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Патент USA US2405936

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Patented Aug. 20, 1946
Edward P. Bartlett, Wilmington, Del., assignor to
E. I'. du Pont de Nemours & Company, Wilming
ton‘, DeL, a corporation of Delaware
No Drawing. Original application November 24»,- ‘
1939, Serial No. 305,929. Divided andthis-ap
plica'tion December 9, 1943, Serial'No. 513,639
5 Claims.
(01. 260-488)
This invention relates-to a process for the prep
aration of formic acid esters and to the products
of‘ that process; It more particularly relates to
the preparation of polyhydric alcohol polyfor
mates‘ by the interaction of polyhydrie alcohols
with carbon monoxide and to- the product of such
reactions. This application'is a division of ap
ethers of'the alcohol, and’ the monoalkoxyalkyl
ethers of ethyleneglycol, such as may be’ desig
natedby the formula, ROCH2O(-CH2) 20H, which;
generically, represents such alcohols as (methoxy
methox-y) ethanol, CHiOCHiO (CH2) 20H; (ethoxy
methoxy) ethanol, C2H5OCH2O<CH2> 20H ;. (prop
oxy , methox-y)ethan0l,
C‘aHqOCI-I2O(CH2) 20H;
(butoxy methoxy) ethanol, C3H9OCH2O (CH2) 20H;
plication Ser. No, 305,929 ?led November 24, 1939.
(methoxy isopropoxy) ethanol,
An object of the present invention is to pro
vide an-improved process for the preparation of 10'
CHsOC (CH3) 2O (CH2) ‘20H
formic acid esters. Another object of the inven
tion is to- provide‘ a process for the preparation
of formates by the interaction of polyhydric alco
(methcxy ethoxy'methoxy) ethanol,
CHsO (CH2) 2O'_CH2O (CH2)_2OH
hols, monoalkyl ethers of polyhydric alcohols or
monoalkyloxy ethers of polyhydric alcohols with 15 (alpha-methoxy ethoxy) ethanol,
carbon monoxide. A further object of the inven
CH3OCH(CH3) 0 (CH2) 201-1
tion is to provide a process for the preparation
of glycol diformate by the interaction of ethylene
and (alpha-ethoxy ethoxy) ethanol,
glycol with carbon monoxide in the presence of an
cznsocmcne 04cm) 20H
alkali metal glycolate or other alkoxide catalyst. 20
Still another object involves the preparation of
and similarly, higher substituted alcohols are‘in
polyformic acid esters of the polyhydric alcohols
eluded‘ such, for ‘example, as (methoxy methoxy) .-,
by interacting the latter with carbon monoxide
propanol, C‘H‘aOCI-IzOiCHzhOI-l; beta-(methoxy
under suitable temperature and pressure condi
methoxy) propanol, CHsOCHzOCI-HCI-Ia‘) CH'zOH;
tions in the presence of their respective alkali 25 (methoxy methoxy) butanol,
metal alcoholates or other alkali metal alkoxide
catalyst. Other obj ects and advantages of the in-,
CHsOCI-IzO (CH2) 40H
vention will hereinafter appear.
corresponding alcoholsas well as.
The process may be describedras involving the
following steps of dissolving in the polyhydric
alcohol or ether derivative thereof an alkaline
catalyst such as an alkali or an’ alkaline earth
their homologues. Other speci?c examples which
may likewise be included are the mono-(methoxy
methyl) ether of diethylene glycol,
metal, or mixing a suitable alkaline catalyst such
as an alkali metal or alkaline earth metal alk
oxide, with a polyhydric alcohol or ether deriva- ,
‘CI-I3OCH2O (CH2) 2O (CI-I2) 20H
as well as the. corresponding (ethoxy methyl);
tive thereof, contacting the resulting mixture
(propoxy methyl), (butoxy methyl), (methoxy
with carbon monoxide in a suitable reaction Ves
ethoxy methyl) ethers of diethylene glycol, as Well
as tri-ethylene glycol. These. alcohols are pre
sel, raising the temperature until the reaction
pared in accord with the process described in the,
starts and when thereaction is substantially com
plete separating the formate from the reaction 40 copending application ofSidney Sussman, 288,587,
?led August 5, 1939, which involves, primarily, the
interaction of an acetal and principally formals
The polyhydric alcohols which may be reacted
with a polyhydric alcohol having at least one un
in accord with the invention include ethylene
substituted hydroxyl group in the presence of a
glycol, propylene glycol, diethylene glycol, tri
ethylene glycol, and the higher analogous and 45 suitable acidic-type catalyst such as sulfuric acid.
Another class of alcohols is likewise included
homologous polyhydric alcohols, as well as glyc
which is prepared by the hydrogenation of the
erol and the like. Derivatives of thepolyhydric
product obtained by the process of the-copending
alcohols in which the OH, or the H of the OH, is
application of Donald J. Loder et al., S_ N. 256,855.~
substituted may also be used, providing there is
present a free hydroxyl group in the molecule. 50 These alcohols have the chemical formula,
CH2OH(CH20)n(CI-I2) 20H, in which n is‘ one '01"
Such derivatives include the monoalkyl ethers of
ethylene glycol and the above-designated glycols,
The polyhydric alcohol acid monoesters may
e. g., monomethyl, ethyl, propyl and higher ethers
likewise be converted to the corresponding for-~-v
of ethylene glycol, the monoaryl ethers of ethyl
ene glycol, such as monobenzyl and monotolyl 55 mates. Examples of this class of compounds are
the ethylene glycol monoalkyl esters, such as
hours. The product was distilled and the distil
late was found to contain:
Per cent
ethylene glycol monomethyl acetate, ethylene gly-r
col monoethyl acetate, ethylene glycol mono
methyl propionate, diethylene glycol monoethyl
ether acetate, and the like.
