вход по аккаунту


код для вставки
Patented Nov. vs, 1946'
" 2.410.551
FECE, ,v
mm, m warmer. names or mono
m mna-Aca'roxrrnorromo aoms
Che a. Rehberg, Glenside, and Charles H.
Fisher, Abington, Pm, ‘ assignors to United
States of America, as represented by the Secre- '
of Agriculture
No Drawing. Application December 8, 1944,
Serial No. 567,294
4 Claims. ((31. 260-4184)
(Granted under the-act of March 3, 1883, as
amendedAp'ril 30, 1928: 370 0. G. 757),
This application is made under the act of
March 3, 1883. as amended by the act of April 30,
of compounds that are usefulv as solvents, plas
1928, and the invention herein described, if pat
intermediates and as starting materials in the‘
production of allyl and substituted allyl acrylates .
which are substances polymerizable into plastic,
ticizers, insecticides, insect repellants, chemical
ented, may be manufactured and used by or for
' the Government of the United States of America
for governmental purposes without the payment
semi-solid, or solid materials useful in industry -
to us of any royalty thereon.
This is a continuation in part of our copend-i'
because of their tensile strength,,elasticity.{plas
ticity, resistance to water, organic liquids and
gases, and because of other desirable properties.
It is well l-rnownv (Burns, Jones and Ritchie, J.
ing application for patent, Serial No. 474,757, filed
February 4, 1943.
' -
Our invention relates tonew and useful allyl
and substituted allyl esters of lactic and alpha
Chem. Soc. 1935, 400-6, 714-7; Claborn, U. S.
2,222,363, Nov. 19, 1940; Claborn, U. S. 2,229,997,
Jan. 28, 1941; Smith, Fisher, Ratchford and Fein,
Ind. Eng. Chem. 34, 473-9 (1942)) that methyl
acetoxypropionic acids, namely, allyl lactate,
beta-methallyl lactate (hereinafter referred to as
“methallyl lactate”), beta-chloroallyl lactate, 15 alpha-acetoxypropionate can bev decomposed
gamma-chloroallyl lactate, methyl vinyl carbinyl
thermally to yield as a principal product methyl
lactate. crotyl lactate, ally! alpha-acetoxy
acrylate, which can be converted by polymerize?
propionate. beta-methallyl alpha-acetoxypro
tion into substances useful in theplastlcs and
plonate (hereinafter referred to as “methallyl
related industries. However, the alkyl‘ alpha
alpha - acetoxypropionate"), beta -‘chl0roa1lyl 20
,alpha - acetoxypropionate, gamma - chloroallyl
alpha-acetoxypropionate, methyl vinyl carbinyl
alpha - acetoxypropionate, and crotyl alpha
acetoxypwropionate, having the formulae:
allyl lactate
25 vthan the a'crylates, and because the alkyl acry
lates formed yield polymers which lack the prop
erties considered desirable in industry.
We have found that the presence of an ole?n
linkage between the beta and gamma carbon
30 atoms of the alkoxy group decreases the undesir-v
methallyl lactate
beta-chloroallyl lactate
able side reactions encountered in the pyrolysis of
gamma-chloroallyl lactate
the alkyl alpha-acetoxypropionates of higher
molecular weight, and that, owing to the char~
acteristics of the ally] and substituted allyl radii
cals and their, esters, their alpha-acetoxypro- >
methyl vinyl carbinyl lactate
pionates can be converted readily and in good
yields into allyl and substituted allyl acrylates
crotyl lactate
(as shown below), which can be polymerized and
interpolymerized into materials useful in industry.
ally] alpha-acetoxypropionate
cmcoocmcrm COOC'HzCKZ?) :CH:
methaliyl alpha-acetoxypropionate
cnscoocmcmwoocmcwn :cm
cmcoocmcm)coocmtcmycmn Pyrolysis
Ally] or substituted allyl
beta-chloroallyl alpha-acetoxypropionate
acetoxyproplonates of higher molecular weight
have been observed to .be unsuitable for produc
tion of the corresponding alkyl acrylates because
of the preponderance of undesirable reactions
which lead to the formation of products other
gamma-chloroallyl alpha-acetoxypropionate
methyl vinyl carbinyl alpha-acetoxypropionate
crotyl alpha-acetoxypropionate
The object of our invention is the production 56
Ailyl or substituted allyl acryiair-
(where R is hydrogen, a
halogen or an. alkyl group)
Thus we have found that‘allyl, methallyl, chlo
roallyl (of the beta and gamma variety), methyl
vinyl carbinyl, and crotyl lactates, and allyl, meth- ' -
allyl, chloroallyl (oi the beta and gamma variety).
