Trifluoromethylthiolation of 1, 3- and 1, 4-Cyclohexadienes

Treatment of 1, 3-cyclohexadiene with CF 3 SCl at m 80°; furnishes 15 compounds. All but the two dimerized adducts arise from the free radical catalyzed addition of CF 3 S and Cl radicals to carbon-carbon double bonds. One dimerized product arises via dimerization of the substrate itself, while the other results from the cross-coupling of the substrate with the reaction product. The same reaction with 1, 4-cyclohexadiene gives 14 compounds. The mass spectral characterization of various compounds and their probable mechanism of formation are presented in this article.