HOMOLYTIC DISPLACEMENT AT CARBON VI. SYNTHESIS OF TRICHLOROETHYLARENES FROM BENZYLCOBALOXIMES

Article abstract of DOI:10.1016/S0022-328X(00)83473-7

Benzylbis(dimethylglyoximato)pyridinecobalt(III) reacts with bromotrichloromethane at from 50 to 90 deg C in chloroform to give good yields of trichloroethylbenzene, which are higher when imidazole is present in the reaction mixture.Methyl- and polymethyl-substituted benzylbis(dimethylglyximato)pyridinecobalt(III) complexes give higher yields of the corresponding trichloroethylarenes (85-90percent), whereas 4-chlorobenzylbis(dimethylglyoximato)pyridinecobalt(III) only gives the 4-nitro-trichloroethylarene when imidazole is present during the reaciton.Similar reactions were observed with benzylcobaloximes and trichloromethanesulphonyl chloride both thermally and under irradiation by tungsten lamps through all-pyrex apparatus.The reactions are interpreted as a direct attack of the trichloromethyl radical on the α-carbon of the benzyl ligand.