US3042596A - Photoisomeric preparation of trans bis organosulfonyl ethylenes - Google Patents
Photoisomeric preparation of trans bis organosulfonyl ethylenes Download PDFInfo
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- US3042596A US3042596A US42971A US4297160A US3042596A US 3042596 A US3042596 A US 3042596A US 42971 A US42971 A US 42971A US 4297160 A US4297160 A US 4297160A US 3042596 A US3042596 A US 3042596A
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- bis
- ethylene
- organosulfonyl
- ethylenes
- cis
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- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 title description 9
- 238000000034 method Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- -1 1,2-bis (isobutylsulfonyl) ethylene Chemical group 0.000 description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 229950005499 carbon tetrachloride Drugs 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- YTPMCWYIRHLEGM-UHFFFAOYSA-N 1-(2-propylsulfonylethenylsulfonyl)propane Chemical group CCCS(=O)(=O)C=CS(=O)(=O)CCC YTPMCWYIRHLEGM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000006124 n-propyl sulfonyl group Chemical group 0.000 description 3
- ZXPCCXXSNUIVNK-UHFFFAOYSA-N 1,1,1,2,3-pentachloropropane Chemical compound ClCC(Cl)C(Cl)(Cl)Cl ZXPCCXXSNUIVNK-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- YTPMCWYIRHLEGM-BQYQJAHWSA-N 1-[(e)-2-propylsulfonylethenyl]sulfonylpropane Chemical group CCCS(=O)(=O)\C=C\S(=O)(=O)CCC YTPMCWYIRHLEGM-BQYQJAHWSA-N 0.000 description 2
- DBCLLYFDDUBSML-UHFFFAOYSA-N 1-ethenylsulfonylpropane Chemical group CCCS(=O)(=O)C=C DBCLLYFDDUBSML-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- GYSFJIQTRDNGAM-WAYWQWQTSA-N (z)-1,2-bis(ethylsulfonyl)ethene Chemical group CCS(=O)(=O)\C=C/S(=O)(=O)CC GYSFJIQTRDNGAM-WAYWQWQTSA-N 0.000 description 1
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 1
- ZWKSNOSGZRTFMP-UHFFFAOYSA-N 1,2-dichloro-1-methylsulfonylethene Chemical group CS(=O)(=O)C(Cl)=CCl ZWKSNOSGZRTFMP-UHFFFAOYSA-N 0.000 description 1
- HDWYHVPCGLDOIL-UHFFFAOYSA-N 1-(2-chloro-2-propylsulfonylethenyl)sulfonylpropane Chemical group C(CC)S(=O)(=O)C(=CS(=O)(=O)CCC)Cl HDWYHVPCGLDOIL-UHFFFAOYSA-N 0.000 description 1
- IBJGVAOFRSKZPY-UHFFFAOYSA-N 1-chloro-4-ethenylsulfonylbenzene Chemical group ClC1=CC=C(S(=O)(=O)C=C)C=C1 IBJGVAOFRSKZPY-UHFFFAOYSA-N 0.000 description 1
- AKASKBOZOXUFST-UHFFFAOYSA-N 1-ethenylsulfonyl-2-methylbenzene Chemical group CC1=CC=CC=C1S(=O)(=O)C=C AKASKBOZOXUFST-UHFFFAOYSA-N 0.000 description 1
- SGMIFOKONPWISF-UHFFFAOYSA-N 1-ethenylsulfonyl-3-methylbenzene Chemical group CC1=CC=CC(S(=O)(=O)C=C)=C1 SGMIFOKONPWISF-UHFFFAOYSA-N 0.000 description 1
