Aug. 7, 1945. W. J.

COTTON 2,381,210
PRODUCTION OF ZINGERONE.
Filed Aug. 20, 1943

INVENTOR.
teal. A 2.É.
BY

V-- /.4444
477 oa/way
Patented Aug. 7, 1945 2,381,210

UNITED STATES PATENT OFFICE 2,381,210

PRODUCTION OF ZNGERONE
William J. Cotton, Chicora, Pa., assignor to
Pennsylvania Coal Products Company, Petro
lia, Pa., a corporation of Pennsylvania
Application August 20, 1943, Serial No. 499,408
4 Claims. (C. 260-590)
The present invention relates to the produc dissolved out of the mixture by the caustic soda;
tion of Zingerone from vanillalacetone. the resulting sodium aluminate is then washed
One of the objects of the present invention is away, leaving a finely divided nickel catalyst.
to economically and efficiently produce zinger With the reactor in place, the rubber stopper
one from vanillalacetone in a relatively short 0 is tightly adjusted to the neck 2 of the flask,
time and in good yields of a substantially pure valve a controlling the entry of hydrogen by
product. means of the conduit into the flask f is closed;
It is an additional object of the present inven and valve 2a of air exhaust conduit 2 opened.
tion to synthesize the zingerone by hydrogena The conduit 2 is connected to a vacuum which
tion in the presence of a catalyst which because 0. is not shown, and the air content of the flask,
of its activity accelerates the reaction producing or as much thereof as possible, is removed from
good yields in relatively short periods of time. the flask. Thereafter, the valve 2 is closed.
Another object of the present invention is to The conduit is connected to a burette 6,
carry Out the hydrogenation of the vanillal which is provided with a valve 3a fitted on the
acetone in the presence of a hydrogen activated 5 conduit f3, said burette being also connected by
nickel catalyst so that when a ketonic solvent means of the conduit 5 to the leveling flask 4,
is used for the vanillalacetone, said solvent is said conduit 5. being provided with a valve
not hydrogenated to alcohol. member 5a adjacent the lower portion of the
Other objects of the invention will appear leveling flask 4, and a valve 5b adjacent the
from the following description: 20 end of the conduit which enters the lower por
The present invention will be described in con tion of the burette 6. The valve 3a is opened
nection with the accompanying drawing in and the leveling flask 4 is raised until the water
which level 6d. in the burette 6 rises to a point that
Figure 1 is a side view partially in section of practically fills the burette. Thereafter, the
an apparatus suitable for carrying out the in 25 Valve 3a is closed and the valve a opened, said
vention; and valve connecting with the hydrogen cylinder 7
Fig. 2 is a cross sectional view taken on line wherein there is provided a Source of hydrogen
2-2, looking in the direction of the arrows. under pressure. There is also provided a mer
Referring to the accompanying drawing, there cury cell 9 into which dips the leg i8, the lower
is provided a reactor which, as illustratively 30 portion of said leg being sealed in the mercury
set forth, in a two liter flask. The neck 2 of the 9a. If excessive pressure of hydrogen develops
flask is rotatively mounted in a bearing 3. in the System, then the System fails by blowing
Means are provided for agitating the contents said excess of hydrogen through the mercury
of the flask , Said means comprising a rubber Seal, thereby preventing the apparatus from
band 4 fastened at 5 to the cam arm 6, which is 35 bursting. With valve la open, hydrogen from
pivoted eccentrically at the pivot point 7 on the the hydrogen container passes through pipe
cam wheel 8, which is driven by the motor 9. 18, and through and over the barometric leg 20,
The reciprocation of the cam arm 6 serves to and then into the bottom of the hydrogen burette
agitate the contents of the reactor member . 40 16, valve 20a having been first opened. The
The charge may be introduced in the reactor lower portion 2 of the barometric leg 20 termi
with the latter either fastened in place, as nates, as shown in the lower part of the burette
shown in the drawing, or the retactor may be 6. The purpose of the barometric leg 20 is to
removed from its mounting and after charging prevent water from the hydrogen burette 6
reinserted in the bearing member 3. Illustra 45 from passing into the mercury trap 9 and
tively, there may be placed in the reactor 1, 200 through the pipe 8. As hydrogen rises in the
grams of vanillalacetone having a melting point burette 6, it displaces the water, forcing it into
of about 124° C., together with a 1000 cc. of ace the leveling flask f4 which should be lowered at
tone. To the solution of vanillalacetone dis Such a rate as to maintain the water level in
Solved in acetone, there may be added approxi 50 flask 4 at about the same height as the water.