methyl vinyl carbinyl, and crotyl alpha-acetoxy
propionates are new and useful compounds, which.
are solvents and plasticizers, and which are read
ily convertible into the corresponding acrylates
and polymers
interpolymers thereof;
4 .
Allyl lactate can be made by the interaction
g.) of beta-methallyl alcohol 143 g. of ester,
this being 33 percent or the theoretical amount.
of lactic acid and aliyl alcohol or by treating me
tallic salts of lactic acid with an aliyl halide.
As before, more 0! the ester was obtained by
Methaliyl lactate can be made from lactic acid
treating the distillation residue with beta-meth
and methallyl alcohol by esteri?cation, from an 5 ylaliyl alcohol, re?uxing and distilling.
alkyl lactate, such as methyl or ethyl lactate and
Example IV.-Five moles (450 g.) of lactic acid
methallyl alcohol by aicoholysis, or from a metal
and 5.5 moles (396 g.) of beta-methallyl alco
lactate, such as sodium lactate, and a beta~meth
hol were treated as in Example I, the yield of '
aliyl halide. Methyl vinyl carbinyl, beta-chloro
ester being 212 g. The recovered alcohol was
allyl. and crotyl lactates are prepared by‘the in 10 then returned to the reaction ?ask containing the;
teraction of lactic acid and the respective alco
hols, while gamma-chloroallyl lactate can be con
yeniently prepared by the action oi‘ gamma
chloroallyl alcohol or methyl lactate.
lactic acid ‘residue and re?uxed for several
hours. Distillation then gave 115 g. of ester. A
can be prepared from allyl and methallyl lac
tates, respectively, by acetylation with any of the
alcohol and ice. of phosphoric acid raised the
yield in the sixth period to 29 g. A further addi
third period oi re?ux of alcohol and lactic acid
residue yielded 39 g. of ester, a fourth yielded 34
Allyl and methallyl alpha-acetoxypropionates is g., and a ?fth, 16.6 g. Addition of 50 cc. of fresh
common acetylating agents, such as acetic an
tion or 100 cc. of alcohol gave a yield of 14 g. in
hydride. They can also be prepared by treating
the ?nal reaction period, the total yield being
aipha-acetoxypropionyl chloride or‘ alpha~acet 20 460 g., or 64.6 percent of'the theoretical. The
oxypropionic anhydride with ally] and methaliyl
product was collected at 77-79° C. under 11 mm.‘
alcohol, respectively. Beta-chloroallyl, gamma
- chloroallyl, methyl vinyl carbinyl, and crotyi al
Beta-methallyl lactate is a clear, colorless,
pha-acetoxypropionates can'be conveniently pre
mobile liquid at room temperature, with mild
pared by treating the corresponding iactates with g5 odor; having boiling points of 69° C. under 8
an acetylating agent such as acetic anhydride.
The ,iollowing are several examples or the in
mm. and 78° C. under 11 mm. of pressure; having
Example I.-~Two moles (180.2 g.) of essentially
100 percent lactic acid, 2.2 moles (127.8 g.) oi‘ 30
allyl alcohol, 200 cc. of benzene and 3 cc. of con
centrated sulfuric acid were re?uxed three hours
a speci?c gravity of 1.0181 at 20° C., and having a
refractive index for the yellow sodium line of
1.4389 at 20° _C..
