, there were obtained 29 mg (yield 3.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.00 (1H, doublet, J = 4.7 Hz);
7.88 - 7.83 (1H, multiplet);
7.78 - 7.72 (1H, multiplet);
7.62 - 7.51 (1H, multiplet);
7.41 - 7.30 (1H, multiplet);
3.51 (4H, quartet, J = 7.0 Hz);
1.25 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-cyanophenylsulphonyl)-4-fluoropyrazole (Compound No. 2.65)
Following the procedure of Example 19, there were obtained 72 mg (yield 7.4%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.34 - 8.26 (2H, multiplet);
8.02 (1H, doublet, J = 4.8 Hz);
7.94 (1H, triplet of doublets, J = 7.4 & 1.3 Hz);
7.73 (1H, triplet, J = 7.4 Hz);
3.51 (4H, broad quartet, J = 7.0 Hz);
1.26 (6H, triplet, J = 7.0 Hz).
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1-(Diethylcarbamoyl)-3-(3-methoxyphenylsulphonyl)-4-fluoropyrazole (Compound No. 2.66)
Following the procedure of Example 19, there were obtained 35 mg (yield 3.8%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.98 (1H, doublet, J = 4.8 Hz);
7.66 - 7.61 (1H, multiplet);
7.55 - 7.53 (1H, multiplet);
7.50 - 7.42 (1H, multiplet);
7.20 - 7.14 (1H, multiplet);
3.87 (3H, singlet);
3.51 (4H, broad quartet, J = 7.0 Hz);
1.25 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chlorophenylsulphonyl)-4-fluoropyrazole (Compound No. 2.68)
Following the procedure of Example 7, there were obtained 15 mg (yield 0.3%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.04 (1H, triplet, J = 1.8 Hz);
8.00 (1H, doublet, J = 4.8 Hz);
7.95 (1H, triplet of doublets, J = 7.7 & 1.8 Hz);
7.64 (1H, triplet of doublets, J = 7.7 & 1.8 Hz);
7.51 (1H, triplet, J = 7.7 Hz);
3.51 (4H, quartet, J = 7.0 Hz);
1.25 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-trifluoromethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 2.83)
Following the procedure of Example 7, there were obtained 12 mg (yield 2.3%) of the title compound,
melting at 70 - 73 DEG C.
1-(Diethylcarbamoyl)-3-(3-fluorophenylthio)-4-cyanopyrazole (Compound No. 2.104)
Following the procedure of Example 14, there were obtained 190 mg (yield 51.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.54 (1H, singlet);
7.40 - 7.21 (3H, multiplet);
7.10 - 7.00 (1H, multiplet);
3.63 - 3.46 (4H, multiplet);
1.18 - 1.08 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(3-fluorophenylsulphonyl)-4-cyanopyrazole (Compound No. 2.105)
Following the procedure of Example 14, there were obtained 145 mg (yield 41.2%) of the title
compound, melting at 110 - 111 DEG C.
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1-(Diethylcarbamoyl)-3-(3-fluorophenylthio)-4-fluoropyrazole (Compound No. 2.120)
Following the procedure of Example 19, there were obtained 33 mg (yield 4.1%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.03 (1H, doublet, J = 5.1 Hz);
7.32 - 6.87 (4H, multiplet);
3.57 (4H, quartet, J = 7.1 Hz);
1.24 (6H, triplet, J = 7.1 Hz).
1-(Diethylcarbamoyl)-3-(3-methoxyphenylthio)-4-fluoropyrazole (Compound No. 2.121)
Following the procedure of Example 19, there were obtained 43 mg (yield 5.1%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.01 (1H, doublet, J = 5.1 Hz);
7.24 - 7.17 (1H, multiplet);
6.98 - 6.93 (2H, multiplet);
6.82 - 6.76 (1H, multiplet);
3.78 (3H, singlet);
3.57 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-fluorophenylsulphonyl)pyrazole (Compound No. 3.1)
Following the procedure of Example 1, there were obtained 193 mg (yield 72.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.16 (1H, doublet, J = 2.6 Hz);
8.09 - 8.03 (2H, multiplet);
7.25 - 7.19 (2H, multiplet);
6.86 (1H, doublet, J = 2.6 Hz);
3.48 (4H, broad quartet, J = 6.7 Hz);
1.22 (6H, broad triplet, J = 6.7 Hz).
1-(Diethylcarbamoyl)-3-(4-fluorophenylthio)pyrazole (Compound No. 3.2)
Following the procedure of Example 1, there were obtained 700 mg (yield 73.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.10 (1H, doublet, J = 2.6 Hz);
7.51 - 7.43 (2H, multiplet);
7.07 - 6.98 (2H, multiplet);
6.99 (1H, doublet, J = 2.6 Hz);
3.55 (4H, broad quartet, J = 7.1 Hz);
1.19 (4H, broad triplet, J = 7.1 Hz).
1-(Diethylcarbamoyl)-3-(4-chlorophenylsulphonyl)pyrazole (Compound No. 3.3)
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Following the procedure of Example 1, there were obtained 198 mg (yield 78.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.16 (1H, doublet, J = 2.6 Hz);
7.98 - 7.54 (2H, multiplet);
7.54 - 7.49 (2H, multiplet);
6.87 (1H, doublet, J = 2.6 Hz);
3.48 (4H, broad quartet, J = 6.9 Hz);
1.22 (6H, broad triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(4-chlorophenylthio)pyrazole (Compound No. 3.4)
Following the procedure of Example 1, there were obtained 790 mg (yield 79.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.13 (1H, doublet, J = 2.9 Hz);
7.38 - 7.34 (2H, multiplet);
7.30 - 7.25 (2H, multiplet);
6.27 (1H, doublet, J = 2.9 Hz);
3.56 (4H, broad quartet, J = 6.9 Hz);
1.21 (6H, broad triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(4-chlorobenzylsulphonyl)pyrazole (Compound No. 3.5)
Following the procedure of Example 1, there were obtained 100 mg (yield 29.6%) of the title
compound, melting at 96 - 98 DEG C.
1-(Diethylcarbamoyl)-3-(4-bromophenylsulphonyl)pyrazole (Compound No. 3.6)
Following the procedure of Example 1, there were obtained 204 mg (yield 79.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.16 (1H, doublet, J = 2.9 Hz);
7.92 - 7.87 (2H, multiplet);
7.71 - 7.67 (2H, multiplet);
6.86 (1H, doublet, J = 2.9 Hz);
3.48 (4H, broad quartet, J = 7.0 Hz);
1.22 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-bromophenylthio)pyrazole (Compound No. 3.7)
Following the procedure of Example 1, there were obtained 885 mg (yield 79.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.13 (1H, doublet, J = 2.7 Hz);
7.45 - 7.40 (2H, multiplet);
7.31 - 7.26 (2H, multiplet);
6.28 (1H, doublet, J = 2.7 Hz);
3.56 (4H, broad quartet, J = 7.0 Hz);
1.21 (6H, broad triplet, J = 7.0 Hz).
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1-(Diethylcarbamoyl)-3-(4-methylphenylthio)pyrazole (Compound No. 3.8)
Following the procedure of Example 1, there were obtained 731 mg (yield 72.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.08 (1H, doublet, J = 2.9 Hz);
7.37 (2H, doublet, J = 8.1 Hz);
7.13 (2H, doublet, J = 8.1 Hz);
6.18 (1H, doublet, J = 2.9 Hz);
3.57 (4H, broad quartet, J = 7.0 Hz);
2.34 (3H, singlet);
1.21 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-methylphenylsulphonyl)pyrazole (Compound No. 3.9)
Following the procedure of Example 1, there were obtained 197 mg (yield 70.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.13 (1H, doublet, J = 2.9 Hz);
7.91 (2H, doublet, J = 7.9 Hz);
7.33 (2H, doublet, J = 7.9 Hz);
6.84 (1H, doublet, J = 2.9 Hz);
3.48 (4H, broad quartet, J = 6.9 Hz);
2.43 (3H, singlet);
1.22 (6H, broad triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(4-ethylphenylthio)pyrazole (Compound No. 3.10)
Following the procedure of Example 1, there were obtained 813 mg (yield 83.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.90 (1H, doublet, J = 2.6 Hz);
7.40 (2H, doublet, J = 8.3 Hz);
7.15 (2H, doublet, J = 8.3 Hz);
6.20 (1H, doublet, J = 2.6 Hz);
3.56 (4H, broad quartet, J = 7.0 Hz);
2.64 (2H, quartet, J = 7.6 Hz);
1.22 (3H, triplet, J = 7.6 Hz);
1.20 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-ethylphenylsulphonyl)pyrazole (Compound No. 3.11)
Following the procedure of Example 1, there were obtained 209 mg (yield 83.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.7 Hz);
7.99 - 7.91 (2H, multiplet);
7.38 - 7.33 (2H, multiplet);
6.85 (1H, doublet, J = 2.7 Hz);
3.48 (4H, broad quartet, J = 7.0 Hz);
2.72 (2H, quartet, J = 7.6 Hz);
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1.29 - 1.18 (9H, multiplet).
1-(Diethylcarbamoyl)-3-(4-isopropylphenylsulphonyl)pyrazole (Compound No. 3.12)
Following the procedure of Example 1, there were obtained 1.08 g (yield 44.2%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.8 Hz);
7.94 (2H, doublet, J = 8.4 Hz);
7.38 (2H, doublet, J = 8.4 Hz);
6.85 (1H, doublet, J = 2.8 Hz);
3.48 (4H, quartet, J = 7.0 Hz);
2.98 (1H, septet, J = 6.7 Hz);
1.26 (6H, doublet, J = 6.7 Hz);
1.30 - 1.12 (6H, broad).
1-(Diethylcarbamoyl)-3-(4-isopropylphenylthio)pyrazole (Compound No. 3.13)
Following the procedure of Example 1, there were obtained 1.11 g (yield 47.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, doublet, J = 2.6 Hz);
7.40 (2H, doublet, J = 8.3 Hz);
7.18 (2H, doublet, J = 8.3 Hz);
6.21 (1H, doublet, J = 2.6 Hz);
3.55 (4H, quartet, J = 7.1 Hz);
3.45 (1H, septet, J = 6.9 Hz);
1.24 (6H, doublet, J = 6.9 Hz);
1.20 (6H, triplet, J = 7.1 Hz).
1-(Diethylcarbamoyl)-3-(4-sec-butylphenylthio)pyrazole (Compound No. 3.14)
Following the procedure of Example 1, there were obtained 987 mg (yield 91.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.01 (1H, doublet, J = 2.8 Hz);
7.42 - 7.37 (2H, multiplet);
7.16 - 7.11 (2H, multiplet);
6.21 (1H, doublet, J = 2.8 Hz);
3.56 (4H, broad quartet, J = 7.0 Hz);
2.59 (1H, sextet, J = 7.2 Hz);
1.58 (2H, quintet, J = 7.2 Hz);
1.24 - 1.16 (9H, multiplet);
0.81 (3H, triplet, J = 7.2 Hz).
1-(Diethylcarbamoyl)-3-(4-sec-butylphenylsulphonyl)pyrazole (Compound No. 3.15)
Following the procedure of Example 1, there were obtained 201 mg (yield 91.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.7 Hz);
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7.97 - 7.91 (2H, multiplet);
7.37 - 7.31 (2H, multiplet);
6.86 (1H, doublet, J = 2.7 Hz);
3.48 (4H, broad quartet, J = 7.0 Hz);
2.69 (1H, sextet, J = 7.3 Hz);
1.61 (2H, quintet, J = 7.3 Hz);
1.26 - 1.17 (9H, multiplet);
0.81 (3H, triplet, J = 7.3 Hz).
1-(Diethylcarbamoyl)-3-(4-t-butylphenylsulphonyl)pyrazole (Compound No. 3.16)
Following the procedure of Example 1, there were obtained 231 mg (yield 65.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.7 Hz);
7.94 (2H, broad doublet, J = 8.8 Hz);
7.54 (2H, broad doublet, J = 8.8 Hz);
6.85 (1H, doublet, J = 2.7 Hz);
3.48 (4H, quartet, J = 7.0 Hz);
1.33 (9H, singlet);
1.20 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-t-butylphenylthio)pyrazole (Compound No. 3.17)
Following the procedure of Example 1, there were obtained 842 mg (yield 66.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.10 (1H, doublet, J = 2.7 Hz);
7.41 (2H, broad doublet, J = 8.8 Hz);
7.34 (2H, broad doublet, J = 8.8 Hz);
6.22 (1H, doublet, J = 2.7 Hz);
3.56 (4H, quartet, J = 7.0 Hz);
1.31 (9H, singlet);
1.19 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-phenoxyphenylsulphonyl)pyrazole (Compound No. 3.18)
Following the procedure of Example 1, there were obtained 227 mg (yield 76.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.7 Hz);
7.98 (2H, broad doublet, J = 6.9 Hz);
7.5 - 7.0 (7H, multiplet);
6.85 (1H, doublet, J = 2.7 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-phenoxyphenylthio)pyrazole (Compound No. 3.19)
Following the procedure of Example 1, there were obtained 756 mg (yield 78.2%) of the title
compound, as an oily substance.
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Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.10 (1H, doublet, J = 2.8 Hz);
6.94 - 7.49 (9H, multiplet);
6.20 (1H, doublet, J = 2.8 Hz);
3.59 (4H, quartet, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-cyanophenylsulphonyl)pyrazole (Compound No. 3.20)
Following the procedure of Example 1, there were obtained 216 mg (yield 48.9%) of the title
compound, melting at 74 - 75 DEG C.
1-(Diethylcarbamoyl)-3-(4-cyanophenylthio)pyrazole (Compound No. 3.21)
Following the procedure of Example 1, there were obtained 428 mg (yield 49.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.22 (1H, doublet, J = 2.7 Hz);
7.53 (2H, doublet of doublets, J = 2.0 & 6.8 Hz);
7.33 (2H, doublet of doublets, J = 2.0 & 6.8 Hz);
6.45 (1H, doublet, J = 2.7 Hz);
3.59 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-phenoxyphenylsulphonyl)-5-(dimethylcarbamoyl)pyrazole (Compound No.
3.29)
Following the procedure of Example 15, there were obtained 183 mg (yield 57.3%) of the title
compound, melting at 43 - 45 DEG C.
1-(Diethylcarbamoyl)-3-(4-phenoxyphenylthio)-5-(dimethylcarbamoyl)pyrazole (Compound No. 3.30)
Following the procedure of Example 15, there were obtained 233 mg (yield 61.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.50 - 6.93 (9H, multiplet);
6.22 (1H, singlet);
3.47 (4H, quartet, J = 7.0 Hz);
3.06 (3H, singlet);
3.01 (3H, singlet);
1.21 (6H, triplet, J = 7.0 Hz).
Ethyl 1-(diethylcarbamoyl)-3-(4-t-butylphenylthio)pyrazole-5-carboxylate (Compound No. 3.31)
Following the procedure of Example 15, there were obtained 72 mg (yield 15.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.39 (2H, doublet, J = 9.0 Hz);
7.32 (2H, doublet, J = 9.0 Hz);
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6.75 (1H, singlet);
4.36 (2H, quartet, J = 7.0 Hz);
3.54 (2H, quartet, J = 7.0 Hz);
3.20 (2H, quartet, J = 7.0 Hz);
1.33 (6H, triplet, J = 7.0 Hz);
1.31 (9H, singlet);
1.13 (3H, triplet, J = 7.0 Hz).
Ethyl 1-(diethylcarbamoyl)-3-(4-t-butylphenylsulphonyl)pyrazole-5-carboxylate (Compound No. 3.32)
Following the procedure of Example 15, there were obtained 67 mg (yield 14.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.94 (2H, doublet, J = 8.7 Hz);
7.53 (2H, doublet, J = 8.7 Hz);
7.30 (1H, singlet);
4.35 (2H, quartet, J = 7.1 Hz);
3.53 (2H, quartet, J = 7.1 Hz);
3.03 (2H, quartet, J = 7.1 Hz);
1.33 (9H, singlet);
1.38 - 1.29 (6H, multiplet);
1.08 (3H, triplet, J = 7.1 Hz).
1-(Diethylcarbamoyl)-3-(4-isopropylphenylsulphonyl)-5-(methoxymethyl)pyrazole (Compound No.
3.33)
Following the procedure of Example 16, there were obtained 81 mg (yield 33.6%) of the title
compound, melting at 71 - 73 DEG C.
1-(Diethylcarbamoyl)-3-(4-chlorobenzylsulphonyl)-4-chloropyrazole (Compound No. 3.34)
Following the procedure of Example 3, there were obtained 127 mg (yield 25.1%) of the title
compound, melting at 106 - 109 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-dichlorophenylsulphonyl)pyrazole (Compound No. 4.1)
Following the procedure of Example 1, there were obtained 179 mg (yield 80.8%) of the title
compound, melting at 100 - 101.5 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-dichlorophenylthio)pyrazole (Compound No. 4.2)
Following the procedure of Example 1, there were obtained 1.01 g (yield 94.0%) of the title compound,
melting at 60 - 61.5 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-2-methylphenylsulphonyl)pyrazole (Compound No. 4.3)
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Following the procedure of Example 1, there were obtained 527 mg (yield 77.1%) of the title
compound, melting at 76 - 77 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-2-methylphenylthio)pyrazole (Compound No. 4.4)
Following the procedure of Example 1, there were obtained 1.28 g (yield 78.7%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.13 (1H, doublet, J = 2.8 Hz);
7.30 (2H, doublet, J = 7.6 Hz);
7.06 (1H, triplet, J = 7.6 Hz);
6.22 (1H, quartet, J = 2.8 Hz);
3.53 (4H, quartet, J = 7.0 Hz);
2.51 (3H, singlet);
1.17 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,3-dimethylphenylsulphonyl)pyrazole (Compound No. 4.5)
Following the procedure of Example 1, there were obtained 196 mg (yield 39.4%) of the title
compound, melting at 87 - 88 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-dimethylphenylthio)pyrazole (Compound No. 4.6)
Following the procedure of Example 1, there were obtained 981 mg (yield 44.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, doublet, J = 2.6 Hz);
7.32 (1H, doublet of doublets, J = 1.1 & 7.2 Hz);
7.12 (1H, broad doublet, J = 6.2 Hz);
7.04 (1H, triplet, J = 7.2 Hz);
6.13 (1H, doublet, J = 2.6 Hz);
3.54 (4H, quartet, J = 7.0 Hz);
2.88 (3H, singlet);
2.31 (3H, singlet);
1.18 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)pyrazole (Compound No. 4.7)
Following the procedure of Example 1, there were obtained 224 mg (yield 46.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.21 (1H, doublet, J = 2.8 Hz);
7.91 - 7.82 (1H, multiplet);
7.53 - 7.40 (1H, multiplet);
7.35 - 7.24 (1H, multiplet);
6.96 (1H, doublet, J = 2.8 Hz);
3.48 (4H, quartet, J = 7.0 Hz);
1.19 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,3-difluorophenylthio)pyrazole (Compound No. 4.8)
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Following the procedure of Example 1, there were obtained 297 mg (yield 50.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.13 (1H, doublet, J = 2.6 Hz);
7.26 - 7.00 (3H, multiplet);
6.32 (1H, doublet, J = 2.6 Hz);
3.53 (4H, quartet, J = 7.0 Hz);
1.17 (6H, triplet, J = 7.0 Hz).
