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Патент USA US2403686

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2,403,686
Patented July 9, ‘1946
] UNITED STATES PATENT OFFICE
MONO-GLYCOL ' ETHERS
AND - UINS’A'ITU1
RATED NITRILES‘
‘
_
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-
. Edward John S’chwoegler, Wya'ndotte,’Mich., as
>
-'
slgnor‘ to Wyandotte Chemicals Corporation,‘
Wyandotte, Mich., a corporation of Michigan " '
'7 No Drawing.
‘
"31:1
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7
Application November 22, 1944,
Serial No. 564,716
.
.14 Claims.
'
v
_
(01. 260——34;5)
' carbon atom of the nitrile becomes linked to" the
“The present invention relates to chemical com-'
pounds of the following indicated general for
mula, and. their method of preparation:
oxygen of such hydroxyl group, substantially as
illustrated by the following equation:
,
a.
v.
,
Suzanne
CHz=GHCH1O CHICHIOH + CHFCHCEN -—->
h
R=wlunsaturated hydrocarbon vradical
R1=a hydrogen or alkyl group
.
'
'~
“
v
_
catalyst
OHFOHCHQO omomoomCmoN
I V'I'he products of myrpresentiinventien amuse:
iul intermediates in organic synthesis. ‘
~ The alkaline condensinjgrorr catalytical agents
used in the present reaction. are of I agstrongly
7
._, 1A1; example of such product isv the following; ’
alkaline nature, such as alkali oxides. hydroxides,
..
g
.
.
amines, alcoholates or plienates; alkali or alkaline
earth. metals, alkaline earth hydroxides, alkali
wwlweemmeme,
hydrides, strongly alkaline quaternary ammonia
“Brie?y outlined, my invention involves the re
' action of a "monoglycol etherjof; anrunsaturated
alcohol, with‘ an cz? unsaturated open chain
nitrile, inthepresence of an alkaline condensing
agent. V'Such' open chain (nltrile possesses the
annular
.
‘
capo-GEN
"
1;
~
:
hydroxides and the like; In general, the amount
of such condensing agent or catalyst to be used
is. from 1/2. to 5% by weight of the unsaturated
mono-glycol ether employed in the‘ reaction.
20 . ‘The following unsaturated mono-‘glycol ethers
a’
- may be employed inthe performance of my pres
entinventioni ethylene, propylene and butylene
where 1i’.v
"glycol ethers of the following listed unsaturated
‘hydrogen or a methyl group, vizzé
acrylonitrile‘or a methyl aorylonitrilet I
alcoholsf
‘
#:The mono-‘glycol ethers of an unsaturatedalco
hol are suitably’prepared by the reaction of ole?n
trated by the following chemical equatiom-j
30
om=onomoomomon _
reaction of the alkali metal salt of the unsatu
rated alcohol and an ole?n chlorhydrin, thusly:
'
A
Furfuryl alcohol
Crotyl alcohol
Oleyl alcohol
Propargyl alcohol
Cinnamyl alcohol
Geraniol
Methylvinylcarbinol
Allylcarbinol
Pentene-1-ol-5
Linalool
Citronellol
Alpha terpineol
Methylallyl alcohol
oxides and the unsaturated. alcohol, such as illus
Such ethers may alternatively be prepared by
'
Anyl alcohol
. In' the case of the propylene and butylene ethers
of the unsaturated alcohols, it isto be understood
that two or more isomers may be formed by in
teraction of the ole?n oxide and the unsaturated
alcohol; The inclusion of such isomeric forms
of ethers is within the purview and scope of my _
present invention.
Mixtures ; of
ole?n
chlorhydrins,
such . ‘as
ethylene .and propylene chlorhydrin may also be
employed in the abovereaction to produce mixed
.
-
.