mately 6 grams of Raney finely precipitated level in the burette 6. When the burette 6
nickel catalyst, that is 10 cc. of prepared sludge, is filled with hydrogen, valves 7a and 20a are
Said Raney catalyst being prepared by treating
the Raney mixture as it is commercially fur closed, and the leveling flask f4 carefully ad
nished with a caustic soda solution. During justed to the level the same as that in burette
the preparation of the catalyst, the aluminum is s f 6. The volume on the burette is read as well
2 2,381,210
as the barometric reading, and the temperature solved in any solvent which will not be affected
of the water in the leveling flask f A. by the hydrogenation under the conditions under
Thereafter, the valve a is opened and the which the reaction is carried out. Among the
leveling flask 4 is raised, thereby forcing the solvents that may be used are methanol, ethanol,
hydrogen from the burette into the reactor . 5 acetone, ether, petroleum ether, dioxan and the
As pressure develops in the reactor due to a com like. It is preferred to use a solvent in which the
pression of the hydrogen, the pressure is gradu Vanillalacetone is soluble to a maximum extent.
ally released by means of the valve 2a. In order For this reason it is preferred that the vanila
to ascertain the volume of hydrogen delivered to acetone be dissolved in acetone in preference to
the flask , the water level in the burette 6 is O ethanol. It is desired to point out that when the
raised to almost the top of the burette, then the VanillalacetOne is dissolved in solvents which
Water levels in burette 6 and in flask 4 are ad contain ketonic oxygen, as for example acetone,
justed to the same level, and the volume is then the pressure of the system must be adjusted
read on the burette 6. The difference between to prevent the hydrogenation of the ketonic
the initial and final readings is the volume of Oxygen or the solvent containing the same to
hydrogen forced in the reactor at the given alcohol. Therefore, in carrying out the present
barometer pressure and at the temperature of invention, the hydrogenation of the acetone or
the Water. Thereafter the valve a may be other ketonic oxygen solvent to alcohol is pre
closed and the reactor again evacuated by Vented.
connecting valve 2 to a vacuum if it is desired In the example herein set forth, a fairly con
to completely remove all the air in the system. centrated solution of vanillalacetone in acetone
In fact, by repeating this procedure a number of is used. While high concentration is preferable
times, the air in the system may be completely because increased capacity is obtained, it is not
displaced and if the readings are carefully taken necessary to work with concentrated solutions.
the percentage of air remaining in the system For example, 5 grams of vanillalacetone may be
may be accurately calculated. w dissolved in 100 cc. of 95% ethanol and the solu
In starting operations, the motor 9 is caused tion introduced into the reactor together with
to agitate the contents of the reactor , said motor an appropriate amount of Raney catalyst, as for
being connected to the rubber band 4 by the example 1 cc. of Raney nickel sludge.
assemblage of elements hereinbefore described. In accordance with one form of the present
In the manner hereinbefore set forth, hydrogen invention, a slurry of vanillalacetone may be
is forced into the reactor with the valve 2a hydrogenated in the presence of a finely divided
closed, there being maintained preferably a activated nickel catalyst. This slurry may be
slight pressure of hydrogen. Even at room tem obtained by dissolving as much of the vanilal
perature the hydrogen is rapidly absorbed by the acetone as possible in the solvent, as for example
VanillalacetOne. For the charge above set forth, acetone or ethanol, and then having present an
namely 200 grams of vanillalacetone and 1000 cc. excess of vanillalacetone, as for example 10 to
of acetone, the theoretical requirement of hydro 25% of undissolved vanillalacetone. The vanillal
gen is 24.9 liters at 712 millimeter barometer acetone in the presence of the hydrogen and in
pressure after correcting for the vapor pressure 40 the presence of a saturated solution of vanillal
of Water which in this case was 22 millimeters. acetone in the solvent becomes hydrogenated.
ASSuming that the burette 6 is a one liter burette, In carrying out the present invention, the hy
in the course of one reaction it will have to be drogen activated nickel catalyst may be used,
filled and emptied about twenty-five times. In and especially the Raney hydrogenated nickel
this example, the average time for absorption Catalyst may be used in amounts varying from
for one liter of hydrogen was four minutes and 3 to 12%, taken on the weight of the vanillalace
the average time for refilling the burette was one tone which is reacted. It is preferred to have 3