1-(Dimethylcarbamoyl)-3-(2,3-difluorophenylthio)-4-chloropyrazole (Compound No. 4.42)
Following the procedure of Example 4, there were obtained 236 mg (yield 44.6%) of the title
compound, melting at 76 - 78 DEG C.
1-(Dimethylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 4.43)
Following the procedure of Example 4, there were obtained 192 mg (yield 41.9%) of the title
compound, melting at 98 - 102 DEG C.
1-(N-Ethyl-N-methylcarbamoyl)-3-(2,3-difluorophenylthio)-4-chloropyrazole (Compound No. 4.44)
Following the procedure of Example 4, there were obtained 228 mg (yield 41.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, singlet);
7.21 - 6.97 (3H, multiplet);
3.53 (2H, quartet, J = 7.1 Hz);
3.11 (3H, singlet);
1.15 (3H, broad).
1-(N-Ethyl-N-methylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)-4-chloropyrazole (Compound No.
4.45)
Following the procedure of Example 4, there were obtained 183 mg (yield 40.1%) of the title
compound, melting at 89 - 91 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 4.46)
Following the procedure of Example 4, there were obtained 121 mg (yield 32.0%) of the title
compound, melting at 71 - 72 DEG C.
1-(N-Ethyl-N-propylcarbamoyl)-3-(2,3-difluorophenylthio)-4-chloropyrazole (Compound No. 4.47)
Following the procedure of Example 4, there were obtained 256 mg (yield 42.7%) of the title
compound, as an oily substance.
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Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, singlet);
7.21 - 7.00 (3H, multiplet);
3.51 (2H, broad quartet, J = 6.7 Hz);
3.39 (2H, broad triplet, J = 7.5 Hz);
1.68 - 1.53 (2H, multiplet);
1.14 (3H, broad);
0.84 (3H, broad).
1-(N-Ethyl-N-propylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)-4-chloropyrazole (Compound No.
4.48)
Following the procedure of Example 4, there were obtained 203 mg (yield 41.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, singlet);
7.96 - 7.87 (1H, multiplet);
7.57 - 7.44 (1H, multiplet);
7.39 - 7.28 (1H, multiplet);
3.55 - 3.38 (4H, multiplet);
1.69 (2H, broad sextet, J = 7.6 Hz);
1.22 (3H, broad);
0.92 (3H, broad).
1-(Dipropylcarbamoyl)-3-(2,3-difluorophenylthio)-4-chloropyrazole (Compound No. 4.49)
Following the procedure of Example 4, there were obtained 265 mg (yield 43.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, singlet);
7.19 - 6.96 (3H, multiplet);
3.42 (4H, broad triplet, J = 7.1 Hz);
1.61 (4H, broad);
0.83 (6H, broad).
1-(Dipropylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 4.50)
Following the procedure of Example 4, there were obtained 212 mg (yield 42.3%) of the title
compound, melting at 41 - 46 DEG C.
1-(N-Butyl-N-methylcarbamoyl)-3-(2,3-difluorophenylthio)-4-chloropyrazole (Compound No. 4.51)
Following the procedure of Example 4, there were obtained 248 mg (yield 42.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, singlet);
7.19 - 6.98 (3H, multiplet);
3.51 (2H, broad triplet, J = 6.6 Hz);
3.13 (3H, broad singlet);
1.62 - 1.51 (2H, multiplet);
1.39 - 1.15 (2H, multiplet);
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0.90 (3H, broad triplet, J = 7.1 Hz).
1-(N-Butyl-N-methylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)-4-chloropyrazole (Compound No.
4.52)
Following the procedure of Example 4, there were obtained 207 mg (yield 42.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
7.96 - 7.87 (1H, multiplet);
7.57 - 7.44 (1H, multiplet);
7.39 - 7.27 (1H, multiplet);
3.52 (2H, broad);
3.21 - 3.11 (3H, multiplet);
1.72 - 1.57 (2H, multiplet);
1.37 - 1.25 (2H, multiplet);
0.93 (3H, broad).
1-(Diethylcarbamoyl)-3-(2,3-dichlorophenylsulphonyl)-4-chloropyrazole (Compound No. 4.56)
Following the procedure of Example 4, there were obtained 291 mg (yield 41.8%) of the title
compound, melting at 110 - 113 DEG C.
1-(Diethylcarbamoyl)-3-(2.3-dimethylphenylsulphonyl)-4-chloropyrazole (Compound No. 4.58)
Following the procedure of Example 5, there were obtained 38 mg (yield 4.8%) of the title compound,
melting at 102 - 102.5 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-dichlorophenylthio)-4-bromopyrazole (Compound No. 4.61)
Following the procedure of Example 4, there were obtained 833 mg (yield 43.8%) of the title
compound, melting at 67 - 70 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-dichlorophenylsulphonyl)-4-bromopyrazole (Compound No. 4.62)
Following the procedure of Example 4, there were obtained 301 mg (yield 40.8%) of the title
compound, melting at 109 - 112 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-dimethylphenylsulphonyl)-4-bromopyrazole (Compound No. 4.64)
Following the procedure of Example 5, there were obtained 97 mg (yield 10.3%) of the title compound,
melting at 94 - 96 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-dichlorophenylsulphonyl)-4-fluoropyrazole (Compound No. 4.65)
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Following the procedure of Example 19, there were obtained 40 mg (yield 6.3%) of the title compound,
melting at 68 - 69 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-2-methylphenylsulphonyl)-4-fluoropyrazole (Compound No. 4.66)
Following the procedure of Example 7, there were obtained 16 mg (yield 3.7%) of the title compound,
melting at 74 - 77 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-dimethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 4.67)
Following the procedure of Example 7, there were obtained 14 mg (yield 4.0%) of the title compound,
melting at 78 - 81 DEG C.
1-(Diethylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)-4-fluoropyrazole (Compound No. 4.69)
Following the procedure of Example 19, there were obtained 70 mg (yield 6.8%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.04 (1H, doublet, J = 4.7 Hz);
7.93 - 7.84 (1H, multiplet);
7.52 - 7.43 (1H, multiplet);
7.38 - 7.27 (1H, multiplet);
3.58 - 3.44 (4H, broad quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 5.6 Hz).
1-(Diethylcarbamoyl)-3-(2,3-difluorophenylthio)-4-cyanopyrazole (Compound No. 4.133)
Following the procedure of Example 14, there were obtained 142 mg (yield 37.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.52 (1H, singlet);
7.38 - 7.10 (3H, multiplet);
3.46 (4H, quartet, J = 7.0 Hz);
1.12 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,3-difluorophenylsulphonyl)-4-cyanopyrazole (Compound No. 4.134)
Following the procedure of Example 14, there were obtained 125 mg (yield 35.1%) of the title
compound, melting at 124 - 125 DEG C.
1-(Diethylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)pyrazole (Compound No. 5.1)
Following the procedure of Example 1, there were obtained 110 mg (yield 73.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, doublet, J = 2.5 Hz);
8.16 - 8.08 (1H, multiplet);
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7.12 - 7.02 (1H, multiplet);
6.95 (1H, doublet, J = 2.5 Hz);
6.93 - 6.88 (1H, multiplet);
3.49 (4H, quartet, J = 6.8 Hz);
1.3 - 1.1 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,4-difluorophenylthio)pyrazole (Compound No. 5.2)
Following the procedure of Example 1, there were obtained 257 mg (yield 75.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.10 (1H, doublet, J = 2.6 Hz);
7.56 - 7.43 (1H, multiplet);
6.94 - 6.82 (2H, multiplet);
6.23 (1H, doublet, J = 2.6 Hz);
3.51 (4H, quartet, J = 7.0 Hz);
1.16 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,4-dichlorophenylsulphonyl)pyrazole (Compound No. 5.3)
Following the procedure of Example 1, there were obtained 120 mg (yield 66.0%) of the title
compound, melting at 85 - 86 DEG C.
1-(Diethylcarbamoyl)-3-(2,4-dichlorophenylthio)pyrazole (Compound No. 5.4)
Following the procedure of Example 1, there were obtained 219 mg (yield 66.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.8 Hz);
7.42 (1H, singlet);
7.16 (2H, singlet);
6.38 (1H, doublet, J = 2.8 Hz);
3.56 (4H, quartet, J = 7.1 Hz);
1.12 (6H, triplet, J = 7.1 Hz).
1-(Diethylcarbamoyl)-3-(2,4-dibromophenylsulphonyl)pyrazole (Compound No. 5.5)
Following the procedure of Example 1, there were obtained 86 mg (yield 54.5%) of the title compound,
melting at 103 - 105 DEG C.
1-(Diethylcarbamoyl)-3-(4-bromo-2-fluorophenylsulphonyl)pyrazole (Compound No. 5.6)
Following the procedure of Example 1, there were obtained 110 mg (yield 58.3%) of the title
compound, melting at 96 - 97 DEG C.
1-(Diethylcarbamoyl)-3-(4-chloro-2-trifluoromethylphenylthio)pyrazole (Compound No. 5.7)
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Following the procedure of Example 1, there were obtained 873 mg (yield 74.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.6 Hz);
7.68 (1H, broad singlet);
7.43 - 7.36 (2H, multiplet);
6.33 (1H, doublet, J = 2.6 Hz);
3.55 (4H, broad quartet, J = 7.0 Hz);
1.21 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-chloro-2-trifluoromethylphenylsulphonyl)pyrazole (Compound No. 5.8)
Following the procedure of Example 1, there were obtained 202 mg (yield 74.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.43 (1H, doublet, J = 8.2 Hz);
8.18 (1H, doublet, J = 2.9 Hz);
7.85 (1H, doublet, J = 2.3 Hz);
7.76 (1H, doublet of doublets, J = 2.3 & 8.2 Hz);
6.91 (1H, doublet, J = 2.9 Hz);
3.42 (4H, broad quartet, J = 7.0 Hz);
1.12 (6H, broad).
1-(Diethylcarbamoyl)-3-(4-bromo-2-trifluoromethylphenylsulphonyl)pyrazole (Compound No. 5.9)
Following the procedure of Example 1, there were obtained 129 mg (yield 36.5%) of the title
compound, melting at 60 - 62 DEG C.
1-(Diethylcarbamoyl)-3-(4-bromo-2-trifluoromethylphenylthio)pyrazole (Compound No. 5.10)
Following the procedure of Example 1, there were obtained 265 mg (yield 48.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, doublet, J = 2.7 Hz);
7.72 (1H, doublet, J = 2.2 Hz);
7.62 (1H, doublet, J = 8.4 Hz);
7.38 (1H, doublet of doublets, J = 2.2 & 2.6 Hz);
6.36 (1H, doublet, J = 2.7 Hz);
3.56 (4H, quartet, J = 7.0 Hz);
1.20 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-chloro-4-methylphenylsulphonyl)pyrazole (Compound No. 5.11)
Following the procedure of Example 1, there were obtained 391 mg (yield 36.7%) of the title
compound, melting at 89 - 91 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-4-methylphenylthio)pyrazole (Compound No. 5.12)
299/2194
Following the procedure of Example 1, there were obtained 477 mg (yield 41.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.5 Hz);
7.27 - 7.21 (2H, multiplet);
7.01 - 6.97 (1H, multiplet);
6.30 (1H, doublet, J = 2.5 Hz);
3.56 (4H, quartet, J = 7.0 Hz);
1.20 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-chloro-2-methylphenylsulphonyl)pyrazole (Compound No. 5.13)
Following the procedure of Example 1, there were obtained 271 mg (yield 61.5%) of the title
compound, melting at 62 - 65 DEG C.
1-(Diethylcarbamoyl)-3-(4-chloro-2-methylphenylthio)pyrazole (Compound No. 5.14)
Following the procedure of Example 1, there were obtained 1.24 g (yield 64.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.11 (1H, doublet, J = 2.7 Hz);
7.33 (1H, doublet, J = 6.2 Hz);
7.24 (1H, doublet, J = 2.5 Hz);
7.12 (1H, doublet of doublets, J = 6.2 & 2.5 Hz);
6.18 (1H, doublet, J = 2.7 Hz);
3.52 (4H, quartet, J = 7.0 Hz);
2.39 (3H, singlet);
1.16 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,4-dimethylphenylsulphonyl)pyrazole (Compound No. 5.15)
Following the procedure of Example 1, there were obtained 188 mg (yield 44.9%) of the title
compound, melting at 57 - 59 DEG C.
1-(Diethylcarbamoyl)-3-(2,4-dimethylphenylthio)pyrazole (Compound No. 5.16)
Following the procedure of Example 1, there were obtained 471 mg (yield 56.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.70 (1H, doublet, J = 2.7 Hz);
7.36 (1H, doublet, J = 7.7 Hz);
7.07 - 6.95 (2H, multiplet);
6.08 (1H, doublet, J = 2.7 Hz);
3.54 (4H, quartet, J = 7.0 Hz);
2.38 (3H, singlet);
2.32 (3H, singlet);
1.17 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-methoxy-2-methylphenylsulphonyl)pyrazole (Compound No. 5.17)
300/2194
Following the procedure of Example 1, there were obtained 108 mg (yield 68.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.8 Hz);
8.12 (1H, doublet, J = 8.8 Hz);
6.87 (1H, doublet of doublets, J = 8.8 & 2.6 Hz);
6.83 (1H, doublet, J = 2.8 Hz);
6.76 (1H, doublet, J = 2.6 Hz);
3.85 (3H, singlet);
3.47 (4H, quartet, J = 7.0 Hz);
2.55 (3H, singlet);
1.30 - 1.05 (6H, broad).
1-(Diethylcarbamoyl)-3-(4-methoxy-2-methylphenylthio)pyrazole (Compound No. 5.18)
Following the procedure of Example 1, there were obtained 269 mg (yield 68.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.04 (1H, doublet, J = 2.8 Hz);
7.5 (1H, doublet, J = 8.5 Hz);
6.8 (1H, doublet, J = 2.7 Hz);
6.75 (1H, doublet of doublets, J = 8.5 & 2.7 Hz);
6.0 (1H, doublet, J = 2.8 Hz);
3.8 (3H, singlet);
3.58 (4H, quartet, J = 7.0 Hz); ,
2.4 (3H, singlet);
1.16 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-bromo-2-chlorophenylsulphonyl)pyrazole (Compound No. 5.19)
Following the procedure of Example 1, there were obtained 192 mg (yield 63.1%) of the title
compound, melting at 109 - 110 DEG C.
1-(Diethylcarbamoyl)-3-(4-bromo-2-chlorophenylthio)pyrazole (Compound No. 5.20)
Following the procedure of Example 1, there were obtained 355 mg (yield 67.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, doublet, J = 2.6 Hz);
7,56 (1H, doublet, J = 2.0 Hz);
7.28 (1H, doublet of doublets, J = 8.5 & 2.0 Hz);
7.07 (1H, doublet, J = 8.5 Hz);
6.39 (1H, doublet, J = 2.6 Hz);
3.56 (4H, quartet, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Dimethylcarbamoyl)-3-(2,4-difluorophenylthio)-4-chloropyrazole (Compound No. 5.25)
Following the procedure of Example 3, there were obtained 174 mg (yield 47.3%) of the title
compound, as an oily substance.
301/2194
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, singlet);
7.47 - 7.39 (1H, multiplet);
6.93 - 6.82 (2H, multiplet);
3.13 (6H, singlet).
1-(Dimethylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 5.26)
Following the procedure of Example 3, there were obtained 148 mg (yield 47.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.24 - 8.12 (1H, multiplet);
8.14 (1H, singlet);
7.16 - 7.06 (1H, multiplet);
6.99 - 6.89 (1H, multiplet);
3.22 (3H, broad);
3.17 (3H, broad).
1-(N-Ethyl-N-methylcarbamoyl)-3-(2,4-difluorophenylthio)-4-chloropyrazole (Compound No. 5.27)
Following the procedure of Example 3, there were obtained 185 mg (yield 46.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.10 (1H, singlet);
7.52 - 7.41 (1H, multiplet);
6.93 - 6.83 (2H, multiplet);
3.50 (2H, quartet, J = 7.0 Hz);
3.08 (3H, singlet);
1.10 (3H, broad).
1-(N-Ethyl-N-methylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)-4-chloropyrazole (Compound No.
5.28)
Following the procedure of Example 3, there were obtained 152 mg (yield 43.8%) of the title
compound, melting at 77 - 79 DEG C.
1-(Diethylcarbamoyl)-3-(2,4-difluorophenylthio)-4-chloropyrazole (Compound No. 5.29)
Following the procedure of Example 3, there were obtained 657 mg (yield 57.1%) of the title
compound, melting at 84 - 86 DEG C.
1-(Diethylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 5.30)
Following the procedure of Example 3, there were obtained 554 mg (yield 54.9%) of the title
compound, melting at 99 - 100 DEG C.
1-(N-Ethyl-N-propylcarbamoyl)-3-(2,4-difluorophenylthio)-4-chloropyrazole (Compound No. 5.31)
302/2194
Following the procedure of Example 3, there were obtained 198 mg (yield 45.0%) of the title
compound, melting at 60 - 64 DEG C.
1-(N-Ethyl-N-propylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)-4-chloropyrazole (Compound No.
5.32)
Following the procedure of Example 3, there were obtained 162 mg (yield 41.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.23 - 8.12 (1H, multiplet);
8.16 (1H, singlet);
7.15 - 7.05 (1H, multiplet);
6.99 - 6.88 (2H, multiplet);
3.54 - 3.36 (4H, multiplet);
1.73 - 1.61 (2H, multiplet);
1.22 (3H, broad);
0.91 (3H, broad).
1-(Dipropylcarbamoyl)-3-(2,4-difluorophenylthio)-4-chloropyrazole (Compound No. 5.33)
Following the procedure of Example 3, there were obtained 197 mg (yield 43.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.11 (1H, singlet);
7.52 - 7.40 (1H, multiplet);
6.93 - 6.83 (2H, multiplet);
3.39 (4H, broad triplet, J = 7.5 Hz);
1.66 - 1.50 (4H, multiplet);
0.81 (6H, broad).