The process is carried out in general by slowly
adding acrylo- or metha‘crylonitrile to the ether
containing the catalyst; the rate of addition being 7
regulated so that‘ the temperature of the reaction
open chain nitrile, as subsequently" described.
mixture-remains below 70‘? C. External cooling
When such'a mono-glycol ether of the unsatu; 45 may be employe'd'if desired. The reactants may
ratedv alcohol is reacted with the open‘ chain . beemployed in 'equimolar proportions although
it is sometimes advantageous to use a small ex
nltrile', and-in the presence of ‘an ‘alkaline cata
alcohols which are in turn condensed with an,
lyst, the _‘hydrogen of thehydroxy group in the
cess of ‘unsaturated ether.
ether-attaches itself to the double bonded carbon
‘By way of further'explanation and illustration
in the‘beta position of the nitrile, and the‘ alpha
of my invention, in order that it may readilybe
2,403,686
3
4
understood and practiced by those skilled in the
dissolved sodium. The oily reaction mass was
separated from the aqueous layer, washed with
water, dried and distilled. Fifty-four grams of
art, the following examples are given:
Example 1
Mfurfuroxy ethoxy) propionitrile boiling at 152°
Mono allyl ether of ethylene glycol in the Ca to 154° C. at 1 mm. Hg pressure were obtained.
amount of 671 grams was placed in a reaction
Nitrogen analysis showed this compound to be
vessel ?tted with an agitator and surrounded by
practically pure.
a jacket suitable for heating or cooling. Methyl
I claim:
alcohol (10 grams) were added to the ether fol
1. As anew composition of matter, thereaction
lowed by the addition of 5 grams ofv sodium in 10 product of an ether of a saturated glycol and an
small chips. The mixture was agitated until all
unsaturated alcohol, and an an unsaturated open
sodium had dissolved. Acrylonitrile (265 grams)
chain nitrile,
were added to the agitated mixture over a period
2. As a new composition of matter, the reac
of 2 hours while the reactants mixture was main
tion product of an ether of a saturated glycol and
tained at a temperature of 18-20" C. The reac 15 an unsaturated alcohol, and acrylonitrile.
tion mixture was agitated for 1 hour at the above
3. As a new composition of matter, ,8- (allyloxy
temperature on completion of acrylonitrile addi
ethoxy) propionitrile-.
tion and then poured into 200 cc. of water and
4. As a new composition of matter, a mixture
neutralized with dilute sulfuric acid. The oily
of [i cyano ethyl ethers of mono allyl propylene
layer was separated from the aqueous layer, 20 glycol ethers.
washed two times with sodium chloride solution,
5. As a new composition of matter, l-allyloxy
dried and distilled. A water white product boil
-2 [i cyanoethoxy propane.
‘
ing at 110° C. at 2 mm. Hg pressure (and weighing
6. As a new composition of matter, 18(furfuroxy
620 grams) was obtained. Its analysis agreed '
ethoxy) propionitrile,
‘
with the formula:
'7. The method of making chemical compounds
25
of the formula
CI~Iz='CH—CH2—O—-CI-lz——"
.
CH2,——OCH2—CH2—-CEN
B(allyloxy ethoxy) propionitrile
Example 2
Mixed mono allyl ether of propylene glycol
where R is an unsaturated hydrocarbon radical,
30 and Y is an alkylene» group, consisting in react
(232 grams) were placed in a reaction vessel ?t
ted with an agitator, dropping device and a re?ux
condenser. — Two grams of sodium were added to
the ether in small chips and the mixture warmed 35
to~80° C. to effect solution. The solution was
cooledv to 15° C. by means of an ice bath. Acrylo--v
nitri'le (98' grams) was added to the agitated gly
ing an ether of asaturated glycol and an un
saturated alcohol with an unsaturated open chain
nitrile in the presence of. an alkaline condensing
agent.
.
'
n
8. The method of making chemical compounds
of the formula
.
'
- .