Formic acid ____________________________ __
In addition to the. above polyhydricalcohols in
Propylene glycol ______ _; __________ __' ____ __ 19.3
which the OH group vor the hydrogen of the OH
Propylene glycol monof0rmate___; _______ __ 41.9
Propylene glycol diformate ______________ __ 36.3
group is substituted by organic groups, there may I
be reacted, in accord with my invention, poly-r "
Propylene diformate has a boiling point of 116°
hydric alcohols in which these groupsare sub 10
C. at 101 mm., a refractive index to the sodium
lime of 1.4130 at 23° C. and a density of 1.136
stituted by an inorganic group, providing, of
course, there is present in the resulting compound
a free hydroxyl group. Examples of members of
this class of compounds include the hydrins, such
at .25‘! C; It is water-white, odorless. and solu
ble in all proportions in alcohol and ether and
as chlorhydrin, alpha-propylene chlorhydrin, 15 to the extent of 8.6 grams in 100 cc. of water at
room temperature.
trimethylene chlorhydrin, andvthe like.
Example 3.—The reaction illustrated by Exam
Generally, it is advantageous to work at moder
ple 1 was repeated using 3575 parts of a mixture
ately elevated temperature, but the reaction pro
containing 3481 parts of ethylene glycol, in which
ceeds also at ordinary temperatures with su?i
cient speed, if the carbon monoxide is brought in 20 had been dissolved 94 parts of sodium metal.
The same pressure, temperature and. time of re
to intimate contact with the liquid.‘ The-tem
action speci?ed in Example _1 were used. How
perature may range from in the order ofv50° to
ever, because of the higher concentration of cat
250°‘ C. with the preferred temperature between
alyst, reaction rate was greater and the product
approximately 60° and 150° C.‘ The reaction, as
has been indicated, is vconducted preferablya-t 25 richer in ester. The products from the two syn
theses were combined and distilled. Analysis of
superatmospheric pressures usually in the neigh
. the distillate showed:
borhood of 10 to 700 atmospheres, although the
reaction will proceed down to in the proximity of
Per cent
Formic acid
atmospheric pressures and also at pressures above
700 atmospheres.
In addition to the alkali and alkaline earth
30 Water
Ethylene glycol ________________________ __ 17.0
Ethylene glycol monoformate ____________ __ 55.0
metal alkoxide catalysts disclosed, other alkaline
Ethylene glycol diformate___________ _‘_____ 20.8
catalysts may be used, such as the formates of
the same metals. Such catalysts as, for example,
The polyhydric alcohol formates of this inven
sodium formate usually require a somewhat 35 tion are particularly useful as solvents for ex
higher temperature to be as effective as the alkox
tracting purposes, as solvents in cellulose ester
ide-type catalysts, i. e., temperatures of 100° C.
or above.
The carbon monoxide used in this reaction may
be derived from any suitable source and is pref
erably substantially pure and particularly free
from gases which will contaminate theester pro
duced or form undesirable products. There may
and ether lacquers and the like and especially
for use as intermediates in organic synthesis.
From a. consideration of the above speci?ca
tion, it. will be appreciated that many changes
may be made therein without departing from the
scope of the invention or sacri?cing any of the
advantages that may be derived therefrom.
be'present with the‘ carbon monoxide, however,‘
diluent gases which do not enter into the reaction 45
1. A process for the preparation of ethylene
such, for example, as nitrogen, hydrogen, or
glycol diformate which comprises reacting eth
methane and similar inert diluents.
ylene glycol with a carbon monoxide in the pres
Examples will now be given illustrating pre
ence of an alkali metal alkoxide catalyst at a
ferred embodiments of ‘the invention, which is
pressure between 200 and 700 atmospheres and
not restricted to the particular details therein 50 at a temperature between 50° and 250° C.
given. The parts are by weight unless otherwise
2. A process for the preparation of 1,2-propyl
ene glycol diformate which comprises'reacting
Example 1.—An autoclave was charged with a
1,2-propylene glycol with carbon monoxide in
mixture of 3542 parts containing approximately
the presence of an alkali metal alkoxide catalyst
3495 parts of ethylene glycol, in which was dis 55 at a pressure between 200 and 700 atmospheres
and at a temperature betewen 50° and 250° C.
solved 47 parts of metallic sodium. Cal‘bOnll'lO-n
3. A process for the preparation of ethylene
oxide was introduced into the closed autoclave
glycol diformate which comprises contacting car
andv the’pressure therein increased by the intro
bon monoxide and ethylene glycol with sodium
duction of carbon monoxide until a pressure be
methoxide at a pressure between 10 and 700 at
tween 200 and 400 atmospheres was obtained.
mospheres and a temperature between 50° and
The temperature was'raised to between 70° and
250° C.
100° C. and held within approximately that range
for 5% hours. Ethylene glycol diformate was
ene glycol diformate which comprises contacting
carbon monoxide and 1,2-propylene glycol with
Example 2.-An autoclave was charged with
sodium methoxide at a. pressure between 10 and
3321 parts of a mixture containing 3285 parts of
700 atmospheres and a temperature between 50°
propylene glycol (propanediol-1:2), in which had
and 250° C‘.
been dissolved 36 parts of metallic sodium. Car
5. A process for the preparation of vicinal gly
bon monoxide was introduced and the pressure
col diformate which comprises heating carbon‘
raised thereby to between 200 and 400 atmos
monoxide and a. liquid vicinal glycol with a metal
pheres. The temperature was raised to between
alkoxide catalyst at a pressure above atmos
70° and 100° C. and the reaction held between
these temperature limits for approximately 5
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