Reaction of benzeneselenol with tri- and tetrachloroethylenes under conditions of phase-transfer catalysis
The reaction of benzeneselenol with trichloroethylene in concentrated sodium hydroxide solution, catalyzed by ammonium salts, leads to Z-phenyl /alpha/,/beta/-dichlorovinyl selenide with an equimolar ratio of the catalyst and the selenol or to a mixture of the Z and E isomers with a ratio of 1:10. In addition to the expected trichlorovinyl selenide PhSeCCl=CCl/sub 2/, the analogous reaction with tetrachloroethylene also gives a mixture of the Z and E isomers of /alpha/-/beta/-dichlorovinyl selenides, and in addition, 1,2-bis(phenylseleno)-1,2-dichloroethylene PhSeCCl = CClSePh. If trialkylbenzylammonium chlorides R/sub 3/PhCH/sub 2/N/sup +/Cl/sup /minus// are used as catalyst, phenyl benzyl selenide PhSeCH/sub 2/Ph is formed as a side product. The results of the reaction in the case of trichloroethylene are explained by the addition of the selenolate ion to the CCl/identical to/CCl, generated from the trichloroethylene in situ, and isomerization of the initially formed Z-phenyl /alpha/,/beta/-dichlorovinyl selenide to the thermodynamically more stable E isomer. In the case of tetrachloroethylene they are explained by the usual addition-elimination mechanism with the formation of trichlorovinyl selenide, accompanied by reductive dechlorination of the CCl/sub 2/-CCl/sub 2/ to CHCl=CCl/sub 2/ by the selenolate and subsequent reaction of the selenolate with CHCl=CCl/sub 2/.
- Research Organization:
- Irkutsk Institute of Organic Chemistry (USSR)
- OSTI ID:
- 5950047
- Journal Information:
- J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 24:3; ISSN JOCYA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKENES
AMINES
AMMONIUM CHLORIDES
AMMONIUM COMPOUNDS
AMMONIUM HALIDES
AROMATICS
BENZENE
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
CHLORIDES
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE COMPOUNDS
CHROMATOGRAPHY
DECHLORINATION
DEHALOGENATION
ETHYLENE
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HETEROGENEOUS CATALYSIS
HYDROCARBONS
INFRARED SPECTRA
IODIDES
IODINE COMPOUNDS
ISOMERIZATION
ISOMERS
MASS SPECTRA
NMR SPECTRA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
QUATERNARY COMPOUNDS
SELENIUM COMPOUNDS
SEPARATION PROCESSES
SPECTRA