ljatented Nov. 7, 195.

0
2,529,186

' UNITED STATES PATENT OFFICE ‘

PREPARATION OF CINNAMALDEHYDE
Henry H.’ Richmond, Guelph, Ontario, Canada, ,
assignor to United States Rubber Company,
New York, N. Y., a corporation of New Jersey
No Drawing. Application April 5, 1947,
> Serial No. 739,661
3 Claims. (01. 260—599)
1 2
' This invention relates to the preparation of staying in the pink'range of phenolphthalein in
cinnamaldehyde by the alkaline catalyzed con dicator. The pH of the reaction mixture tends
densation of acetaldehyde and benzaldehyde ac to fall due to the formation of benzoic acidfrom '
cording to the equation '_ Y , the benzaldehyde. .At the enclof the reaction
. _ p H the mixture is slightly acidi?ed ‘to remove the
0110- ‘ OH_- CH=CHCO + 1120 alkali and then is made slightly basic by the ad
I + omcno -— ,- -
dition of sodium bicarbonate., In practice it has
been found easier to. acidify and then make
faintly alkaline ‘with sodium bicarbonate, than
It has» been found that a high yield (i. e., on 10 to reach the same pH by addition of acid; this
the‘ order of 75-85%, based on the benzaldehyde) procedure removes any- benzoic acid present.
of cinnamaldehyde can-be obtained by adding The unreacted benzaldehyde can be recovered
the acetaldehyde gradually to the benzaldehyde. by ‘fractional distillation and in the same
A reversal in the order of addition, or the simul fractionation, cinnamaldehyde is obtained in a
taneous mixing, of the reagents results in low state of -high purity leaving behind high boiling
yields, i. e., on the order of 18, and 49%, respec by-products. .
tively. 5-‘ ' The duration of theperiod of time in which
Preferably, the reaction is carried out at a the acetaldehyde is added to the reaction mix
moderately elevated temperature such as '70‘.’ C., ture materially affects theyield of cinnamalde
although this reaction temperature may be hyde obtained. For the batch size and e?icient
varied from 60-80” C. without too substantial a stirring, as set forth in Example. 1, the preferred
loss in yield. As usual in this condensation a di addition time is 90 minutes, although this addi
lute alkalicatalyst is used, such as sodium hy tion time may be varied from‘ 1 hour to 2 hours
droxide, potassium hydroxide, lithium hydroxide, without too substantial a loss in yield. When
trimethyl benzyl~_ ammonium hydroxide, etc. the addition time is lowered from 90 minutes to
The addition of the acetaldehyde to the benz 20 minutes the yield falls from 81% to 72%.
aldehyde avoids'having present at'any time an When the addition time is increased from 90
excess of acetaldehyde and thereby minimizes minutes to 3 hours the yield falls from 81% to
the self-condensation of the acetaldehyde as well 68%. . . .. I

