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Патент USA US2409087

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Patented Oct. 8, 1946
Joseph Frederic Walker, Lewiston, N. Y., assignor
to E. 1. du Pont de Nemours & Company, Wil
mington, DeL, a corporation of Delaware
No Drawing. Application May 1,1943, ‘
Serial No. 485,361
'1 Claim.
(Cl. 260-464)
This invention relates to reactions between or
ganic carbonyl compounds and ethylenic unsatu
rated compounds, and to the novel chemical
products resulting therefrom. More particularly,
gives products di?erent in character from those
it is directed to certain novel reactions between
resulting when higher aldehydes are reacted.
aliphatic aldehydes, including aldehydes contain
_, I
Examples of aldehydes which may be utilized.
in my process are acetaldehyde,propionaldehyde,
ing alkyl, aryl, cycloaliphatic, and aralkyl sub
stituents, and acrylonitrile, and to the new and
butyraldehyde, isobutyraldehyde, valeraldehyde,
isovaleraldehyde, heptaldehyde, phenylacetalde4
useful chemical compounds resulting from these
" drogen. atom attached- to a carbon atom posi
tioned alpha to the aldehyde group, is not one of
the reactants which I employ in the reaction with,“
acrylonitrile, as I have found that formaldehyde
’ hyde, hydrocinnamaldehyde, etc.
It is an object of this invention to produce by
reaction of acrylom‘trile and aldehydes new and
valuable chemical compounds containing one or
more B-cyanoethyl groups attached to that car
bon atom which is positioned adjacent to the al
In the reaction it is possible to introduce one
?-cyanoethyl group in place of a hydrogen atom
attached to the carbon atom which is positioned
15 adjacent the aldehyde group or two or three 13
cyanoethyl groups may beintroduced where this
carbon atom contains two .or three replaceable
hydrogen atoms. Thus, with acetaldehyde, it is
dehyde group in the particular aldehyde reacted
with acrylonitrile. It is, moreover, another ob
ject of my invention to provide a method for car
possible to produce B-cyanoethyl acetaldehyde
rying out such reactions in the presence of alka
CNCl-IzCI-IzCHzCl-IO by introducing one B-cyano
line condensing agents. Another object of my 20 ethyl group in place of a reactive hydrogen atom
invention is to provide a method for preparing
positioned alpha to the aldehyde group. Similar
new chemical compounds, the aldehydonitriles
having the generic formula
ly, it is possible ‘to introduce two B-cyan'oethyl
groups to form y-formyl pimelonitrile
or tri-1,'1,l,-(pi-cyanoethyl)acetaldehyde by the
where R1 is hydrogen or methyl and R2 is hydro
gen, methyl, or p-cyanoethyl. These and still
further objects of my invention will be apparent
replacement of three reactive hydrogen atoms by
c-cyanoethyl groups. Of course where there are
less than three reactive hydrogen atoms on the
carbon atom adjacent the aldehyde group, as in
from the ensuing disclosure of certain preferred
embodiments thereof.
The aldehydes which, in accordance with my
invention, are reacted with acrylonitrile (vinyl
cyanide) are those having at least one active hy
drogen atom' attached to the carbon atom which
is positioned alpha to the aldehyde group. They
may be characterized generically as compounds
of the chemical constitution:
propionaldehyde or isobutyraldehyde the number
of ls-cyanoethyl groups replacing hydrogen on
this carbon atom cannot exceed the number of
reactive hydrogen atoms attached thereto.
In carrying out the reaction the acrylonitrile
and aldehyde are brought together in the pres
ence of a substance which is alkaline in reaction.
Any of the usual alkaline condensing agents have
been found effective in promoting the reaction.
These alkaline condensing agents are generally
more alkaline than sodium carbonate, although
with less alkaline compounds, such for example
wherein Y and Z represent hydrogen, alkyl, aryl, 45 as the alkyl amines, the reaction will proceed but
cycloaliphatic and aralkyl radicals, the radicals
generally at a slower rate. Among alkaline con
Y and Z being the same or different organic
When acrylonitrile is reacted with an aldehyde
of the above-identi?ed formula in which Y and
Z are both alkyl groups, the resultant product will
be a cyano-ethyl di-alkyl aldehyde in which the
two alkyl groups are joined to the carbon atom
alpha to the aldehyde group.
It is obvious from the foregoing de?nition that
formaldehyde, which does not have a reactive hy
densing agents which I have found particularly
useful in the process may be mentioned the ‘alkali
_metal and alkaline earth metal oxides, hydrox
ides, carbonates, hydrides, cyanides and alcohol
ates, as well as the alkali metals themselves, as
for example, metallic sodium. The'alkali metal
hydroxides and cyanides, as sodium hydroxide
and sodium cyanide, have been found particu
55 larly effective.
Generally the catalyst or condensing agent
stirrer, a re?ux condenser and a thermometer.
Five cubic centimeters of a saturated solution of
sodium hydroxide was added as alkaline condens
ing agent and the reaction mixture was agitated
and heated at re?ux temperature for two hours.
should be present in amounts sufiicient to render
the reaction mixture alkaline in reaction.
