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Патент USA US3042607

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3,042,596
PHQTOISQMERIC PRER’ARATION 0F TRANS BIS
@RGANGSULFONYL ETHYLENES
James D. Johnston, Baton Rouge, Lat, assignor to Pitts
burgh Chemical Company, ‘Pittsburgh, Pa., a corpora
tion of Pennsylvania
No Drawing. Filed July 15, 1960, Ser. No. 42,971
7 Claims. (Cl. 204-458)
This invention relates to the conversion of cis bis
organosulfonyl ethylenes and haloethylenes to the cor
responding trans bis organosulfonyl ethylenes and halo
ethylenes.
Bis organosulfonyl ethylenes and haloethylenes have
been ‘found to be good fungicides, Johnston Belgian 15
Patent 543,377, June 6, 1956, Raasch United States
Patent 2,893,911 and Riden Belgian Patent 567,981,
June 14. 1958.
The trans isomer has been found in many cases to be
superior to the cis isomer.
3,042,596
Patented July 3, 1962
Unfortunately, the normal 20
procedures for preparing the his organosulfonyl ethyl
enes and haloethylenes either prepare the cis isomer or
a mixture of cis and trans isomers containing a large
1,2-bis (octylsulfonyl) ethylene;
l,2~bis (nonylsnlfonyl) ethylene;
l,2~bis (decylsulfonyl) ethylene;
1,2-bis (dodecylsulfonyl) ethylene;
1,2-bis (octadecylsulfonyl) ethylene;
1,2-bis (benzylsulfonyl) ethylene;
1,2-bis (phenylsulfonyl) ethylene;
1,2-bis (o-tolylsulfonyl) ethylene;
1,2-bis (p-tolylsul-fonyl) ethylene;
1,2-bis (m-tolylsulfonyl) ethylene;
1,2-bis (Z-naphthylsulfonyl) ethylene;
1,2-bis ( o-nitrophenylsulfonyl) ethylene;
1,2-bis (p-nitrophenylsulfonyl) ethylene;
1,2—bis (m-nitrosulfonyl) ethylene;
1,2-bis (o‘chlorophenylsulfonyl) ethylene;
1,2-bis (p-chlorophenylsulfonyl) ethylene;
1,2-bis (m-chlorophenylsulfonyl) ethylene;
1,2—bis (o-bromophenylsulfonyl) ethylene;
1,2-bis (ethylsulfonyl) -1,2—dichloroethylene;
1,2-bis (methylsulfonyl) -1,2-dichloroethylene;
1,2-bis (n-propylsulfonyl)~1,2-dichloroethylene;
1,2-bis (n-propylsulfonyD-1,2-dibromoethylene;
1,2-bis ( n-propylsulfonyl ) -1 ,Z-di?uoroethylene;
1,2-bis (n-propylsulfonyl) -1,2~diiodoethylene;
proportion of the cis isomer.
Accordingly, it is an object of the present invention 25 1,2-bis (isopropylsulfonyl)-1,2-dichloroethyl-ene;
1,2-bis (n-butylsulfonyl) -1,2—dichloroethylene;
to convert cis bis organosulfonyl ethylenes and haloethyl
enes to the corresponding trans compounds.
Another object is to convert cis bis alkyl sulfonyl ethyl
enes to the corresponding trans compounds.
A more speci?c object is to convert cis bis n-propyl
sulfonyl ethylene to trans n-propyl sulfonyl ethylene.
Still further objects and the entire scope of applica
bility of the present invention will become apparent from
the detailed description given hereinafter; it should be
understood, however, that the detailed description and
speci?c examples, While: indicating preferred embodiments
~1,2~bis (ethylsulfonyl)-1~chloro-2?uoroethylene;
1- ( me thylsulfonyl) -2-( ethylsulfonyl) - 1,2-dichloro
ethylene;
l- (n-propylsulfonyl) -2- (n-butylsulfonyl) ethylene;
1,2-bis ( dodeeylsulfonyl) -1,2—dichloroethylene; '
1,2-bis ( methylsulfonyl) ~1-chloroethylene;
1,2-bis (ethylsulfonyl)-1-chloroethylene;
1,2-bis (n-propylsulfonyl) -1-chloroethylene;
1,2-bis (n-propylsulfonyl) -1-brornoethylene;
1,2-bis (n-propylsulfonyl) -1-?uoroethylene;
1,2-bis (isopropylsulfonyD-l-chloroethylene;
of the invention, are given by way of illustration only,
1,2-bis (n—butylsul~fonyl) -1-chloroethylene;
since various changes and modi?cations within the spirit
1,2-bis (isobutylsulfonyl)-1-chloroethylene;
and scope or" the invention will become apparent to those
40 1,2-bis (sec. butylsulfonyl) -1-chloroethylene;
‘skilled in the art from this detailed description.
1,2-bis (tert. butylsul‘fonyl ) - l-chloroethylene;
It has now been found that these objects can be at
1-methylsulfonyl-2-butylsulfonylel-chloroethylene;
tained by treating a cis bis organosulfonyl ethylene or
1-propylsulfonyl-2~butylsulfonyl ethylene;
haloethylene with bromine, preferably in the presence
1,2-bis (octylsulfonyl)-‘l-chloroethylene;
of ultraviolet light.