1-(Dipropylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 5.34)
Following the procedure of Example 3, there were obtained 179 mg (yield 43.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.23 - 8.12 (1H, multiplet);
8.17 (1H, singlet);
7.15 - 7.05 (1H, multiplet);
6.99 - 6.88 (1H, multiplet);
3.93 (4H, broad);
1.65 (4H, broad);
0.90 (6H, broad).
1-(N-Butyl-N-methylcarbamoyl)-3-(2,4-difluorophenylthio)-4-chloropyrazole (Compound No. 5.35)
Following the procedure of Example 3, there were obtained 199 mg (yield 46.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.10 (1H, singlet);
7.50 - 7.39 (1H, multiplet);
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6.93 - 6.82 (2H, multiplet);
3.48 (2H, broad triplet, J = 7.4 Hz);
3.10 (3H, singlet);
1.60 - 1.53 (2H, multiplet);
1.26 - 1.19 (2H, multiplet);
0.90 (3H, broad triplet, J = 7.2 Hz).
1-(N-Butyl-N-methylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)-4-chloropyrazole (Compound No.
5.36)
Following the procedure of Example 3, there were obtained 157 mg (yield 42.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.23 - 8.12 (1H, multiplet);
8.14 (1H, singlet);
7.15 - 7.05 (1H, multiplet);
6.98 - 6.88 (1H, multiplet);
3.56 (3H, broad);
3.19 (2H, broad);
1.77 - 1.54 (2H, multiplet);
1.43 - 1.21 (2H, multiplet);
0.93 (3H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-4-methylphenylthio)-4-chloropyrazole (Compound No. 5.37)
Following the procedure of Example 4, there were obtained 403 mg (yield 38.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
7.26 (1H, doublet, J = 1.4 Hz);
7.17 (1H, doublet, J = 8.1 Hz);
7.00 (1H, doublet of doublets, J = 8.1 & 1.4 Hz);
3.50 (4H, broad quartet, J = 6.6 Hz);
2.32 (3H, singlet);
1.15 (6H, broad triplet, J = 6.6 Hz).
1-(Diethylcarbamoyl)-3-(2-chloro-4-methylphenylsulphonyl)-4-chloropyrazole (Compound No. 5.38)
Following the procedure of Example 4, there were obtained 167 mg (yield 38.9%) of the title
compound, melting at 105 - 107 DEG C.
1-(Diethylcarbamoyl)-3-(4-chloro-2-methylphenylsulphonyl)-4-chloropyrazole (Compound No. 5.39)
Following the procedure of Example 4, there were obtained 154 mg (yield 27.7%) of the title
compound, melting at 84 - 85 DEG C.
1-(Diethylcarbamoyl)-3-(4-bromo-2-fluorophenylsulphonyl)-4-chloropyrazole (Compound No. 5.40)
304/2194
Following the procedure of Example 4, there were obtained 103 mg (yield 65.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
8.00 (1H, triplet, J = 8.5 Hz);
7.53 (1H, doubled doublet of doublets, J = 8.5, 1.8 & 0.8 Hz);
7.39 (1H, doublet of doublets, J = 9.0 & 1.8 Hz);
3.51 (4H, broad quartet, J = 6.4 Hz);
1.30 - 1.15 (6H, broad).
1-(Diethylcarbamoyl)-3-(4-chloro-2-trifluoromethylphenylthio)-4-chloropyrazole (Compound No.
5.41)
Following the procedure of Example 3, there were obtained 265 mg (yield 42.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
7.69 (1H, doublet, J = 2.1 Hz);
7.40 (1H, doublet of doublets, J = 8.4 & 2.1 Hz);
7.29 (1H, doublet, J = 8.4 Hz);
2.55 (4H, multiplet);
1.17 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(4-chloro-2-trifluoromethylphenylsulphonyl)-4-chloropyrazole (Compound
No. 5.42)
Following the procedure of Example 3, there were obtained 184 mg (yield 28.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.47 (1H, doublet, J = 8.6 Hz);
8.15 (1H, singlet);
7.83 (1H, doublet of doublets, J = 8.6 & 1.6 Hz);
7.71 (1H, doublet, J = 1.6 Hz);
3.5 - 3.3 (4H, broad);
1.4 - 0.8 (6H, broad).
1-[N-(4-Chlorophenyl)-N-methylcarbamoyl]-3-(4-chloro-2-trifluoromethylphenylsulphonyl)-4chloropyrazole (Compound No. 5.59)
Following the procedure of Example 3, there were obtained 137 mg (yield 29.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
8.07 (1H, doublet, J = 8.4 Hz);
7.83 - 7.65 (2H, multiplet);
7.11 - 7.01 (2H, multiplet);
6.80 - 6.71 (2H, multiplet);
3.36 (3H, singlet).
1-(Diethylcarbamoyl)-3-(2,4-difluorophenylthio)-4-bromopyrazole (Compound No. 5.69)
305/2194
Following the procedure of Example 5, there were obtained 480 mg (yield 71.8%) of the title
compound, melting at 95 - 96 DEG C.
1-(Diethylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)-4-bromopyrazole (Compound No. 5.70)
Following the procedure of Example 5, there were obtained 375 mg (yield 69.7%) of the title
compound, melting at 95 - 97 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-4-methylphenylthio)-4-bromopyrazole (Compound No. 5.71)
Following the procedure of Example 4, there were obtained 727 mg (yield 63.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, singlet);
7.27 - 7.26 (1H, multiplet);
7.18 (1H, doublet, J = 8.0 Hz);
7.02 - 6.98 (1H, multiplet);
3.49 (4H, broad quartet, J = 7.1 Hz);
2.32 (3H, singlet);
1.13 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-4-methylphenylsulphonyl)-4-bromopyrazole (Compound No. 5.72)
Following the procedure of Example 4, there were obtained 164 mg (yield 60.0%) of the title
compound, melting at 98 - 100 DEG C.
1-(Diethylcarbamoyl)-3-(4-chloro-2-methylphenylsulphonyl)-4-bromopyrazole (Compound No. 5.73)
Following the procedure of Example 5, there were obtained 273 mg (yield 51.1%) of the title
compound, melting at 94 - 95 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-4-methylphenylsulphonyl)-4-fluoropyrazole (Compound No. 5.74)
Following the procedure of Example 7, there were obtained 16 mg (yield 3.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.03 (1H, doublet, J = 8.1 Hz);
7.97 (1H, doublet, J = 4.7 Hz);
7.37 (1H, doublet, J = 8.1 Hz);
7.20 (1H, singlet);
3.47 (4H, broad quartet, J = 7.0 Hz);
2.41 (3H, singlet);
1.30 - 1.10 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(4-chloro-2-trifluoromethylphenylsulphonyl)-4-fluoropyrazole (Compound
No. 5.75)
306/2194
Following the procedure of Example 7, there were obtained 27 mg (yield 4.3%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.48 (1H, doublet, J = 8.5 Hz);
7.98 (1H, doublet, J = 4.7 Hz);
7.83 (1H, doublet of doublets, J = 8.5 & 2.1 Hz);
7.71 (1H, doublet, J = 2.1 Hz);
3.45 (4H, quartet, J = 7.0 Hz);
1.30 - 1.06 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,4-difluorophenylsulphonyl)-4-fluoropyrazole (Compound No. 5.76)
Following the procedure of Example 19, there were obtained 50 mg (yield 4.5%) of the title compound,
melting at 74 - 76 DEG C.
1-(Diethylcarbamoyl)-3-(2,4-difluorophenylthio)-4-fluoropyrazole (Compound No. 5.107)
Following the procedure of Example 19, there were obtained 68 mg (yield 6.5%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
7.97 (1H, doublet, J = 5.0 Hz);
7.84 - 7.46 (2H, multiplet);
6.91 - 6.83 (2H, multiplet);
3.50 (4H, quartet, J = 7.0 Hz);
1.16 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-fluoro-5-methylphenylsulphonyl)pyrazole (Compound No. 6.1)
Following the procedure of Example 1, there were obtained 123 mg (yield 40.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 3.1 Hz);
7.89 (1H, doublet of doublets, J = 2.2 & 3.1 Hz);
7.45 - 7.37 (1H, multiplet);
7.13 (1H, triplet, J = 9.0 Hz);
6.95 (1H, doublet, J = 3.1 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
2.41 (3H, singlet);
1.45 - 1.08 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-fluoro-5-methylphenylthio)pyrazole (Compound No. 6.2)
Following the procedure of Example 1, there were obtained 153 mg (yield 40.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.11 (1H, doublet, J = 2.7 Hz);
7.27 - 7.22 (1H, multiplet);
7.14 - 7.06 (1H, multiplet);
6.99 (1H, triplet, J = 8.6 Hz);
6.26 (1H, doublet, J = 2.7 Hz);
3.54 (4H, quartet, J = 7.0 Hz);
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2.29 (3H, singlet);
1.18 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylsulphonyl)pyrazole (Compound No. 6.3)
Following the procedure of Example 1, there were obtained 390 mg (yield 39.5%) of the title
compound, melting at 62 - 66 DEG C.
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylthio)pyrazole (Compound No. 6.4)
Following the procedure of Example 1, there were obtained 531 mg (yield 44.9%) of the title
compound, melting at 62 - 64 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-5-trifluoromethylphenylthio)pyrazole (Compound No. 6.5)
Following the procedure of Example 1, there were obtained 613 mg (yield 64.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.23 (1H, doublet, J = 2.7 Hz);
7.53 - 7.37 (3H, multiplet);
6.46 (1H, doublet, J = 2.7 Hz);
3.56 (4H, quartet, J = 6.9 Hz);
1.21 (6H, triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(2-chloro-5-trifluoromethylphenylsulphonyl)pyrazole (Compound No. 6.6)
Following the procedure of Example 1, there were obtained 208 mg (yield 59.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.61 (1H, doublet, J = 2.0 Hz);
8.22 (1H, doublet, J = 2.7 Hz);
7.82 (1H, doublet of doublets, J = 8.4 & 2.0 Hz);
7.63 (1H, doublet, J = 8.4 Hz);
7.03 (1H, doublet, J = 2.7 Hz);
3.43 (4H, doublet, J = 7.0 Hz);
1.35 - 1.00 (6H, broad).
1-(Diethylcarbamoyl)-3-(5-chloro-2-methylphenylthio)pyrazole (Compound No. 6.7)
Following the procedure of Example 1, there were obtained 750 mg (yield 75.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.8 Hz);
7.32 (1H, broad singlet);
7.15 (2H, doublet, J = 1.3 Hz);
6.27 (1H, doublet, J = 2.8 Hz);
3.55 (4H, broad quartet, J = 7.0 Hz);
2.38 (3H, singlet);
1.19 (6H, broad triplet, J = 7.0 Hz).
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1-(Diethylcarbamoyl)-3-(5-chloro-2-methylphenylsulphonyl)pyrazole (Compound No. 6.8)
Following the procedure of Example 1, there were obtained 197 mg (yield 75.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.19 (1H, doublet, J = 2.3 Hz);
8.18 (1H, doublet, J = 2.3 Hz);
7.47 (1H, doublet of doublets, J = 2.3 & 8.1 Hz);
7.22 (1H, doublet, J = 8.1 Hz);
6.89 (1H, doublet, J = 2.3 Hz);
3.47 (4H, broad quartet, J = 7.0 Hz);
2.54 (3H, singlet);
1.18 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,5-dimethylphenylthio)pyrazole (Compound No. 6.9)
Following the procedure of Example 1, there were obtained 914 mg (yield 74.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, doublet, J = 2.6 Hz);
7.24 (1H, broad singlet);
7.14 - 7.01 (2H, multiplet);
6.14 (1H, doublet, J = 2.6 Hz);
3.55 (4H, broad quartet, J = 6.8 Hz);
2.37 (3H, singlet);
2.27 (3H, singlet);
1.18 (6H, broad triplet, J = 6.8).
1-(Diethylcarbamoyl)-3-(2,5-dimethylphenylsulphonyl)pyrazole (Compound No. 6.10)
Following the procedure of Example 1, there were obtained 186 mg (yield 68.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
8.17 (1H, doublet, J = 2.6 Hz);
7.99 (1H, broad singlet);
7.32 - 7.30 (1H, multiplet);
7.16 (1H, doublet, J = 8.1 Hz);
6.86 (1H, doublet, J = 2.6 Hz);
3.46 (4H, broad quartet, J = 7.0 Hz);
2.53 (3H, singlet);
2.40 (3H, singlet);
1.16 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-methoxy-5-methylphenylsulphonyl)pyrazole (Compound No. 6.11)
Following the procedure of Example 1, there were obtained 139 mg (yield 70.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.7 Hz);
7.95 (1H, doublet, J = 2.2 Hz);
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7.37 (1H, doublet of doublets, J = 2.2 & 2.7 Hz);
6.93 (1H, doublet, J = 2.7 Hz);
6.85 (1H, doublet, J = 8.4 Hz);
3.76 (3H, singlet);
3.47 (4H, quartet, J = 7.0 Hz);
2.36 (3H, singlet);
1.45 - 1.00 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-methoxy-5-methylphenylthio)pyrazole (Compound No. 6.12)
Following the procedure of Example 1, there were obtained 330 mg (yield 70.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.12 (1H, doublet, J = 2.4 Hz);
7.09 - 7.03 (2H, multiplet);
6.80 (1H, doublet, J = 8.3 Hz);
6.25 (1H, doublet, J = 2.4 Hz);
3.84 (3H, singlet);
3.58 (4H, quartet, J = 7.0 Hz);
2.23 (3H, singlet);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(5-chloro-2-methoxyphenylthio)pyrazole (Compound No. 6.13)
Following the procedure of Example 1, there were obtained 133 mg (yield 45.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, doublet, J = 2.7 Hz);
7.20 - 7.15 (2H, multiplet);
6.82 - 6.78 (1H, multiplet);
6.37 (1H, doublet, J = 2.7 Hz);
3.87 (3H, singlet);
3.59 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(5-chloro-2-methoxyphenylsulphonyl)pyrazole (Compound No. 6.14)
Following the procedure of Example 1, there were obtained 123 mg (yield 45.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.7 Hz);
8.13 (1H, doublet, J = 2.7 Hz);
7.53 (1H, doublet of doublets, J = 2.7 & 8.8 Hz);
6.95 (1H, doublet, J = 2.7 Hz);
6.90 (1H, doublet, J = 8.8 Hz);
3.80 (3H, singlet);
3.47 (4H, quartet, J = 7.0 Hz);
1.38 - 1.05 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-5-methoxyphenylthio)pyrazole (Compound No. 6.15)
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Following the procedure of Example 1, there were obtained 289 mg (yield 89.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.8 Hz);
7.29 (1H, doublet, J = 9.9 Hz);
6.76 (1H, doublet, J = 2.8 Hz);
6.71 (1H, doublet of doublets, J = 9.9 & 2.8 Hz);
6.39 (1H, doublet, J = 2.8 Hz);
3.70 (3H, singlet);
3.58 (4H, broad quartet, J = 6.9 Hz);
1.22 (6H, triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(2-chloro-5-methoxyphenylsulphonyl)pyrazole (Compound No. 6.16)
Following the procedure of Example 1, there were obtained 224 mg (yield 85.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.7 Hz);
7.84 (1H, doublet, J = 3.0 Hz);
7.35 (1H, doublet, J = 8.8 Hz);
7.08 (1H, doublet of doublets, J = 3.0, 8.8 Hz);
6.98 (1H, doublet, J = 2.7 Hz);
3.88 (3H, singlet);
3.43 (4H, broad quartet, J = 7.0 Hz);
1.14 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,5-dibromophenylsulphonyl)pyrazole (Compound No. 6.17)
Following the procedure of Example 1, there were obtained 144 mg (yield 21.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.50 (1H, doublet, J = 2.1 Hz);
8.20 (1H, doublet, J = 2.5 Hz);
7.58 - 7.56 (2H, multiplet);
7.01 (1H, doublet, J = 2.1 Hz);
3.43 (4H, quartet, J = 7.0 Hz);
1.35 - 0.90 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,5-difluorophenylthio)pyrazole (Compound No. 6.18)
Following the procedure of Example 1, there were obtained 134 mg (yield 55.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, doublet, J = 2.6 Hz);
7.11 - 6.90 (3H, multiplet);
6.38 (1H, doublet, J = 2.6 Hz);
3.56 (4H, quartet, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,5-difluorophenylsulphonyl)pyrazole (Compound No. 6.19)
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Following the procedure of Example 1, there were obtained 109 mg (yield 48.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.21 (1H, doublet, J = 2.8 Hz);
7.82 (1H, doubled doublet of doublets, J = 5.2, 3.2 & 2.2 Hz);
7.37 - 7.29 (1H, multiplet);
7.21 - 7.10 (1H, multiplet);
6.98 (1H, doublet, J = 2.8 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
1.22 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylsulphonyl)-4-fluoropyrazole (Compound No. 6.60)
Following the procedure of Example 19, there were obtained 12 mg (yield 2.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.4 Hz);
8.00 (1H, doublet, J = 4.7 Hz);
7.45 (1H, doublet of doublets, J = 8.4 & 2.4 Hz);
7.31 (1H, doublet, J = 8.4 Hz);
3.50 - 3.37 (4H, multiplet);
1.30 - 1.08 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,5-dimethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 6.61)
Following the procedure of Example 7, there were obtained 16 mg (yield 3.1%) of the title compound,
melting at 96 - 97 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-5-trifluoromethylphenylsulphonyl)-4-fluoropyrazole (Compound
No. 6.62)
Following the procedure of Example 7, there were obtained 49 mg (yield 4.7%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.60 (1H, doublet, J = 1.5 Hz);
8.05 (1H, doublet, J = 4.7 Hz);
7.85 (1H, doublet of doublets, J = 8.5 & 1.5 Hz);
7.66 (1H, doublet, J = 8.5 Hz);
3.45 (4H, quartet, J = 7.2 Hz);
1.20 - 1.07 (6H, broad).
1-(Diethylcarbamoyl)-3-(5-chloro-2-methylphenylsulphonyl)-4-fluoropyrazole (Compound No. 6.63)
Following the procedure of Example 7, there were obtained 12 mg (yield 3.3%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.2 Hz);
8.02 (1H, doublet, J = 4.7 Hz);
7.50 (1H, doublet of doublets, J = 2.2 & 8.1 Hz);
7.25 (1H, doublet, J = 8.1 Hz);
3.48 (4H, broad quartet, J = 7.1 Hz);
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2.58 (3H, singlet);
1.22 (6H, broad triplet, J = 7.1 Hz).
