Price, As.
12.1
OF THE
1.
SOME REACTIONS OF CARONE.
BY
Kottiazath Narayana Menon and John Lionel Sitnomen.
11.
A SYNTHESIS OF IMORINDONE.
BY
Ramkanta Bhattacharya and John Lionel Simonsen.
111.
DERIVATIVES OF ACENAPHTWYRIDINE. PART I.
BY
Srikurnaran Unni Nair and John Lionel %Ionsen.
PAGE,
Part
1.-I.
Part
11.-Oils
Some Reactions of Carone. By Kottiazath Narayana Menon
and John Lionel Sin1on:;en. 11. A Synthesis of Mnrindone.
By Ramkanta Bhattacharya and John Lionel Simonsen.
111. Derivatives of Acenayhthpyridine. Part I. By Srikumaran Unni Nair and John Lionel Simonsen
...
...
1
and Pats from the Seeds oE Indian Forest Plants. Part
VIII. The Oil from the Seeds o f Thew:ia Neriifolia(Jnss.).
By Ramkanta Bhattacharya and P. Ramsswami Ayyar.
Part IX. The Oil froin the Seeds of Cerbcrn Odollaam
(Gaertn.). Part X . The Oil from the Seeds of NoZ~zn+ima
Antidysenfwica. Part XI. T h e Oil from the Seeds of
Anona Sqzamosa (Linn.).
By Ramachandra Vishnu
Ghanekar and P. Ramaswatni Ayyar
...
...
15
Part
111.-Influence of the Sulphur Atom on Optical Rotatory Power.
By P. P. Shukla
...
...
...
...
Part
1V.-The
Constitution of the Acid formed by the Action of Sulphuric Acid o n Camphorquinone. By Madhav RaIaji Bhagvat
...
...
...
and John Lionel Simomen
43
Part
V.-isoErucic Acid. By Tahilram Jethanand Mirchandani and John
...
Lionel Simonsen
...
...
...
57
Part
V1.-Note on the Sorting, Classification and Briqiietting of Chrome
and Manganese Ores. By K. R. Krishnaswami...
...
65
Part
VIT.-Esterification
Watson
in Mixed Solvents.
...
...
By B.
...
\7.
Bhide and H. E.
...
Part V111.-Nitrogen-Fixation
by ' Azotobacter Chroococcnm'.
Ranga~latl~an
and Roland V. Norris
...
Part
...
71
By S.
...
79
1X.-Studies in Intensive Bacterial Oxidation. The Oxidation of
Ammonia to Nitric Acid, Parts I-IV. By Gilbert J. Fowler,
Y. N. Kotwal, Roland V. Norris, S. Racganatban and M. B.
...
...
...
...
Roy
97
X.-The Decomposition of Alkaline Earth Sulphates. By L. A.
P k t t and H..E. Watson
117
...
Part
33
.-.
...
...
ABBREVIATIONS OF TITLES.
Name of Penbdicid
Abbreviation
Agric. J, of India
...
Amer. J. Sci. and Arts
...
...
Annalen
Am. de la Science Agronolnique
Ann. de l'Inst. Pasteur
...
Arch. Pharm.
...
Ber.
...
...
...
...
...
Biochem. J.
...
Bull. Amer. Inst. Mining Eng.
Bull. Intr. Ac. Sci. Cracovia
Bull. Soc. Chim ...
Chem. Ztg.
Compt. rend.
...
...
Gazzetta
...
Helv. C h i . A d a
J.
J. Agric. Sci. ...
J. Amer. Chem. S o c
...
...
J. Bact.
...
...
J. Biol. Chem.
J. Chem. Soc. ...
J. C h i . physique
J.C.S.
...
3. Ind. Eng. Chem,
3. Indian Inst. Sci.
Journ. Chem. Soc.
J. pr. Chem. ...
J.S.C.I.
...
J. Soc. Chem. Ind.
Landw. Versuch. Stat.
Monatsh.
,..
Agricultural Jonrnal of India.
American Journal of Science and Arts.
Justus Liebig's Annalen der Chemie.
Annales de la Sclence ~ g r ~ n o m i ~ ~ e .
Annales de 1'Institul Pastcur.
Archiv der Pharmazie.
Berichte der deutschen ci~cmischen
Gesellschaft.
The Biochemical Journal.
Bulletin of the American Institute of
Mining Engineers.
Bulletin internation:il iie l'Acad6mie
Polonaise des Sciences.
Bulletin de la SociBti. chirniqur dr
France.
Chemiker Zeitung.
Comptes rendus hebdoinndaires iles
SCances de l'Acad6mie des Sciences.
Gazzetta Chimica Italiana.
Helvetica Chimica Acta.
Journal of the Chemical Society.
Journal of Agricultural Science.
Journal of the American Chemical
Society.
Journal of Pathology and Bacteriology.
Journal of Biological Chemistry.
Journal of the Chemical Society.
Journal de la Chimie physique.
Journal of the Chemical Society.
Journal of Industrial and Engineering
Chemistry.
Journal of the Indian Institute of
Science.
Journal of the Chemical Society.
Journal far praktische Chemie.
Journal of the Society of Chemical
Industry.
Journal of the Society of Chemical
Industry.
Die landwirthschaftlichen Versuchs
Stationen.
Monatshefte ffir Chemie und verwandte
Theile anderer Wissenschaften.
.
Pharm Tndica ...
Proc. Chem Soc
Rec Trav Chim
.
...
.
...
. .
.
...
Soil Sci.
...
...
Trans.Amer . Inst . Mining Eng.
...
Z . finorg . Chem .
Zentr . Bakt . . . .
...
Z. physikal . Chem .
...
.
Z . physiol Chem
.
.
IJharmacographia Indica
Proceedings of the Chemical Society .
Recueil des travaux chimiques des
Pays-Bas e i de la Belgique
Soil Science
Transactions of the American Institute
of Mining Engineers
Zeitschrift fer anorganische und
allgemeine Chemie
Centralblatt fiir Bakteriologie. Parasitenkunde und Infektionskrankheiten.
Zeitschrift fdr physikalische Chemie.
Stdchiometrie und Verwandtschafts-Lehre .
Koppe-Seyler's Zeitschrift fiir physiologische Chemie
.
.
.
.
.
...
.
.
Author Index
.
....
...
