JOURNAL

OF THE AGRICULTURAL

CHEMICAL

SOCIETY

OF JAPAN .

Vol.1,

No.1.

October

, 1924. ORIGINAL PAPERS .

No.1.

ABSTRACTS

FROM

THE

The

Constitution of

Kojic Acitl,

-Pyrone

D erivative Ortzae

Formed from
By T.

by Aspergillus Carbigydrates.
YABUTA.

Previous work (J. Chem. Soc. Tokyo, 1916 , 37, 1185, 1234) has shown that kojic acid (I) is probably the alcohol corresponding with comenic acid . Interconversion by oxidation of kojic acid or reduction of comenic acid has not been accomplished, pyridine.
and acetic

but both compounds

m. allomaltol

furnish the same 4:5-dihydroxy-2-methylwith thionyl

, and

Kojic acid on treatment

acid gives

chloride yields 5-hydroxy-2on reduction with , prisms, zine m.p.166. dust

chloromethyl--pyrone, meedles,

p.119-121

(5-hydroxy-2-methyl--pyrone)

Allomaltol is distinct from maltol (Brand, Ber., 1894, 27, 806) and from isomaltol (Backe, Compt. rend., 1910, 150, 540; 151, 78), the distinction being confirmed by the preparation of the following derivatives. Allomaltol methyl ether (5methoxy-2-methyl--pyrone), benzoylallomaltol prisms, m.p.70-71, b.p. prisms, (approx.)93/0.1mm.; m.p.128-129; phe(3-benzoyloxy-6-methyl--pyrone),

mylcarbamate

of

allornaltol,

NHPh.

CO. C'6H5O3, plates,

m.p.

186-188;
171-173. by treating

bromoBenallo-

allomatol (6-bromo-5-hydroxy-2-methyl-y-pyrone),
zene azoallomaltol (6-benzeneazo-5-hydroxy-2-methyl--pyrone),

crystals, m.p.

maltol in solution with diazobenzene definite m.p.

acetate, forms reddish-brown

needles, no

Oxidation of the following kojic acid derivatives did not give the corresponding comenic acid derivatives: monobenzoyl kojic acid;
-pyrone),

monoethyl
by the

ether

of
of

kojic acid, (5-ethoxy-2-hydroxy-methylkojic acid, ethyl p-toluenesulphonate,

p.110; ether, 5-ethoxy-2-hydroxymethyl-4-pyridine, and isolated as the piorate

prepared

iuteraction

and sodium ethoxide in alcohol, needles, m.

prepared needles, m.p. from kojic 184-185; acid monoethyl 5-hydroxy-2-

2 chloromethyl--pyrone and its

T. YABUTA: methyl ether; 5-hydroxy-2-iodomethyl--pyrone,

prepared

from

the

corresponding
prisms,

clloro-compound
m.p. 135-137.

as

crystalline

plates;

5-methoxy-2-iodomethyl--pyrone,

The following derivatives of comenic acid were prepared, but reduction did not give the corresponding
from 282; m.p. aleollol, methyl 156; m.p. ether 227-228; of methyl

kojic acid derivatives.

methyl
comenate,

Benzoylcomenic
acid, ether prisms, methyl

acid, prisms
m.p. 280comenate,

ether
m.p.

of

comeuic

197;

of ethyl

the hydrochloride
action methyl the of thionyl ether the by

of the methyl ether of comenyl chloride (II), prechloride of comenyl acetate, on comenic acid prepared
148:

pared
m.p.

by the
103;

methyl from

ether, the methyl

prisms, previous ether,

chloride, m.p.

compound

action

of sodium

comenamide

The catalytic prepared by the action of ammonia on (II), needles, m.p. 178. reduction of the methyl ether of comenyl chloride by Rosenmund's method (Ber.,

