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Патент USA US2410009

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Patented Oct. 29,1946
2,410,008
UNITED ,0 STATES PATENT OI’FICUEv
CHEMICAL COMPOUNDS
Joseph E. Bludworth and‘ (Donald, P. Easter,
Cumberland, Md., assignors to ,Celanese Cor
- poration of America, a corporation of Delaware
N0 Drawing. Application January 22, 1944,
Serial No. 519,353
0
1
1 Claim. (01. ‘200-475)
I
2
1
This invention relates to novel organic com
pounds and relates more particularly to certain
, We have now discovered that the esters'and
ether-esters of hexahydrobenzyl alcohol of the
esters and ether-esters of hexahydrobenzyl al
cohol.
.
following general formula‘
.
0
CH2
An object of our invention is the preparation of
ester and ether-ester derivatives of hexahydro
benzyl alcohol.
I‘ Ha
0
Ha
Another object of our invention is the prepa
CH2
ration of ester and ether-ester derivatives of hex
wherein
R
isa
substituted or unsubstituted cyclic
ahydrobenzyl alcohol which are useful in various 10
radical, form a valuable series of organic com
commercial applications due to their plasticizing,
pounds Which are suitable for use as plasticizers,
surface active and other properties.
waxes, synthetic intermediates, binding agents,
Other objects of our invention will appear from
solvents or lubricants. As examples of suitable
the following detailed description.
As is well known, the Diels-Alder condensa 15 acids with which the hexahydrobenzyl alcohol or
monoethylene glycol ether thereof may be ester
tion of acrolein with butadiene yields A3-tetra
i?ed to form said valuable esters, there may be
hydrobenzaldehyde
mentioned na-tetrahydrobenzoic acid, hexahydro
benzoic acid, naphthoic acid, tetrahydronaph
thoic acid, phthalic acid, tetrahydrophthalic acid
and hexahydrophthalic acid. The dicarboxylic
CH2
CH-—CHO
CH2
acids may form mono- as well as di-esters with
hexahydrobenzyl alcohol or with the mono
CH2
This unsaturated cyclic aldehyde is a highly re
ethylene glycol ether thereof.
active starting material for the development of
The novel esters of our invention may be pre
new and valuable'organic compounds. On oxi
dation of the above aldehyde, there may be ob
pared by reacting hexahydrobenzyl alcohol or
the mono-ethylene glycol ether of hexahydro
tained A3-tetrahydrobenzoic acid
benzyl alcohol with the desired acid or acid an
hydride, preferably, in the presence of a suitable
/
esteri?cation catalyst such as anhydrous hydro
011-00013
30 gen chloride, sulfuric acid or p-toluene sulfonic
OH
Hi
acid. From 1 to 2 equivalents of hexahydro
benzyl alcohol or the mono-ethylene glycol ether
CH2
thereof are reacted with from 1 to 2 equivalents
which, when reduced, yields hexahydrobenzoic
of acid or anhydride. The esteri?cation may be
acid
effected without the application of external heat
CH2
by mixing the hexahydrobenzyl alcohol or the
/
CH2
(IT‘H
mono-ethylene glycol ether thereof with the de- » »
CH2 (‘DH-00011
CH;
sired acid, and then bubbling dry hydrogen
chloride through the mixture until the reaction
om
CH2
is completed. The completion of the reaction is
indicated by the fact that no further heat is
however, not only is the aldehyde group reduced
evolved from the reaction mixture. The product
but the nuclear double ‘bond of the ng-tetrahydro
may be separated from the reaction mixture by
benzaldehyde is saturated as Well, and hexahy
distillation, extraction, crystallization or like
45 method, or by a combination of those methods
drcbenzyl alcohol
which are usually employed for the separation of
CH1
pure compounds from reaction mixtures in which
Under more vigorous conditions of reduction,
CH2 (EH-CHzOH
H:
CH2
is obtained.
they are prepared.
CH2’
50 but without being limited thereto the following
examples are given:
Example I
50 parts by weight of hexahydrobenzyl alcohol
Since this compound has an alco
- holic hydroxyl group, it may be etheri?ed, for
example, with ethylene oxide, to yield‘a mono
ethylene glycol ether or it may be esteri?ed.
‘
In order further to illustrate our invention
55
and 55 parts by Weight of M-tetrahydrobenzoic
2,410,008
c
4
a
of excellent properties. Thus, for example, ?lms
plasticized with 33% of di-hexahydrobenzyl
phthalate show an extension of about 21%.
evolution of heat ceases. The resulting reac
Example III
tion mixture is distilled under high vacuum and :3
‘ 50 parts by weight of the mono-ethylene glycol
hexahydrobenzyl-A3-tetrahydrobenzoate is re
ether of hexahydrobenzyl‘alcohol, formed by re
moved in'the fraction boiling at 112 to114° C.
action of hexahydrobenzyl alcohol with ethylene
under a pressure of 8 mm. of mercury. The
oxide, are mixed with 26 parts by weight of
yieldvobtained is 88% of theoretical.
phthalic acid. Dry hydrogen chloride is bubbled
Example II
_
through the mixture until esteri?cation is com
plate,’ completion being indicated by the fact
50 parts by weight of hexahydrobenzyl alcohol
acid are mixed‘together and dry hydrogen chlo
ride bubbled through the mixture. The hydro
gen chloride is bubbled through untilfurther
and 37 parts by weight of phthalic anhydride '
are mixed together, and dry hydrogen chloride
gas is bubbled through the mixture until no
further heat e?ect is noted.
100 parts by weight
of a saturated aqueous solution of sodium bi
carbonate are then added to neutralize ‘any ex.- 7
cess hydrogen chloride and unreacted phthalic
that the generation of heat ceases. The di-p
hexahydrobenzyloxyethyl phthalate is separated
from the reaction mixture by ?ltration and is
washed and dried.
It is to be understood that the foregoing de- ‘
tailed description is given merely by way of
illustration and that many variations may be
acid. The di-hexahydrobenzyl phthalate formed
made therein without departing from the spirit
is ?ltered from the solution, washed and dried.
of our invention.
The product isa white crystalline solid having
a melting point of approximately 104° C. This
ester is fully compatible with cellulose acetate
and when employed as a plasticizer in cellulose 25
acetate compositions yields plastic compositions
>
Having described our invention, what we de
sire to secure by Letters Patent is:-
Di~5-hexahydrobenzyloxyethyl-phthalate.
JOSEPH
BLUDWORTH.
DONALD P. EASTER.
‘
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