Ayyar. P Ramaswami. see Bhattachatya. R
Ayyar. P . Ramaswami. see Ghanekar. R V
Bhagvat. Madhay Balaji and Simonsen. John Lionel
...
Bhatt. L A and Watson. 8 E
...
Bhattacharya. Ramkanta and Ayyar. P . Ramasrvami
Bhattacharya. Ramkanta and Simonsen. John Lionel
Bhide. B V and Watson. H E
...
Fowler. Gilbert J .
...
Ghanekar. Ramachandra Vishnu and Ayyar. P Ramaswami
Kotwal. Y . N
...
Krishnaswami. K K
Menon. Kottiazath Narayana and Simonsen. John Lionel
Mirchandani. Tahilram Jethanand and Simonsen. John Lionel
...
Nair. Srikumaran Unni and Simonsen. John Lionel
Norris. Roland V.. see Ranganathan. S
...
Ranganathan. S and Norris. Roland V
...
...
Roy. M B
...
Shnkla. P P ....
Simonsen. John Lionel. see Bhagvat. M B
...
Simonsen. John Lionel. see Bhattacharya. R . . . .
...
Simonsen. John Lionel. see Menon. K N
S'imonsen..John Lionel. see Mirchandani. T J
Simonsen. John Lionel. see Nair. S . Unni
...
Watson. H E.. see Bhatt. L A
...
Watson. H E.. see Bhide. B V
. ....
. .
. .
. ....
...
.
...
. ....
.
. ....
.
.
.
. ....
...
...
...
...
...
...
...
...
...
.
...
. . . .
.
...
...
...
...
...
. ....
. ....
. ....
. ....
...
. ......
...
...
...
...
...
...
...
...
...
...
.
Subject Index
Acenaphrhene-Condensation of ethyl acetoacetate with 5-an:lno-Condensation of paraidehyde with 5amino-
..
~.5.~cena~hth~laminocroton.5.acenaphthylamide
d-5-Acenaphthyiaminocrotonicacid, ethyl ester ...
5-Acetoacetamidoacenaphthene
...
...
...
...
Acetoacetic ester-Condensation of 5-aminoacenaphthene with
Acetic acid from Azotobacter fermentations
...
...
-rAcetyl~pmethylbnrane- ag-dicarboxylic acid
1.4Acetyl-? : E : 3-trimethyl-Ag-cycbhexen-11~~rborylic
acid
...
Activated slndge-Nitrification by
Aldehyde from Azofobacier fermentations
...
Aikaiine earth sulphates-Decomposition of
...
Ammonia-oxidation by activated sludge
Anow sgzlamsa-Oil from seeds of
...
Krachidic acid from ethyl isoerucate ...
Tkmefia neriifolia
Azolobactev chvoococcum-Fixation of nitrogen by
Bacterial oxidation-Studies in intensive
Behenic acid. dihydroxy.. from erucic and brassidic acids ...
Brassylic acid from ethyl isoerncate
n-Butyric acid-Esterification of
...
Calcium suiphate-Effect of heat on
Calcium sulphite-Effect of heat on ...
...
...
Camphor-Optical influence of sulphur in compounds of ...
Camphorqninone-Action of acetic anhydride on
...
and sulphuric acid-Constitution of aoid from
.,
condensed with aromatic tbio-bases
Carbon as reducing agent for calcium sulphate ...
...
Carbon-balance in Azofobacter fermentations
...
A4.Carene. attemptedpioduction from methyl carylxa~lrhenogel~ate
&Carol from d.carylamine
d-Caronecyanhydrin
Carone from Lcarol by oxidation
...
...
Caroneoxime-Reduction of
d-Carylamine-Action of nitrous acid on
...
Lcarylxanthenogeuate. methyl
...
...
Cerdeiu odollam-Oil from seeds of
...
Cerotic acid from Anoua sqwrmsa
...
Chromite-Sortmg, class&ation and briquetting of
...
...
...
...
...
...
...
...
...
...
...
...
..
...
...
...
...
...
...
...
...
...
...
...
...
...
..
4
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
PAGE.
...
Conductivity measurements in mixed solvevts
...
Decane-ax-dicarboxylic acid from methyl isoerucate
...
Dehydrothiotoluidine-Preparation of
...
...
Dextrose-concentration in Azotabacfer fermentations-Influence
s-Di-5-acenaphthylcarbamide
...
Dithioaniline-Preparation
of
...
...
...
of
...
.
...
...
PP'-Dithiodiphenylenebisiminocamphor
...
PP1-Dithiotoluidine-Preparation of ...
Dodecane-~~dicarboxylic
acid from methyl isoerucate
isoErucic acid. methyl and ethyl esters-Oxidation of
Esterification in mixed solvents
...
...
Ethyl alcohol from Azofobacfcr lermentations ...
Fermentation of dextrose by Azotobacier chroococcun~
Formic acid from Azotodacfe~
.fermentations ...
Glycerides :om vegetable oils
...
...
Hoiarvhe~zaaniidyscnterica-Oil from seeds of ...
Hydrogen-ion concentration for optimum nitrification
Iron as decomposing agent for calcium snlphate
salts-Influence of. on nitrification
...
Lactic acid from Azoto6acfer fermentations
..
Lignoceric acid from Cerliera odallaslz
...
Noiawhena antidysenterica ...
Linolenic acid from Halarrhemz antidysnzterica ...
Linolic acid from Amna squamosa ...
...
Cw6era adoilam
,..
...
Uolar dmza a7rtidysenterica
...
lBevctia neviifolia ...
...
Magnesium methyl iodide-Action on I-carol of
.
sulphateDecomposition of
...
...
Manganese-Influence of. on nitrification
ores-Briquetting
of
...
...
3-Methylacenaphthpyridine and its salts
...
4hydroxy...
4Methylacenaphthpyridine. 2-chloro...
Ghydroxy...
6-Methylanthraquinone. 2 :5-dihydroxy2 : S-dimethoxy1 : 2: 5-trihydroxy...
6-Methyl-9-anthrone 2 : 5-dimethoxy...
3-Methylbenzophenone-6-carboxylicacid-Reduction of 2 : 4'-dimethoxy...
...
Methylbenzothiazolbenzenylimioocamphor
...
...
yMethylbutane-a&-tricarboxylic acid
...
3-Methyldiphenylmethane-6-carboxylicacid. 2 : 4'-dimethoxy...
3.Methylphenylphthaiide. 2 : 4'dimethoxy...
