Steric effects in the reaction of alkyl-phenyl and dialkyl-sulphides with chloramine-T

The rate of the reaction of dialkyl- and alkyl-phenyl-sulphides with TsNHCl increases with the increasing +I effect of the S-substituents, while the steric effect is only of minor importance. Rate constants of the reaction of dialkyl sulphides can be correlated with the Taft equation (?^* = ?1.96, δ = 0.285). The effect of ring size of cyclic sulphides on the reaction is discussed. The change of the rate constants with varying S-alkyl substituents is in agreement with a sterically unhindered electrophilic addition of Cl⁺ on bivalent sulphur, leading to chlorosulphonium ion. Sulphimides and sulphoxides are formed from the chlorosulphonium intermediates in the subsequent S_N-type reactions with different steric control.