ljatented Nov. 7, 195.

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. 260599)

staying in the pink'range of phenolphthalein in

' This invention relates to the preparation of

cinnamaldehyde by the alkaline catalyzed con

dicator. The pH of the reaction mixture tends

densation of acetaldehyde and benzaldehyde ac

cording to the equation '_
.

0110I

omcno

to fall due to the formation of benzoic acidfrom '

Y ,

the benzaldehyde. .At the enclof the reaction

the mixture is slightly acidi?ed to remove the

alkali and then is made slightly basic by the ad
dition of sodium bicarbonate., In practice it has
been found easier to. acidify and then make

OH_-

CH=CHCO + 1120

,-

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 acetaldehyde gradually to the benzaldehyde.

The unreacted benzaldehyde can be recovered

by fractional

A reversal in the order of addition, or the simul

taneous mixing, of the reagents results in low
yields, i. e., on the order of 18, and 49%, respec
tively. 5-

distillation

and in the same

fractionation, cinnamaldehyde is obtained in a

state of -high purity leaving behind high boiling
by-products.

'

The duration of theperiod of time in which

the acetaldehyde is added to the reaction mix

Preferably, the reaction is carried out at a

moderately elevated temperature such as '70. C.,
although this reaction temperature may be

ture materially affects theyield of cinnamalde

hyde obtained. For the batch size and e?icient
stirring, as set forth in Example. 1, the preferred
addition time is 90 minutes, although this addi

varied from 60-80 C. without too substantial a

loss in yield. As usual in this condensation a di
lute alkalicatalyst is used, such as sodium hy

tion time may be varied from 1 hour to 2 hours

without too substantial a loss in yield. When
the addition time is lowered from 90 minutes to

droxide, potassium hydroxide, lithium hydroxide,

trimethyl benzyl~_ ammonium hydroxide, etc.
The addition of the acetaldehyde to the benz

aldehyde avoids'having present at'any time an

excess of acetaldehyde and thereby minimizes
the self-condensation of the acetaldehyde as well
as the further condensation of cinnamaldehyde 30

with acetaldehyde.

>_ By vcondensing a molecular'proportion of the

acetaldehyde with a slight excess over a molecu

20 minutes the yield falls from 81% to 72%.

When the addition time is increased from 90
minutes to 3 hours the yield falls from 81% to
68%.

..

vThe duration of the period of time subsequent

to the addition of the acetaldehyde, and during
which the reaction mixture is stirred while main

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

.iorniation of high boiling products which may be

> in Example 1, the preferred'duration of the 'pe

riod of time subsequent to 'the addition. of .the '-
'acetaldehyde and during which the reaction mixe '

formed in part if the acetaldehyde were in excess

to condense with formed cinnamaldehyde as
aforesaid.

The acetaldehyde used in this process may be

ture is stirred While maintaining the tempera

40 ture at 70 C., is 90 minutes, although this pe

riod of time may be varied from 30 minutes to 3

hours without too substantial a loss in yield.
When this period of time is increased to 4' hours

added as a liquid or a gas or in aqueous solution.

Further, it is not necessary that the benzaldehyde

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 isconveniently done by

55

aldehyde is 5:1, although the ratio may be varied

$2,529,186
analysis the cinnamaldehyde is found to be 90%

from 6.5:1 to 2.511 without too substantial a loss

pure.
While I have shown and described various em

in yield. Decreasing the reaction volume in

creases the productivity of the equipment used.

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

The high boiling by-product which is recovered

after the removal of the unreacted benzaldehyde
and the cinnamaldehyde is a pleasant smelling

invention and the scope of the appended claims.

oil'which issuitable as a masking odorant for

Having thus described my invention, what I

claim and desire to protect by Letters Patent is:

such industrial products as rubber.

The following example is given to illustrate the

invention.

10

'

> 1. A method for preparing cinnamaldehyde

which consists in heating a mixture of benzalde

Example

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

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

thereto acetaldehyde over a period of time of

can be cooled by tap water, and whose tip is in

from one hour to two hours, the amount of benz

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.

heating the resulting mixture at the same temper

atureufor a period of time of from thirty minutes

7 water.
of

aldehyde exceeding that molecularly equivalent

to the total acetaldehyde employed, thereafter

to three hours, agitating vthe mixture throughout

The temperature of the mixture is

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

heating steps, maintaining. a, molecular excessof v .

.

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

said heating steps, maintaining the pH of the re

action mixture atfrom 8.011012 throughout. said

benzaldehyde over acetaldehyde in the reaction

mixture throughout said heating steps, andfrle
covering cinnamaldehyde from, the resulting re
action mixture.

'

'

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

and a. half at thesame temperature.
3?- illhehreaction'mixture is then acidi?ed to pH 4 40 Periqdsof time. is substantially 90 mineteawhere
in the weight ratioriof aqueous alkali medium to
with 10% aqueous sulfuric acid solution, and al
benzaldehyde plus acetaldehyde is substantially
lowed to cool to room temperature; the excess sul
51.1 and wherein- said. temperature is; substan
furi'clv acid and anybenzoic acid present is neu
tially 7.0? C.
,
.

V
>
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
REFERENCES cumin.

solvent (200v cc. of benzene) and the whole is sub-'

sequently. poured into a sep'aratory funnel. The

The following references are of record
the
organic layer is separated; most of the solvent
?le or this patent?
'
I -
i
and all the water is removed by atmospheric ?ash 50,,
distillation, and the residue consisting of; benzal
.Nllmber
_
- 7
Date-r,
dehyde, cinnamaldehyde, and high boiling. by

UNITED STAT-Es PATEETS.

products, fractionated invacuo.

i ,

531,053

,__ Apr; 20km!

''..:The products are: 63.9 g. benzaldehyde boiling

I
l'
. I FQBEIGNJPATENTS
Knoll et. a1
42-?
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,'
Numbi'i
eounir'r
,
' and a: higher boiling residue of 25 g. This repre

sentsa yield of 81 %_ and a conversion of 46%. By

melee? V

'

Date.