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Патент USA US2127660

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2,127,660
Patented Aug. 23, 1938 I
UNITED STATES PATENT OFFICE
2,127,660
"'“UNSATURATED ESTERS OF ~2-CHLOROALLYL
ALCOHOL
Gerald H. Coleman and Bartholdt C. Hadler,
.Midland, Mich., assignors to The Dow‘ Chemi
cal Company, Midland, Mich, a corporation of
'Michigan
No Drawing. Application October 23, 1937,.
Serial No. 170,647
8 Claims. (Cl. 260-469)
This invention concerns esters of 2-chloroallyl at 105°-10'l° C. under 4 millimeters pressure and
having a speci?c gravity of 1.253 at 20/4" 0., and
alcohol with unsaturated carboxylic acids; par
ticularly esters having the general formula
'
a refractive index,
n’,2= 1.530
Example 2_
R- ’C—O—CHz-C=CH2 1:
A mixture of 58.0 grams (0.50 mol.) of maleic
acid, 92.5 grams (1 mol.) of 2-chloroallyl alcohol,
.and 5 grams of benzene sulphonic acid was heated
All such esters are new compounds useful as inter
at 83°-91° C. for 6 hours. During the heating
10 mediates in the'preparation of other organic com
pounds and as modi?ers in the polymerization of benzene was added drop-wise to facilitate the dis
tillation of water from the mixture. The reacted
vinyl compounds, particularly styrene.
The unsaturated esters of 2-chloroallyl alcohol mixture was dissolved in benzene and washed with
may be prepared by, ‘ esterifying 2-chloroallyl dilute aqueous sodium bicarbonate solution and
alcohol with an unsaturated carboxylic acid, e. g. water. Benzene was removed by distillation and
wherein R is a hydrocarbon radical containing at
least one ethyienic linkage and n is an integer.
acrylic acid, methacrylic acid, crotonic acid, sorbic
acid, fumaric acid, citraconic acid, cinnamic aid,
furoic acid, etc. The esteri?cation may be car
ried out by heating a mixture of 2-chloroallyl
2O
alcohol and approximately one chemical equiva
lent of an unsaturated carboxylic acid, together
the ester product fractionally distilled. There
was obtained 80 grams (60 per cent of the theo
retical yield) of di-(Z-chlo'roallyl) maleate, a
colorless liquid distilling at _155°-160° C. under 5 20
millimeters pressure.
Example 3 ’
with a small proportion of a catalyst, e. g. approx
imately 0.01-0.04 molecular equivalents of a
strong acid, such as sulphuric or benzene sul
phonic acid, at a temperature of approximately
80°-120° C. Water is formed in the reaction and,
if desired, a water-immiscible organic solvent,
such as benzene or toluene, may be added, for the
purpose of promoting the vaporization and re
30 moval of water as an azeotropic mixture with the
_ solvent. The reacted mixture is treated with suf
?cient alkali to neutralize the acid contained
therein, after which the ester product is separated
by fractional distillation under vacuum.
The following examples illustrate a number of
ways in which the principle of our invention may
be employed, but are not to be construed as limit
ing the same:
Example 1
40
A mixture of 112.0 grams (1 mol.) of furoic
acid, 92.5 grams (1 mol.) ‘of 2-chloroal1yl alcohol,
and 5 grams of benzene sulphonic acid was heated
at 95°-105° C. for 6% hours in a flask ?tted with
dropping funneL'condenser, and receiver arranged
A mixture of 86.0 grams (1 mol.) of crotonic
acid, 92.5 grams (1 mol.) of 2-chloroallyl alcohol,
5
and 5 grams of sulphonic acid was heated at 96°
108° C. for 5 hours as in Example 1. The reacted
mixture was dissolved in benzene andwashed with
dilute aqueous sodium bicarbonate solution and
water. Benzene was removed by distillation and
the ester product fractionally distilled. There
was obtained 131.5 grams (82 per cent of the theo
retical yield) of 2-chloroallyl crotonate, a color
less liquid distilling at 65°~67° C. under 4 milli
meters pressure, having a speci?c gravity of 1.102
at 20/40 0., and a refractive index,
h§3= 1.4690
Example 4
A mixture of 69 grams (0.47 mol.) of cinnamic
acid, 43 grams (0.47 mol.) of 2-chloroallyl alcohol,
and 2.5 grams of benzene sulphonic acid was
heated at 93°-l05° C. for8 hours as in Example 1.