2-Methyl-1 : 2 : 3 : 4-tetrahydroacenaphthpyridine
...
2
73
62
37
82
...
..
..
..
.
.
...
...
...
...
...
...
8
38
51. 52
8
8
11
4-:~et;lyl.i
. ? : $:
1
4-tetrahYdroacena~~hti~l>yridine
...
...
Yorindone (1 : 2 : 5-trihydrory-6-mclhylanthraquinone)-Synthesisof ...
...
...
...
Myristic acid from Cerbera odolhm ...
...
...
Nitrate-concen:ra:ion and its e!lect on nitrification
...
...
...
Nitrification-Kate of
...
Nitrooen-iixation b y .4zoto6n~terchroococcz~~~ ...
...
...
...
...
...
n-Octoic acid from methy! iroetucate ...
Oil born Anom sq7~amosa
...
...
...
...
...
Cerbwandollam ...
...
...
...
H&nh&nn anfidyse~~ierica...
...
...
Theuefia neriifoZia
...
...
...
...
Ujeander. yellow-Oil from seeds of
...
...
...
Oleic acid irorn .4nom squamosa
...
...
...
...
Cerbera odollam
...
...
...
...
...
Hnlarrhenn a ,itidyscnterica
...
...
Thz'etia neriifolia ...
...
...
...
Oxidatiou-Bacteriiil
...
...
...
...
...
50ximloo-2 . ? . :i-tri1neti1ylcycIohexaj~-4-one-1-carbol
acid. me thy]
ester
...
Ozone in oxidising izoerncic esters-Use of
Palmitic acid from I n o m squznwsa ...
...
Cer6ee~a
odoUam ...
...
Holarrhexa antidysenterica ....
Thcuefia mriifolia
...
paraldehyde condensation with 5-aminoacenaphthene
Pelargonic acid from ethyl jsoerucate
...
Peptone-Stimulation of nitrification by
Phosphates on h a t i o n of nitiogen-Influence of
nitrificatiom-Influence of
...
Phytosterol from Ha2arrhru anlidysenterica
...
Primuline-Preparation
of
...
...
Silica as decomposing agent for calcium sulphate
Sitosterol from vegetable oils
...
...
Sodium silicate for briquetting ores ...
...
Stearic acid from A 7 m squaneosa ...
...
Cerbera odoIZam
...
...
...
HoZarrkna antidysentwic@
Theucfia 7wiifolia ...
...
Strontium suipbate-Decomposition of
...
Suberic acid-Esterification of
...
...
Sulphur atom as an influence on rotatory power ...
...
Surface effect in nitrification
...
Tartaric acid from Azotobacfer fermentations
...
Terpenes from Icarol-Mixture of ...
TJmxtia ~riifolia-Oil from seeds of
...
......
....
..
.
..
...
Thioaniline-Preparation of
...
p$'-Thiodiphenylenebisirninocamphor
...
...
...
...
...
...
...
...
...
$p'-Thioditolylenebisiminocamphor
...
p$'-Thiotoluidine-Preparation of ...
...
2 : 2 : 3-TrimethylcycZohexsn-4-one-1-carboxylic
acid. 5 : 5-dibromo2 : 2 : 3-Trimethylcyclohesan-4-one-I-carboxylic acid. methyl esterBromination of
...
. .
...
2 : 2 : 3-Trimethyl-A3-cyclohexen-5-one-1-carboxylic
acid. 4-hydroxy4 : 4 : 5-Trimethylcyclopentane-1: 3-dicarboxylic acid
...
...
4 : 4 : 5-Trimethylcyclopentane-1 : 3-dicarboxylic acid I-hydroxy...
4 : 4 : 5-Trimethyl- A 5-cyclopentene-l : 3-dicarboxylic acid ...
...
...
...
...
...
.
Viscosity of benzene mixed with isoamyl alcohol
...
...
Indian Institute of Science, with pric~r.
Past
Part
I.-I.
Some Reactions of Catone. By Xo:tiazath Narayana Menno and
John Lionel Simonsen. TI. A Synthesis of Morindone. BY
Ramkanta Bhattaclxarga and Juhn Lionel Simmmen. Ill.
Derivat~ves of Aceuaphthpq.ridine. Part I. By Srikumaran
Unni Nair and John Lionel Simonse~i. Pricc, As. 1 2 .
11.-Oils and Fats from the Sccds of Indian Forest Plants. Part VIII.
The Oii from the Seeds of Thzortia Nzriifolia (9uss.j.
Ramkanta Bhattacharya and P. Ramaswami Ayyar. Part IX.
The Oil from the Seed, of Ceideva OdoNnn~(Gaertn.). Part X.
The Oil h.om the Secds of Hvlaryhcm Awiidyse?zle~ica. Part XI.
T h e Oil tram thc Seeds of Am?in Squamosa (Linn.). By
Ramachandra Vishnu Ghanekar and P. Ramaswami Ayyar.
Price As. 12.
Part
111.-Influence of the Su!phur Atom on Opticai Rotatory Power.
P. Shukla. Price, As. 8.
Part
IV.-The
BY P.
Constitution oi the Acid f o r n c d by the Action of Sulphuric
Acid on Camphorquinone. By Madhav Balaji Bhagvat and
John Lmnel Simonsen. Pr~ce,As. 8.
Part
V.-isoEmcir:
Add. Kq. Tahihsn? Jethanand Mirchandani and John
Llonel Simonsen. Price, As. 8.
Part
VI.-Note on the Sorting, Classificarion and Briquetting of Chrome
and Manganese Ores. By K. R. Krishnaswami. Price, As. 8.
VIL-Esterification
in Mixed Solvents. By B. V. Bhide and 13[. E.
Watson. Price, As. 8.
Part
by ' Azotobacter Chroococcum '. By S. Ranganathan and Roland V. Noxris. Price, Rs. 1-4.
1X.-Studies
in Intensive Bacterial Oxidation.
The Oxidation of
Ammonia to Nitric Acid, Parts I-IV.
By Gilbert J, fowler.
Y.N. Kotwal, Roland V.. Norris, S. Rauganathan and M. B.
Roy. Price, Re. 1.
Part V1II.-Nitropen-Fixation
Part
Part
X.-The
De~ompositionof Alkaline Earth Sn!phates.
and H. E. Watson. Price, As. 12.
By L. A. Bhaht
Price, As.
