Nucleophilic Substitution Reactions of 1- and 2-Naphtylmethyl Arenesulfonates with Anilines

摘要

Kinetic studies are carried out on the reactions of 1- and 2-naphthylmethyl arenesulfonates with anilines in acetonitrile at 25.0 ∩. The rates are faster for the 2-naphthylmethyl series than for the corresponding 1-naphthylmethyl series suggesting that there is a greater stabilization of positive charge development in the TS at the arylmethyl reaction center carbon for the former. The sign and magnitude of ヱxz (=-0.12) are similar to those of the benzylic series. Thus, benzyl, 1- and 2-naphthylmethyl derivatives belong to a class of compounds which react with aniline nucleophiles through a relatively loose SN2 TS. Kinetic secondary deuterium isotope effects indicated that a stronger nucleophile and nucleofuge lead to a later TS as the definition of ヱxz requires.