- MZKZSNKRTIDCRI-UHFFFAOYSA-N 1-ethenylsulfonyl-4-nitrobenzene Chemical group [O-][N+](=O)C1=CC=C(S(=O)(=O)C=C)C=C1 MZKZSNKRTIDCRI-UHFFFAOYSA-N 0.000 description 1
- JEFPBNFVEIQBGE-UHFFFAOYSA-N 1-ethenylsulfonyldecane Chemical group CCCCCCCCCCS(=O)(=O)C=C JEFPBNFVEIQBGE-UHFFFAOYSA-N 0.000 description 1
- HTAMRUHHHVQRON-UHFFFAOYSA-N 1-ethenylsulfonyldodecane Chemical group CCCCCCCCCCCCS(=O)(=O)C=C HTAMRUHHHVQRON-UHFFFAOYSA-N 0.000 description 1
- UBDLKKKJTYCRRJ-UHFFFAOYSA-N 1-ethenylsulfonylhexane Chemical group CCCCCCS(=O)(=O)C=C UBDLKKKJTYCRRJ-UHFFFAOYSA-N 0.000 description 1
- GJNYFOAXSMOBIG-UHFFFAOYSA-N 1-ethenylsulfonyloctadecane Chemical group CCCCCCCCCCCCCCCCCCS(=O)(=O)C=C GJNYFOAXSMOBIG-UHFFFAOYSA-N 0.000 description 1
- KWFGVRYYABRBHO-UHFFFAOYSA-N 1-ethenylsulfonyloctane Chemical group CCCCCCCCS(=O)(=O)C=C KWFGVRYYABRBHO-UHFFFAOYSA-N 0.000 description 1
- ONVBDYWGWKUWMH-VAWYXSNFSA-N 1-methyl-4-[(e)-2-(4-methylphenyl)sulfonylethenyl]sulfonylbenzene Chemical group C1=CC(C)=CC=C1S(=O)(=O)\C=C\S(=O)(=O)C1=CC=C(C)C=C1 ONVBDYWGWKUWMH-VAWYXSNFSA-N 0.000 description 1
- ONVBDYWGWKUWMH-UHFFFAOYSA-N 1-methyl-4-[2-(4-methylphenyl)sulfonylethenylsulfonyl]benzene Chemical group C1=CC(C)=CC=C1S(=O)(=O)C=CS(=O)(=O)C1=CC=C(C)C=C1 ONVBDYWGWKUWMH-UHFFFAOYSA-N 0.000 description 1
- WUIJTQZXUURFQU-UHFFFAOYSA-N 1-methylsulfonylethene Chemical group CS(=O)(=O)C=C WUIJTQZXUURFQU-UHFFFAOYSA-N 0.000 description 1
- CODBNMJEAYHFOU-UHFFFAOYSA-N 2-(2-propan-2-ylsulfonylethenylsulfonyl)propane Chemical group CC(C)S(=O)(=O)C=CS(=O)(=O)C(C)C CODBNMJEAYHFOU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001080173 Ridens Species 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- UJTPZISIAWDGFF-UHFFFAOYSA-N ethenylsulfonylbenzene Chemical group C=CS(=O)(=O)C1=CC=CC=C1 UJTPZISIAWDGFF-UHFFFAOYSA-N 0.000 description 1
- CYHFPQIAMFXACF-UHFFFAOYSA-N ethenylsulfonylmethylbenzene Chemical group C=CS(=O)(=O)CC1=CC=CC=C1 CYHFPQIAMFXACF-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004999 nitroaryl group Chemical group 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S204/00—Chemistry: electrical and wave energy
- Y10S204/90—Effecting a change in isomerization by wave energy
Definitions
- the trans isomer has been found in many cases to be superior to the cis isomer.
- the normal procedures for preparing the his organosulfonyl ethylenes and haloethylenes either prepare the cis isomer or a mixture of cis and trans isomers containing a large proportion of the cis isomer.
- Another object is to convert cis bis alkyl sulfonyl ethylenes to the corresponding trans compounds.
- a more specific object is to convert cis bis n-propyl sulfonyl ethylene to trans n-propyl sulfonyl ethylene.