12.1
OF THE
1.
SOME REACTIONS OF CARONE.
BY
Kottiazath Narayana Menon and John Lionel Sitnomen.
11.
A SYNTHESIS OF IMORINDONE.
BY
Ramkanta Bhattacharya and John Lionel Simonsen.
111.
DERIVATIVES OF ACENAPHTWYRIDINE. PART I.
BY
Srikurnaran Unni Nair and John Lionel %Ionsen.
I. S O M E REACTIONS OF GARONE.
I n a recent communication (/ou~n. Chem. Soc., 1926, 2049)
experiments were described which had as their object the preparation
of the secondary alcohol (11) for which the name carolis suggested.
I t was found that when carone was catalytically hydrogenated it
behaved like an a h n s a t u r a t e d ketone, fission of the cycbpropane
ring taking place with formation of monocyclic derivatives. We
decided to attempt the preparation of the alcohol by the action oi
nitrous acid on carylamine (I). d-Carylamine was prepared by Baeyer
Me
Ebn
6
I
,
8.:'
CH
'
'r~~~
H,/I
'C(OH
I ).CN
(Bey., 1894, 27, 3485) by the reduction of rd-caroneoxime with alcohol
and sodium, the base, which was not isolated in a pure state, being
characterised by the preparation of derivatives. Although the
hydrochloride of the base is unstable and passes readily into the
monocyclic unsaturated base, vestrylamine, we have found no difficulty
in obtaining d-carylamine in considerable quantity as a mobile oil
b.p. 86-89"/15 mm. When the sulphate is treated with nitrous acid
it is readily converted into 1-carol (11) although the yield is poor.
T h e alcohol is laevorotatory and is undoubtedly bicyclic since it is
comparatively stable to an alkaline solution of potassium permanganate
and on oxidation with chromic acid yields carone. T h e alcohol has
a remarkably high molecular refraction [R,] 46.78 ; calc. 46.2) and
we cannot offer any explanation of this abnormality.
.
It was of interest to attempt the elimination of water from carol
since if this proceeded normally it should yield a4-carene (111).
Owing to the marked instability of the bicyclic structure the reagents
available for this reaction were somewhat limited; we have only
examined the action of the Grignard reagent on the alcohol and the
decomposition of its methyl xanthogenate.
When L-carol is treated with a large excess of the Grignard
reagent elimination of water takes place but the reaction proceeds
apparently in a complex manner since the hydrocarbon obtained
distils over a wide range. A consideration of the physical constants
of the oil and an examination of its reaction with bromine lead US
to the conclusion that the mixture consists essentially of monocyclic
terpenes. On treatment with hydrogen chloride a sinall quantity of
a crystalline hydrochloride was obtained which was identified as
terpinene dihydrochloride, The amount of terpinene present in the
hydrocarbon mixture cannot however be large since we were unable
to prepare the characteristic nitrosate nor could my-dihydroxy-a,-methyl8-ibpropyladipic acid be separated from the acids formed on oxidation
with potassium permanganate. We were not able to identify the other
terpenes present, but no evidence could be obtained of the presence
of either dipentene or sylvestrene.
When the sodium derivative of Z-carol is treated with carbon
bisulphide followed by methyl iodide, wzethj/l cavyZ'xa~zthofenate is
obtained as a viscid oil which shows no tendency to crystallise. On
distillation at the ordinary pressure the xanthogcnate is decomposed
with formation of a hydrocarbon which after repeated distillation over
sodium boils at 165-170'/685 mm. This hydrocarbon has constants
agreeing very closely with those of n4-carene as will be seen from the
foIlowing comparative table.
b.p.
a%
.D""
[a],
d-h4-Cavene
165'5-167~/707 mm.
08552
1.474
6 2 . 2 O
Synihetic Hydmcar6on
165-'7o0/685 mm.
0.8551
1.473
-5'96" (in acetic acid)
When available only in small quantity a4-carene is not readily
identified, since it does not yield an37 crystalline derivatives and it can
only be characterised by conversion into sylvestrene dihydrochloride
acid.
or by oxidation to I : I-dimethyl-~-y-ketocycZopropane-~-carboxylic
The quantity (2 g.) of synthetic hydrocarbon was insufficient for
oxidation and we therefore treated an acetic acid solution with
hydrogen chloride. The resulting product was an oil which, when
cooled in a mixture of solid carbon dioxide and acetone crystallised,
but melted below -15'. In view of the low rotation of the hydrocarbon
the products of the reaction, assuming it to have been a4-carene
mould consist of carvestrene and dipentene dihydrochlorides, a
mixture which would undoubtedly have a very low melting point. W e
do not therefore consider that the result of this experiment can be
regarded as definite evidence that the terpene was not a4-carene.
The yield of the hydrocarboq by this method of synthesis is however
so extremely poor that we are not at present in a position to repeat its
preparation.
I t was mentioned ahove that on reduction carone behaved like an
a@-unsaturated ketone, and it appeared to us of interest to examine
its 'eactions with hydrogen cyanide and ethyl sodiocyanoacetate.
With hydrogen cyanide carone behaves like a saturated ketone
yielding the corresponding cya~zkydv;i?z( W ) . Attempts to hydrolyse
this to the hydroxy-acid by means of alkali were unsuccessful,
hydrogen cyanide being eliminated with regeneration of the ketone.
This result was not unexpected in view of the previous work oi
Lapworth (Jouwa. Chem. SOL.,1910, 97, 12) and Auwers and Krollpfeiler (BEY.,rgr j, 48, 1389). With ethyl sodiocyanacetate carone
shows 110 tendency to react although the experiment was made under
various conditions.
EXPERIMENTAL.
rl-Car~laminewas prepared by the reduction of caroneoxime as
described by Baeyer (Zoc. czt.). It was a colourless mobile oil possessIng a somewhat characteristic basic smell ; b.p. 86-8g0/r5 mm., in
1.8 per cent. alcoholic solution [a]go ~ 2 . 3(Found
~
: N, 9.5 ; CloHl,N
requires N, 9.2 per cent.).