Example V.—To 1.5 moles (195 g.) of allyl lac
tate there was slowly added, with stirring, 1.85
.moles (168 g.), 10 percent excess, of acetic an
hydride. The mixture was warmed to 50-60" C.
to start the reaction, after which cooling was
while water was continuously removed as formed
by use of a trap. Benzene and unreacted ailyl
alcohol were removed by distillation under about 85 used to keep the temperature below 100-110° C. :
20 ‘mm. pressure, after which allyl lactate was
Alter standing an hour, the mixture was irac
distilled under 1 mm. pressure, its boiling point
tionated under a pressure or 7 mm., the product
under this pressure being 27-29" C. The yield
being collected at 80-81° C. The yield was 230
was 88 g., or 34 percent or the theoretical. More
g., or 89 percent of the theoretical.
or the ester, allyl lactate, was obtained by adding co Ailyl alpha-acetoxypropionate is a clear, color
allyl alcohol, benzene and acid catalyst to the
distillation residueLr'e?uxing and then distilling
less, mobile liquid of slight, though pleasant.
odor; having a boiling point of 81“ C. under 7
mm.; having a specific gravity of 1.0544 at 20°
_ Example II.-Two moles (180.2 g.) of essen
C.: and having a refractive index for the yellow
tialiy 100 ‘percent lactic acid was dehydrated by 45 sodium line of 1.4270 at 20° 0.
re?uxing with benzene, a trap vbeing used to re
Example VI.--Using essentially the procedure
move water. After complete removal or water
described in Example V. except that 1-2 cc. phos
(34 cc.), 6 moles of allyl alcohol was added and
phoric ‘acid was used as a catalyst and the tem
the mixture was re?uxed several hours. The ben
perature was maintained at 60-80° 0.. there was
zene and excess alcohol were then removed by 50 obtained from 1.5 moles of beta-methallyl lac
vfractional distillation, the ?nal stage being car
tate and 1.8 moles of acetic anhydride 8. yield of
ried out under a pressure oi.’ about 20 mm. The
260 g. of beta-methallyl alpha-acetoxypro
allyl lactate was then distilled at 60° C. under 7
pionate,ethis being 93 percent of the theoretical
mm. pressure, 45 g. being obtained. The re
yield. The product was collected at 100-102° C.
the reaction mixture as before.
covered alcohol was returned to the reaction ves
sel containing the distillation residue, 1-2 g. of
p-toluenesullonic acid was added. and the mix
ture again re?uxed for several hours. Upon dis
tillation, 159 g. of allyl lactate was obtained. The
55 at 12 mm. pressure.’
‘ ~
Beta-methallyl alpha-acetomropionate is a
clear, colorless, mobile liquid with a slight, pleas
ant odor: having boiling points of 76° C. under
3 mm., 87° C. under 5 mm., and 95° C. under 10
total yield was thus 204 g., or 78 percent of the 60 mm. pressure; having a speci?c gravity of 1.0330
theoretical. The residue (presumably polylactlc
at 20° C., and having a refractive index for the
acid) could doubtless be used again‘ or added to -
a new batch of material, thus eventually convert
ing virtually all of it into ester.
yellow sodium line of 1.4314 at 20° C.
Example Vile-Aqueous sodium lactate (84.5
g. of 64 percent by weight sodium lactate) and
Allyl lactate is a clear, colorless, mobile liquid‘ 55 67.8 g. of beta-methallyl chloride were heated
at room temperature with a mild and not un
pleasant odor; boiling at 60° C. under 7 mm. of
in a rocking stainless steel autoclave at 120-180‘
C. for 5 hours.v A moderate yield of methallyl
lactate was obtained by fractional distillation of
mercury pressure, 79° C. under 25 mm., and 175.5“
C, under 754 mm. pressure: having a speci?c grav
reaction mixture.
ity 01 1.0452 at 20° C.. and having a refractive 70 theExample
VIII.—Ten moles (1125 a.) o! 80 Per
' index {or} the yellow sodium line of 1.4369 at
cent lactic acid, 400 ml. benzene. and 5 ml. of sul
20° C.
{uric acid were re?uxed in a still having a 841;.
