NUCLEOPHILIC SUBSTITUTION REACTION OF BENZYL BENZENESULFONATES WITH ANILINES IN MeOH-MeCN MIXTURES-I. EFFECTS OF SUBSTITUENT AND SOLVENT ON THE TRANSITION-STATE STRUCTURE.

Article abstract of DOI:10.1016/S0040-4020(01)96365-3

Kinetic studies on nucleophilic substitution reaction of benzyl tosylates with anilines are reported.The reaction was found to proceed via a dissociative S^N2 mechanism with less than 50 percent bond formation and extensive bond breaking at the transition state.It was found that positive charge development at the benzylic carbon is substantial and para-substituent effect on the substrate is predominantly of resonance type.Bond formation is shown to be favored by a better nucleophile, by an electron withdrawing group on the substrate and by the more polar(higher MeCN content) solvent.The substrate, nucleophile and solvent were found to follow the RSP.