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Патент USA US2406590

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Patented Aug. 27, 1946
2,406,590
UNITED STATES "PATENT OFFICE
21.406590 .
7 METHOD OF PREPARING ALLYL
METH
ETHER ESTER?
Gestalt» F- D’Alelio,..No1-thamhion, Mass-i assign
or to General Electric Company, a corporation
of New York" '
No Drawing! Application June- 28, 1944,
serial No. 542,599
'1 (Elaine-.7 (Giza-11,811).
..
This invention relates generally to the prepa!
ration of new chemical compounds. Moreapar-i
ticularly the present inventionis directed to the
preparation of allyl and inethallyl ether‘- esters
which may be polymerized alone or with other
polymerizable compounds to yield new and useful
resinous products.
’
'
The chemical compounds produced in accord—
ance with this invention maybe represented
graphically by the generalformula i
2
after the other acid. is estori?od to obtain the
corresponding ester derivative.
Illustrative examples of hydrohalide acceptors,
or reasohts which act as bases; that. may be used
aretho' inorsoiuo has/es.’ e, a, the alkalhmetal
vht’sli'oiiiiiet. such as‘sodium hydroxide. potassium
hydroxide! at, alkaline-earth metal hydroxides,
e. a. calcium hrdroiiide, barium hydroxide, etc...
thé carbonates of such bases, and. organic bases,
1.9 for instance, ' trimethyl amine, tributyl amine,
dimethyl aniline, pyridine, quinoline, etc. I pre
for to use. sodium hydroxide as the hydrohalide
acceptor.
I
wherein R and R.’ may each be a‘ mgnber hr ‘the,
class consisting of hydrogen and‘ 1 .
radical. Thus in the formula
ethyl
maybe hydrogen
and R’ may be the methyl radical or vice versa.
Again R- and B! may both he hydrogen or both
may be. the methyl radical,
.
..
.
The allyl and math llyl. ether esters may he
used as. intermediates, in the. preparation of; other
compounds and are especially valuable
the
preparation of synthetic resinous compositions.
'
"
‘
-
,
The reaction between the allyl or methallyl
alcohol and the halogenated acetic acid may be
carried out in any suitable manner, but prefer
ably is e?ected in the presence of a suitable sol
vent or mixture of solvents. Although various
Solvents anti Solvent mixtures may be employed,
29 for economic teas-9H5 and because of its eminent
suitability, I prefer to use water. The reaction
may be carried out under a variety of tempera
ture and pressure conditions, for instance at nor
mal, sub-hormal or at elevated. temperatures, and
Thus, they may be polymerized alone .01: with 25 at atmospheric, sub-atmospheric or super-atmos
pheric pressures.
other nolym
.blo. ma rials to form resinous.
a degrees of . insoluhil:
was
‘ .asmmoré completely disclosed
antl'shooiiically claimed mr'conehdihs apnlie
cation, Serial No; 542,690. filed concurrently here
withiahd assigned to the asstenee of the QIQSQht
invention
.
V
In order that those skilled in the art better
may understand how the present invention may
be practiced, the following examples are given
by Way of illustration and not by way of limita
tion. ‘All parts are by weight.
Example 1
.
By. adding varying amounts. of these allyl and
This example illustrates the, preparation of
methallyl ether esters; to other nolymeriaahle ina
allyl
allyloxyacetate, the formula for which is
vserials. bubble-free castings are ob. and which. 35
in most cases, are ihiusihle and insoluble,v 9n
the. other hanol, castings prepared from. such
nolymerizahle materials alone, i. a, wit- out the
use of the. ether ester derivatives. usually yield
Parts M01 ratio
products. which areiilled. with bubbles and are
thermoplastic.
ether esters.
bit a.
Qhlorcacetic gcid__.-_ .
142
1
de?nite cross-linking property!
:
v. /
Several methods maybe employed to produce
the ‘aboveedosorihed other esters. It it is do ' d
that the two terminal groups oi the .oomhouhéi
Allyl alcohol‘
' '
261
3
123
2
(that is, the allyl group or the .hiethollyl group?
erabl-y
be. alike.prepared
then the by
etherestor
reacting.eerivativos
s oioht allyl
i1, .
The chloroacetic acid was added slowly at room
temperature (about 25° C.) to a stirred mixture
methallyloxyacetic'acid isl?rst iormedand theme
allyloxyacetate- The ?ltrate was then acidi?ed
containing the allyl alcohol, sodium hydroxide
and water- A very vigorous‘ reaction restated and
methallyl alcohol with
aluhwhalogoheted
acetic acid. iii-the presence of a suitable h¥9h9~ 59 a Solid. material “precipitated, "l‘ho reaction mix
ture-was refluxed at‘ its boiling temperature for
halide acceptor or reagent which acts as a. hate
If the terminal groups of the compounds are to
four h
‘hiterallo'wih the mixture to cool.
the precipitate, was removed, by ?ltration, leaving
be di?erent, e. g., one allyl and the other meth:
allyl, or vice verse; then‘allyloxyacetic m or
behind théf excess‘ allyl alcohol and the sodium
2,466,596
3
cohol in separate portions as disclosed in the
above examples, a mixture of allyl and methallyl
alcohols may be employed.