- organosulfonyl ethylenes and haloethylenes there can be employed compounds having the formula where Q and Q are selected from the group consisting of alkyl having 1 to 18 carbon atoms, phenyl, lower alkyl phenyl, benzyl, chlorophenyl, bromophenyl, nitrophenyl and naphthyl and X and X are selected from the group consisting of hydrogen and halogen.
- Q and Q are both alkyl groups of 2 to 5 carbon atoms and preferably both X, and X are hydrogen.
- 1,2-bis(methylsul-fonyl) ethylene 1,2-bis (ethylsulfonyl) ethylene; 1,2-bis (n-propylsulfonyl) ethylene; 1,2-bis (isopropylsulfonyl) ethylene; 1,2-bis (n-butylsultonyl) ethylene; 1,2-bis (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;
- butylsulfonyl -1-chloroethylene
- 1,2-bis tert. butylsulfonyl l-chloroethylene; 1-methylsulfonyl-2-butylsulfonyl l-chloroethylene; 1-propylsulfonyl-2-butylsulfonyl ethylene; 1,2-bis (octylsulfonyl)-l-chloroethylene;
- the preferred solvents are hydrocarbons and halohydrocarbons such as benzene, toluene, Xylene, ethylene dichloride, 1,1,2-trichlorethane, carbon tetrachloride, carbon tetrabromide, trichloroethylene, methylene chloride, perchloroethylene and chloroform.
- 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.
- Example 1 20 grams of bis (p-tolylsulfonyl) ethylene (35% cis isomer and trans isomer) and ml. of chloroform were placed in a flask and two drops of a concentrated bromine solution in carbon tetrachloride were added. The orange color persisted even on Warming. The flask 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 filtration, washed with chloroform until white and dried. There were collected 12.8 grams of trans 1,2-bis (p-tolylsulfonyl) ethylene, melting point 225-227 C. There were recovered by concentration of the mother liquor an additional 6.2 grams of the trans compound.
- Example 2 25.5 grams of the pure cis 1,2-bis (n-propylsulfonyl) ethylene was dissolved in 150 ml. of carbon tetrachloride and a few drops of bromine added. The mixture was then irradiated with an ultraviolet light lamp (sunlamp). A copious precipitate formed as soon as the light source was turned on. After fifteen minutes, this precipitate was removed from the filtrate by filtration and air dried free of carbon tetrachloride. The precipitate Weighed 25 grams. The melting point of the precipitate was 155 156 C. which is the melting point of pure trans 1,2-bis (propylsulfonyl) ethylene. (The cis isomer melts at 42-44 C.)
- Example 2 The same isomerizat-ion was observed when the carbon tetra-chloride in Example 2 was replaced by benzene, ethylene dichloride, 1,1,2-trichlorethane, trichloroethylene, methylene chloride and perchloroethylene.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Ult
3,042,596 Patented July 3, 1962 3,042,596 PHQTOISQMERIC PRERARATION F TRANS BIS @RGANGSULFONYL ETHYLENES James D. Johnston, Baton Rouge, Lat, assignor to Pittsburgh Chemical Company, Pittsburgh, Pa., a corporation 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 corresponding trans bis organosulfonyl ethylenes and haloethylenes.
Bis organosulfonyl ethylenes and haloethylenes have been found to be good fungicides, Johnston Belgian 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. Unfortunately, the normal procedures for preparing the his organosulfonyl ethylenes and haloethylenes either prepare the cis isomer or a mixture of cis and trans isomers containing a large proportion of the cis isomer.
Accordingly, it is an object of the present invention to convert cis bis organosulfonyl ethylenes and haloethylenes to the corresponding trans compounds.
Another object is to convert cis bis alkyl sulfonyl ethylenes to the corresponding trans compounds.
A more specific object is to convert cis bis n-propyl sulfonyl ethylene to trans n-propyl sulfonyl ethylene.
Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, While: indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope or" the invention will become apparent to those skilled in the art from this detailed description.
It has now been found that these objects can be attained by treating a cis bis organosulfonyl ethylene or haloethylene with bromine, preferably in the presence of ultraviolet light.