1-(Diethylcarbamoyl)-3-(2-fluoro-5-methylphenylsulphonyl)-4-fluoropyrazole (Compound No. 6.66)
Following the procedure of Example 19, there were obtained 35 mg (yield 3.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.02 (1H, doublet, J = 4.7 Hz);
7.89 (1H, doublet of doublets, J = 6.6 & 2.0 Hz);
7.44 (1H, doublet of doublets of doublets, J = 8.5, 4.9 & 2.0 Hz);
7.07 (1H, triplet, J = 8.5 Hz);
3.50 (4H, broad quartet, J = 7.0 Hz);
2.42 (3H, singlet);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-chloro-5-methoxyphenylsulphonyl)-4-fluoropyrazole (Compound No. 6.70)
Following the procedure of Example 19, there were obtained 52 mg (yield 4.7%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.02 (1H, doublet, J = 4.7 Hz);
7.83 (1H, doublet, J = 3.1 Hz);
7.38 (1H, doublet, J = 8.8 Hz);
7.10 (1H, doublet of doublets, J = 8.8 & 3.1 Hz);
3.89 (3H, singlet);
3.47 (4H, quartet, J = 7.0 Hz);
1.31 - 1.04 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylsulphonyl)-4-chloropyrazole (Compound No. 6.101)
Following the procedure of Example 5, there were obtained 85 mg (yield 31.5%) of the title compound,
melting at 97 - 98 DEG C.
1-(Diethylcarbamoyl)-3-(2,5-dimethylphenylsulphonyl)-4-chloropyrazole (Compound No. 6.102)
Following the procedure of Example 4, there were obtained 201 mg (yield 23.7%) of the title
compound, melting at 108 - 108.5 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-5-trifluoromethylphenylsulphonyl)-4-chloropyrazole (Compound
No. 6.103)
Following the procedure of Example 3, there were obtained 63 mg (yield 9.6%) of the title compound,
melting at 80 - 81.5 DEG C.
1-(Diethylcarbamoyl)-3-(5-chloro-2-methylphenylsulphonyl)-4-chloropyrazole (Compound No. 6.104)
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Following the procedure of Example 4, there were obtained 203 mg (yield 14.4%) of the title
compound, melting at 59 - 63 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-5-methoxyphenylthio)-4-chloropyrazole (Compound No. 6.105)
Following the procedure of Example 4, there were obtained 222 mg (yield 38.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, singlet);
7.30 (1H, doublet of doublets, J = 1.0 & 8.0 Hz);
6.77 (1H, multiplet);
6.73 (1H, doublet, J = 8.0 Hz);
3.72 (3H, singlet);
3.53 (4H, broad quartet, J = 6.7 Hz);
1.18 (6H, broad triplet, J = 6.7 Hz).
1-(Diethylcarbamoyl)-3-(2-chloro-5-methoxyphenylsulphonyl)-4-chloropyrazole (Compound No.
6.106)
Following the procedure of Example 4, there were obtained 180 mg (yield 35.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, singlet);
7.86 (1H, doublet, J = 3.0 Hz);
7.37 (1H, doublet, J = 8.8 Hz);
7.11 (1H, doublet of doublets, J = 3.0 & 8.8 Hz);
3.89 (3H, singlet);
3.48 (4H, broad quartet, J = 6.9 Hz);
1.24 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-fluoro-5-methylphenylthio)-4-chloropyrazole (Compound No. 6.108)
Following the procedure of Example 4, there were obtained 323 mg (yield 61.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.12 (1H, singlet);
7.22 - 6.93 (3H, multiplet);
3.47 (4H, quartet, J = 7.0 Hz);
2.28 (3H, singlet);
1.12 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-fluoro-5-methylphenylsulphonyl)-4-chloropyrazole (Compound No. 6.109)
Following the procedure of Example 4, there were obtained 251 mg (yield 49.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, singlet);
7.94 - 7.83 (1H, multiplet);
7.49 - 7.39 (1H, multiplet);
7.10 - 6.92 (1H, multiplet);
3.60 - 3.38 (4H, broad);
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2.43 (3H, singlet);
1.30 - 1.06 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,5-difluorophenylthio)-4-chloropyrazole (Compound No. 6.110)
Following the procedure of Example 3, there were obtained 218 mg (yield 38.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, singlet);
6.92 - 7.13 (3H, multiplet);
3.52 (4H, quartet, J = 7.0 Hz);
1.18 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,5-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 6.111)
Following the procedure of Example 3, there were obtained 112 mg (yield 20.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
7.88 - 7.80 (1H, multiplet);
7.42 - 7.31 (1H, multiplet);
7.23 - 7.12 (1H, multiplet);
3.6 - 3.4 (4H, multiplet);
1.3 - 1.2 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(5-chloro-2-methoxyphenylsulphonyl)-4-chloropyrazole (Compound No.
6.112)
Following the procedure of Example 5, there were obtained 80 mg (yield 17.8%) of the title compound,
melting at 94 - 95 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-5-trifluoromethylphenyl sulphonyl)-4-bromopyrazole (Compound
No. 6.115)
Following the procedure of Example 3, there were obtained 140 mg (yield 9.4%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.49 (1H, doublet, J = 1.9 Hz);
8.21 (1H, singlet);
7.74 (1H, doublet of doublets, J = 1.9 & 8.4 Hz);
7.52 (1H, doublet, J = 8.4 Hz);
3.45 (4H, quartet, J = 6.9 Hz);
1.19 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylsulphonyl)-4-bromopyrazole (Compound No. 6.117)
Following the procedure of Example 5, there were obtained 132 mg (yield 55.0%) of the title
compound, melting at 100 - 102 DEG C.
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1-(Diethylcarbamoyl)-3-(2-fluoro-5-methylphenylthio)-4-bromopyrazole (Compound No. 6.118)
Following the procedure of Example 4, there were obtained 178 mg (yield 29.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
7.24 - 6.94 (3H, multiplet);
3.46 (4H, quartet, J = 7.0 Hz);
2.29 (3H, singlet);
1.21 - 1.00 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-fluoro-5-methylphenylsulphonyl)-4-bromopyrazole (Compound No. 6.119)
Following the procedure of Example 4, there were obtained 147 mg (yield 25.9%) of the title
compound, melting at 93 - 95 DEG C.
1-(Diethylcarbamoyl)-3-(5-chloro-2-methylphenylthio)-4-bromopyrazole (Compound No. 6.120)
Following the procedure of Example 4, there were obtained 482 mg (yield 39.8%) of the title
compound, melting at 74 - 76 DEG C.
1-(Diethylcarbamoyl)-3-(5-chloro-2-methylphenylsulphonyl)-4-bromopyrazole (Compound No. 6.121)
Following the procedure of Example 4, there were obtained 359 mg (yield 39.8%) of the title
compound, melting at 115 - 117 DEG C.
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylsulphonyl)-4-allylpyrazole (Compound No. 6.126)
Following the procedure of Example 4, there were obtained 41 mg (yield 6.5%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.11 (1H, doublet, J = 2.5 Hz);
7.98 (1H, singlet);
7.41 (1H, doublet of doublets, J = 2.5 & 8.5 Hz);
7.28 (1H, doublet, J = 8.5 Hz);
5.99 - 5.83 (1H, multiplet);
5.17 - 5.08 (2H, multiplet);
3.55 - 3.27 (6H, multiplet);
1.01 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylthio)-4-cyanopyrazole (Compound No. 6.144)
Following the procedure of Example 6, there were obtained 140 mg (yield 19.4%) of the title
compound, melting at 93 - 96 DEG C.
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1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylsulphonyl)-4-cyanopyrazole (Compound No. 6.145)
Following the procedure of Example 6, there were obtained 50 mg (yield 8.0%) of the title compound,
melting at 101 - 104 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-5-trifluoromethylphenylthio)-4-cyanopyrazole (Compound No.
6.147)
Following the procedure of Example 14, there were obtained 167 mg (yield 22.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.58 (1H, singlet);
7.74 (1H, singlet);
7.63 - 7.56 (2H, multiplet);
3.47 (4H, quartet, J = 7.0 Hz);
1.25 - 1.00 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(2-chloro-5-trifluoromethylphenylsulphonyl)-4-cyanopyrazole (Compound
No. 6.148)
Following the procedure of Example 14, there were obtained 129 mg (yield 18.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.65 (1H, doublet, J = 2.0 Hz);
8.62 (1H, singlet);
7.88 (1H, doublet of doublets, J = 8.4 & 2.0 Hz);
7.68 (1H, doublet, J = 8.4 Hz);
3.46 (4H, quartet, J = 7.0 Hz);
1.33 - 1.07 (6H, multiplet).
Ethyl 1-(diethylcarbamoyl)-3-(2,5-dichlorophenylthio)pyrazole-4-carboxylate (Compound No. 6.150)
Following the procedure of Example 9, there were obtained 172 mg (yield 16.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.63 (1H, singlet);
7.66 (1H, doublet, J = 2.5 Hz);
7.42 (1H, doublet, J = 8.5 Hz);
7.29 (1H, doublet of doublets, J = 2.5 & 8.5 Hz);
4.35 (2H, quartet, J = 7.2 Hz);
3.40 (4H, quartet, J = 7.0 Hz);
1.36 (3H, triplet, J = 7.2 Hz);
1.30 - 0.73 (6H, broad).
Ethyl 1-(diethylcarbamoyl)-3-(2,5-dichlorophenylsulphonyl)pyrazole-4-carboxylate (Compound No.
6.151)
Following the procedure of Example 9, there were obtained 149 mg (yield 15.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
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8.68 (1H, singlet);
8.35 (1H, doublet, J = 2.5 Hz);
7.55 (1H, doublet of doublets, J = 2.5 & 8.5 Hz);
7.43 (1H, doublet, J = 8.5 Hz);
4.32 (2H, quartet, J = 7.0 Hz);
3.47 (4H, quartet, J = 7.0 Hz);
1.34 (3H, triplet, J = 7.0 Hz);
1.32 - 1.17 (3H, broad);
1.12 - 0.96 (3H, broad).
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylthio)-4-methylthiopyrazole (Compound No. 6.159)
Following the procedure of Example 9, there were obtained 128 mg (yield 13.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, singlet);
7.33 (1H, doublet, J = 9.1 Hz);
7.16 - 7.11 (2H, multiplet);
3.54 (4H, quartet, J = 6.8 Hz);
2.36 (3H, singlet);
1.19 (6H, triplet, J = 6.8 Hz).
1-(Diethylcarbamoyl)-3-(2,5-dichlorophenylsulphonyl)-4-methylsulphonylpyrazole (Compound No.
6.160)
Following the procedure of Example 9, there were obtained 88 mg (yield 10.8%) of the title compound,
melting at 55 - 60 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-5-methoxyphenylsulphonyl)-4-fluoropyrazole (Compound No.
6.172)
Following the procedure of Example 19, there were obtained 22 mg (yield 3.4%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.06 (1H, doublet, J = 5.1 Hz);
7.31 - 7.26 (1H, multiplet);
6.74 - 6.69 (2H, multiplet);
3.72 (3H, singlet);
3.56 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-fluoro-5-methylphenylthio)-4-fluoropyrazole (Compound No. 6.173)
Following the procedure of Example 9, there were obtained 39 mg (yield 4.7%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
7.98 (1H, doublet, J = 5.1 Hz);
7.18 (1H, doublet, J = 7.5 Hz);
7.09 - 6.92 (2H, multiplet);
3.52 (4H, quartet, J = 7.0 Hz);
2.28 (3H, singlet);
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1.18 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,6-difluorophenylsulphonyl)pyrazole (Compound No. 7.1)
Following the procedure of Example 1, there were obtained 97 mg (yield 69.3%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.21 (1H, doublet, J = 2.6 Hz);
7.65 - 7.51 (1H, multiplet);
7.02 (2H, triplet, J = 8.4 Hz);
6.97 (1H, doublet, J = 2.6 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
1.45 - 1.05 (6H, broad).
1-(Diethylcarbamoyl)-3-(6-chloro-2-fluorophenylsulphonyl)pyrazole (Compound No. 7.2)
Following the procedure of Example 1, there were obtained 519 mg (yield 86.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.21 (1H, doublet, J = 2.5 Hz);
7.55 - 7.42 (1H, multiplet);
7.34 - 7.30 (1H, multiplet);
7.19 - 7.09 (1IH, multiplet);
6.98 (1H, doublet, J = 2.5 Hz);
3.47 (4H, quartet, J = 7.0 Hz);
1.4 - 1.0 (6H, broad).
1-(Diethylcarbamoyl)-3-(6-chloro-2-fluorophenylthio)pyrazole (Compound No. 7.3)
Following the procedure of Example 1, there were obtained 1.38 g (yield 87.3%) of the title
compound, melting at 30 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-dichlorophenylsulphonyl)pyrazole (Compound No. 7.4)
Following the procedure of Example 1, there were obtained 111 mg (yield 78.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, doublet, J = 2.8 Hz);
7.47 - 7.34 (3H, multiplet);
6.99 (1H, doublet, J = 2.8 Hz);
3.43 (4H, quartet, J = 7.0 Hz);
1.40 - 0.88 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,6-dibromophenylsulphonyl)pyrazole (Compound No. 7.6)
Following the procedure of Example 1, there were obtained 88 mg (yield 93.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.23 (1H, doublet, J = 2.7 Hz);
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7.76 (2H, doublet, J = 8.0 Hz);
7.43 (1H, triplet, J = 8.0 Hz);
7.03 (1H, doublet, J = 2.7 Hz);
3.44 (4H, quartet, J = 7.0 Hz);
1.40 - 0.90 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,6-dimethylphenylsulphonyl)pyrazole (Compound No. 7.7)
Following the procedure of Example 1, there were obtained 189 mg (yield 64.9%) of the title
compound, melting at 91 - 92 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-dimethylphenylthio)pyrazole (Compound No. 7.9)
Following the procedure of Example 1, there were obtained 134 mg (yield 72.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.04 (1H, doublet, J = 2.8 Hz);
7.19 - 7.10 (3H, multiplet);
5.96 (1H, doublet, J = 2.8 Hz);
3.48 (4H, broad quartet, J = 7.0 Hz);
2.48 (6H, singlet);
1.11 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-fluoro-6-methoxyphenylthio)pyrazole (Compound No. 7.13)
Following the procedure of Example 1, there were obtained 769 mg (yield 71.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.04 (1H, doublet, J = 2.8 Hz);
7.35 (1H, triplet of doublets, J = 8.4 & 6.5 Hz);
6.83 - 6.73 (2H, multiplet);
6.12 (1H, doublet, J = 2.8 Hz);
3.86 (3H, singlet);
3.49 (4H, broad quartet, J = 7.0 Hz);
1.12 (3H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-fluoro-6-methoxyphenylsulphonyl)pyrazole (Compound No. 7.14)
Following the procedure of Example 1, there were obtained 117 mg (yield 71.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.6 Hz);
7.50 (1H, triplet of doublets, J = 6.0 & 5.8 Hz);
6.93 (1H, doublet, J = 2.6 Hz);
6.85 - 6.73 (2H, multiplet);
3.80 (3H, singlet);
3.48 (4H, broad quartet, J = 7.0 Hz);
1.35 - 1.05 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-methyl-6-isopropylphenylsulphonyl)pyrazole (Compound No. 7.15)
320/2194
Following the procedure of Example 1, there were obtained 447 mg (yield 69.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, doublet, J = 2.6 Hz);
7.45 - 7.32 (2H, multiplet);
7.14 - 7.10 (1H, multiplet);
6.87 (1H, doublet, J = 2.6 Hz);
4.15 (1H, septet, J = 6.7 Hz);
3.44 (4H, quartet, J = 7.0 Hz);
2.74 (3H, singlet);
1.14 (6H, doublet, J = 6.7 Hz);
1.3 - 0.9 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-methyl-6-isopropylphenylthio)pyrazole (Compound No. 7.16)
Following the procedure of Example 1, there were obtained 1.00 g (yield 74.3%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.03 (1H, doublet, J = 2.8 Hz);
7.33 - 7.11 (3H, multiplet);
5.93 (1H, doublet, J = 2.8 Hz);
3.81 (1H, septet, J = 7.0 Hz);
3.47 (4H, quartet, J = 7.0 Hz);
2.45 (3H, singlet);
1.18 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)pyrazole (Compound No. 7.17)
Following the procedure of Example 1, there were obtained 793 mg (yield 42.1%) of the title
compound, melting at 83 - 83.5 DEG C.
1-(Diethylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)pyrazole (Compound No. 7.20)
Following the procedure of Example 1, there were obtained 343 mg (yield 32.9%) of the title
compound, melting at 93 - 94 DEG C.
1-(Diethylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)pyrazole (Compound No. 7.21)
Following the procedure of Example 1, there were obtained 381 mg (yield 34.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.02 (1H, doublet, J = 2.6 Hz);
7.27 (1H, triplet, J = 8.0 Hz);
6.92 (1H, broad doublet, J = 8.0 Hz);
6.80 (1H, broad doublet, J = 8.0 Hz);
5.99 (1H, doublet, J = 2.6 Hz);
3.83 (3H, singlet);
3.50 (4H, broad quartet, J = 7.0 Hz);
2.47 (3H, singlet);
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1.12 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,6-diethylphenylsulphonyl)pyrazole (Compound No. 7.22)
Following the procedure of Example 1, there were obtained 308 mg (yield 72.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, doublet, J = 2.9 Hz);
7.42 (1H, triplet, J = 8.1 Hz);
7.20 (2H, doublet, J = 7.7 Hz);
6.88 (1H, doublet, J = 2.9 Hz);
3.43 (4H, quartet, J = 7.0 Hz);
3.08 (4H, quartet, J = 7.3 Hz);
1.26 (6H, triplet, J = 7.3 Hz);
1.40 - 0.90 (6H, broad).
1-(Diethylcarbamoyl)-3-(2.6-diethylphenylthio)pyrazole (Compound No. 7.23)
Following the procedure of Example 1, there were obtained 1.21 g (yield 77.4%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.01 (1H, doublet, J = 2.9 Hz);
7.30 (1H, doublet, J = 2.0 Hz);
7.18 (1H, singlet);
7.14 (1H, doublet, J = 2.0 Hz);
5.93 (1H, doublet, J = 2.9 Hz);
3.46 (4H, quartet, J = 7.0 Hz);
2.88 (4H, quartet, J = 7.4 Hz);
1.17 (6H, triplet, J = 7.4 Hz);
1.08 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2,6-diisopropylphenylsulphonyl)pyrazole (Compound No. 7.24)
Following the procedure of Example 1, there were obtained 20 mg (yield 5.7%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.22 (1H, doublet, J = 2.9 Hz);
8.09 - 7.89 (1H, multiplet);
7.65 - 7.30 (2H, multiplet);
6.86 (1H, doublet, J = 2.9 Hz);
4.24 (2H, septet, J = 6.7 Hz);
3.45 (4H, quartet, J = 7.0 Hz);
1.35 - 0.90 (6H, multiplet);
1.19 (12H, doublet, J = 6.7 Hz).
