Radical-type addition of benzyl bromide to vinyl chloride: the kinetics and activation energy of the process

Article abstract of DOI:10.1007/BF00698942

Radical telomerization of vinyl chloride with benzyl bromide and the competitive reaction of benzyl bromide with vinyl chloride and trimethylvinylsilane have been studied.The relative rate constant for the addition of C6H5C(*)H2 to vinyl chloride, k_rel (with respect to trimethylvinylsilane), is close to unity, whereas the activation energy of the addition of C6H5C(*)H2 to vinyl chloride is considerably lower (by 7 kcal mol^-1) than in the reaction involving trimethylvinylsilane.The possible fragmentation of the radical-adduct C6H5CH2CH2C(*)HCl was suggested as one of the possible reasons of underestimation of k_rel^Cl.The activation energy was estimated by the MPDO/3 method.