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

Kinetic studies have been made of the AlCl₃-catalyzed reaction of phenylmethanesulfonyl chloride with benzene or toluene in nitromethane at 20 °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 Me 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 appeM to be exceptions to Brown's selectivity relationship.