1-(N-Methyl-N-phenylcarbamoyl)-3-(6-ethyl-2-methylphenylthio)pyrazole (Compound No. 7.75)
Following the procedure of Example 1, there were obtained 246 mg (yield 40.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 270 MHz), delta ppm:
7.87 (1H, doublet, J = 2.9 Hz);
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7.26 - 7.00 (8H, multiplet);
5.74 (1H, doublet, J = 2.9 Hz);
3.47 (3H, singlet);
2.75 (2H, quartet, J = 7.5 Hz);
2.25 (3H, singlet);
1.11 (3H, triplet, J = 7.5 Hz).
1-(N-Methyl-N-phenylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)pyrazole (Compound No.
7.76)
Following the procedure of Example 1, there were obtained 224 mg (yield 19.4%) of the title
compound, melting at 94 - 96 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-5-allylpyrazole (Compound No. 7.91)
Following the procedure of Example 15, there were obtained 62 mg (yield 13.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.37 - 7.32 (1H, multiplet);
7.25 - 7.18 (2H, multiplet);
5.95 - 5.74 (1H, multiplet);
5.87 (1H, singlet);
5.14 - 5.04 (2H, multiplet);
3.56 - 3.51 (2H, multiplet);
3.33 (4H, broad);
2.52 (3H, singlet);
1.10 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,6-dichlorophenylsulphonyl)5-(methoxymethyl)pyrazole (Compound No.
7.93)
Following the procedure of Example 15, there were obtained 151 mg (yield 37.3%) of the title
compound, melting at 71 - 73 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-difluorophenylthio)-5-(methoxymethyl)pyrazole (Compound No. 7.94)
Following the procedure of Example 15, there were obtained 95 mg (yield 52.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.39 - 7.28 (1H, multiplet);
6.97 (2H, doublet of doublets, J = 8.4 & 6.6 Hz);
6.23 (1H, singlet);
4.61 (2H, singlet);
3.45 - 3.25 (4H, broad);
3.39 (3H, singlet);
1.30 - 0.98 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,6-difluorophenylsulphonyl)-5-(methoxymethyl)pyrazole (Compound No.
7.95)
323/2194
Following the procedure of Example 15, there were obtained 69 mg (yield 38.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.63 - 7.49 (1H, multiplet);
7.00 (2H, triplet, J = 8.4 Hz);
6.94 (1H, singlet);
4.64 (2H, singlet);
3.46 (2H, quartet, J = 7.0 Hz);
3.41 (3H, singlet);
3.21 (2H, quartet, J = 6.9 Hz);
1.26 (3H, triplet, J = 6.9 Hz);
1.12 (3H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)-5-(methylthio)pyrazole (Compound No. 7.96)
Following the procedure of Example 15, there were obtained 65 mg (yield 27.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.24 - 7.11 (3H, multiplet);
5.72 (1H, singlet);
3.38 (4H, quartet, J = 7.0 Hz);
2.90 (2H, quartet, J = 7.5 Hz);
2.45 (3H, singlet);
2.35 (3H, singlet);
1.19 (3H, triplet, J = 7.5 Hz);
1.2 - 1.0 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-5-(ethylsulphonyl)pyrazole (Compound
no. 7.97)
Following the procedure of Example 15, there were obtained 144 mg (yield 42.8%) of the title
compound, melting at 92 - 93.5 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)-5-(ethylthio)pyrazole (Compound No. 7.98)
Following the procedure of Example 15, there were obtained 55 mg (yield 53.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.35 - 7.33 (1H, multiplet);
7.26 - 7.19 (2H, multiplet);
5.94 (1H, singlet);
3.36 (4H, quartet, J = 7.3 Hz);
2.85 (2H, quartet, J = 7.3 Hz);
2.52 (3H, singlet);
1.31 (3H, triplet, J = 7.3 Hz);
1.20 - 0.97 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-5-cyanopyrazole (Compound No. 7.99)
324/2194
Following the procedure of Example 16, there were obtained 72 mg (yield 14.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.42 (1H, singlet);
7.42 (1H, doublet of doublets, J = 7.6 & 7.3 Hz);
7.23 (1H, doublet, J = 7.6 Hz);
7.17 (1H, doublet, J = 7.3 Hz);
3.53 - 3.22 (4H, broad);
3.08 (2H, quartet, J = 7.4 Hz);
2.66 (3H, singlet);
1.29 (3H, triplet, J = 7.4 Hz);
1.40 - 0.95 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-5-cyanopyrazole (Compound No. 7.100)
Following the procedure of Example 15, there were obtained 130 mg (yield 28.7%) of the title
compound, melting at 92 - 93 DEG C.
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-5-chloropyrazole (Compound No. 7.103)
Following the procedure of Example 16, there were obtained 72 mg (yield 14.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.38 (1H, triplet, J = 6.6 Hz);
7.17 (2H, doublet, J = 6.6 Hz);
6.79 (1H, singlet);
3.47 (2H, quartet, J = 7.3 Hz);
3.10 (4H, broad quartet, J = 7.4 Hz);
2.67 (3H, singlet);
1.28 (3H, triplet, J = 7.3 Hz);
1.26 (3H, triplet, J = 7.4 Hz);
1.03 (3H, triplet, J = 7.3 Hz).
1-(Diethylcarbamoyl)-3-(2,6-dimethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 7.112)
Following the procedure of Example 7, there were obtained 31 mg (yield 6.1%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.02 (1H, doublet, J = 4.5 Hz);
7.35 - 7.31 (1H, multiplet);
7.16 (2H, doublet, J = 7.1 Hz);
3.48 (4H, quartet, J = 7.0 Hz);
2.71 (6H, singlet);
1.03 - 1.08 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-fluoropyrazole (Compound No. 7.113)
Following the procedure of Example 7, there were obtained 12 mg (yield 3.5%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.02 (1H, doublet, J = 4.7 Hz);
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7.40 (1H, triplet, J = 7.6 Hz);
7.22 (1H, doublet, J = 7.6 Hz);
7.15 (1H, doublet, J = 7.6 Hz);
3.46 (4H, quartet, J = 7.0 Hz);
3.13 (2H, quartet, J = 7.4 Hz);
2.70 (3H, singlet);
1.31 - 1.08 (9H, multiplet).
1-(Diethylcarbamoyl)-3-(2.6-diethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 7.114)
Following the procedure of Example 7, there were obtained 14 mg (yield 1.9%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.02 (1H, doublet, J = 4.7 Hz);
7.48 - 7.41 (1H, multiplet);
7.21 (2H, doublet, J = 7.6 Hz);
3.45 (4H, quartet, J = 7.0 Hz);
3.11 (4H, quartet, J = 7.3 Hz);
1.27 (6H, triplet, J = 7.3 Hz);
1.35 - 1.03 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-4-fluoropyrazole (Compound No. 7.115)
Following the procedure of Example 7, there were obtained 44 mg (yield 11.1%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.01 (1H, doublet, J = 4.7 Hz);
7.43 - 7.23 (3H, multiplet);
3.48 - 3.38 (4H, multiplet);
2.83 (3H, singlet);
1.35 - 0.9 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(2,6-difluorophenylsulphonyl)-4-fluoropyrazole (Compound No. 7.119)
Following the procedure of Example 19, there were obtained 32 mg (yield 2.9%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.04 (1H, doublet, J = 4.7 Hz);
7.65 - 7.54 (1H, multiplet);
7.10 - 6.99 (2H, multiplet);
3.50 (4H, broad);
1.22 (6H, triplet, J = 6.9 Hz).
1-(Diethylcarbamoyl)-3-(2-methyl-6-methoxyphenylsulphonyl)-4-fluoropyrazole (Compound No.
7.120)
Following the procedure of Example 7, there were obtained 20 mg (yield 2.6%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
7.98 (1H, doublet, J = 4.8 Hz);
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7.40 (1H, triplet, J = 8.0 Hz);
6.89 (1H, doublet, J = 8.0 Hz);
6.81 (1H, doublet, J = 8.0 Hz);
3.78 (3H, singlet);
3.47 (4H, quartet, J = 7.0 Hz);
2.79 (3H, singlet);
1.19 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-chloro-6-fluorophenylsulphonyl)-4-fluoropyrazole (Compound No. 7.121)
Following the procedure of Example 19, there were obtained 44 mg (yield 4.6%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz),
8.04 (1H, doublet, J = 4.7 Hz);
7.58 - 7.44 (1H, multiplet);
7.36 - 7.11 (2H, multiplet);
3.48 (4H, quartet, J = 6.8 Hz);
1.25 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-isopropyl-6-methylphenylsulphonyl)-4-fluoropyrazole (Compound No.
7.122)
Following the procedure of Example 19, there were obtained 47 mg (yield 4.4%) of the title compound,
melting at 85 - 86 DEG C.
1-(Dimethylcarbamoyl)-3-(2,6-dimethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 7.126)
Following the procedure of Example 7, there were obtained 24 mg (yield 14.5%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
7.99 (1H, doublet, J = 4.7 Hz);
7.34 (1H, triplet, J = 7.0 Hz);
7.15 (2H, doublet, J = 7.0 Hz);
3.30 - 3.08 (6H, broad);
2.72 (6H, singlet).
1-(N-Ethyl-N-propylcarbamoyl)-3-(2.6-dimethylphenylsulphonyl)-4-fluoropyrazole (Compound No.
7.142)
Following the procedure of Example 7, there were obtained 22 mg (yield 11.9%) of the title compound,
melting at 68 - 70 DEG C.
1-(Dipropylcarbamoyl)-3-(2,6-dimethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 7.150)
Following the procedure of Example 7, there were obtained 15 mg (yield 5.8%) of the title compound,
melting at 66 - 67 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-dimethylphenylthio)-4-chloropyrazole (Compound No. 7.166)
327/2194
Following the procedure of Example 4, there were obtained 188 mg (yield 30.3%) of the title
compound, melting at 95 - 96 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-dimethylphenylsulphonyl)-4-chloropyrazole (Compound No. 7.167)
Following the procedure of Example 4, there were obtained 169 mg (yield 27.5%) of the title
compound, melting at 78 - 78.5 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)-4-chloropyrazole (Compound No. 7.172)
Following the procedure of Example 5, there were obtained 180 mg (yield 54.6%) of the title
compound, melting at 85 - 87 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-4-chloropyrazole (Compound No. 7.173)
Following the procedure of Example 5, there were obtained 94 mg (yield 32.7%) of the title compound,
melting at 88 - 89 DEG C.
1-(Dimethylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)-4-chloropyrazole (Compound No. 7.174)
Following the procedure of Example 3, there were obtained 216 mg (yield 52.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.01 (1H, singlet);
7.25 (1H, triplet, J = 8.0 Hz);
6.71 (1H, broad doublet, J = 8.0 Hz);
6.76 (1H, broad doublet, J = 8.0 Hz);
3.78 (3H, singlet);
3.05 (6H, singlet);
2.48 (3H, singlet).
1-(Dimethylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)-4-chloropyrazole (Compound No.
7.175)
Following the procedure of Example 3, there were obtained 158 mg (yield 47.6%) of the title
compound, melting at 116 - 117 DEG C.
1-(N-Ethyl-N-methylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)-4-chloropyrazole (Compound No.
7.176)
Following the procedure of Example 3, there were obtained 227 mg (yield 50.2%) of the title
compound, melting at 68 - 71 DEG C.
328/2194
1-(N-Ethyl-N-methylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)-4-chloropyrazole
(Compound No. 7.177)
Following the procedure of Example 3, there were obtained 179 mg (yield 50.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, singlet);
7.41 (1H, broad triplet, J = 8.0 Hz);
6.90 (1H, broad doublet, J = 8.0 Hz);
6.80 (1H, broad doublet, J = 8.0 Hz);
3.71 (3H, singlet);
3.54 (2H, broad quartet, J = 7.2 Hz);
3.11 (3H, broad);
2.81 (3H, singlet);
1.23 (3H, broad).
1-(Diethylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)-4-chloropyrazole (Compound No. 7.178)
Following the procedure of Example 3, there were obtained 706 mg (yield 41.8%) of the title
compound, melting at 90 - 91.5 DEG C.
1-(Diethylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)-4-chloropyrazole (Compound No.
7.179)
Following the procedure of Example 3, there were obtained 157 mg (yield 41.3%) of the title
compound, melting at 93 - 94 DEG C.
1-(N-Ethyl-N-propylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)-4-chloropyrazole (Compound No.
7.181)
Following the procedure of Example 3, there were obtained 230 mg (yield 49.6%) of the title
compound, melting at 90 - 92 DEG C.
1-(N-Ethyl-N-propylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)-4-chloropyrazole
(Compound No. 7.182)
Following the procedure of Example 3, there were obtained 193 mg (yield 49.6%) of the title
compound, melting at 113 - 115 DEG C.
1-(Dipropylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)-4-chloropyrazole (Compound No. 7.183)
Following the procedure of Example 3, there were obtained 246 mg (yield 50.2%) of the title
compound, melting at 92 - 94 DEG C.
1-(Dipropylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)-4-chloropyrazole (Compound No.
7.184)
329/2194
Following the procedure of Example 3, there were obtained 208 mg (yield 50.2%) of the title
compound, melting at 93 - 96 DEG C.
1-(N-Butyl-N-methylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)-4-chloropyrazole (Compound No.
7.185)
Following the procedure of Example 3, there were obtained 232 mg (yield 50.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.03 (1H, singlet);
7.25 (1H, triplet, J = 8.0 Hz);
6.89 (1H, broad doublet, J = 8.0 Hz);
6.76 (1H, broad doublet, J = 8.0 Hz);
3.79 (3H, singlet);
3.47 (3H, singlet);
3.41 (2H, broad triplet, J = 7.5 Hz);
3.01 (3H, singlet);
1.45 (2H, broad);
1.15 (2H, broad);
0.85 (3H, broad triplet, J = 6.6 Hz).
1-(N-Butyl-N-methylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)-4-chloropyrazole
(Compound No. 7.186)
Following the procedure of Example 3, there were obtained 182 mg (yield 50.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, singlet);
7.41 (1H, triplet, J = 8.0 Hz);
6.90 (1H, broad doublet, J = 8.0 Hz);
6.80 (1H, broad doublet, J = 8.0 Hz);
3.70 (3H, singlet);
3.48 (2H, broad triplet, J = 7.2 Hz);
3.14 (3H, broad);
2.80 (3H, singlet);
1.60 (2H, broad);
1.25 (2H, broad);
0.91 (3H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-6-fluorophenylthio)-4-chloropyrazole (Compound No. 7.187)
Following the procedure of Example 4, there were obtained 132 mg (yield 61.1%) of the title
compound, melting at 72 - 73 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-fluorophenylsulphonyl)-4-chloropyrazole (Compound No. 7.188)
Following the procedure of Example 4, there were obtained 121 mg (yield 60.5%) of the title
compound, melting at 90 - 91 DEG C.
330/2194
1-(Diethylcarbamoyl)-3-(2.6-difluorophenylthio)-4-chloropyrazole (Compound No. 7.189)
Following the procedure of Example 3, there were obtained 333 mg (yield 30.0%) of the title
compound, melting at 56 - 57 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 7.190)
Following the procedure of Example 3, there were obtained 291 mg (yield 27.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
7.66 - 7.55 (1H, multiplet);
7.10 - 7.00 (2H, multiplet);
3.51 (4H, quartet, J = 7.0 Hz);
1.30 - 1.19 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-fluoro-6-methoxyphenylsulphonyl)-4-chloropyrazole (Compound No.
7.191)
Following the procedure of Example 3, there were obtained 55 mg (yield 56.4%) of the title compound,
melting at 102 - 103 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-dimethylphenylsulphonyl)-4-bromopyrazole (Compound No. 7.211)
Following the procedure of Example 4, there were obtained 548 mg (yield 19.7%) of the title
compound, melting at 70 - 72 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-dimethylphenylthio)-4-bromopyrazole (Compound No. 7.212)
Following the procedure of Example 4, there were obtained 677 mg (yield 24.1%) of the title
compound, melting at 103 - 105 DEG C.
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-bromopyrazole (Compound No. 7.213)
Following the procedure of Example 4, there were obtained 129 mg (yield 20.7%) of the title
compound, melting at 63 - 64 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-4-bromopyrazole (Compound No. 7.215)
Following the procedure of Example 4, there were obtained 1.73 g (yield 26.9%) of the title compound,
melting at 99 - 100 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)-4-bromopyrazole (Compound No. 7.216)
331/2194
Following the procedure of Example 4, there were obtained 2.11 g (yield 34.0%) of the title compound,
melting at 96 - 99 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-fluorophenylthio)-4-bromopyrazole (Compound No. 7.217)
Following the procedure of Example 4, there were obtained 143 mg (yield 30.4%) of the title
compound, melting at 82 - 83 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-fluorophenylsulphonyl)-4-bromopyrazole (Compound No. 7.218)
Following the procedure of Example 4, there were obtained 93 mg (yield 27.3%) of the title compound,
melting at 108 - 109 DEG C.
1-(Diethylcarbamoyl)-3-(2-methoxy-6-methylphenylthio)-4-bromopyrazole (Compound No. 7.219)
Following the procedure of Example 5, there were obtained 882 mg (yield 46.1%) of the title
compound, melting at 88 - 92 DEG C.
1-(Diethylcarbamoyl)-3-(2-methoxy-6-methylphenylsulphonyl)-4-bromopyrazole (Compound No.
7.220)
Following the procedure of Example 5, there were obtained 180 mg (yield 46.1%) of the title
compound, melting at 142 - 146 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-difluorophenylsulphonyl)-4-bromopyrazole (Compound No. 7.221)
Following the procedure of Example 3, there were obtained 79 mg (yield 7.6%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.21 (1H, singlet);
7.68 - 7.48 (1H, multiplet);
7.09 - 7.01 (2H, multiplet);
3.51 (4H, quartet, J = 7.0 Hz);
1.29 - 1.13 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-isopropyl-6-methylphenylthio)-4-iodopyrazole (Compound No. 7.222)
Following the procedure of Example 4, there were obtained 265 mg (yield 88.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
7.32 - 7.10 (3H, multiplet);
3.74 (1H, septet, J = 6.9 Hz);
3.28 (4H, quartet, J = 7.0 Hz);
2.41 (3H, singlet);
1.18 (6H, doublet, J = 6.9 Hz);
1.2 - 0.6 (6H, broad).
