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Патент USA US3071603

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3,971,593
United States Patent O??ce
Patented Jan. 1, 1963
1
2
3,071,593
PREPARATHON 0F ALKENE SULFIDES
Paul F. Warner, Phillips, Tex, assignor to Phillips
Petroleum Company, a corporation of Delaware
No Drawing. Filed July 27, I959, Ser. No. 829,518
8 Claims. (Cl. 2-60—327)
5
wherein each R is selected from the group consisting of
hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl
groups having 1 to 8 carbon atoms, the combined R
groups having up to 12 carbon atoms. Examples of suit
This invention relates to a method of preparing alkene
able compounds are ethylene oxide, propylene oxide, iso
sul?des. Another aspect relates to a method of convert
ing an alkene oxide to the corresponding sul?de at rela
butylene oxide, a-amylene oxide, styrene oxide, isopropyl
ethylene oxide, methylethylethylene oxide, 3-phenyl-1,
Z-propylene oxide, (3-methylphenyl) ethylene oxide,
cyclohexylethylene oxide, 1-phenyl-3,4-epoxyhexane, and
tiively high yields Without refrigeration.
By the term “alkene sul?de” as used in this speci?ca
‘tion and in the claims, I mean to include not only un
the like.
"substituted alkene sul?des such as ethylene sul?de, propyl- salts of thiocyanic acid which I prefer to use are
'ene sul?de, isobutylene sul?de, and the like, but also 15 theThe
salts of the alkali metals or ammonium. I especially
hydrocarbon-substituted alkene sul?des such as styrene
oxide, and in general all compounds conforming to the
formula
prefer ammonium thiocyanate, sodium thiocyanate, and
potassium thiocyanate. These compounds can be reacted
hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl
methylcyclopropane, cyclopentane, methylcyclopentane,
methylcyclohexane, ethylcyclopentane, 1,1-dimethylcyclo
with ethylene oxide in a cyclopara?in diluent to produce
substantial yields of ethylene sul?de and with little or
20
no polymer formation.
It is essential in my invention that the reaction diluent
IMO/QC R:
The a cycloparaf?n having from 4 to 10 carbon atoms and
preferably 5 to 8 carbon atoms per molecule. Examples
wherein each R is selected from the group consisting of
of suitable cyclopara?ins are cyclohexane, cyclobutane,
25
‘groups, said IR groups having up to 8 carbon atoms in
dividually and up to 12 carbon atoms combined.
‘pentane, 1,2-dimethylcyclopentane (both cis and trans),
11,3-dimethylcyclopentane (both cis and trans), cyclo
Alkene sul?des are having increasing importance in
the synthesis of organic sulfur compounds. They can
octane, ethylcyclohexane, 1,3-dimethylcyclohexane (both
also be employed as insecticides or fungicidal agents as 30 cis and trans), 1-isopropyl-4-methylcyclohexane, and the
described in US. Patent 2,225,573. These compounds
can be prepared from the corresponding alkene oxides by
_ like.
The reaction between the ethylene oxide and the thio~
reaction with salts of thiocyanic acid in the presence of
cyanate‘ occurs readily in the cycloparaf?n diluent at a
such solvents as Water, alcohol, and ether or mixtures
temperature in the range of about 50 to 150° F. Elevated
thereof. In such processes refrigeration is necessary for 35 pressures ‘are not necessary unless the reaction diluent
appreciable yields of the desired sul?de; generally, the
‘selected requires an elevated pressure to maintain a liquid
reaction temperature being about —5 to —l0° C.
phase at the temperature chosen to conduct the reaction.
I have discovered quite unexpectedly that alkene sul- . ~
Generally, a pressure slightly above atmospheric is used,
The alkene sul?de is
?des can be prepared by the reaction between an alkene 40 for example, about 1 to 5 p.s.i.g.
oxide and a salt of, thiocyanic acid without the necessity
preferably separated from the reaction diluent following
of refrigeration if the reaction is conducted in a diluent
of cyclopara?‘in.
completion of the reaction by distillation. It is therefore
Generally, the cycloparaf?n should
have from 4 to 12 carbon atoms per molecule and I prefer
desirable to select a diluent which has a boiling point suffi
ciently dilferent from that of the desired alkene sul?de to
to use as a diluent for the reaction of my invention a
permit a good separation.
cyclopara?‘in having from 5 to 8 carbon atoms per 45
To further illustrate the advantages of my invention,
molecule.
the following example is presented which should be
It is an object of my invention to provide a method of
interpreted as being typical and not unduly limiting.
preparing alkene sul?des. Another object is to provide
EXAMPLE
a process by which alkene sul?des can be prepared from
the corresponding alkene oxides without the necessity of
refrigeration. Still another object of my invention is to
improve the yield of alkene sul?de which can be obtained
by reacting a salt of thiocyanic acid with an alkene oxide
at about room temperature. Other objects, advantages
Ethylene oxide and ammonium thiocyanate were re
acted in several runs employing a variety of solvents. In
each case the reaction temperature was about: room tem
perature or slightly above. The ethylene sul?de was re
covered in those runs with measurable yields by distilla
tion. Ethylene sul?de has a boiling point of l30° F. and
can be separated from cyclohexane at atmospheric pres
sure to yield a product of better than 95 percent purity.
