Regiochemistry and reactivity in the chlorination of sulfides

Abstract

Huheey's original method for the calculation of substituent electronegativities is modified so that isomeric groups have different electronegativities. The modified form of Huheey's method is then employed to show that our previously published method for anticipating regiochemistry in asymmetric sulfide chlorinations, i.e., ΔXP calculations for the α and α′ substituents in the sulfide substrates, is successful in all fifty known cases. A new reactivity function (RP) is defined, for the sulfenium ion intermediates, which permits one to anticipate when substrates become inert to chlorine in exhaustive chlorinations conducted in aprotic media.