332/2194
1-(Diethylcarbamoyl)-3-(2-isopropyl-6-methylphenylsulphonyl)-4-iodopyrazole (Compound No.
7.223)
Following the procedure of Example 4, there were obtained 1.06 g (yield 76.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.25 (1H, singlet);
7.48 - 7.32 (2H, multiplet);
7.13 (1H, doublet, J = 8.0 Hz);
4.01 (1H, septet, J = 6.8 Hz);
3.42 (4H, quartet, J = 7.0 Hz);
2.75 (3H, singlet);
1.10 (6H, doublet, J = 6.8 Hz);
1.4 - 0.8 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-methylpyrazole (Compound No. 7.231)
Following the procedure of Example 14, there were obtained 53 mg (yield 6.1%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.96 (1H, broad quartet, J = 1.0 Hz);
7.38 (1H, triplet, J = 7.6 Hz);
7.21 - 7.11 (2H, multiplet);
3.37 (4H, quartet, J = 7.0 Hz);
3.07 (2H, quartet, J = 7.4 Hz);
2.62 (3H, singlet);
2.32 (3H, doublet, J = 1.0 Hz);
1.24 (3H, triplet, J = 7.4 Hz);
0.87 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-ethylpyrazole (Compound No. 7.234)
Following the procedure of Example 14, there were obtained 197 mg (yield 24.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.99 (1H, triplet, J = 1.0 Hz);
7.38 (1H, triplet, J = 7.8 Hz);
7.21 - 7.11 (2H, multiplet);
3.36 (4H, broad quartet, J = 7.0 Hz);
3.06 (2H, quartet, J = 7.4 Hz);
2.80 (2H, doublet of quartets, J = 1.0 & 7.5 Hz);
2.60 (3H, singlet);
1.30 - 1.20 (6H, multiplet);
0.85 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-4-allylpyrazole (Compound No. 7.235)
Following the procedure of Example 14, there were obtained 70 mg (yield 13.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
333/2194
7.96 (1H, singlet);
7.35 (1H, doublet, J = 6.3 Hz);
7.34 (1H, triplet, J = 6.3 Hz);
7.24 (1H, doublet, J = 6.3 Hz);
6.05 - 5.91 (1H, multiplet);
5.30 - 5.10 (2H, multiplet);
3.57 (2H, doublet, J = 6.7 Hz);
3.36 (4H, quartet, J = 6.7 Hz);
2.82 (3H, singlet);
1.13 (3H, broad);
0.89 (3H, broad).
1-(Diethylcarbamoyl)-3-(2,6-diethylphenylsulphonyl)-4-allylpyrazole (Compound No. 7.236)
Following the procedure of Example 14, there were obtained 69 mg (yield 12.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.98 (1H, singlet);
7.43 (1H, triplet, J = 7.7 Hz);
7.19 (2H, doublet, J = 7.7 Hz);
6.05 - 5.91 (1H, multiplet);
5.30 - 5.10 (2H, multiplet);
3.56 (2H, doublet, J = 6.9 Hz);
3.34 (4H, quartet, J = 6.9 Hz);
3.03 (4H, quartet, J = 7.4 Hz);
1.23 (6H, triplet, J = 6.9 Hz);
1.10 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-allylpyrazole (Compound No. 7.237)
Following the procedure of Example 14, there were obtained 42 mg (yield 10.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.98 (1H, singlet);
7.38 (1H, triplet, J = 7.5 Hz);
7.19 (1H, doublet, J = 7.5 Hz);
7.12 (1H, doublet, J = 7.5 Hz);
6.09 - 5.90 (1H, multiplet);
5.20 - 5.09 (2H, multiplet);
3.53 (2H, doublet, J = 6.4 Hz);
3.35 (4H, quartet, J = 7.7 Hz);
3.06 (2H, quartet, J = 7.3 Hz);
1.23 (3H, triplet, J = 7.3 Hz);
0.96 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-(methoxymethyl)pyrazole (Compound
No. 7.241)
Following the procedure of Example 14, there were obtained 23 mg (yield 12.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, singlet);
7.39 (1H, triplet, J = 7.7 Hz);
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7.17 (2H, doublet, J = 7.7 Hz);
4.67 (2H, singlet);
3.43 (3H, singlet);
3.36 (4H, quartet, J = 7.0 Hz);
3.07 (2H, quartet, J = 7.4 Hz);
2.61 (3H, singlet);
1.24 (3H, triplet, J = 7.4 Hz);
1.05 - 0.70 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,6-diethylphenylthio)-4-cyanopyrazole (Compound No. 7.254)
Following the procedure of Example 14, there were obtained 134 mg (yield 30.3%) of the title
compound, melting at 50 - 51 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-diethylphenylsulphonyl)-4-cyanopyrazole (Compound No. 7.255)
Following the procedure of Example 14, there were obtained 117 mg (yield 28.2%) of the title
compound, melting at 79 - 80 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)-4-cyanopyrazole (Compound No. 7.256)
Following the procedure of Example 14, there were obtained 127 mg (yield 29.3%) of the title
compound, melting at 82 - 85 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-4-cyanopyrazole (Compound No. 7.257)
Following the procedure of Example 14, there were obtained 105 mg (yield 27.9%) of the title
compound, melting at 120 - 123 DEG C.
Ethyl 1-(diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)pyrazole-4-carboxylate (Compound No.
7.262)
Following the procedure of Example 14, there were obtained 137 mg (yield 20.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.60 (1H, singlet);
7.23 - 7.10 (3H, multiplet);
4.37 (2H, quartet, J = 7.0 Hz);
3.50 - 3.18 (4H, broad);
2.86 (2H, quartet, J = 7.4 Hz);
2.43 (3H, singlet);
1.39 (3H, triplet, J = 7.0 Hz);
1.15 (6H, triplet, J = 7.4 Hz);
0.70 - 0.50 (3H, broad).
Ethyl 1-(diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)pyrazole-4-carboxylate (Compound
No. 7.263)
335/2194
Following the procedure of Example 14, there were obtained 122 mg (yield 19.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.70 (1H, singlet);
7.39 (1H, triplet, J = 7.6 Hz);
7.22 - 7.12 (2H, multiplet);
4.35 (2H, quartet, J = 7.1 Hz);
3.48 - 3.24 (4H, broad);
3.02 (2H, quartet, J = 7.4 Hz);
2.60 (3H, singlet);
1.36 (3H, triplet, J = 7.1 Hz);
1.22 (3H, triplet, J = 7.4 Hz);
1.27 - 1.13 (3H, broad);
0.82 - 0.65 (3H, broad).
Ethyl 1-(diethylcarbamoyl)-3-(2,6-diethylphenylthio)pyrazole-4-carboxylate (Compound No. 7.264)
Following the procedure of Example 14, there were obtained 259 mg (yield 43.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.60 (1H, singlet);
7.31 - 7.13 (3H, multiplet);
4.37 (2H, quartet, J = 7.0 Hz);
3.37 - 3.18 (4H, broad);
2.84 (4H, quartet, J = 7.6 Hz);
1.39 (3H, triplet, J = 7.0 Hz);
1.16 (6H, triplet, J = 7.6 Hz);
0.65 - 0.40 (6H, broad).
Ethyl 1-(diethylcarbamoyl)-3-(2,6-diethylphenylsulphonyl)pyrazole-4-carboxylate (Compound No.
7.265)
Following the procedure of Example 14, there were obtained 138 mg (yield 38.1%) of the title
compound, melting at 87 - 88 DEG C.
Ethyl 1-(diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)pyrazole-4-carboxylate (Compound No.
7.266)
Following the procedure of Example 14, there were obtained 210 mg (yield 35.8%) of the title
compound, melting at 103 - 105 DEG C.
Ethyl 1-(diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)pyrazole-4-carboxylate (Compound
No. 7.267)
Following the procedure of Example 14, there were obtained 186 mg (yield 32.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.67 (1H, singlet);
7.42 - 7.24 (3H, multiplet);
4.28 (2H, quartet, J = 7.1 Hz);
336/2194
3.45 (4H, quartet, J = 7.0 Hz);
2.83 (3H, singlet);
1.31 (3H, triplet, J = 7.1 Hz);
1.32 - 1.13 (3H, broad);
1.08 - 0.88 (3H, broad).
1-(Diethylcarbamoyl)-3-(2,6-diethylphenylthio)-4-methylthiopyrazole (Compound No. 7.268)
Following the procedure of Example 14, there were obtained 235 mg (yield 45.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, singlet);
7.27 - 7.13 (3H, multiplet);
3.29 (4H, quartet, J = 6.7 Hz);
2.40 (3H, singlet);
2.85 (4H, quartet, J = 7.4 Hz);
1.17 (6H, triplet, J = 7.4 Hz);
1.10 - 0.50 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)-4-methylthiopyrazole (Compound No. 7.269)
Following the procedure of Example 14, there were obtained 144 mg (yield 21.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, singlet);
7.26 - 7.10 (3H, multiplet);
3.30 (4H, quartet, J = 6.9 Hz);
2.88 (2H, quartet, J = 7.4 Hz);
2.43 (3H, singlet);
2.39 (3H, singlet);
1.17 (3H, triplet, J = 7.4 Hz);
1.12 - 0.84 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylthio)-4-methylthiopyrazole (Compound No. 7.270)
Following the procedure of Example 14, there were obtained 206 mg (yield 41.6%) of the title
compound, melting at 75 - 78 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-diethylphenylsulphonyl)-4-methylsulphonylpyrazole (Compound No.
7.271)
Following the procedure of Example 14, there were obtained 206 mg (yield 39.7%) of the title
compound, melting at 183 - 187 DEG C.
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-methylsulphonylpyrazole (Compound
No. 7.272)
Following the procedure of Example 14, there were obtained 111 mg (yield 19.6%) of the title
compound, melting at 154 - 157 DEG C
337/2194
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-4-methylsulphonylpyrazole (Compound
No. 7.273)
Following the procedure of Example 14, there were obtained 159 mg (yield 32.5%) of the title
compound, melting at 157 - 160 DEG C.
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)-4-difluoromethylpyrazole (Compound No.
7.300)
Following the procedure of Example 13, there were obtained 224 mg (yield 30.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.30 (1H, triplet, J = 1.8 Hz);
7.27 - 7.10 (3H, multiplet);
6.61 (1H, triplet, J = 55.5 Hz);
3.32 (4H, quartet, J = 7.0 Hz);
2.88 (2H, quartet, J = 7.5 Hz);
2.42 (3H, singlet);
1.17 (3H, triplet, J = 7.5 Hz);
1.11 - 0.72 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-difluoromethylpyrazole (Compound No.
7.301)
Following the procedure of Example 13, there were obtained 135 mg (yield 27.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.45 (1H, singlet);
7.41 (1H, triplet, J = 7.6 Hz);
7.24 - 6.90 (3H, multiplet);
3.45 - 3.30 (4H, multiplet);
3,07 (2H, quartet, J = 7.3 Hz);
2.62 (3H, singlet);
1.25 (3H, triplet, J = 7.3 Hz);
1.21 - 0.84 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylthio)-4-(dimethylcarbamoyl)pyrazole (Compound No.
7.311)
Following the procedure of Example 14, there were obtained 139 mg (yield 8.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.28 (1H, singlet);
7.26 - 7.09 (3H, multiplet);
3.30 (4H, quartet, J = 7.0 Hz);
3.13 (6H, singlet);
2.88 (2H, quartet, J = 7.5 Hz);
2,43 (3H, singlet);
1.16 (6H, triplet, J = 7.0 Hz);
0.85 - 0.55 (3H, broad).
338/2194
1-(Diethylcarbamoyl)-3-(2-ethyl-6-methylphenylsulphonyl)-4-(dimethylcarbamoyl)pyrazole
(Compound No. 7.312)
Following the procedure of Example 14, there were obtained 121 mg (yield 7.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.22 (1H, singlet);
7.38 (1H, triplet, J = 7.6 Hz);
7.21 - 7.11 (2H, multiplet);
3.39 (4H, quartet, J = 7.0 Hz);
3.15 - 3.03 (2H, multiplet);
3.11 (3H, singlet);
3.02 (3H, singlet);
2.63 (3H, singlet);
1.26 (3H, triplet, J = 7.5 Hz);
1.30 - 0.85 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-chloro-6-methylphenylsulphonyl)-4-bromo-5-methylthiopyrazole
(Compound No. 7.330)
Following the procedure of Example 16, there were obtained 136 mg (yield 10.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.44 - 7.24 (3H, multiplet);
3.51 (2H, quartet, J = 7.2 Hz);
3.03 (2H, quartet, J = 7.1 Hz);
2.97 (2H, quartet, J = 7.4 Hz);
2.87 (3H, singlet);
1.30 (3H, triplet, J = 7.2 Hz);
1.24 (3H, triplet, J = 7.4 Hz);
1.04 (3H, triplet, J = 7.1 Hz).
1-(Diethylcarbamoyl)-3-(2,6-difluorophenylthio)-4-fluoropyrazole (Compound No. 7.331)
Following the procedure of Example 19, there were obtained 49 mg (yield 4.9%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
7.94 (1H, doublet, J = 4.8 Hz);
7.40 - 7.29 (1H, multiplet);
6.96 (2H, doublet of doublets, J = 8.4 & 6.3 Hz);
3.46 (4H, quartet, J = 7.0 Hz);
1.12 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(2-chloro-6-fluorophenylthio)-4-fluoropyrazole (Compound No. 7.332)
Following the procedure of Example 19, there were obtained 60 mg (yield 6.8%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
7.95 (1H, doublet, J = 5.8 Hz);
7.92 - 7.26 (2H, multiplet);
339/2194
7.08 - 7.01 (1H, multiplet);
3.44 (4H, quartet, J = 7.0 Hz);
1.09 (6H, broad).
1-(Diethylcarbamoyl)-3-(2-isopropyl-6-methylphenylthio)-4-fluoropyrazole (Compound No. 7.333)
Following the procedure of Example 19, there were obtained 67 mg (yield 6.9%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
7.92 (1H, doublet, J = 5.1 Hz);
7.26 - 7.08 (3H, multiplet);
3.86 (1H, septet, J = 6.9 Hz);
3.37 (4H, quartet, J = 7.0 Hz);
2.47 (3H, singlet);
1.19 (3H, singlet);
1.16 (3H, singlet);
0.98 (6H, broad).
1-(N-Ethyl-N-propylcarbamoyl)-3-(2,6-dimethylphenylthio)-4-fluoropyrazole (Compound No. 7.334)
Following the procedure of Example 7, there were obtained 25 mg (yield 14.5%) of the title compound,
melting at 49 - 52 DEG C.
1-(Dipropylcarbamoyl)-3-(2,6-dimethylphenylthio)-4-fluoropyrazole (Compound No. 7.335)
Following the procedure of Example 7, there were obtained 28 mg (yield 11.6%) of the title compound,
melting at 40 - 43 DEG C.
1-(Dimethylcarbamoyl)-3-(2,6-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 7.336)
Following the procedure of Example 3, there were obtained 17 mg (yield 13.9%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.15 (1H, singlet);
7.69 - 7.54 (1H, multiplet);
7.26 - 6.98 (2H, multiplet);
3.28 - 3.10 (6H, broad).
1-(Dimethylcarbamoyl)-3-(2,6-difluorophenylthio)-4-chloropyrazole (Compound No. 7.337)
Following the procedure of Example 3, there were obtained 25 mg (yield 21.1%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.05 (1H, singlet);
7.44 - 7.29 (1H, multiplet);
7.01 - 6.92 (2H, multiplet);
3.08 (6H, singlet).
340/2194
1-(N-Ethyl-N-propylcarbamoyl)-3-(2,6-difluorophenylsulphonyl)-4-chloropyrazole (Compound No.
7.338)
Following the procedure of Example 3, there were obtained 20 mg (yield 15.2%) of the title compound,
melting at 70 - 72 DEG C.
1-(N-Ethyl-N-propylcarbamoyl)-3-(2,6-difluorophenylthio)-4-chloropyrazole (Compound No. 7.339)
Following the procedure of Example 3, there were obtained 26 mg (yield 19.5%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.08 (1H, singlet);
7.43 - 7.32 (1H, multiplet);
7.00 - 6.92 (2H, multiplet);
3.44 (2H, quartet, J = 7.1 Hz);
3.33 (2H, triplet, J = 7.1 Hz);
1.75 - 1.48 (2H, multiplet);
1.03 - 0.95 (3H, broad);
0.95 - 0.65 (3H, broad).
1-(Dipropylcarbamoyl)-3-(2,6-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 7.340)
Following the procedure of Example 3, there were obtained 29 mg (yield 9.8%) of the title compound,
melting at 85 - 87 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-4-fluorophenylsulphonyl)pyrazole (Compound No. 8.1)
Following the procedure of Example 1, there were obtained 391 mg (yield 75.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.6 Hz);
8.12 (1H, doublet of doublets, J = 2.2 & 6.6 Hz);
7.98 - 7.90 (1H, multiplet);
7.31 (1H, triplet, J = 8.4 Hz);
6.68 (1H, doublet, J = 2.6 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chloro-4-fluorophenylthio)pyrazole (Compound No. 8.2)
Following the procedure of Example 1, there were obtained 443 mg (yield 79.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.5 Hz);
7.53 (1H, doublet of doublets, J = 2.2 & 6.8 Hz);
7.37 - 7.30 (1H, multiplet);
7.10 (1H, triplet, J = 8.7 Hz);
6.28 (1H, doublet, J = 2.5 Hz);
3.56 (4H, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
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1-(Diethylcarbamoyl)-3-(3-chloro-4-methoxyphenylthio)pyrazole (Compound No. 8.3)
Following the procedure of Example 1, there were obtained 791 mg (yield 51.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.09 (1H, doublet, J = 2.7 Hz);
7.55 (1H, doublet, J = 2.2 Hz);
7.38 (1H, doublet of doublets, J = 2.2 & 8.5 Hz);
6.87 (1H, doublet, J = 8.5 Hz);
6.18 (1H, doublet, J = 2.7 Hz);
3.89 (3H, singlet);
3.55 (4H, quartet, J = 7.0 Hz);
1.19 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chloro-4-methoxyphenylsulphonyl)pyrazole (Compound No. 8.4)
Following the procedure of Example 1, there were obtained 214 mg (yield 50.4%) of the title
compound, melting at 91 - 92 DEG C.
