Патент USA US3042607код для вставки
Ult€ rates Patent ?lice 2 1 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.