Electrophilic Aromatic Substitution. 7. A Kinetic Study of the Aluminum Chloride Catalyzed Desulfonylative Benzylation of Aromatics with Phenylmethanesulfonyl Chloride in Nitromethane.

Article abstract of DOI:10.1021/jo00195a017

Kinetic studies have been made of the AlCl3-catalyzed reaction of phenylmethanesulfonyl chloride with benzene or toluene in nitromethane at 20 deg C.The reaction follows first-order dependence upon phenylmethanesulfonyl chloride and catalyst but zero-order dependence upon aromatic hydrocarbon.It is proposed that the reaction involves a benzyl cation which is formed in situ.Competitive results are also reported for the reaction with (p-chlorophenyl)methanesulfonyl chloride.In both cases, the relative reactivities, k_T/k_B, and toluene isomer product distributions appear to be exceptions to Brown's selectivity relationship.