1-(Diethylcarbamoyl)-3-(3,4-dichlorophenylsulphonyl)pyrazole (Compound No. 8.5)
Following the procedure of Example 1, there were obtained 239 mg (yield 55.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, doublet, J = 2.9 Hz);
8.11 (1H, doublet, J = 2.1 Hz);
7.85 (1H, doublet of doublets, J = 2.1 & 8.4 Hz);
7.62 (1H, doublet, J = 2.9 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,4-dichlorophenylthio)pyrazole (Compound No. 8.6)
Following the procedure of Example 1, there were obtained 1.02 g (yield 56.2%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.6 Hz);
7.49 (1H, doublet, J = 2.1 Hz);
7.36 (2H, doublet, J = 8.4 Hz);
7.22 (1H, doublet of doublets, J = 2.1 & 8.4 Hz);
6.34 (1H, doublet, J = 2.6 Hz);
3.56 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3.4-dimethylphenylsulphonyl)pyrazole (Compound No. 8.7)
Following the procedure of Example 1, there were obtained 208 mg (yield 42.2%) of the title
compound, melting at 85 - 86 DEG C.
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1-(Diethylcarbamoyl)-3-(3,4-dimethylphenylthio)pyrazole (Compound No. 8.8)
Following the procedure of Example 1, there were obtained 381 mg (yield 45.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.08 (1H, doublet, J = 2.7 Hz);
7.26 - 7.06 (3H, multiplet);
6.18 (1H, doublet, J = 2.7 Hz);
3.58 (4H, quartet, J = 7.0 Hz);
2.24 (3H, singlet);
2.23 (3H, singlet);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-bromo-3-methylphenylsulphonyl)pyrazole (Compound No. 8.9)
Following the procedure of Example 1, there were obtained 196 mg (yield 45.8%) of the title
compound, melting at 59 - 60 DEG C.
1-(Diethylcarbamoyl)-3-(4-bromo-3-methylphenylthio)pyrazole (Compound No. 8.10)
Following the procedure of Example 1, there were obtained 855 mg (yield 50.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.12 (1H, doublet, J = 3.0 Hz);
7.45 (1H, doublet, J = 8.2 Hz);
7.30 (1H, doublet, J = 2.2 Hz);
7.10 (1H, doublet of doublets, J = 2.2 & 8.2 Hz);
6.26 (1H, doublet, J = 3.0 Hz);
3.56 (4H, quartet, J = 7.0 Hz);
2.35 (3H, singlet);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylthio)pyrazole (Compound No. 8.11)
Following the procedure of Example 1, there were obtained 392 mg (yield 71.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.7 Hz);
7.76 - 7.71 (1H, multiplet);
7.67 - 7.59 (1H, multiplet);
7.17 (1H, triplet, J = 9.5 Hz);
6.31 (1H, doublet, J = 2.7 Hz);
3.54 (4H, quartet, J = 7.0 Hz);
1.89 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylsulphonyl)pyrazole (Compound No. 8.12)
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Following the procedure of Example 1, there were obtained 213 mg (yield 65.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.36 - 8.18 (2H, multiplet);
8.10 (1H, doublet, J = 2.8 Hz);
7.40 (1H, triplet, J = 8.8 Hz);
6.91 (1H, doublet, J = 2.8 Hz);
3.49 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,4-dichlorophenylthio)-4-chloropyrazole (Compound No. 8.16)
Following the procedure of Example 5, there were obtained 220 mg (yield 22.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, singlet);
7.50 (1H, doublet, J = 2.1 Hz);
7.37 (1H, doublet, J = 8.4 Hz);
7.22 (1H, doublet of doublets, J = 2.1 & 8.4 Hz);
3.54 (4H, quartet, J = 7.0 Hz);
1.20 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,4-dichlorophenylsulphonyl)-4-chloropyrazole (Compound No. 8.17)
Following the procedure of Example 5, there were obtained 173 mg (yield 20.2%) of the title
compound, melting at 113 - 115.5 DEG C.
1-(Dimethylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylsulphonyl)-4-chloropyrazole (Compound
No. 8.18)
Following the procedure of Example 3, there were obtained 123 mg (yield 78.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.38 - 8.26 (2H, multiplet);
8.13 (1H, singlet);
7.42 (1H, triplet, J = 8.8 Hz);
3.19 (6H, broad singlet).
1-(N-Ethyl-N-methylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylsulphonyl)-4-chloropyrazole
(Compound No. 8.19)
Following the procedure of Example 3, there were obtained 116 mg (yield 33.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.37 - 8.26 (2H, multiplet);
8.15 (1H, singlet);
7.42 (1H, triplet, J = 9.2 Hz);
3.54 (2H, quartet, J = 7.2 Hz);
3.15 (3H, broad);
1.25 (3H, triplet, J = 7.2 Hz).
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1-(Diethylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylthio)-4-chloropyrazole (Compound No.
8.20)
Following the procedure of Example 3, there were obtained 219 mg (yield 52.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
7.76 - 7.72 (1H, multiplet);
7.68 - 7.61 (1H, multiplet);
7.25 - 7.13 (1H, multiplet);
3.50 (4H, broad quartet, J = 6.8 Hz);
1.15 (6H, broad triplet, J = 6.8 Hz).
1-(Diethylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylsulphonyl)-4-chloropyrazole (Compound
No. 8.21)
Following the procedure of Example 3, there were obtained 196 mg (yield 52.8%) of the title
compound, melting at 75 - 77 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-4-fluorophenylthio)-4-chloropyrazole (Compound No. 8.22)
Following the procedure of Example 4, there were obtained 141 mg (yield 54.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, singlet);
7.53 (1H, doublet of doublets, J = 6.8 & 2.3 Hz);
7.34 (1H, doubled doublet of doublets, J = 8.7, 4.4 & 2.3 Hz);
7.09 (1H, triplet, J = 8.7 Hz);
3.51 (4H, quartet, J = 7.0 Hz);
1.18 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chloro-4-fluorophenylsulphonyl)-4-chloropyrazole (Compound No. 8.23)
Following the procedure of Example 4, there were obtained 132 mg (yield 53.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, singlet);
8.13 (1H, doublet of doublets, J = 6.6 & 2.4 Hz);
7.98 (1H, doubled doublet of doublets, J = 8.6, 4.4 & 2.2 Hz);
7.33 (1H, triplet, J = 8.6 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,4-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 8.24)
Following the procedure of Example 3, there were obtained 385 mg (yield 37.9%) of the title
compound, as a gum-like substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, singlet);
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7.95 - 7.83 (2H, multiplet);
7.37 (1H, doublet of triplets, J = 7.0 & 9.3 Hz);
3.51 (4H, broad quartet);
1.25 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylthio)-4-bromopyrazole (Compound No.
8.26)
Following the procedure of Example 3, there were obtained 306 mg (yield 12.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, singlet);
7.75 (1H, doublet of doublets, J = 2.2 & 7.0 Hz);
7.68 - 7.62 (1H, multiplet);
7.18 (1H, triplet, J = 9.2 Hz);
3.48 (4H, quartet, J = 7.0 Hz);
1.14 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylsulphonyl)-4-bromopyrazole (Compound
No. 8.27)
Following the procedure of Example 3, there were obtained 204 mg (yield 11.9%) of the title
compound, melting at 67 - 69 DEG C.
1-(Diethylcarbamoyl)-3-(3,4-dichlorophenylthio)-4-bromopyrazole (Compound No. 8.28)
Following the procedure of Example 5, there were obtained 222 mg (yield 26.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, singlet);
7.51 (1H, doublet, J = 2.2 Hz);
7.38 (1H, doublet, J = 8.4 Hz);
7.23 (1H, doublet of doublets, J = 2.2 & 8.4 Hz);
3.52 (4H, quartet, J = 7.0 Hz);
1.19 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,4-dichlorophenylsulphonyl)-4-bromopyrazole (Compound No. 8.29)
Following the procedure of Example 5, there were obtained 158 mg (yield 20.9%) of the title
compound, melting at 128 - 129 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-4-fluorophenylthio)-4-bromopyrazole (Compound No. 8.30)
Following the procedure of Example 4, there were obtained 164 mg (yield 52.8%) of the title
compound, as an amorphous product.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, singlet);
7.53 (1H, doublet of doublets, J = 6.7 & 2.3 Hz);
7.34 (1H, doubled doublet of doublets, J = 8.6, 4.5 & 2.3 Hz);
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7.10 (1H, triplet, J = 8.6 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
1.16 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chloro-4-fluorophenylsulphonyl)-4-bromopyrazole (Compound No. 8.31)
Following the procedure of Example 4, there were obtained 149 mg (yield 52.2%) of the title
compound, melting at 73 - 74 DEG C.
1-(Diethylcarbamoyl)-3-(4-fluoro-3-trifluoromethylphenylsulphonyl)-4-fluoropyrazole (Compound
No. 8.32)
Following the procedure of Example 7, there were obtained 15 mg (yield 5.7%) of the title compound,
melting at 117 - 119 DEG C.
1-(Diethylcarbamoyl)-3-(3,4-dichlorophenylsulphonyl)-4-fluoropyrazole (Compound No. 8.34)
Following the procedure of Example 7, there were obtained 8 mg (yield 0.6%) of the title compound,
melting at 58 - 60 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-4-fluorophenylsulphonyl)-4-fluoropyrazole (Compound No. 8.35)
Following the procedure of Example 19, there were obtained 47 mg (yield 5.2%) of the title compound,
melting at 75 - 78 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-4-fluorophenylthio)-4-fluoropyrazole (Compound No. 8.57)
Following the procedure of Example 19, there were obtained 65 mg (yield 7.1%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum CDC l 3, 200 MHz), delta ppm:
8.00 (1H, doublet, J = 5.1 Hz);
7.51 (1H, doublet, J = 6.8 Hz);
7.36 - 7.28 (1H, multiplet);
7.08 (1H, triplet, J = 6.8 Hz);
3.55 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.1)
Following the procedure of Example 1, there were obtained 221 mg (yield 84.5%) of the title
compound, melting at 86 - 87 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylthio)pyrazole (Compound No. 9.3)
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Following the procedure of Example 1, there were obtained 877 mg (yield 89.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, doublet, J = 2.8 Hz);
7.26 - 7.21 (3H, multiplet);
6.40 (1H, doublet, J = 2.8 Hz);
3.50 - 3.40 (4H, broad quartet);
1.25 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dibromophenylsulphonyl)pyrazole (Compound No. 9.4)
Following the procedure of Example 1, there were obtained 383 mg (yield 70.2%) of the title
compound, melting at 97 - 98 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dibromophenylthio)pyrazole (Compound No. 9.5)
Following the procedure of Example 1, there were obtained 491 mg (yield 73.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.6 Hz);
7.52 (1H, triplet, J = 1.6 Hz);
7.44 (2H, doublet, J = 1.6 Hz);
6.39 (1H, doublet, J = 2.6 Hz);
3.59 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz ).
1-(Diethylcarbamoyl)-3-(3,5-dimethylphenylsulphonyl)pyrazole (Compound No. 9.6)
Following the procedure of Example 1, there were obtained 451 mg (yield 61.1%) of the title
compound, melting at 71 - 73 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dimethylphenylthio)pyrazole (Compound No. 9.7)
Following the procedure of Example 1, there were obtained 514 mg (yield 63.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.11 (1H, doublet, J = 2.6 Hz);
7.07 (2H, broad singlet);
6.90 (1H, broad singlet);
6.25 (1H, doublet, J = 2.6 Hz);
3.59 (4H, quartet, J = 7.0 Hz);
2.28 (6H, singlet);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-difluorophenylsulphonyl)pyrazole (Compound No. 9.8)
Following the procedure of Example 1, there were obtained 302 mg (yield 54.1%) of the title
compound, melting at 73 - 74 DEG C.
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1-(Diethylcarbamoyl)-3-(3,5-difluorophenylthio)pyrazole (Compound No. 9.9)
Following the procedure of Example 1, there were obtained 377 mg (yield 60.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, doublet, J = 2.7 Hz);
7.26 - 6.83 (2H, multiplet);
6.71 - 6.61 (1H, multiplet);
6.42 (1H, doublet, J = 2.7 Hz);
3.59 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dimethoxyphenylthio)pyrazole (Compound No. 9.10)
Following the procedure of Example 1, there were obtained 200 mg (yield 52.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.13 (1H, doublet, J = 2.7 Hz);
6.53 (2H, doublet, J = 2.2 Hz);
6.35 (1H, triplet, J = 2.2 Hz);
6.32 (1H, doublet, J = 2.7 Hz);
3.75 (6H, singlet);
3.69 (4H, quartet, J = 7.0 Hz);
1.24 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dimethoxyphenylsulphonyl)pyrazole (Compound No. 9.11)
Following the procedure of Example 1, there were obtained 182 mg (yield 49.9%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, doublet, J = 2.7 Hz);
7.15 (2H, doublet, J = 2.0 Hz);
6.85 (1H, doublet, J = 2.7 Hz);
6.65 (1H, triplet, J = 2.0 Hz);
3.83 (6H, singlet);
3.50 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Methylcarbamoyl)-3-(3,5-dichlorophenylthio)pyrazole (Compound No. 9.13)
Following the procedure of Example 1, there were obtained 2.22 g (yield 75.7%) of the title compound,
as a gum-like substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.27 (1H, doublet, J = 2.6 Hz);
7.24 - 7.18 (3H, multiplet);
7.03 (1H, broad);
6.42 (1H, doublet, J = 2.6 Hz);
3.03 (3H, doublet, J = 5.1 Hz).
1-(Dipropylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.14)
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Following the procedure of Example 2, there were obtained 131 mg (yield 33.9%) of the title
compound, melting at 58 - 60 DEG C.
1-(N-Ethyl-N-propylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.18)
Following the procedure of Example 2, there were obtained 165 mg (yield 45.7%) of the title
compound, melting at 47 - 50 DEG C.
1-(Dimethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.22)
Following the procedure of Example 2, there were obtained 229 mg (yield 68.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, doublet, J = 2.8 Hz);
7.90 (2H, doublet, J = 1.9 Hz);
7.58 (1H, triplet, J = 1.9 Hz);
6.88 (1H, doublet, J = 2.8 Hz);
3.28 - 3.10 (6H, broad).
1-(N-Ethyl-N-methylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.26)
Following the procedure of Example 2, there were obtained 131 mg (yield 37.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.8 Hz);
7.91 - 7.90 (2H, multiplet);
7.59 (1H, triplet, J = 1.9 Hz);
6.89 (1H, doublet, J = 2.8 Hz);
3.54 (2H, quartet, J = 7.0 Hz);
3.14 - 3.08 (3H, broad);
1.27 (3H, triplet, J = 7.0 Hz).
1-(N-Butyl-N-methylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.27)
Following the procedure of Example 2, there were obtained 131 mg (yield 34.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.6 Hz);
7.90 (2H, doublet, J = 2.7 Hz);
7.61 - 7.58 (1H, multiplet);
6.89 (1H, doublet, J = 2.6 Hz);
3.56 - 3.48 (2H, multiplet);
3.19 - 3.10 (3H, broad);
1.69 - 1.60 (2H, multiplet);
1.36 - 1.27 (2H, broad);
1.03 - 0.90 (3H, multiplet).
1-(Diallylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.34)
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Following the procedure of Example 2, there were obtained 92 mg (yield 23.4%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.21 (1H, doublet, J = 2.6 Hz);
7.91 - 7.88 (2H, multiplet);
7.61 - 7.59 (1H, multiplet);
6.91 (1H, doublet, J = 2.6 Hz);
5.89 - 5.79 (2H, multiplet);
5.29 - 5.15 (4H, multiplet);
4.15 - 4.06 (4H, multiplet).
1-(Pyrrolidin-1-ylcarbonyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No. 9.37)
Following the procedure of Example 2, there were obtained 29 mg (yield 8.1%) of the title compound,
melting at 88 - 91 DEG C.
1-[N-Methyl-N-(2-methylphenyl)carbamoyl]-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound
No. 9.40)
Following the procedure of Example 2, there were obtained 82 mg (yield 25.8%) of the title compound,
melting at 81 - 84 DEG C.
1-[(N-Methyl-N-(3-methylphenyl)carbamoyl]-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound
No. 9.41)
Following the procedure of Example 2, there were obtained 57 mg (yield 17.8%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.7 Hz);
7.57 (3H, singlet);
7.09 (1H, quartet, J = 7.9 Hz);
6.99 (1H, doublet, J = 7.3 Hz);
6.81 (1H, doublet, J = 2.7 Hz);
6.80 - 6.76 (2H, broad);
3.47 (3H, singlet);
2.23 (3H, singlet).
1-[N-(2-Chlorophenyl)-N-methylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound
No. 9.42)
Following the procedure of Example 2, there were obtained 26 mg (yield 8.1%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.25 (1H, doublet, J = 1.8 Hz);
7.60 - 7.59 (2H, multiplet);
7.35 - 7.21 (5H, multiplet);
6.79 (1H, doublet, J = 1.8 Hz);
3.42 (3H, singlet).
351/2194
1-[N-(3-Chlorophenyl)-N-methylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound
No. 9.43)
Following the procedure of Example 2, there were obtained 155 mg (yield 46.0%) of the title
compound, melting at 117 - 119 DEG C.
1-[N-(4-Chlorophenyl)-N-methylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound
No. 9.44)
Following the procedure of Example 2, there were obtained 146 mg (yield 43.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.18 (1H, doublet, J = 2.9 Hz);
7.62 (3H, singlet);
7.22 (2H, doublet, J = 8.7 Hz);
6.92 (2H, doublet, J = 8.7 Hz);
6.85 (1H, doublet, J = 2.9 Hz);
3.45 (3H, singlet).
1-[N-(3-Chlorophenyl)-N-ethylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound No.
9.45)
Following the procedure of Example 2, there were obtained 167 mg (yield 48.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, doublet, J = 2.9 Hz);
7.59 (3H, singlet);
7.21 - 7.18 (2H, multiplet);
6.92 - 6.86 (2H, multiplet);
6.84 (1H, doublet, J = 2.9 Hz);
3.89 (2H, quartet, J = 7.1 Hz);
1.24 (3H, triplet, J = 7.1 Hz).
1-[N-(4-Chlorophenyl)-N-isopropylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound
No. 9.46)
Following the procedure of Example 2, there were obtained 209 mg (yield 58.1%) of the title
compound, melting at 150 - 153 DEG C.
