Kinetics of solvolysis of 2-p-benzylphenyl-2-chloropropane and 1-p-benzylphenyl-1-chloroethane in aqueous acetone

Abstract

2-p-Benzylphenyl-2-chloropropane and 1-p-benzylphenyl-1-chloroethane were prepared from the corresponding methanols by action of hydrogen chloride. The methanols were, respectively, prepared from p-benzylacetophenone by reaction with methylmagnesium iodide and reduction by aluminium isoproproxide. The solvolysis rates of the two methyl chlorides were measured in 90% aqueous acetone at various temperatures. The energies of activation for the solvolyses were calculated. The results are compared with those obtained for cumyl chloride and its alkyl substituted derivatives. The comparison allows the evaluation of the substituent constant for the p-benzyl group. The value obtained, satisfactorily, correlates the data for the inefluence of the p-benzyl group in electrophilic aromatic substitution. The products of the reaction consist of a mixture of alcohol and olefin. The structures of the olefins produced were determined by oxidative degradation.