45
As the starting cis organosulfonyl ethylenes and halo
and 1,2-bis (octadecylsulfonyl)-l-ehloroethylene.
ethylenes there can be employed compounds having the
Since most of the cis organosulfonyl compounds set
formula
forth above are solids, it is desirable to carry out the
isomerization in the presence of a solvent. The pre
50 ferred solvents are hydrocarbons and halohydrocarbons
such as benzene, toluene, Xylene, ethylene dichloride,
1,1,2-trichlorethane, carbon tetrachloride, carbon tetra
bromide, trichloroethylene, methylene chloride, per
alkyl phenyl, benzyl, chlorophenyl, bromophenyl, nitro
chloroethylene and chloroform.
phenyl and naphthyl and X1 and X2 are selected from 55 Only a few drops of bromine need be added, although
considerably more bromine can be employed but this is
the group consisting of hydrogen and halogen. Pref
where Q1 and Q2 are selected from the group consisting
of alkyl having 1 to 18 carbon atoms, phenyl, lower
erably Q1 and Q2 are both alkyl groups of 2 to 5 car
bon atoms and preferably both X, and X2 are hydrogen.
As typical examples of cis organosulfonyl ethylenes
and haloethylenes which can be converted to the corre
sponding trans isomers there can be used
1,2-bis(methylsul-fonyl) ethylene;
1,2-bis
1,2-bis
1,2-bis
1,2-bis
1,2-bis
(ethylsulfonyl) ethylene;
(n-propylsulfonyl) ethylene;
(isopropylsulfonyl) ethylene;
(n-butylsultonyl) ethylene;
(isobutylsulfonyl) ethylene;
1,2-bis (t-butylsulfonyl) ethylene;
1,2-bis (amylsulfonyl) ethylene;
1,2-bis (sec.buty1sulfonyl) ethylene;
l,2~bis (hexylsulfonyl) ethylene;
1,2-bis (heptylsulfonyl) ethylene;
not preferred for economic reasons.
The ultraviolet irradiation can be carried out with a
conventional sunlamp or any other source of ultraviolet
light. Ultraviolet light irradiation of the cis isomer in
the absence of bromine did not cause isomerization.
The isomerization reaction goes satisfactorily at room
temperature but either elevated or reduced temperatures
can be employed.
In the speci?cation and claims, all parts and percent
ages are by weight unless otherwise indicated.
Example 1
20 grams of bis (p-tolylsulfonyl) ethylene (35% cis
isomer and 65% trans isomer) and 100 ml. of chloro
form were placed in a ?ask and two drops of a concen
trated bromine solution in carbon tetrachloride were
3,042,596
3
4
added. The orange color persisted even on Warming.
The ?ask was irradiated with a sunlamp and the orange
color was rapidly dissipated with the formation of a
precipitate. More bromine solution was added slowly
until the orange color was not discharged on standing.
The product was collected by ?ltration, washed with
chloroform until white and dried. There were collected
1. The method of converting the cis isomer of a com
pound having the ‘formula
S Q2
/ 1%
X2
0
0
wherein Q1 and Q2 are selected from the group consist
ing of alkyl, aryl, haloaryl and nitroaryl and X1 and X2
12.8 grams of trans 11,2-bis (p-tolylsulfonyl) ethylene,
melting point 225-227° C. There were recovered by
are selected vfrom the group consisting of hydrogen and
halogen to the trans isomer comprising treating said cis
concentration of the mother liquor an additional 6.2 1O isomer with bromine in the presence of ultraviolet light.
grams of the trans compound.
2. A method according to claim 1 wherein the cis
compound is dissolved in a solvent.
Example 2
3. A method according to claim 2 wherein X1 and X2
25.5 grams of the pure cis 1,2-bis (n-propylsulfonyl)
are both hydrogen.
ethylene was dissolved in 150 ml. of carbon tetrachloride 15
4. The method of converting the cis isomer of a bis
and a few drops of bromine added. The mixture was
alkylsulfonyl ethylene to the trans isomer comprising
then irradiated with an ultraviolet light lamp (sunlamp).
treating said cis isomer with bromine in the presence of
A copious precipitate formed as soon as the light source
ultraviolet light.
was turned on. After ?fteen minutes, this precipitate
5. A method according to claim 4 wherein the cis
was removed from the ?ltrate by ?ltration and air dried 20 compound is dissolved in a solvent.
free of carbon tetrachloride. The precipitate Weighed
6. A method ‘according to claim 5 wherein the alkyl
25 grams. The melting point of the precipitate was 155—
groups have 2 to 5 carbon atoms each.
156° C. which is the melting point of pure trans 1,2-bis
(propylsulfonyl) ethylene.
42-44° C.)
7. The method of converting cis bis (n-propylsulfonyl)
ethylene to trans bis (n-propylsulfonyl) ethylene com
(The cis isomer melts at
25 prising treating said cis isomer while dissolved in a sol
The same isomerizat-ion was observed when the car
vent with bromine in the presence of ultraviolet light.
bon tetra-chloride in Example 2 was replaced by benzene,
ethylene ‘dichloride, 1,1,2-trichlorethane, trichloroethyl
ene, methylene chloride and perchloroethylene.
The results obtained are surprising since other meth 30
ods which have been employed for converting cis isomers
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,893,911
Raa-sch _______________ __ July 7, 1959
to trans isomers are ineffective. Among such procedures
which do not work with the organosulfonyl ethylenes
are heating the cis isomer to 150° C. ‘for 28 hours.
What is claimed is:
OTHER REFERENCES
Journal of the American Chemical Society, vol. 59
35 (1937), page 1155.
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