Although in the above examples only chloro
to allyloxyacetic acid and created an acid medium
for the esteri?cation process which followed.
Approximately 150 parts benzene were added to
the ?ltrate, and the water, resulting from the
esteri?cation process and from the initial addi
acetic acid is employed, other mono-halogenated
acetic acids and water-soluble salts of halo-alkyl
tion, was removed in the form of an azeotropic 5
mixture with the benzene in a continuous water;
removal esteri?cation apparatus. The elimina 10
tion of water from the system required twelve
hours of continuous boiling.
4
Instead of using allyl alcohol or methallyl a1
with 149 parts of aqueous 37.1% hydrochloric
acid which converted the sodium allyloxyacetate
.
monobasic acids may be employed, for instance
chloroacetic acid, bromoacetic acid and iodo
acetic acid, and the alkali-metal and ammonium
salts of such acids, e. g., the sodium, potassium,
lithium, etc., salts thereof.
Mono-halogenated
monobasic‘acids other than mono-halogenated
acetic acidiand water-soluble salts thereof may
Theoretically only two mols of allyl alcohol are
necessary for the reaction: one mol to obtain the
ether acid and another mol to yield the ether 15 be employed in a similar manner to obtain other
ester. However, an excess of allyl‘ alcohol is - ' iallyl and methallyl ether esters. Illustrative ex
' amples of these are:
employed to increase the yield of the ester.‘
A yield of 91 parts allyl allyloxyacetate was; j - ‘Alpha-chloropropionlc acid
obtained which boiled at 95°-97° C. at 18 mm.
Beta-chloropropionic acid
pressure and had a refractive index of 1.4435 at 20 Alpha-bromopropionic acid
20° C. The molar refractivity was 41.35 (calcu
Beta-bromopropionic acid
lated value=41.51) .
Alpha-iodopropionic acid
'
Instead of adding all the allyl alcohol .at the
Alpha-chlorobutyric acid
start, the allyloxyacetic acid may be formed ?rst
Alpha-chloro isobutyric acid
by reacting only one mol allyl alcohol with one 25 Beta-chlorobutyric acid
mol of chloroacetic acid by the above described
Beta-chloro isobutyric acid
method. The allyloxyacetic acid may then be
Alpha-.bromo isobutyric acid
esteri?ed by adding the remainder of the allyl
Phenyl chloroacetic acid
alcohol at the same time as the benzene.
Alpha-chloropentanoic acid
30 Beta-chloropentanoic acid
Example 2
Beta-iodopropionic acid
Methallyl methallyloxyacetate, the formula for
which is
O
.
I
CHr=C—GH2-0—CH2—-é—O—CHz-C=CH2
CH3
.
Alpha-tolyl beta-phenyl betaechlorobutyri'c acid
Alpha-naphthyl beta-chloro-phenyl beta-bromo
butyric acid
Beta-iodopentanoic acid
Alpha-benzyl alpha-cyclopentyl beta, beta'-di
.naphthyl beta-iodo propionic acid
CH3
is prepared in essentially the same manner as
described under Example 1 with the exception and the alkali-metal and ammonium salts of
that 324 parts methallyl alcohol are used instead 40' halo-alkyl monobasic acids such as above men
tioned by way of illustration, for example, the
of 261 parts allyl alcohol.
sodium, potassium, lithium, etc., salts of such
Example 3
halo-alkyl monobasic acids.
Allyl methallyloxyacetate, the formula for
» What I claim as new and desire to secure by
Letters Patent of the United States is:
which is
_1. The method of ‘producing allyl allyloxyace
tate which comprises preparing an aqueous mix
ture containing (1) allyl alcohol, (2) chloro
, acetic acid, and (3) a reagent which acts as a
50 base, said allyl alcohol and chloroacetic acid
is prepared in accordance with the procedureof; _ being present in the said mixture in the ratio of
Example 1 except that 72 parts (1 mol) meth
at least two mols of the former per mol of the
allyl alcohol are ?rst reacted with 142 parts
latter, effecting reaction between the said re
chloroacetic acid, 50 parts water and 123 parts
actants in the said aqueous mixture to obtain a
sodium hydroxide to yield sodium methallyloxy
of allyloxyacetic acid, thereafter acidifying
acetate. Upon acidi?cation the methallyloxy 55 salt
the reaction mass‘ containing the said salt to
acetic acid obtained is esteri?ed, as in Example
yield allyloxyacetic acid, effecting further reac
1, with 116 parts (2 mols) allyl alcohol to yield
tion in acid medium to obtain a reaction mass’
the allyl methallyloxyacetate.