Amounts ranging from 0.5% to 10% by weight,
based on the weight of the reaction mixture, are
suitable. With relatively stronger alkaline con
densing agents, such as metallic sodium and the
alkali metal hydroxides and cyanides, amounts
A reddish-orange colored solution resulted, and
the re?ux temperature rose gradually during the
course of the reaction from 65° C. to about 80° C.
not exceeding 3% will ordinarily be found to give
Precautions were observed during the reaction to
satisfactory results.
10 maintain the temperature at or below 80° C. The
Since the reaction is exothermic in character,
resulting mixture, after cooling and neutraliz
after initially bringing the reaction mixture to
ing with hydrochloric acid, was distilled at a
the reaction temperature, one within the range
pressure slightly below atmospheric in order to
0 to 100° 0., further heating is unnecessary and
remove unreacted material.
cooling may be necessary to dissipate any exces 16
The residue was distilled at a pressure of 3
sive amount of heat developed. The reaction may
mm. A product boiling at 125° C. to 135° C. at
be carried out without employment of diluting
3 millimeters of mercury pressure was obtained,
agents, but if diluents are added I have found
along with a fraction boiling at 100° C. to 115°
inert liquids such as hexane, benzene, ether, and
C. at 3 millimeters of mercury pressure. The
petroleum ether most satisfactory.
20 latter was isobutyraldol. The higher boiling
The particular sequence of adding the reagents
product was identi?ed as a,a-dimethyl-~/-cyano
is unimportant, as all that is necessary in order
butyraldehyde. By operation in this manner
that the reaction may proceed is to bring the re
yields of ¢,a-dimethyl-'y-cyanobutyraldehyde cor
agents together in intimate admixture in the
responding to 35 to ‘10% of theory may be realized.
presence of the alkaline condensing agent. In 25
Example 3
practice it is generally preferred ?rst to mix the
aldehyde and acrylonitrile, and then introduce
Five cc. of a saturated solution of sodium hy
the alkaline condensing agent, at the same time
droxide was added cautiously to 212 grams (4
applying initial heating, if necessary, in order to
mols) of acrylonitrile heated under re?ux. To
bring the contents of the reaction vessel to a 30 the resulting mixture there was then added, in
temperature at which the reaction will proceed
small increments, 58 grams (1 mol) of propion
rapidly and smoothly.
aldehyde, after which the mixture was cooled
The products resulting by reaction of acryloni
and treated for recovery of product as in Ex
trile with aldehydes, the new aldehydonitriles, are
ample 1.
valuable as intermediates in the preparation of 35
Two products were obtained. The ?rst chem
a large number of organic compounds and for
ical compound boiled at 92° C. to 94° C. at 3 mil
other purposes, such as in the manufacture of
limeters of mercury pressure, and had molecular
plastic products.
weight and nitrogen content corresponding to
The following examples illustrate this inven
Example 1
a - methyl - 'y - cyanobutyraldehyde.
The second
40 chemical compound boiled at 135.5° ‘C. to 137°
C. at 3 millimeters pressure, and was identi?ed
as 'y-methyl-y-formyl-pimelonitrile. The yields
' In a one-liter ?ask ?tted with a stirrer, a re
flux condenser, a thermometer and a delivery
of the lower-boiling and higher-boiling products
tube extending to a point adjacent the bottom of
were 4.9% and 25.1 %, respectively.
the ?ask, there was placed 212 grams (4 mols) 45
of acrylonitrile. While stirring and heating un
' ‘Example '4
Acrylonitrile (4 mols) and acetaldehyde (2
der re?ux were continued, 3 cc. of a 50% solution
mols) were reacted as described in Example‘l
of sodium hydroxide was added to the acryloni
utilizing sodium cyanide as alkaline condensing
trile, after which 88 grams (2 mols) of acetal
dehyde was vaporized and the vapors passed 50 agent in place of sodium hydroxide.v The com
bined yield of 'y-cyanobutyraldehyde and 7-for
into the acrylonitrile. The rate of addition of
myl-pimelonitrile was 38% of the theoretical
the acetaldehyde was controlled so as to pre
based on the amount of acetaldehyde reacted.
vent heat surges. The addition required about
The new chemical compounds produced by re
2 to 3 hours, after which stirring was continued
for an additional period of one hour.
55 acting aldehydes and acrylonitrile, in accordance
with the process described, are those character
ized generically by the formula:
with dilute hydrochloric acid, and unreacted ma
terials were distilled off. The resulting residue
was subjected to vacuum distillation whereby
products boiling at 86° C. to 95° C., and 145° C. 60
The resulting mixture was cooled, neutralized
to 149° C., at a pressure of 3 millimeters of mer
cury were obtained. The lower boiling material,
identi?ed as y-cyanobutyraldehyde, had a molec
said compounds being aldehydonitriles. In this
generic formula R1 represents hydrogen or a
ular weight and nitrogen content corresponding
methyl group; and R2 represents hydrogen, meth
to those values for that compound. The higher 65 yl, or the p-cyanoethyl radical (CNCH2CH2—~).
boiling material was identi?ed as y-formyl
Various changes may be made in the process
pimelo-nitrile. The combined yield of the two
for reacting acrylonitrile with aldehydes as here
‘products was about 40 to 50% of theoretical.
in described which would come within the sco
or‘ my invention.
Example 2
I claim:
A mixture of 72 grams (1 mol) of isobutyraL
As a new chemical compound 'y-formyl pimelo
dehyde and 159 grams (3 mols) of acrylonitrile
was placed in a reaction ?ask provided with a
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