T o sulphuric acid (32.2 cc. ; 9.62 per cent.) which was well
cooled in a freezing mixture and mechanically stirred, d-carylamine
(5 g.) was slowly added, care being taken that the temperature did
not rise above 0". When the addition was complete a solution of
barium nitrite (7.5 g.) was added, the temperature being maintained
between 5" and 10". A brisk evolution of nitrogen was observed and
the stirring was continued until this ceased (about 8 hours). W h e n
the reaction was con~plete the solution was basified and distilled
in steam, the aqueous distillate saturated with ammonium sulphate
and repeatedly extracted with ether. T h e combined ethereal extract
mas mashed with dilute snlphuric acid (10 per cent.) to remove any
~ulchanged base, then with dilute sodium carbonate solution, dried
and evaporated. T h e oil which remained (30 per cent.) had b.p.
r q r - r ~ z 0 / ~ omm.
o
K a r o l is a colourless oil with a pleasant smell
reminiscent of linalol ; in alkaline solution i t only very slowly
decolorises a solution of potassium permanganate. T h e following
constants were observed :--rd;E 0.9181, n y 11'472 ; [a]F - 4 ~ - 9 2;~
[R,]. 46.78 (Foupd : C, 77.8 ; H, r 1.9 ; C,,Ij,C) requires C , 77'9 ;
H, r1.7 per cent.).
2
When the alcohol was dissolved in acetic acid and the solution
treated with the calculated quantity of chromic acid, it was slowly
oxidised to carone which was identified by the preparation of the
semicarbazow.
2-Carol (50 g.) dissolved in twice its volume of ether was added
gradually to a well-cooled solution of the Grignard reagent prepared
from 30 grams of magnesium. T h e reaction was vigorous, and after
three days at the room-temperature ice was added and sufficient
hydrochIcric acid to decompose the magnesium salts. On removal of
the solvent an oil remained which on distillation was separated into
:
; ~ 8 3 9 ;2 ?zi0\-4678,
two main fractions (i) b.p. 172-174~1683 mm. ; d
[a2r-46-j2", [ R j 4j.07 ; (ii) b.p. 1%-1go"/683 mm. : dgi 0.8624,
$ 1.4745, [a]g-58.48", [R,] ,.44'42.
Titration with bromine indi.
cated that both fractions consisted essentially of monocyclic hydrocarbons containing two ethylene linkages. On treatment with
hydrogen chloride in acetic acid solution an oil was obtained which on
cooling in ice deposited a small quantity of a crystalline solid, m.p.
5 r - p 0 . This was identified as terpinene dihydrochloride by the
method of mixed melting point. The yield of dihydrochloride was
small and the oil did not yield terpinene nitrosite, whilst the product
of oxidation with an alkaline solution of potassiuni perinanganate was
a viscid oil which could not be induced to crystallise.
,
[-Carol (22 g.) was added to finely divided sodium (5 g.) suspended
in toluene (75 g.) and the mixture heated to boiling for 2 0 hours.
The toluene solution of the sodium derivative was decanted from
unchanged sodium and after the addition of ether (100 cc.) the
well-cooled mixture was gradually treated with carbon bisulphide
(25 g.). T o the xanthogenate prepared in this manner methyl iodide
( 2 0 9.) was added and the conversion into the methyl ester completed
by digestion on the water bath for one hour. T h e reaction product
waspoured into water, the toluene-ether separated and the solvents
removed under diminished pressure. 1-ni(EthyZ carylxn~zthogenntewas
a viscid yellow oil which did not crystallise. On distillation at the
ordinary pressure an oil was obtained containing considerable
quantities of sulphur compounds. It was purified by repeated
distillation over sodium when it had b.p. 16j-170"/685 mm. and the
constants given on p. 2 (Yield 3 g.) When dissolved in acetic
anhydride and treated with a drop of sulphuric acid a purple colour
developed which on keeping gradually changed to red. T h e action
of hydrogen chloride has already been discussed.
T o a freshly prepared solution of hydrogen cyanide ( 2 g.) in
alcohol (20 cc.) d-carone (10 g.) in alcohol ( 1 0cc.) was added. After
remaining overnight an aqueous solution oi potassium cyanide (4 g. in
10 cc.) was added and the mixture digested on the water bath for
three hours. T h e oil which separated on addition of water was extracted with ether, the ethereal extract washed with dilute alkali and
the solvent removed. T h e crude cyanhydrin stili contained much
unchanged ketone and the treatment with hydrogen cyanide was
repeated when the nearly pure r y a d y d ~ i awas ultimately obtained as
a viscid oil (Found : N, 7.1 ; CllII,,ON requires N, 7.8 per cent.).
When the cyanhydrin was digested with an aqueous solution of
potassium hydroxide, ammonia was evolved and d-carone regenerated,
the yield being quantitative.
The mordant dyestuff, morindone, occurs in the root bark of
2 f i i . i 7 z ~ l a czfrzfolia and PI. 7mzinJZal'a mainly as the glucoside morindin. It
was first isolated by.Anderson (Amznlez, 1849, 11,216) and was subsequently investigated by Thorpe and Greenall (Jouvia. Chem. Soc., 1887,
51, j a ) , Thorpe and Smith (Ibict., 1888, 53, 171) Perkin and Huminel
(ZDin'., 1894, 65, 851) and by Oesterle and Tisza ( A Y cIJhavwz.,
~.
1907,
245, 534). AS the result of these investigations it was established
that n~ormdonewas a trihydroxy-6-methyl-anthraquinone, the position
of the three hydroxy-groups remaining undetermined although from
thc general properties of the substance there appeared to bc little
doubt that two of the hydroxy-groups were in the I : 2-position.
An analytical investigation led one of us to suggest (Jouvz. C/levz.
Soc., 1918, 113, 768) that morindone was either hydroxymethylanthrarufin (I) or hydroxymethylchrysazin (II), the former being preferred,
since in its colour reactions, morindone more closely resen~bles
hydroxyanthrarufin than hydroxychrysazin.
It is well known (cf. Liebermann, Rev., 1876, 11, 1617 ; D.R.P.,
r9jo28, ~96980)that 2-hydroxyanthraquinones on fusion with alkali,
either alone or in the presence of oxidising agents, readily yield
dihydroxyanthraquinones the second hydroxy-group entering the
I-position, a reaction which is analogous to the conversion of resorcinol
into phloroglucinol by fusion with sodium hydroxide. Simonsen
Chem. SOL.,1921, 188, 1340) therefore synthesised
and Iiau (JOWJZ.