Example [IL-Using essentially the same pro~
column fitted with a water trap at its top, water
cedure as in Example I. there was obtained from
being drawn ed, as it collected. at the rate of
3 moles (27 0 g.) of lactic acid and 3.3 moles ‘(233 75 about 300 ml. in about 5 hours. ‘when production
' 2,410,551
of water became slow, 40 moles (2323's.) of allyl _ at the still-head. when production of methanol
ceased, the excess alcohol was distilled at 54° C.
alcohol were added and re?uxin! continued with
and at 13 mm., after which the product was ob
removal of about 220 cc. of water, containing
105° C. and at 12 mm. The yield of
some allyl alcohol, in about 20 hours. When no
gamma-chloroallyl lactate was 65 percent of the
more water was produced, the ?ask was cooled,
20 g. of anhydrous sodium acetate was added to
Example XML-Using the procedure of Ex
neutralize the sulfuric acid, and the benzene
ample XII, methallyl lactate was obtained by in
and about half the excess allyl alcohol were'dls
teracting methyl or ethyl lactate with methallyl
tilled at atmospheric pressure. The remainder of
alcohol. The yield of methallyi lactate was '70
the alcohol was then distilled fairly rapidly un
der about 50 mm. pressure, after which the allyl
Example XIV. -— Beta-chloroallyl alpha-acet
lactate was rapidly distilled at 60° C. and at '7
oxypropionate was prepared by interacting beta
mm. The yield was 1178 g. or 90.5 percent of the
chloroallyl lactate with acetic 'anhydride and
Example IX.—Using the procedure described 15
then distilling to recover the ester.
Example XV.—Gamma-chloroal_lyl alpha-acet
in Example VIII, lactic acid was interacted with
oxypropionate was prepared by reacting gamma
beta-chloroallyl alcohol to give beta-chloroallyl
chloroallyl lactate and acetic anhydride.
lactate in '76 percent yield.
Example XVI.—Methyl vinyl carbinyl alpha
Example X.—The procedure of Example 'V'IH
was prepared by reacting
was slightly modi?ed to prepare methyl vinyl
methyl vinyl "carbinyl lactate and acetic anhy
carbinyl lactate, since methyl vinyl carblnol is
somewhat unstable in the presence of sulfuric
Example XVII. —. Crotyl alpha-acetoxypro
acid. In this case, the lactic acid, alcohol, and
pionate wa'sprepared by reacting crotyl lactate
benzene were mixed and refluxed with removal oi’.
water until little water was produced. Then, 10 95 with acetic anhydride.
The following table illustrates the properties of
g. of p-toluenesulionic' acid was added and heat
some of these compounds:
ing continued. When no more water was pro
Mono- and’ (ii-esters of lactic acid
Moi. refraction
#5." Pillar ND”
Bap. eq.
Calod. Found
Beta-chloroallyl ____________ __
Crotyl _____________________ _ _
7 83
1. 4627
1. 4070
1. M20
1. 2158
1. 2168
1. 0108
37. 49
37. 49
87. 24
87. 23
87. 54
37. 75
164. 6
163. 2
1M. 0 ______ __
144. 2
149. 8
Methyl vinyl carbinyl ..... __
1. 4328
1. 0091
37. 24
37. 10
144. 2
144. 5
102. 0
Beta-chlorodllyl _ _ _ . _ _ _ _ _
_ -_
1. 1792
46. 86
40. 7B
103. 3
Crotyl _______________ .-
Methyl vinyl earbinyl ..... .1
1. 44.80
1. 4255
l. 0233
46. 00
d0. 59
93. 1
9a 2
l Prepared by treating the corresponding aikenyl lactate with acetic anhydride.
duced, the catalyst was neutralized and the product distilled as described in Example ‘VIII.
Example XI.—'I'he same procedure as in Ex 50
ample X was followed to prepare crotyl lactate,
since crotyl alcohol is also unstable in the pres
‘ Having thus described our invention, we claim:
1. Beta-chloroallyl alpha-acetoxypropionate.
2. Gamma - chloroallyl alpha - acetcxypro
ence of sulfuric acid.
Example XII.-Gamma-chloroallyl lactate was
prepared by the alcoholysis of methyl or ethyl 55
lactate. In this case 3 moles (312 g.) of methyl
lactate, 6 moles (555 g.) of gamma-chloroallyl
alcohol, and 10 g. of aluminum tert-butoxide
were mixed and refluxed in a still from which
methanol was withdrawn as fast as it collected
3. Methyl 'vinyl carbinyl alpha-acetoxypro
4. A compound of the general formula
where (X) is a substituted allyl radical chosen.
from the group consisting of chloroallyl, crotyl
and methyl vinyl carbinyl.
Без категории
Размер файла
440 Кб
Пожаловаться на содержимое документа