1-[N-(5-Chloro-2-pyridyl)-N-methylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)pyrazole (Compound
No. 9.47)
Following the procedure of Example 2, there were obtained 159 mg (yield 46.8%) of the title
compound, melting at 103 - 106 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)-5-chloropyrazole (Compound No. 9.48)
352/2194
Following the procedure of Example 15, there were obtained 193 mg (yield 60.7%) of the title
compound, melting at 93 - 94 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dimethoxyphenylthio)-4-chloropyrazole (Compound No. 9.52)
Following the procedure of Example 3, there were obtained 140 mg (yield 39.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.16 (1H, singlet);
6.53 (2H, doublet, J = 2.2 Hz);
6.35 (1H, triplet, J = 2.2 Hz);
3.75 (6H, singlet);
3.55 (4H, quartet, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dimethoxyphenylsulphonyl)-4-chloropyrazole (Compound No. 9.53)
Following the procedure of Example 3, there were obtained 91 mg (yield 28.3%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.12 (1H, singlet);
7.19 (2H, doublet, J = 2.2 Hz);
6.68 (1H, triplet, J = 2.2 Hz);
3.84 (6H, singlet);
3.51 (4H, broad quartet, J = 7.1 Hz);
1.25 (6H, triplet, J = 7.1 Hz).
1-(Diethylcarbamoyl)-3-(3,5-difluorophenylthio)-4-chloropyrazole (Compound No. 9.55)
Following the procedure of Example 3, there were obtained 294 mg (yield 36.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.20 (1H, singlet);
6.90 - 6.81 (2H, multiplet);
6.74 - 6.63 (1H, multiplet);
3.56 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-difluorophenylsulphonyl)-4-chloropyrazole (Compound No. 9.56)
Following the procedure of Example 3, there were obtained 179 mg (yield 27.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.15 (1H, singlet);
7.63 - 7.58 (2H, multiplet);
7.15 - 7.06 (1H, multiplet);
3.51 (4H, quartet, J = 7.0 Hz);
1.26 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dibromophenylthio)-4-chloropyrazole (Compound No. 9.57)
353/2194
Following the procedure of Example 4, there were obtained 156 mg (yield 46.5%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, singlet);
7.55 (1H, triplet, J = 1.8 Hz);
7.45 (2H, doublet, J = 1.8 Hz);
3.55 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dibromophenylsulphonyl)-4-chloropyrazole (Compound No. 9.58)
Following the procedure of Example 4, there were obtained 118 mg (yield 38.6%) of the title
compound, melting at 83 - 84 DEG C.
1-[N-Methyl-N-(2-methylphenyl)carbamoyl]-3-(3,5-dichlorophenylsulphonyl)-4-chloropyrazole
(Compound No. 9.59)
Following the procedure of Example 2, there were obtained 18 mg (yield 6.0%) of the title compound,
melting at 120 - 125 DEG C.
1-[N-Methyl-N-(3-methylphenyl)carbamoyl]-3-(3,5-dichlorophenylsulphonyl)-4-chloropyrazole
(Compound No. 9.60)
Following the procedure of Example 2, there were obtained 51 mg (yield 17.6%) of the title compound,
melting at 155 - 156 DEG C.
1-[N-(2-Chlorophenyl)-N-methylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)-4-chloropyrazole
(Compound No. 9.61)
Following the procedure of Example 2, there were obtained 52 mg (yield 17.1%) of the title compound,
melting at 105 - 108 DEG C.
1-[N-(3-Chlorophenyl)-N-methylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)-4-chloropyrazole
(Compound No. 9.62)
Following the procedure of Example 2, there were obtained 65 mg (yield 21.1%) of the title compound,
melting at 170 - 172 DEG C.
1-[N-(4-Chlorophenyl)-N-methylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)-4-chloropyrazole
(Compound No. 9.63)
Following the procedure of Example 2, there were obtained 42 mg (yield 13.6%) of the title compound,
melting at 145 - 148 DEG C.
354/2194
1-[N-(3-Chlorophenyl)-N-ethylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)-4-chloropyrazole
(Compound No. 9.64)
Following the procedure of Example 2, there were obtained 42 mg (yield 13.1%) of the title compound,
melting at 167 - 170 DEG C.
1-[N-(3-Chlorophenyl)-N-isopropylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)-4-chloropyrazole
(Compound No. 9.65)
Following the procedure of Example 2, there were obtained 140 mg (yield 43.2%) of the title
compound, melting at 130 - 133 DEG C.
1-[N-(5-Chloro-2-pyridyl)-N-methylcarbamoyl]-3-(3,5-dichlorophenylsulphonyl)-4-chloropyrazole
(Compound No. 9.72)
Following the procedure of Example 2, there were obtained 33 mg (yield 10.5%) of the title
compound, melting at 143 - 145 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylthio)-4-bromopyrazole (Compound No. 9.76)
Following the procedure of Example 4, there were obtained 2.67 g (yield 71.3%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.22 (1H, singlet);
7.24 (3H, broad singlet);
3.51 (4H, broad quartet, J = 7.0 Hz);
1.21 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)-4-bromopyrazole (Compound No. 9.77)
Following the procedure of Example 4, there were obtained 2.48 g (yield 56.4%) of the title compound,
melting at 75 - 77 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-difluorophenylthio)-4-bromopyrazole (Compound No. 9.80)
Following the procedure of Example 4, there were obtained 1.02 g (yield 42.9%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.23 (1H, singlet);
6.86 (2H, doublet of triplets, J = 2.2 & 5.2 Hz);
6.68 (1H, triplet of triplets, J = 2.2 & 8.8 Hz);
3.56 (4H, quartet, J = 7.0 Hz);
1.23 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-difluorophenylsulphonyl)-4-bromopyrazole (Compound No. 9.81)
355/2194
Following the procedure of Example 4, there were obtained 211 mg (yield 42.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, singlet);
7.83 - 7.59 (2H, multiplet);
7.10 (1H, triplet of triplets, J = 6.0 & 2.4 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
1.25 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dibromophenylthio)-4-bromopyrazole (Compound No. 9.82)
Following the procedure of Example 4, there were obtained 179 mg (yield 48.7%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.22 (1H, singlet);
7.55 (1H, triplet, J = 1.8 Hz);
7.46 (2H, doublet, J = 1.8 Hz);
3.55 (4H, quartet, J = 7.0 Hz);
1.22 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dibromophenylsulphonyl)-4-bromopyrazole (Compound No. 9.83)
Following the procedure of Example 4, there were obtained 136 mg (yield 40.9%) of the title
compound, melting at 86 - 87 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)-4-fluoropyrazole (Compound No. 9.84)
Following the procedure of Example 7, there were obtained 22 mg (yield 5.6%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.03 (1H, doublet, J = 4.7 Hz);
7.93 (2H, doublet, J = 1.8 Hz);
7.63 (1H, triplet, J = 1.8 Hz);
3.52 (4H, broad quartet, J = 7.0 Hz);
1.26 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dimethylphenylsulphonyl)-4-fluoropyrazole (Compound No. 9.85)
Following the procedure of Example 7, there were obtained 97 mg (yield 20.6%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.97 (1H, doublet, J = 4.8 Hz);
7.66 (2H, singlet);
7.27 (1H, singlet);
3.6 - 3.4 (4H, broad);
2.39 (6H, singlet);
1.25 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-difluorophenylsulphonyl)-4-fluoropyrazole (Compound No. 9.88)
356/2194
Following the procedure of Example 7, there were obtained 8 mg (yield 2.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.02 (1H, doublet, J = 4.8 Hz);
7.61 - 7.75 (2H, multiplet);
7.15 - 7.06 (1H, multiplet);
3.6 - 3.4 (4H, broad);
1.27 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)-4-methylpyrazole (Compound No. 9.109)
Following the procedure of Example 14, there were obtained 63 mg (yield 17.3%) of the title
compound, melting at 87 - 89 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)-4-allylpyrazole (Compound No. 9.111)
Following the procedure of Example 14, there were obtained 67 mg (yield 9.0%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
7.97 (1H, singlet);
7.89 (2H, doublet, J = 1.8 Hz);
7.59 (1H, triplet, J = 1.8 Hz);
6.04 - 5.84 (1H, multiplet);
5.16 - 5.04 (2H, multiplet);
3.54 (2H, doublet, J = 5.5 Hz);
3.47 (4H, quartet, J = 7.0 Hz);
1.21 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylthio)-4-(difluoromethyl)pyrazole (Compound No. 9.117)
Following the procedure of Example 13, there were obtained 219 mg (yield 32.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.41 (1H, triplet, J = 1.6 Hz);
7.27 (3H, singlet);
6.64 (1H, triplet, J = 55.1 Hz);
3.55 (4H, quartet, J = 6.8 Hz);
1.22 (6H, triplet, J = 6.8 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)-4-(difluoromethyl)pyrazole (Compound No.
9.118)
Following the procedure of Example 13, there were obtained 203 mg (yield 31.3%) of the title
compound, melting at 112 - 113 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylthio)-4-cyanopyrazole (Compound No. 9.122)
357/2194
Following the procedure of Example 14, there were obtained 170 mg (yield 30.8%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.57 (1H, singlet);
7.39 (2H, doublet, J = 1.8 Hz);
7.34 (1H, triplet, J = 1.8 Hz);
3.52 (4H, quartet, J = 7.0 Hz);
1.30 - 1.11 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)-4-cyanopyrazole (Compound No. 9.123)
Following the procedure of Example 14, there were obtained 146 mg (yield 28.0%) of the title
compound, melting at 132 - 135 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-difluorophenylthio)-4-cyanopyrazole (Compound No. 9.125)
Following the procedure of Example 14, there were obtained 163 mg (yield 26.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.58 (1H, singlet);
7.05 - 6.96 (2H, multiplet);
6.78 (1H, triplet of triplets, J = 8.8 & 2.2 Hz);
3.58 - 3.48 (4H, multiplet);
1.22 (6H, triplet, J = 6.8 Hz).
1-(Diethylcarbamoyl)-3-(3,5-difluorophenylsulphonyl)-4-cyanopyrazole (Compound No. 9.126)
Following the procedure of Example 14, there were obtained 135 mg (yield 22.6%) of the title
compound, melting at 117 - 118 DEG C.
Ethyl 1-(diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)pyrazole-4-carboxylate (Compound No.
9.127)
Following the procedure of Example 14, there were obtained 121 mg (yield 19.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.65 (1H, singlet);
7.97 (2H, doublet, J = 1.8 Hz);
7.63 (1H, triplet, J = 1.8 Hz);
4.37 (2H, quartet, J = 7.2 Hz);
3.46 (4H, quartet, J = 7.0 Hz);
1.37 (3H, triplet, J = 7.2 Hz);
1.30 - 1.02 (6H, broad).
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylthio)-4-methylthiopyrazole (Compound No. 9.131)
Following the procedure of Example 14, there were obtained 186 mg (yield 40.2%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
358/2194
8.13 (1H, singlet);
7.26 - 7.22 (3H, multiplet);
3.55 (4H, quartet, J = 6.8 Hz);
2.34 (3H, singlet);
1.21 (6H, triplet, J = 6.8 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dichlorophenylsulphonyl)-4-methylsulphonylpyrazole (Compound No.
9.132)
Following the procedure of Example 14, there were obtained 103 mg (yield 18.9%) of the title
compound, melting at 180 - 183 DEG C.
1-(Diethylcarbamoyl)-3-(2,4,6-trimethylphenylsulphonyl)pyrazole (Compound No. 10.1)
Following the procedure of Example 1, there were obtained 335 mg (yield 85.6%) of the title
compound, melting at 72 - 73 DEG C.
1-(Diethylcarbamoyl)-3-(2,4,6-trimethylphenylthio)pyrazole (Compound No. 10.2)
Following the procedure of Example 1, there were obtained 401 mg (yield 85.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.01 (1H, doublet, J = 2.7 Hz);
6.96 (2H, singlet);
5.91 (1H, doublet, J = 2.7 Hz);
3.50 (4H, quartet, J = 7.0 Hz);
2.43 (6H, singlet);
2.28 (3H, singlet);
1.12 (6H, triplet, J = 7.0 Hz).
1-(Dimethylcarbamoyl)-3-(2,4,6-trimethylphenylthio)pyrazole (Compound No. 10.3)
Following the procedure of Example 1, there were obtained 348 mg (yield 74.4%) of the title
compound, melting at 79 - 80 DEG C.
1-(Dimethylcarbamoyl)-3-(2,4,6-trimethylphenylsulphonyl)pyrazole (Compound No. 10.4)
Following the procedure of Example 1, there were obtained 226 mg (yield 85.6%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.14 (1H, doublet, J = 2.9 Hz);
6.94 (2H, singlet);
6.83 (1H, doublet, J = 2.9 Hz);
3.15 (6H, broad);
2.67 (6H, singlet);
2.29 (3H, singlet).
1-(Diethylcarbamoyl)-3-(4-bromo-2,6-dimethylphenylsulphonyl)pyrazole (Compound No. 10.6)
359/2194
Following the procedure of Example 1, there were obtained 278 mg (yield 67.1%) of the title
compound, melting at 87 - 90 DEG C.
1-(Diethylcarbamoyl)-3-(3-chloro-2,6-dimethylphenylthio)pyrazole (Compound No. 10.13)
Following the procedure of Example 1, there were obtained 440 mg (yield 55.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.06 (1H, doublet, J = 2.6 Hz);
7.30 (1H, doublet, J = 8.0 Hz);
7.08 (1H, doublet, J = 8.0 Hz);
6.03 (1H, doublet, J = 2.6 Hz);
3.45 (4H, quartet, J = 7.0 Hz);
2.58 (3H, singlet);
2.45 (3H, singlet);
1.08 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3-chloro-2,6-dimethylphenylsulphonyl)pyrazole (Compound No. 10.14)
Following the procedure of Example 1, there were obtained 325 mg (yield 53.2%) of the title
compound, melting at 57 - 60 DEG C.
1-(Diethylcarbamoyl)-3-(3,5-dichloro-2,6-dimethylphenylthio)pyrazole (Compound No. 10.15)
Following the procedure of Example 1, there were obtained 375 mg (yield 56.0%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.08 (1H, doublet, J = 2.7 Hz);
7.47 (1H, singlet);
6.09 (1H, doublet, J = 2.7 Hz);
3.44 (4H, quartet, J = 7.0 Hz);
2.56 (6H, singlet);
1.08 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(3,5-dichloro-2,6-dimethylphenylsulphonyl)pyrazole (Compound No. 10.16)
Following the procedure of Example 1, there were obtained 271 mg (yield 52.1%) of the title
compound, melting at 87 - 90 DEG C.
1-(Diethylcarbamoyl)-3-(4-chloro-2-fluoro-5-methoxyphenylthio)pyrazole (Compound No. 10.17)
Following the procedure of Example 1, there were obtained 191 mg (yield 79.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.12 (1H, doublet, J = 2.7 Hz);
7.18 (1H, doublet, J = 8.1 Hz);
7.00 (1H, doublet, J = 6.3 Hz);
360/2194
6.28 (1H, doublet, J = 2.7 Hz);
3.83 (3H, singlet);
3.53 (4H, broad quartet, J = 7.0 Hz);
1.18 (6H, triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-chloro-2-fluoro-5-methoxyphenylsulphonyl)pyrazole (Compound No.
10.18)
Following the procedure of Example 1, there were obtained 151 mg (yield 71.1%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.19 (1H, doublet, J = 2.5 Hz);
7.58 (1H, doublet, J = 5.9 Hz);
7.24 (1H, doublet, J = 8.7 Hz);
6.95 (1H, doublet, J = 2.5 Hz);
3.97 (3H, singlet);
3.49 (4H, broad quartet, J = 7.0 Hz);
1.21 (6H, broad triplet, J = 7.0 Hz).
1-(Diethylcarbamoyl)-3-(4-chloro-3,5-dimethoxyphenylsulphonyl)pyrazole (Compound No. 10.19)
Following the procedure of Example 1, there were obtained 21 mg (yield 5.2%) of the title compound,
melting at 148 - 151 DEG C.
1-(Diethylcarbamoyl)-3-(2-chloro-3,5-dimethoxyphenylsulphonyl)pyrazole (Compound No. 10.20)
Following the procedure of Example 1, there were obtained 91 mg (yield 20.2%) of the title compound,
as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, doublet, J = 2.9 Hz);
7.48 (1H, doublet, J = 2.9 Hz);
6.98 (1H, doublet, J = 2.9 Hz);
6.74 (1H, doublet, J = 2.9 Hz);
3.90 (3H, singlet);
3.88 (3H, singlet);
3.44 (4H, quartet, J = 7.1 Hz);
1.16 (6H, multiplet).
1-(Diethylcarbamoyl)-3-(2-bromo-3,5-dimethoxyphenylsulphonyl)pyrazole (Compound No. 10.21)
Following the procedure of Example 1, there were obtained 55 mg (yield 15.3%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.17 (1H, doublet, J = 2.6 Hz);
7.57 (1H, doublet, J = 2.8 Hz);
7.00 (1H, doublet, J = 2.8 Hz);
6.71 (1H, doublet, J = 2.6 Hz);
3.91 (3H, singlet);
3.89 (3H, singlet);
3.42 (4H, quartet, J = 7.0 Hz);
1.15 (6H, multiplet).
361/2194
1-(Diethylcarbamoyl)-3-(3-chloro-2,4,6-trimethylphenylsulphonyl)pyrazole (Compound No. 10.22)
Following the procedure of Example 1, there were obtained 132 mg (yield 30.2%) of the title
compound, melting at 89 - 90 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-dichloro-3-methylphenylsulphonyl)pyrazole (Compound No. 10.23)
Following the procedure of Example 1, there were obtained 164 mg (yield 22.1%) of the title
compound, melting at 63 - 64 DEG C.
1-(Diethylcarbamoyl)-3-(2,6-dichloro-3-methylphenylthio)pyrazole (Compound No. 10.24)
Following the procedure of Example 1, there were obtained 634 mg (yield 29.4%) of the title
compound, as an oily substance.
Nuclear Magnetic Resonance Spectrum (CDC l 3, 200 MHz), delta ppm:
8.07 (1H, doublet, J = 2.6 Hz);
7.32 (1H, doublet, J = 8.1 Hz);
7.24 (1H, doublet, J = 8.1 Hz);
6.18 (1H, doublet, J = 2.6 Hz);
3.45 (4H, quartet, J = 7.0 Hz);
2.38 (3H, singlet);
1.09 (6H, broad).
1-(Diethylcarbamoyl)-3-(2,3,4,5,6-pentafluorophenylsulphonyl)pyrazole (Compound