2 : j-dihydroxy-6-methylanthraquinone ( I : 6-dihydroxy-2-methylanthraquinone, 111) since on fusion with alkali this should yield the
trihydrosy-methylanthraquinone (I). Unfortunately the yield of
2 : i-dimethoxy-6-methylanthraquinone
from 2 : 4'-dimethoxg-3-methylbenzophenone-6-carboxylic acid (IV) was so poor that systematic
experiments on its oxidation were not possible.
Additional evidence of the cc?rrectlless of the suggested iurrnula
for lxorindone was iurnishcd by the syllthesis of 1 : 2. : 8-irimethoxy7.rnethyianthraquinooe (JOZLT~J. C/Iem. .soC., 1 p 4 , 125, ? n 1 ) which was
found not to he identical with nloril~donetriilletllyl ether. In 3925
A d a m aud jacobson (JOZWL. Anr. C/itt~~.
.%c.,
1925, 17, 283) devised
an ingenious synthesis of r : 2 : 5-tuihydroxy-6-methylanthraq~linolle
(I) and showed this to be identical in all respects with morindone.
During the course of their experiments Simonsen and Xau
obtained some evidence of the conversioll of 2 : 5-dihydroxy-6-methy]nnthraquinonc into movindor~e and it appeared to be not without
interest to repeat and extend their experiments sillce it has been
shown by 13istrzycki aud his collaborators in a series of papers (c. j.
H e h . Ch&. Actn, 1923, 6 , 750) that an excelletlt yield of anthraquinone
derivatives can usually be obtained if, instead of the benzophenonecai-boxylic acid, the dipheayln~cthanecarbo~YIic
acid is treated with
sulpiluric acid and the resulting anthrone subsequently oxidised to the
corresponding anthraquinone.
XC
V
'$1
V11
obtained in an excellent yield by Scho]] and ~ e o v i u s ' nlethod
(Bey., 191l , 44,
1075), although it is always accompallie({ by
2 :.
f - e o x - t Z Z h t ( 1 ) . When 2 : ql-dlmethoxy;-~nethyldiphenyl111ethane.6-ca1-bo~~lic
acid is treated at the ordinary
temperature with sulphuric acid it passes readily into 2 : 5 - c i i n ! c f h w
6-~~~~thyZ-9-oitt/i~~o11e
(VII), which on oxidalion yields the ,dinlethyl
(111). T h e dlmethylaether of n : 5-dihyciroxy-6-methylai~thrdquinone
tion of the ether was most readily effected by somewhat prolonged
digestion with aluminium chloride and the yield did not exceed
50 per cent. When the dihydrox~anthrac~uinone
was fused with
potassium hydroxide in presence of sodium arsenate at a temperature
not exceeding 260°, the melt gradually changed from red to, violet
owing to formation of the trihpdroxq.,?nthraquinone. T h e ?xidati@n
above
was never complete, and if the temperature was allowed to
260" profound decomposition took place and the melt , became
colourless. T h e mixture of hydroxyanthraquinones nbtalned 013
acidification of the melt was digested with barium hydroxide solution,
when the sparingly soluble bzriurn salt of I : 2 : 5-trihydroxy-6-methylanthrquinone separated. The liydroxyanthraquime from this
!,arium salt was further purified by conversion into its acetyl derivative which, after repeated crystallisation from acetic acid, melted at
2 4 9 O and was identical in all respects with the triacetyl derivative of
morindoue. On hydrolysis I : 2 : 5-trihydroxy-6-methylanthraquinone,
m.p. 27j0, was obtained and had all the properties of natural
morindone.
EXPERIMENTAL,
2 : 4~-Dimethosy-3-methylbenzophenone-6-carboxylic
acid ( r j g.)
was dissolved in sodium hjdroxide solution ( 2 N ; 475 cc.), an
am~noniacalsolution of copper sulphate (40 cc. from z N ammonia
and 2 N coppersulphate) with zinc dust (25 g.) being added. T h e
mixture was boiled under reflux for 140-150 hours, small additional
quantities of sodium hydroxide solution and zinc dust being added
every r 2 hours. The hot reaction mixture was filtered, the residue
washed with hot dilute ammonia and the filtrate acidified, when a
pasty mass separated which rapidly solidified. T h e solid was dissolved
in ether, the ethereal extract repeatedly washed with sodium bicarbonate solution, dried and evaporated. The viscid oil which remained
slowly crystallised on keeping, more rapidly om inoculation, and was
recrystallised Iron1 methyl alcohol, separating in glistening cubes
2 : q'-Dinzei~~x~~-3-?~eLh~~$/zc~z~L$hthaGide
was found to
m.p. 78-79'.
be readdy soluble in the usual organic solvents ; i n cold allcalies it
was insoluble but dissolved slowly on boiling ( F o ~ m d: C, 71.6 ;
H, 5.7; Cl7H&, requires C, 71.8 ; H,5.6 per cent.).
The sodium bicarbonate solution (see above) on acidification
mid.
deposited 2 : ~'-din~e~ho;zy-3-?neihy~di~henydrnedharze-6-~a~~0~~ZiT h e acid, which was readily soluble in the ordinary organic solvents
and very sparingly so in water, was best purified by crystallisation
from methyl alcohol from which it separated in glistening leaflets,
m.p. 103-104' (Found : C., 71'3 ; H, 6.2 ; M, 284.6 ; C17H180,requires
C, 71.3 ; H, 6-3 per cent. ; M, 286).
2 : ~r-L)imethoxy-3-methyldiphenyllnethane-6-carboxylic
acid (5 g.)
was mixed with sulphuric acid (d. 1.84; 50 cc.) and the brown solution
allowed to stand at room-temperature for ten minutes. The reaction
mixture was poured on ice, the solid which separated collected,
triturated with dilute sodium carbonate solution to remove unchanged
acid and recrystaliised from acetic acid. T h e anthrone separated in
faintly yellow needles, m.p. i I 1-1 r 2' (Yield 4 g. Found : C , 75.9 ;
W, 6.2 ; c,H,,Q, requires C , 76.1 ; H, 6.0 per cent.).
2 : 5-Di~zethaxy-6-r1~~thyIn~~~k~/1~1ii~z~?1~.--The
antbl-one ( I mol.)
having been dissoived i n acetic acid, chromic acid ( 2 mols.) was
gradually added, the oxidation being completed by digestion on the
water bath. T h e anthraquinone was precipitated by water and
recrystallised from either acetic acid or benzene, yellow needles,
m.p. 192"' (Found : C, 72.9; I1, 5.1 ; calc. C,72.3 ; EI, 5.0 per cent.).
