DISTINCTIVE AND SOLVENT-DEPENDENT BEHAVIOUR OF SOME PER(CHLORO,FLUORO)ETHANES IN THEIR REACTIONS WITH PhSNa. COMPETING MECHAMISTIC PATHWAYS IN HALOPHILIC REACTIONS

Article abstract of DOI:10.1016/S0022-1139(00)80535-7

Per(chloro,fluoro)ethanes CF2XCCl2Y (1) react spontaneously with PhSNa at room temperature or below to give PhSCF2CCl2Y (2) in fair to good yield, which as well as the by-products PhSCF2CClYH (3) and PhSCF=CCl2 (4) (for 1b and 1c) are most probably produced by an anionic chain process initiated by the chlorophilic attack of PhS^- on C-Cl bonds.In case of 1c, the coexistence of two competitive reaction pathways is indicated by the two products 2b and PhSCCl2CF3 (10).The reaction rates and the product distribution have been found to be highly solvent-dependent.Products 2b, 4 and 10 all react further with PhSNa to afford multi-substituted ethylenes PhSCF=C(Cl)SPh (7) (PhS)2C=C(Cl)SPh (8) and (PhS)2C=C(SPh)2 (9).