The data of these runs are presented in ‘the following
and features of my invention will be apparent to those
skilled in the art from the following discussion.
The alkene oxides which can be employed in my inven
tion for the preparation of alkene sul?des are those com
pounds which have the general ‘formula
60
table.
“
3,071,593
Table I
Run No.
A
B
C
Solvent .......... _. Cyclohexane Cyclohexane
Run conditions:
Temp, ° F_._
88-100
90
Pressure,
p.s.i.g.--_--.
Reaction
time, hrs____
Charge:
_
Ammonium
3
Ethylene
id
156
2
3. 1
_____ __
f1
E
F
G
H
1
Cyclohexane
Water
Water
Water
Methanol
n-Heptane
SOItrOl 1301
85
2 85-140
88~95
95
85-100
90-108
104
1
2. 5
0
3 65
0.0
5
2
Moles
4
Moles
2
2. 5
G. Moles
thiocyanate. 152
D
1
Polymer ________________ __
1. 2
G.
Moles
G.
602
7. 9
568
' 654
14. 9
454
2, 780
260
None
-_
10. 3
‘i 040
4.3
296
G.
152
2
152
2
70
1
152
2
76
1
152
260
5. 9
280
6
41
0. 9
161
3. 7
86
1. 96
100
150
4. 95
None
__________________ __
6 36
150
_____ __ 4 None _____ _.
_____ __
52
G
3
Moles
G.
2
Moles
5
3
Moles
G.
7. 48
3. 5
Moles
124
_______
150
_-_____
500
._._.._
<4
_____ __ 5<20
_____ __
None
_____ __
G.
500
3
JVIoZes
2
2. 3
-______
_____________________________________________ _.
Ethylene
oxide __________________ __
202
4. 6
72
1. 64
__________________________________________________________________ _.
l Soltrol 130 (Trademark). A mixture of highly branched para?‘inie hydrocarbons boiling over the range of about 335° F. to 410° F.
in: . Hg.
2 No heat applied. Temperature rise was from exothcrmal reaction.
Recovered 52 g. polymer from it.
4 Added Has to reactor et?uent of pH 8. Product consistency of thick gravy and oks like uncoagulated rubber.
5 Distillation of the reactor e?luent yielded 20 ml. of material boiling fr om 119° F. to 133° F .
'1 Reactor product solidi?ed on cooling; after water washing to remove s alts, 36 g. of waxy water insoluble polymer was recovered.
Norn.-—Leaders ( ____ __) in ?gure columns indicate that data was not obtained. Although complete material balances were not made, it is a safe
assumption that most of the ethylene oxide unaccounted for went to polymer which was entrained with the ammonium cyanate reactor product.
wherein each R is selected from the group consisting of
It can be seen from the above data that the conven
hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl
tional solvents, water and methanol, do not permit satis
groups having 1 to 8 carbon atoms, the combined R
groups having up to 12 carbon atoms, with a thiocyanate
factory yields of ethylene sul?de at ambient temperatures
whereas the yields when cyclohexane was employed as
the diluent were unexpectedly high. It is also noted that
acyclic hydrocarbons such as n-heptane and Soltrol 130
selected from the group consisting of ammonium thio
cyanate and alkali metal thiocyanates, in a reaction dilu
did not provide appreciable yields of ethylene sul?de.
ent of {from ‘2 to 10 volumes of cycloparaf?n having from
As will be evident to those skilled in the art, various
modi?cations of this invention can be made, or followed,
actants at a temperature of about 50 to 150° F., and
5 to 8 carbon atoms per molecule per volume of re
separating the alkylene sul?de reaction product from the
in the light of the foregoing disclosure and discussion,
without departing from the spirit or scope thereof.
cyclopara?in by distillation.
4. The process of claim 3 wherein said compound is
I claim:
‘1. A process for making alkene sul?des which com
prises contacting a compound having the formula
ethylene oxide.
5. The process of claim ‘3 wherein said compound is
40
propylene oxide.
‘6. The process of claim 3 w herein said compound is
isobutylene oxide.
7. The process of claim 3 wherein sa id reaction dilu
wherein each R is selected from the group consisting of
hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl
cut is cyclohexane.
groups having .1 to 8 carbon atoms, the combined R 45
8. A process for making ethylene sul?de which com
groups having up to 12 carbon atoms, with a compound
prises contacting ethylene oxide in a cyclohexane diluent
selected from the group consisting of ammonium thio
with ammonium thiocyanate at about 50 to 150° F. and
cyanate and alkali metal thiocyanates in a reaction diluent
separating the ethylene sul?de product from the cycle
of cyclopara?in having 5 to 8 carbon atoms per molecule
at a temperature of about 50 to 150° F.
2. The process of claim 1 wherein said reaction diluent
is cyclohexanc.
50
hexane by distillation.
References Cited in the ?le of this patent
3. A process for making alkene sul?des which com
prises contacting. a compound having the formula
Ric/ACE:
UNITED STATES PATENTS
2,094,837
__
Dachlauer ____________ __ ‘Oct. 5, 1.937
2,094,914
Dachlauer et al. _______ __ Oct. 5, 1937
‘2,183,860
Coltof "a _____ __,_ ____ Dec. 19, 1939
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