1918, 51, 585; 1921, 54, (B), 425, 638), failed owing to the instability

of the

pyrone nucleus. Comenamic acid methyl ether (o-methoxy-4-pyridone-2-carboxylic acid) was prepared by the action of ammonia on comenic acid methyl ether;
ammonium salt, needles, m.p.
263;

hydrochloride, of the methyl

prisms. ether,

Thionyl giving method

chloride 4-chloro-5also failed

introduces

chlorine

into

the

4-position acid

methoxypyridine-2-carboxylic to reduce. carboxylic

the ethyl

chloride, converted
into and the

which into
amide, the

Rosenmund's

The acid,
ester,

acid prisms,

chloride m.p.
m.p.

was
209, 167,

4-chloro-5-methoxy-pyridine-2needles, ethyl ester, m.p. prisms 207-208, m.p. into 140.

prisms,

into

Allomaltol or by
ammonia
m.p. 115,

methyl

ether,

prepared

either

by

the

methylation when

of allomaltol heated with

the
in

reduction
a closed
which gives

of 5-methoxy-2-chloromethyl-4-pyrone,
tube
a

at

100

gives
needles,

5-raethoxy-2-methyl-4-pyridone,
m.p. 205-206. The dimethyl

needles,
ether

piorate,

of kojic acid, when similarly treated, yields the corresponding pyridine derivative,
which
acid

distils
gives

at

200/1mm.,

and

on

heating

with
prisms,

red

phosphoms
280.

and
and

hydriodic
crystallis-

4:5-dihydroxy-2-methylpyridine,

decomp.

ing+1H2O Cemenic acid, tin which and

at low acid when

temperatures. heated with gives thus with ammonia under pressure and gives then comenamic reduced with The the same

when treated acid

phosphorus the same

pentachloride

hydrochloric

4:5-dihydroxy-2-methylpyridine. acids gave on methylation

m.p.

dihydroxy-picolines
5-methoxy-1:2-dimethyl-4-pyridone

obtained

from

both

(+3H2O),

colourless

needles,

98. This

Sinomenine

and

Dehydrosinomenine

Parts

I and

II.

compound, thus tion

needles,

is also formed

by treating

allomaltol

methyl

ether

with methylami

confirming gives
m.p.

the position of the methyl

similarly
208.

groups . 5-methoxy-1-methyl-4-pyridone

Comenamic -2-earboxylic

ne, acid on metbylaacid (+4H2O) ,

(I)
(II)

Sinomenine

and

Dehydrosinomenine. By KAKUJI GOTO.

Parts

I and

II.

Sinomenine and dehydrosinomenine mountain crystalline climbing state. plant,

are alkaloids from the root of a Japanese by Katsuta Taguchi in a pure

Sinomenum acutum, Rehd. et Wils., Menisperaceae. alkaloid Cocculine (and afterwards

The first of them, sinomenine was first isolated He named at first the

Cucoline), according to the obsolute name, Cocculus diversifolius, Diels., formerly given to this plant. He analysed the alkaloid and assigned the formula C17H29NO3 (and afterwards C16H20NO3). Although his descriptions on the melting
point, which is 158,

and

on the

other

properties

seem

to be fairly

well

establi-

shed, his formula seems unfortunately to be incorrect. Dec. 13th.)

(Tokyo Iji Shinshi, 1919,

Shortly after Taguchi, J. Ishiwari published his pharmacological investigations of the alkaloid, in which some of the chemical properties are also given. Jji Shimpo, 1920, No.959 and 1921, No.991.) Succeeding Tab chi, I took up the investigation (Chugai

of the alkaloid and was Society me to

working several years on it, when in June, 1923 a paper on the same alkaloid was read by Heizaburo Kondo and Eiji Ochiai before the Pharmaceutical of Japan (J. Pharm. Soc. Japan, 1923, No.497, 511). This instigated

publish my thitherto obtained results in July, 1923, in the Chemical Society of Tokyo (J. Chem. Soc. Japan, Vol.44, 795, 1923). The results of the last named