minute. Therefore, the total over all time was to 12% of the catalyst present during the reac
135 minutes, the actual time of the reaction being tion. However, it is not necessary to use new
less than two hours. In order to provide for a, catalyst for each reaction as the catalyst can be
slight excess of hydrogen, an additional 2.5 liters reused a great number of times. When opera
of hydrogen is used, making a total of 27.4 liters tions, indicate that the catalyst has been pois
or 110% of the theoretical amount of hydrogen. Oned, it may be removed from the reactor and
The purpose of this additional 10% of hydrogen 55
either revivified or discarded, depending on
is to insure sufficient hydrogen to obtain a sub which is cheaper. In one form of the invention,
stantially complete reaction. there may be automatically added to the reactor
After the hydrogenation is complete, the reac f for each bath a small proportion of new cata
tor f is removed from its bearing member, the lyst, this amount being about 1% to 5% of the
Contents thereof allowed to Settle, and the clear weight of the catalyst used.
supernatant liquor is decanted. The acetone is 60 It may be pointed out that the theoretical
removed by distillation over a water bath in the amount of hydrogen used for hydrogenation
usual manner. The residue after the removal of should only be slightly exceeded, since to use
the acetone is vacuum distilled at a suitable pres more than about 10% excess of the theoretical
sure, as for example 7 to 8 millimeters. The quantity of hydrogen involves the possibility of
yield of the crude Zingerone thus obtained was an initiation of reduction of the carbonyl groups
89.3% of the theoretical, and the crude had a present in the zingerone. Further, it is desired
melting point of 36° C. The crude zingerone is to State that the vanillalacetone should be sub
recrystallized from acetone in the usual manner. stantially completely hydrogenated, since if sub
The yield of recrystallized zingerone approxi 70 Stantial hydrogenation is not effected, vanil
mates 91 to 92% taken on the crude, or 82% over lalacetone appears as an impurity in the zin
all taken on the vanillalacetone charge to the re gerone, and further this increases the difficulty
actor . The melting point of the recrystallized of purifying the crude zingerone produced in
Zingerone ranges from 40.5 to 41.5 C. accordance with the present invention.
Instead of dissolving the vanillalacetone in ace 75 While the production of zingerone in acco d
tone, as set forth, the vanillalacetone may be dis ance with the present invention has been as
 2,381,210. 3
closed in connection with a process wherein room therewith finely divided Raney nickel catalyst,
temperature, that is, about 20 to 35°C., is used, subjecting the mixture to hydrogenation, and re
and substantially atmospheric pressure is used, COvering Zingerone from the reaction product.
it is within the province of the invention to carry 2. The method of producing Zingerone Com
out the process by using slightly higher tem prising forming a Solution consisting of Vanil
peratures and considerably higher pressures, lalacetone dissolved in acetone, mixing therewith
The temperature range may be from 0°C. to the finely divided Raney nickel catalyst, Subjecting
boiling point of the solvent, but preferably as the mixture to hydrogenation, and recovering
indicated above. The pressure may range from Zingerone from the reaction product.
slightly subatmospheric to about 10 atmospheres, 0. 3. The method of producing zingerone com
although preferably from slightly subatmospheric prising forming a solution consisting of vanil
to 3 atmospheres. lalacetone dissolved in ethanol, mixing therewith
The chemical reaction involved in this process, finely divided Raney nickel catalyst, Subjecting
expressed in the usual structural formula, is as the mixture to hydrogenation, and recovering
follows: 5 ZingerOne from the reaction product.
OE O 4. The method of producing zingerone com
prising forming a solution consisting of vanil
OCH OCI lalacetone dissolved in a solvent selected from
-- H --> the group consisting of methanol, ethanol, ace
20 tone, ether, petroleum ether and dioxan, mix
ÖH=CHCOCH
Wanilalacetone Hydrogen
C-C2COCE
Zingerone
ing therewith finely divided Raney nickel cata
lyst, and subjecting the mixture to hydrogena
What is claimed is: tion at a temperature Varying from 20° C. to
1. The method of producing zingerone com about 35° C., and under a presure varying be
prising forming a Solution consisting of vanil 25 tween about atmospheric pressure and about 10
alacetone dissolved in a solvent selected from atmospheres, and recovering the solvent and
the group consisting of methanol, ethanol, ace Zingerone from the reaction product.
tone, ether, petroleum ether and dioxan, mixing WILLIAM J. COTTON.