2 :~-Di/iyd~o~y-6-m~~/iyZ~~zth~a~~~i~zo~ze.-The
dimethyl ether (5 g.)
was rnixed with finely powdered aluminium ch!oride ( 1 0g.), heated
to 200" during one hour and maintained at this temperature for 30
minutes. iZ Iurther quantity of aluminium chloride ( j g.) was added
and the heating continued for another I j minutes. T h e cooled
reaction mixture was treated with ice and hydrochioric acid and the
hydroxyanthraquinone collected. It was purified by solnlion in alkali
and crystallisation Lrom acetic acid, rn.p. 280-281".
2 : 5-Dihydroxy-6-methylanthraquinone
( I g.) was dissolved in
potassium hydroxide solution (10 cc. of 50 per cent.) and the mixture
heated En a nickel crucible with gradual addition of sodium arsenate
(I t o a g.) a t 220-230' (bath-temperature) for i.5 hours. T h e red
melt gradually became bluish violet owing to the conversion of the
di- into trihydr~xyanthra~uinone. After diIution with water (loo cc.)
the solution was boiled for 30 minutes and acidified. T h e mixture
of hydroxyanthraquinones which separated was digested with an
excess of barium hydroxide solution, when a sparingly soluble violet
barium salt was precipitated. This was collected, decomposed with
hydrochloric acid and the somewhat impure I : 2 : 5-trihydroxy-6methylanthraquinone acetylated. T h e triacetyl derivative crystallised
from acetic acid in needles, n1.p. 249' uncorr. and this m.p. was
unaltered on admixture with a specimen of triacetylmorindone. On
hydrolysing the acetyl derivative, I : z : 5-trihydroxy-6-methylanthraquinone was obtained and crystallised from toluene in orange red
needles m.p. 27s0 uncorr. It had all the properties of morindone and
did not depress the 1n.p. of this substance (Found : C, 66.8 ; H, 3.8 ;
calc. C , 66.6 ; H, 3.7 per cent.).
' The m.p. 182°givcn in tlmprer.ious
cornrnuoicntiol~(lo'. c i t . . p. 1347) i? z clerical error.
During an investigation of derivatives of naphthaquinoline
( J o z t ~ ~Chem.
.
Soc., 1926, 2247) it was observed that, while a-naphthylamine itseif could not be condensed with paraldehyde, its derivatives
substituted in the +position readily underwent this reaction. In order
to ascertain whether 4-substitution mas the determining factor, we
decided to examine the condensation of 5-aminoacenaphthene with
paraldehyde, since this base may be regarded as a derivative of
a-naphthylamine in which the 4-position is substituted.
Cyclic nitrogen derivatives containing the acenaphthene nucleus
have been little investigated and it was only when this work was
nearing completion that a paper appeared (Stewart, I., 1925, 127,
~ 3 3 1 ) ,in which an account was given of the preparation of acenaphthp~ridine.~
When digested with hydrochloric acid. 5-aminoacenaphthene and
paraldehyde readily condense with formation of a-methyylacenap/ztA
pyridi~~e
(I), thus confirming the suggestion that substitution in position
4 is the deciding factor in this reaction. O n reduction with sodium
and alcohol, 2-methylacenaphthpyridine is converted into the corresponding t e f m h y d ~ o - h ebut
, the yield is poor owing to the simultaneous
production oi more highly reduced bases. No better results were
obtained by using other reducing agents.
The condensation of 5-aminoacenaphthene with ethyl acetoacetate
proceeds like that of a-and P-naphthylamines. A description of the
products is given below.
lReprintrd from the Journal ot the Chemlcal Society, 1926 3140.
'The name acenaphthpyridine appears to us to be pref&ble
to that qf o-qcepaphthaquinoline, since the latter name should really he given to a substance containing both the
acenaphthene and the quinoline ring.
EXPERIMENTAL.
Co'onderzsatiozoaf 5-Anzinoacelurphth~1~e
and ParaZdekyde. 2-Methylace<zaphUifiyri&zc (I).--A mixture of 5-aminoacenaphthen (ro g.),
hydrochloric acid (d 1-19 ; 2 0 g.), and paraldehyde (15 g.) developed
an Intense red colour at 50°, a v i g o r o ~ sreaction took place at 70°,
and after a s minutes the condensation was completed by heating at
rro0 for 5 hours. An excess of alkali was added, the semi-solid,
viscid brown oil that separated was dissolved in dilute sulphuric acid
and treated with a slight excess of sodium nitrite solution to remove
the secondary base which had been formed, and the filtered solution
was made alkaline with ammonia. The base (6 g.) obtained was
crystallised from dilute alcohol. 2-ilieihyZnce?zaphthp~~~idi~~e
separated
from alcohol in irregular, colourless prisms, m.p. 1 3 r 0 , which became
brown somewhat rapidly on exposure to air. I t was readily soluble
in the ordinary organic solvents except light petroleum (Found : C,
87'6; H, 6.1 ; N, 6.7. C',,H,,N requires C, 87.7 ; H, 5.9 ; N, 6.4
per cent.).
T h e hyd~ochlorideand hyd~06romzdewerc somewhat sparingly
soluble in water and crystallised in needles. T h e #icmte separated
from alcohol in glistening, yellow prisms, decomp. 225-226' (Found :
N,12.9. C,,H,,O,N, requires N, 13.0 per cent.). T h e chZoro#latimzIte,
which was insoluble in water and alcohol, was deposited on the
addition of platinic chloride to a solution of the hydrochloride as a
brown, crystalline powder, decomp. 251-252' (Found: Pt, 23.1.
C,,H,,N,CI,Pt requires Pt, 23,o per cent.).
2-Methyl-I : 2 : 3 : 4-telvnhydvoncennfihthfiy~idine.-A solution of
2-methylacenaphthpyridine (10 g.) in boiling alcohol (600 c.c.) was
treated with sodium (40 g.), the alcohol then removed in steam, and
the Itetrahyn'ro-base separated by ether. It distilled at 215-217~114
mm. ; the distillate, which slowly crystallised, separated from alcohol
in glistening prisms, m.p. 88-89" (Found : C, 85.9 ; 13, 7.9 ; N, 6'5.
