The kinetics of chlorination of toluene, o-methyl toluene, p-methyl toluene, m-methyl toluene, and m-chlorotoluene by chloramine-T(CAT) in aqueous acetic acid in the presence of HClOl have been studied. The reaction is first order with respect to [CAT] as well as [H+].The order with respect to the substrate is unity in the case of toluene and m-chlorotoluene, fractional in the case of o-methyl toluene and p-methyl toluene, and zero order in the case of m-methyl toluene. Nuclear halogenation has been observed with m-methyl toluene, while nuclear and side-chain halogenation for p-methyl toluene and o-methyl toluene, and sidechain halogenation for toluene and m-chlorotoluene are the pathways. An increase in the proportion of acetic acid accelerates the rate. Added acetate ions inhibit the reaction, and added p-toluene sulfonamide causes a pronounced retardation. A mechanism involving AcO+HCl as the important electrophile is discussed.
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