'
containing allyl allyloxyacetate, while removing
Example 4
Methallyl allyloxyacetate, the formula for
which is
'
.
A
water. formed during esteri?cation, and isolating
allyl allyloxyacetate from the said reaction mass.
2. The method of producing methallyl methal
lyloxyacetate _ which comprises preparing an
, aqueous mixture containing (1) methallyl alco
65 hol, (2) chloroacetic acid, and (3) a reagent
which acts as a base, said methallyl alcohol and
chloroacetic acid being present in the said mix
is prepared as in Example 1 except that 58 parts
(1 mol) allyl alcohol are ?rst reacted with _142
parts chloroacetic acid, 50 parts Water and 123
parts sodium hydroxide to yield sodium allyloxy
acetate. Upon acidi?cation, the allyloxyacetic
acid obtained is esteri?ed, as in Example 1, with
144, parts _(2 mols) methallyl alcohol, to yield
methallyl allyloxyacetate.
ture in the ratio of at least two mols of the
former per mol of the latter, effecting reaction
between the said reactants in the said aqueous
mixture to obtain a salt ofemethallyloxyacetic
acid,v thereafter acidifying the reaction,‘ mass
containing the said salt to yield methallyloxy
aceticyacid, effecting further reaction in acid
medium to obtain a reaction mass containing‘
2,406,590
methallyl methallyloxyacetate, While removing‘
Water formed during esteri?cation, and isolating
methallyl methallyloxyacetate from the said re
one of said alcohols, in-acid medium while re
moving water formed during esteri?cation, and
separating the resulting ether ester from the said
action mass.
reaction mass.
3. The method of producing methallyl allyl
oxyacetate which comprises preparing an aque
ous mixture containing a reagent which acts as 1
5. A method as in claim 4 wherein the reagent
which acts as a base is an alkali-metal hydroxide.
6. The method of producing allyl allyloxyace
tate which comprises heating an aqueous mix
a base and equimolecular proportions of allyl
ture' containing sodium hydroxide, allyl alcohol
alcohol and chloroacetic acid, effecting reaction
between the said reactants in the said aqueous 10 and chloroacetic acid in an amount correspond
ing to about two mols sodium hydroxide and
mixture to obtain a salt of allyloxyacetic acid,
about three mols allyl alcohol per mol chloro
thereafter acidifying the reaction mass contain
acetic acid thereby to obtain sodium ‘allyloxy
ing the said salt to yield allyloxyacetic acid, add
acetate, thereafter acidifying the reaction mass
ing methallyl alcohol to the acidi?ed reaction
mass in an amount corresponding to one mol 15 containing the said sodium allyloxyacetate to
yield allyloxyacetic acid, effecting further reac
thereof, effecting esteri?cation of the said allyl
tion in acid medium to obtain a reaction mass
oxyacetic acid with the said methallyl alcohol in
containing allyl allyloxyacetate, while removing
said medium thereby to obtain a reaction mass
water formed during esteri?cation, and separat
containing methallyl allyloxyacetate, while re
ing the allyl allyloxyacetate from the said reac
moving water formed during esteri?catiomand
isolating methallyl allyloxyacetate from the said
reaction mass.
4. The method of producing compounds cor
responding to the formula‘
tion mass.
7. The method of producing allyl allyloxyace
tate which comprises adding chloroacetic acid
slowly to a stirred mixture containing allyl alco
hol, sodium hydroxide and water, the allyl
alcohol and sodium hydroxide being present in
where R and R.’ are each a member of the class
consisting of hydrogen and the methyl radical,
which comprises preparing an aqueous mixture
containing (1) a mono-halogenated acetic acid,
(2) an allyl alcohol corresponding to the formula
the said mixture in an amount corresponding to
about three mols allyl alcohol and about two
mols sodium hydroxide per mol chloroacetic acid
employed, heating the resulting aqueous mixture
under re?ux at the boiling temperature of the
mass for a period suf?cient to form sodium allyl
oxyacetate, ?ltering the cooled reaction mass to
remove solid impurities, acidifying the ?ltrate
containing sodium allyloxyacetate and excess
allyl alcohol with an excess of an aqueous solu
tion of hydrochloric acid thereby .to form allyl
where R is a member of the class consisting of
oxyacetic acid in acid aqueous solution, adding
hydrogen and the methyl radical, and (3) a re
benzene to the ?ltrate, effecting reaction between
agent which acts as a base, effecting reaction
between the said reactants in the said aqueous 40 the allyloxyacetic acid and allyl alcohol in acid
medium while admixed with the benzene, and
mixture to obtain a salt of an allyloxyacetic
separating the resulting allyl allyloxyacetate
acid, thereafter acidifying the reaction mass con
from the reaction mass.
taining the said salt to form the free acid there
GAETANO F. D’ALELIO.
of, effecting esteri?cation of said free acid with
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