As the starting cis organosulfonyl ethylenes and haloethylenes there can be employed compounds having the formula where Q and Q are selected from the group consisting of alkyl having 1 to 18 carbon atoms, phenyl, lower alkyl phenyl, benzyl, chlorophenyl, bromophenyl, nitrophenyl and naphthyl and X and X are selected from the group consisting of hydrogen and halogen. Preferably Q and Q are both alkyl groups of 2 to 5 carbon atoms and preferably both X, and X are hydrogen.
As typical examples of cis organosulfonyl ethylenes and haloethylenes which can be converted to the corresponding trans isomers there can be used 1,2-bis(methylsul-fonyl) ethylene; 1,2-bis (ethylsulfonyl) ethylene; 1,2-bis (n-propylsulfonyl) ethylene; 1,2-bis (isopropylsulfonyl) ethylene; 1,2-bis (n-butylsultonyl) ethylene; 1,2-bis (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;
(octylsulfonyl) ethylene; (nonylsnlfonyl) ethylene; (decylsulfonyl) ethylene; (dodecylsulfonyl) ethylene; (octadecylsulfonyl) ethylene; (benzylsulfonyl) ethylene; (phenylsulfonyl) ethylene; (o-tolylsulfonyl) ethylene; (p-tolylsul-fonyl) ethylene; (m-tolylsulfonyl) ethylene; (Z-naphthylsulfonyl) ethylene; o-nitrophenylsulfonyl) ethylene; (p-nitrophenylsulfonyl) ethylene; (m-nitrosulfonyl) ethylene; (ochlorophenylsulfonyl) ethylene; (p-chlorophenylsulfonyl) ethylene; (m-chlorophenylsulfonyl) ethylene; (o-bromophenylsulfonyl) ethylene; (ethylsulfonyl) -1,2dichloroethylene; (methylsulfonyl) -1,2-dichloroethylene; (n-propylsulfonyl)-1,2-dichloroethylene; (n-propylsulfonyD-1,2-dibromoethylene; n-propylsulfonyl -1 ,Z-difiuoroethylene; (n-propylsulfonyl) -1,2-diiodoethylene; 1,2-bis (isopropylsulfonyl)-1,2-dichloroethyl-ene; 1,2-bis (n-butylsulfonyl) -1,2dichloroethylene; -1,2-bis (ethylsulfonyl)-1-chloro-2fiuoroethylene;
1- me thylsulfonyl) -2-( ethylsulfonyl) 1,2-dichloroethylene; l- (n-propylsulfonyl) -2- (n-butylsulfonyl) ethylene; 1,2-bis dodeeylsulfonyl) -1,2dichloroethylene; 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-fiuoroethylene; 1,2-bis (isopropylsulfonyD-l-chloroethylene; 1,2-bis (nbutylsul-fonyl) -1-chloroethylene; 1,2-bis (isobutylsulfonyl)-1-chloroethylene; 1,2-bis (sec. butylsulfonyl) -1-chloroethylene; 1,2-bis (tert. butylsulfonyl l-chloroethylene; 1-methylsulfonyl-2-butylsulfonyl l-chloroethylene; 1-propylsulfonyl-2-butylsulfonyl ethylene; 1,2-bis (octylsulfonyl)-l-chloroethylene;
1,2-bis l,2-bis l,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2bis 1,2-bis 1,2-bis 1,2-bis 1,2bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis 1,2-bis and 1,2-bis (octadecylsulfonyl)-l-ehloroethylene.
Since most of the cis organosulfonyl compounds set forth above are solids, it is desirable to carry out the isomerization in the presence of a solvent. The preferred solvents are hydrocarbons and halohydrocarbons such as benzene, toluene, Xylene, ethylene dichloride, 1,1,2-trichlorethane, carbon tetrachloride, carbon tetrabromide, trichloroethylene, methylene chloride, perchloroethylene and chloroform.