as the further condensation of cinnamaldehyde 30 vThe duration of the period of time subsequent
with acetaldehyde. to the addition of the acetaldehyde, and during
>_ By vcondensing a molecular'proportion of the which the reaction mixture is stirred while main
acetaldehyde with a slight excess over a molecu taining the temperature at 70° C., materially afr
lar proportion of the benzaldehyde, there 'is fects the yield of the cinnamaldehyde obtained.
maintained throughout, an excess of benzalde P35 For the batch size and e?icient stirring described
hyde which tends to prevent to some extent the > in Example 1, the preferred'duration of the 'pe
.iorniation of high boiling products which may be riod of time subsequent to 'the addition. of .the '- ’
formed in part if the acetaldehyde were in excess 'acetaldehyde and during which the reaction mixe '
to condense with formed cinnamaldehyde as ture is stirred While maintaining the tempera
aforesaid. . ‘
40 ture at 70° C., is 90 minutes, although this pe
The acetaldehyde used in this process may be riod of time may be varied from 30 minutes to 3
added as a liquid or a gas or in aqueous solution. hours without ‘too substantial a loss in yield.
Further, it is not necessary that the benzaldehyde When this period of time is increased to 4' hours‘
be highly puri?ed. Technical grades of benz the yield falls from 81% to ‘70%.
aldehyde containing small amounts of chlorine 45 The ratio of the total Weight of the aqueous ,
may be used, since the chlorine containing im alkali medium to the weight of benzaldehyde and
purities are removed in the ?nal fractionation of acetaldehyde that are condensed, affects the
the cinnamaldehyde. The quality of the cin yield obtained and the reaction time, since this
namic aldehyde obtained is very good, analyzing factor in addition to the concentration of the
as high as 99 % pure and is suitable for the prepa 50 alkali in the aqueous medium regulates the ratio
ration of flavors and perfumes. of benzaldehyde and acetaldehyde to the hy
The pH of the reaction mixture should be droxyl ion present which acts as catalyst.’ The
maintained by the addition of alkali from time preferred ratio of the weight of aqueous alkali
to time in the region of V8 to 12, and especially medium to the Weightof benzaldehyde and acet- '
from'BB to 10. This is‘conveniently done ‘by 55 aldehyde is 5:1, although the ratio may be varied
 $2,529,186
from 6.5:1 to 2.511 without too substantial a loss
in yield. Decreasing the reaction volume in
creases the productivity of the equipment used.
The high boiling by-product which is recovered
after the removal of the unreacted benzaldehyde
and the cinnamaldehyde is a pleasant smelling
oil'which issuitable as a masking odorant for
such industrial products as rubber. ‘
The following example is given to illustrate the
invention. '
Example
To a 2000 cc. three-necked ?ask equipped with
a thermometer, a re?ux condenser, a stirrer, and
a calibrated addition burette, jacketed so that it
can be cooled by tap water, and whose tip is in
serted below the surface of the reaction mixture,
there is introduced 150 g. of technical benzalde
hyde and a solution of 3.0 g. of sodium hydrox
ide in from 500 to 1300, preferably about 1000 cc.
7 water. The temperature of the mixture is
of
raised, with stirring, to 70° C. The temperature '
‘ITO-“'0; is about the optimum temperaturefor high
yields‘ concurrent with the other conditions de
scribed in this example but the reaction can be
carried out in the range 60=80° C. Maintaining
this temperature, 48 grams- of acetaldehyde is in
troduced through the addition burette, uniformly
over a p'eriodof 11/22 hours. This constitutes the
period for one-half of the reaction. The alkalin- d
ity of the reaction mixture-is periodically checked
and adjusted so that it is pink to phenolphthalein
indicator by the addition of small quantities of
sodiumhydroxide solution. 'This acidi?cation is
due-to the oxidation of benzaldehyde to benzoic
acid. The optimum alkalinity is that indicated
by: thepink color of the phenolphthalein indica
torr The stirring is continued for another hour
and a. half at thesame temperature.
3?- ill‘hehreaction'mixture is then acidi?ed to pH 4 40 Periqdsof time. is substantially 90 mineteawhere»
with 10% aqueous sulfuric acid solution, and al
lowed to cool to room temperature; the excess sul
furi'clv acid and anybenzoic acid present is neu
tralized with an excess of sodium bicarbonate
bringing the pH to 8. The slightly alkaline mix 45
ture" is ‘extracted with a, water insoluble organic
solvent (200v cc. of benzene) and the whole is sub-'
sequently. poured into a sep'aratory funnel. The
organic layer is separated; most of the solvent
and all the water is removed by atmospheric ?ash 50,,
‘distillation, and the residue consisting of; benzal
dehyde, cinnamaldehyde, and high boiling. by
products, fractionated invacuo. . v
''..:The products are: 63.9 g. benzaldehyde boiling
at 63? C. and15. mm. nD‘=1.546; 86.9 g. cinnamale 55 £1,715,822
dehyde boiling at 123° C. and 15v mm. n1);1.622,'
' and a‘: higher boiling residue of 25 g. This repre
sentsa yield of 81 %_ and a conversion of 46%. By
analysis the cinnamaldehyde is found to be 90%
pure.
While I have shown and described various em
bodiments of the invention, it is to be understood
that the invention is susceptible to other modi
?cations which appear Within the spirit of the
invention and the scope of the‘ appended claims.
Having thus described my ‘invention, what I
claim and desire to protect by Letters Patent is:
10 > 1. A method for preparing cinnamaldehyde
which consists in heating a mixture of benzalde
hyde and aqueous alkali solution of a concentra
tion of from 0.23 to 0.6% by weight at a tempera
ture of from 60 to 80° C. while gradually adding
thereto acetaldehyde over a period of time of
from one hour to two hours, the amount of benz
aldehyde exceeding that molecularly equivalent
to the total acetaldehyde employed, thereafter
heating the resulting mixture at the same temper
atureufor a period of time of from thirty minutes
to three hours, agitating vthe mixture throughout
said heating steps, maintaining the pH of the re
action mixture atfrom 8.011012 throughout. said
heating steps, maintaining. a, molecular excessof v .
. benzaldehyde over acetaldehyde in the reaction
mixture‘ throughout said heating steps, andfrle
covering cinnamaldehyde from, the resulting re
action mixture. ' v ‘ '
2. The method (if/claim 1 wherein said cinnam
aldehyde is recovered from the reaction mixture
and from any, benzoic acid present therein by
acidifying the reaction mixture, neutralizing~vv the
acidi?ed mixture Wither; excess of; sesiium bie ,
carbonate and therebrneutrelizing any benzoic
acid present, and separately recovering cinnam
aldehyde and the unreacted benzaldehydev i“ .m
the resulting mixture by a method incIudingAf-rac}
tional distillation. ' '
"3. The processef claiml wherein each of said
in the weight ratioriof aqueous alkali medium to
benzaldehyde plus acetaldehyde is substantially
51.1 and wherein- said. temperature is; substan
tially 7.0?‘ C. , . ‘ V >
REFERENCES cumin. 7
‘The following references are of record the
?le or this patent? ' I - » i
UNITED’ STAT-‘Es PAT‘EETS.
.Nllmber ’_ - 7 Date-r“,
i ,
531,053 . ,__ Apr; 20km!‘
I l' . I FQBEIGNJPATENTS
Knoll et. a1 42-”? '
Numbi'i eounir'r , Date.
melee?» V .