The benzoyl peroxide initiated addition of carbon tetrachloride to olefins

The initiation, propagation and termination steps of the benzoyl perioxide initiated additon of carbon tetrachloride to olefins are described. Initiation follows two main routes, viz. a) addition of benzoate and of phenyl radicals to the olefinic double bond, followed by chlorine abstraction from carbon tetrachloride by the new radicals and b) formation of trichloromethyl radicals from carbon tetrachloride and phenyl radicals. The propagation mechanism proposed by Kharasch et al.2) is confirmed and the extent of telomer *) formation estimated for the case of cetene. Chain termination consists in the formation of stable allyl‐type radicals, which are incapable of starting a new chain; in the case of cyclohexene, these radicals were found in the form of their dimer 3,3′‐dicyclohexenyl. Supporting evidence is based on detailed analyses of the reaction mixtures, peroxide decomposition products and other by‐products being isolated and identified. Further arguments follow from the influence of retarders and the results obtained with olefins of a special structure.