CI6H,,N requires C, 86.1 ; H, 7.6 ; N, 6.3 per cent.). T h e base,
whlch was readily soluble in ,all the ordinary organic media except
alcohol, gave strongly fluorescent solutions which darkened rapidly
on exposure to the air. T h e yield of tetrahydro-base was very poor,
a considerable quantity of liquid bases of lower boiling point being
formed simultaneously. When other reducing agents such as sodium
amalgam, tin and hydrochloric acid, and amalgamated zinc and
hydrochloric acid were used, the original base was recovered unchanged.
T h e hydrochloride separated from dilute alcohol in ill-defined
crystals, decomp. 260-261' (Found : C1, 13.8. C,,H,,N,I-IC1 requires
CI, 13-7 per cent.). The benzoyd derivative crystallised from alcohol
in rectangular plates, m.p. 187-188' (Found: C , 84-1 ; 11, 6.8.
C,H,ON requires C , 84'4 ; H7 6.4 per cent.).
Condematioioiz of 5-Amiltoace+zaphfhme and EthyZ Acetoacetate.-(i) E ~ h y l ~ - ~ - m n a p h t k y Z a m i r z o ~ ~ o (11).
t o n a t eT o a mixture of 5-aminoacenaphthene (9 g.), ethyl acetoacetate (7 g.)., and sufficient alcohol
to give a clear solution, piperidine (2 drops) was added. After
1 2 hours, the crystalline solid was collected; it recrystallised from
alcohol in plates, m.p. 93-84'.
T h e ester was readily soluble in the
ordinary organic solvents (Found : C, 76.9 ; H, 6.9 ; N, 5.3. C,H,,O,N
requires C, 76.9; H, 6 - 8 ; N, 5.0 per cent.).
4-Hyd~o~y-z-meth3~Za~enaphthpy~idine,
obtained in a quantitative
yield when ethyl 8-5-acenaphthylaminocrotonatewas heated to zzoO,
crystailised from acetic acid in thin, glistening plates, m.p. above
3 3 ~ ~It. was insoluble in all the ordinary solvents except acetic
a c ~ dand nitrobenzene, showed very feeble basic properties, and gave
no colour with ferric chloride (Found : C, 81.5 ; H, 5.6; N, 6-0.
C,H,,ON requires C, 81-7 ; H, 5.5 ; N, 6.0 per cent.).
(ii) P-5-Acemphthyhnzinocroto?z-5-acena#hthyZamide
(I I I).-A mixture of 5-aminoacenaphthene (23 g.) and ethyl acetoacetate (18 g.)
was heated on the water-bath for 8 hours, a further equal quantity of
ethyl acetoacetate then added, and the heating continued for 5 hours
at 170". The cooled solid residue was powdered, thoroughly washed
with alcohol, and crystallised from toluene, which left undissolved a
small quantity of a substance (A).
b-5-AcenapAthyZydami~c~oton-5-ace?zap/ithyZamide
crystallised in rosettes of needles, m.p. 189-190". It was insoluble in water, somewhat readily soluble in acetic acid, ethyl acetate, acetone, or pyridine;
and more sparingly soluble in benzene or chloroform (Found : C, 83.2,
H, 6.2; N, 7.1. Cz8HzaON2requires C, 83.2 ; H, 5'9; N, 6.9 per
cent.).
5-Acetoacetamidomenaphtbe~zee-The crotonamide (111) (20 g.) was
mixed with hydrochloric acid (320 C.C. of 4 per cent.) and heated on
the water-bath for 15 minutes. T h e solid product, after being washed
with boiling water to remove 5-aminoacenaphthene hydrochloride,
crystallised from dilute alcohol in fine needles, m.p. 142-143~(Found :
C, 76.0 ; H, 6.2 ; N, 5.9. C16H1502Nrequires C, 75-9 ; H, 5.9 ;
N, 5'5 per cent.).
2-Hydvoxy4-methyIacenaphthpydine.--Amixture of s-acetoacetamidoacenaphthene (I I g.) and concentrated hydrochloric acid (10 c.c.)
was heated on the water-bath for 10 minutes ; the solid that separated
on pouring the product into water was repeatedly extracted with
boiling water to remove g-aminoacenaphthene hydrochloride formed
by hydrolysis. T h e hydroxy-dase crystallised from nitrobenzene in
glistening prisms, m.p. above 350". It was extremely sparingly
soluble in the ordinary solvents and gave no colour with ferric
chloride (Found: C, 82.0; H , 5%; N, 6.3. C,,H,,ON requires C , 81.7;
II, 5'5 ; N, 6'0 per cent.). A solution In hot hydrochloric acid, on
cooling, deposited a sparingly soluble kydrochbride which was readily
dissociated by water.
2-CkZoro-4-methylacena$LtLpj~ridim.-A suspension of the hydroxybase (0.6 g.) and phosphorus pentachloride ( I g.) in phosphorus
oxychloride (10 c.c.) was heated at 107' for 3 hours. After addition
of ice, the chloro-compound was collected ; it crystallised from alcohol
in needles, m.p. zoo-201". I t was readily soluble in benzene, chloroform, or acetic acid, somewhat sparingly soluble in alcohol, and
insoluble in light petroleum (Found : N, 5-6 ; C1, 14.0. C,,H,NCl
requires N, 5.5 ; C1, 14.0 per cent.).
was obtained by
4-Methyl-I : 2 : 3 : 4-tefrah~~droacenaphtApy~zdine
reducing the above chloro-derivative with sodium and alcohol. After
purification through the sparingly soluble hydrobromide, it crystallised
from alcohol in fine needles, m.p. 87-88' (Found : C, 85.9 ; H , 7'8.
C,,H,,N requires C, 86.1 ; H. 7.6 per cent.).
s-Di-g-acem~ktLyl~a~bamzde
(IV).--The substance ( A ) (see p. I 2)
which was insoluble in toluene crystallised from much nitrobenzene
in prismatic needles, m.p. 318" I t was identified as the substituted
carbamide by direct comparison with a specimen prepared by heating
a mixture of urea and 5-aminoacenaphthene at 200' for 2 hours
requires
(Found: C, 82'5, 82.1' ; H, 5.6, 5.5' ; N, 8.4. C25HzoONz
C, 82.4; H, 5.5 ; N, 7.7 per cent.).
[Accepted,
8-2-27.]
Department of Organic Chemistry,
Indian Institute of Science,
BangaZove.
Spccitcen prepared from ares