The reacted mixture was dissolved in benzene,
Washed and the Product recovered as in Example
in such manner as to permit distillation of water
1~
from themixture. During the heating benzene
was added drop-wise to facilitate the distillation
of the theoretical yield) of 2-chloroallyl cinna
mate, a colorless liquid distilling at 153°-155° c.
of water.
under 4 millimeters pressure, having a Specific
50
gravity Of
at 20/40 C., and a refractive index,
n23: 1_ 5775
The reacted mixture was allowed to
50 c001’ dissolved in benzene and washed unce
250 cc. of a 5 per cent aqueous sodium bicarbonate
solution and once with 250 cc. of water. Benzene
was removed by distillation and the ester product
distilled under vacuum. There was obtained
56 2-chloroallyl furoate, a colorless liquid distilling
There was Obtained 63-0 gl‘ams (59 per cent
Example 5
A mixture of 44.3 grams (0.25 mol.) of beta
benzoyl-acrylic/acid, 23.1 grams (0.25‘ mol.) of
2,127,660
z-chloroallyl alcohol, and 2 grams of benzene
sulphonlc acid was heated at 85°-88° C. for 4%
hours as in Example 1. The reacted mixture
was dissolved in benzene, washed, and the product
recovered as in Example 1. There was obtained
10
2-chloroallyl beta-benzoyLacrylate, a colorless
liquid which distills at approximately 175°—l85° C.
under 4 millimeters pressure, and which poly
merizes during distillation to a dark-brown, brit
tle solid, soluble in acetone, benzene, carbon tetra
chloride and other organic solvents.
Other unsaturated esters of 2-chloroallyl al
cohol may be prepared from 2-chloroallyl alcohol
and unsaturated carboxylic acids.’ For example,
2-chloroallyl alcohol may be reacted with furyl
4. An unsaturated carboxylic acid ester of 2
chloroallyl ‘alcohol having the general formua
c1
0
0
01
I
ll
[é —"O-—CH2-—- b =CH|
CHa=C-—CHz—O-C—R—
wherein R represents a hydrocarbon group con
taining at least one ethylenic linkage.
5. An unsaturated carboxylic acid ester of 2~
chloroallyl alcohol having the general formula
/0
c1
R-——C:Q_\CH:-—é=CH:
10
wherein R represents an aralkylene radical con
taining at least one ethylenic linkage.
6. 2-chloroallyl cinnamate, a colorless liquid
acrylic acid to produce z-chloroallyl furylacrylate ; - distilling at approximately 153°-155° C. under 4
with oleic acid to produce z-chloroallyl oleate;
with allylacetic acid to produce 2-ch1oroallyl a1
lylacetate; with linoleic acid to produce 2-ch1oro
allyl linoleate; with beta-chloro-acrylic acid to
millimeters pressure, and having a speci?c
gravity of 1.171 at 20/4° .C. and the formula
produce 2-chloroallyl beta- chloroacrylate; etc.
20
Other modes of applying the principle of our
invention may be employed instead of those ex
plained, change being made as regards the ma
terials employed, provided the ingredients stated ‘
by any of the following claims or the equivalent
of such stated ingredients be employed.
We therefore particularly point out and dis
tinctly claim as our invention:—‘
30
1. An ester of 2-chloroally1 alcohol with an
unsaturated carboxylic acid.
2. An unsaturatedcarboxylic acid ester of 2
chloroallyl alcohol having the general formula
/<>
$1
)
R—-(C£O—~CHr-C=CH2 ?
‘
.
'7. 2-chloroallyl crotonate, a colorless liquid dis
tilling at 65°-67° C. under 4 millimeters pressure,
and having a speci?c gravity of 1.102 at 20/4“ 0.,
and the formula
0
c1
CH:—CH=CH—C€O—CHz—é=CHz
8. Di-(Z-chloroallyl) maleate, a colorless liq
uid distilling at approximately 155°-160° C. under
5 millimeters pressure, and the formula
wherein R represents a hydrocarbon group con
taining at least one ethylenic linkage, and n
represents an integer.
3. An unsaturated carboxylic acid ester of 2
40
chloroallyl alcohol having the general formula
/
0
_.
.
Cl
R—c:0—om—<|3=cm
wherein R represents a hydrocarbon group con
taining at least one ethylenic linkage.
25
GERALD H. COLEMAN.
BARTHOLDT C. HADLER.
30
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