STATES ofPATENT

UNITED “IROSHINOMURA, SENDAI, JAPAN.

OFFICE.
METHOD of PREPARING “ZENGIBERON E. (NEETHYL 3-METHOXY-4-HYDROXYPHENYL
ETHYL KETONE.) viratocuroixrukturmuri

Specification of Letters Patent, Pateated Apr. 23, 1928.

1,263,296, Application filed June 6, 1917. Serial No. 178,114.
No Drawing.
To all whom it may concern; cinale,) of which the following is a specifi O

Be it known that I, HIROSHINoMURA, pro- cation. I have found . . .. . . ;Zingiberone,

s " . . . that . . .. . .. . ..
is easily pre
fessor of chemistry, a subject of the Emperor paired by the reduction of vanillaiacetone
of Japan, residing at No. 30 Kadan, city of which is obtained by the condensation of
5 Sendai, Miyagi Prefecture, Empire of Ja 'anillin, and acettine in presence of caustic 5
pan, have invented
Preparing a certain(Methyl
“Zingiberone.” new Method of
3-Meth alkali, the process being illustrated in the
oxy-4-Hydroxyphenylethyl Ketone), a pull following scheme: . . . . . .
gent principle of ginger-root; (Zingiber offi () oH
. . .

:-
on
. . .. .
/Nach,
.. +CH3COCH3-r)
.. .. . . .. . .

CEO CH3CH.CoCH, CEECH, Coch, . . .

Vanillin. . Acetone. Vaillalacetone. ; Zigil crone. .
The procedure is for instance. as follows: means of hydrogen in the restice of plati
ni liack. . ''{: hydrogen absorbed was
1. Vanillalacetone al) of SO().c. c. (at 23.24° and 752.75.4 mm.)
for ille (lis. After. Fifering off the plati 55
20 in H i) { k, the filli"; t is all (I ethereal Wash
. /Nacil . ings () the litti II, lik were evaporated
:lict the resil: oil on tistillation boiled con
stantly it is iss' titler ini. The yield
25
Y
C :0II.COCEI.
*:I is. The oil was twice recrys
tallized ir)} : ixtti'e ()f ether and petro 60
70 ?. c. of 10% caustic soda Solution were let in the r ( i. i. elow (30°). The crystals
added to the solution of 25 grains of ya this titaine( i) { {:} at 40-41° and were
nillin in 100 c. c. of acetone, and after he a lialyzed with the following results:
ing allowed to stand for four days, the so 0.1 (329 gave (). 105S CO, and 0.1090 H.O. 65
30 lution was acidified with dilute hydrot:lioric is {3. ...i.4).
acid, when a yellow precipitate was obtained. {}, .22 gave 0.3 13 CO, and 0.0850 H.O.
The precipitate was filtered, washed with (-(3S.2i; ; ; c. 7.64.
water until free front chioid and secrystal
lized from dilute alcohol,s from which if sepa ('ent.
C, II.O., requires C=68,00; H=7.27 per
35 rated in yellow crystals & Ici meited at 128 The saibstance produced no lowering of 70
129°. The ywield was 28 g :' ' ' is'' fier oikte the netig point by mixing with the natu
crystallizing. i": Zingieroine. The beinzoyl derivative
2. lifetity 3-methosey-A-igid, 'oa: ld the () Xian of methyl ether of the sub
ethyl ketone, (zingibefore).--- -

stance melted respectively at 126-127° and

0. oH 93-93.5", and also produced no depression of 5
$he netting point by Inixing with the corre.
/ OCH, spoiding derivatives of Zingiberone. From
scCaita is hese acts, its identity with Zingiberone is
icy (ind doubt.
HavingS.now described my invention, what 80
CHCH-COCE CE: J.
CHs(CF,CECOCH)(C-CE)(Oji). 1. A new method of preparing “zingiber
one” (incthyl 3-methoxy-4-hydroxyphony
6 grams of vanillalacetone were siisipended eihyl ketone
in 100 c. (, of absolute either and reduced by a pungent principle of ginger
50
 2 1,268,796
comprising adding a 10% solution of caus
root (Zingiber officinale) having the consti tic
tntional formula, soda to a solution of vanillin and acetone
OH
and allowing the same to stand, then add
ing hydrochloric acid to the solution to ob
/N-och, sci-CuH403(Ml.P.-40-41)
tain a precipitate, then filtering and washing
the precipitate, then dissolving the precipitate
in alcohol, then crystallizing the vanillalace
N/ tone out of the solution, then dissolving the
vanillalacetone crystals in a solvent and re 50
10
airlgibert. ducing the solution by means of hydrogen
(') rising adding an alkaline solution to a off in the presence of platinum black, filtering
solition of vanillin and acetone, then acidi filtrate the platinum black, then evaporating the
lying the solution to obtain a precipitate, (tissolving to an oil, then distilling the oil. then
the tissolving the precipitate in a solvent finally crystallizing the distillate in a solvent and
15 : ) ('ystallizing the vanillalacetone out of
the Zingilberone out of 55
the solution.
the solition, then dissolving the vanillalace 4. The method of preparing Zingiberone
tone crystals in a solvent and reducing the comprising a cling a 10% solution of caus
solution by means of hydrogen in the pres tic
elice of platinum black, filtering off the andsoda to a solution of vanillin and acetone
allowing the same to stand, then add
20 platin black, then evaporating the filtrate ing hydrochloric acid to the solution to
to an oil, then distilling the oil, then dis obtain
solving the listillate in a solvent and finally ing thea precipitate, precipitate, then filtering and wash
crystallizing the Zingiberone out of the so 'cilitate in alcohol,then then
dissolving the pre
crystallizing the
|tition.
25 2. The method of preparing Zingiberoni: Vanilia acetone out of the solution, then dis.
'(t) rising adding an allaline solution to a solving the vanillalace one crystals in ther,
Solution of Vanillin and acetone, the acidi trogel in the the
then 'educing solution by means of ivy
fying the solution to obtain a precipitate, then filtering ofpresence the
of platinum lack,
platinum black, the 7 (
the dissolving the precipitate in a solvent
30 an 'rystallizing the vanillalacetos out of evaporating the filtrate to an oil, the lis
the stilition, the dissolving the vanillalace tilling the oil, then lissolving the distillate
in a mixture of ether all etrole in ether
to the crystals in ether, then reducing the so and
littiol) by meals of hydrogen in the presence of thefinally crystallizing the vigilbero e out
solution.
of platinui black, then filtering of the ln islinnolly whereof I afix illy signature
platinum black, the evaporating the filtrate
to an oil, then distilling the oil, the dis in presence of twoIIwitnesses. ROS NOMIURA
solving the distillate in a mixture of ether Witnesses:
and petroleum, ether, and finally crystaliz
ig the Zingiberone out of the solation. I. F. IIA will Y,
M. M. cityu R.
40 3. The method of prepairing Zingiheroic