..
col ethers containing the dissolved sodium over , where R is an unsaturated hydrocarbon radical,
a'period of 3 hours. The temperature of the re 40 and Y is an alkylene group, consisting in react
action mass was maintained between 15 and 25°
ing an ole?n oxide and an unsaturated alcohol,
C; during ‘theaddition period. After all acrylo
to form an unsaturated mono-glycol ether-and
nitrile had been added, the reaction mass was agi
then reacting the latter with an open chain nitrile
tated for 30 minutes at 20° C., poured into water
in the presence of an alkaline condensing agent.
and neutralized with hydrochloric acid. The 45
9. The method of making chemical compounds
aqueous, layer was separated from the oily con
densation product. The crude condensation
product was then distilled under vacuum. Two
of the formula
W
"
'
hundred and forty-?ve grams of the desired‘ con
where R is an unsaturated hydrocarbon radical,
densation products boiling at 138° to 142° C. at 50 and 'Y is an alkylene. group, consisting in react
12 mm. Hg pressure were obtained. Analysis
ing the sodium salt of an. unsaturated alcohol
showed they products. to be ,B-cyano ethyl ethers
with an ole?n chlorhydrin to form an unsatu
of mono allyl propylene glycol ethers.
rated mono-glycol. ether jandthen. reacting the
latter with an open chain nitrile, in the presence
Example 3
of an alkaline condensing agent.
One hundred and sixteen grams“ of 1,-allyloxy
10. The method of making chemical compounds
propanol-2, prepared by the interaction of sodium
_ of the formula
allylate and l-chloro-propanol-Z, were condensed
with 49 grams of acrylonitrile, 1 gram of sodium
being used‘ as a catalyst, by the same procedure 60 Where R is an unsaturated hydrocarbonradical,
as set out in Example 2. One hundred and twenty
and Y is an alkylene group consisting in reacting
grams of l-allyloxy 2(B-cyanoethoxy) propane
the sodium salt of an unsaturated alcohol with
boiling at 140° to 142°C. at 12 mm. Hg pressure
a mixture of ethylene and ‘propylene chlorhy
were obtained.
drins to form mixed unsaturated mono-glycol
'
'
Escample 4
65 ethers and then reacting the. latter with an open
chain nitrile. in. the presence ofv analkaline con
Metallic-sodium (1 gram) in the form of thin
chips was dissolved in 108 grams of the furfuryl
ether of ethylene glycol by vigorously agitating
11. The method oimaking aichemical.v com
pound ofclaim 3 consisting vin reacting, mono allyl
the vmixturevat 25° to 28° C.v Acrylonitrile (38
grams) Was added to the agitated ether over a 70 ether of ethylene glycol with acrylonitrile in. the
period of 2 hours while the temperature was
presence of dissolved metallic sodium. at a tem
maintained below 25° C. by meansof an external
perature of 18° to 20° C., neutralizing, thereaction
mixture and then‘ separating and distilling the
cooling bath. The reaction mixture was then
stirred for ‘,5 hour at 25° C. and poured into water
desired product therefrom.v
1
.
containing just sufficient H2804 to neutralize the 75
12. The method of making a chemical com
densing
agent,
.
,
~
,
.
.
2,403,686
5
6.
pound of claim 4 consisting of reacting a mix
ture of mono allyl ethers of mono propylene glycol
with acrylonitrile in the presence of dissolved
metallic sodium at a temperature of 15° to 25“ C.,
temperature of 15° to 25° 0., neutralizing the re
neutralizing the reaction mixture, separating and
distilling the desired product.
'
r
13. The method of making a product of ‘claim
5 consisting in reacting sodium allylate and 1
chloro-propanol-Z to form l-allyloxy propionol-2,
condensing the product thereof with acrylonitrile 10
in the presence of dissolved metallic sodium at a
sultant mixture andthen separating and distilling
the desired product.
14. The method of making the product or claim
6 consisting in reacting furfuryl ether of ethylene
glycol with acrylonitrile in“ the presence or dis
solved metallic sodium at a temperature below 25°
0., neutralizing the resultant mixture and then
separating and distilling the desired product.
EDWARD JOHN SCHWOEGLER.
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