Only a few drops of bromine need be added, although considerably more bromine can be employed but this is 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 specification and claims, all parts and percentages are by weight unless otherwise indicated.
Example 1 20 grams of bis (p-tolylsulfonyl) ethylene (35% cis isomer and trans isomer) and ml. of chloroform were placed in a flask and two drops of a concentrated bromine solution in carbon tetrachloride were added. The orange color persisted even on Warming. The flask 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 filtration, washed with chloroform until white and dried. There were collected 12.8 grams of trans 1,2-bis (p-tolylsulfonyl) ethylene, melting point 225-227 C. There were recovered by concentration of the mother liquor an additional 6.2 grams of the trans compound.
Example 2 25.5 grams of the pure cis 1,2-bis (n-propylsulfonyl) ethylene was dissolved in 150 ml. of carbon tetrachloride and a few drops of bromine added. The mixture was then irradiated with an ultraviolet light lamp (sunlamp). A copious precipitate formed as soon as the light source was turned on. After fifteen minutes, this precipitate was removed from the filtrate by filtration and air dried free of carbon tetrachloride. The precipitate Weighed 25 grams. The melting point of the precipitate was 155 156 C. which is the melting point of pure trans 1,2-bis (propylsulfonyl) ethylene. (The cis isomer melts at 42-44 C.)
The same isomerizat-ion was observed when the carbon tetra-chloride in Example 2 was replaced by benzene, ethylene dichloride, 1,1,2-trichlorethane, trichloroethylene, methylene chloride and perchloroethylene.
The results obtained are surprising since other methods which have been employed for converting cis isomers 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:
4 1. The method of converting the cis isomer of a compound having the formula S Q2 1% X2 0 0 wherein Q and Q are selected from the group consisting of alkyl, aryl, haloaryl and nitroaryl and X and X are selected from the group consisting of hydrogen and halogen to the trans isomer comprising treating said cis isomer with bromine in the presence of ultraviolet light.
2. A method according to claim 1 wherein the cis compound is dissolved in a solvent.
3. A method according to claim 2 wherein X and X are both hydrogen.
4. The method of converting the cis isomer of a bisalkylsulfonyl ethylene to the trans isomer comprising treating said cis isomer with bromine in the presence of ultraviolet light.
5. A method according to claim 4 wherein the cis compound is dissolved in a solvent.
6. A method according to claim 5 wherein the alkyl groups have 2 to 5 carbon atoms each.
7. The method of converting cis bis (n-propylsulfonyl) ethylene to trans bis (n-propylsulfonyl) ethylene comprising treating said cis isomer while dissolved in a solvent with bromine in the presence of ultraviolet light.
References Cited in the file of this patent UNITED STATES PATENTS 2,893,911 Raa-sch July 7, 1959 OTHER REFERENCES Journal of the American Chemical Society, vol. 59 (1937), page 1155.
Claims (1)
1. THE METHOD OF CONVERTING THE CIS ISOMER OF A COMPOUND HAVING THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42971A US3042596A (en) | 1960-07-15 | 1960-07-15 | Photoisomeric preparation of trans bis organosulfonyl ethylenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42971A US3042596A (en) | 1960-07-15 | 1960-07-15 | Photoisomeric preparation of trans bis organosulfonyl ethylenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3042596A true US3042596A (en) | 1962-07-03 |
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| US42971A Expired - Lifetime US3042596A (en) | 1960-07-15 | 1960-07-15 | Photoisomeric preparation of trans bis organosulfonyl ethylenes |
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| Country | Link |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2893911A (en) * | 1957-09-12 | 1959-07-07 | Du Pont | 1, 2-bis(alkylsulfoxy)-1, 2-dihaloethylenes and fungicidal compositions comprising them |
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1960
- 1960-07-15 US US42971A patent/US3042596A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2893911A (en) * | 1957-09-12 | 1959-07-07 | Du Pont | 1, 2-bis(alkylsulfoxy)-1, 2-dihaloethylenes and fungicidal compositions comprising them |
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