NUCLEOPHILIC-SUBSTITUTION REACTIONS OF 1-NAPHTHYLMETHYL AND 2-NAPHTYLMETHYL ARENESULFONATES WITH ANILINES

Kinetic studies are carried out on the reactions of 1- and 2-naphthylm ethyl arenesulfonates with anilines in acetonitrile at 25.0 degrees C. The rates are faster for the 2-naphthylmethyl series than for the cor responding 1-naphthylmethyl series suggesting that there is a greater stabilization of positive charge development in the TS at the arylmeth yl reaction center carbon for the former. The sign and magnitude of rh o(xz) (=- 0.12) are similar to those of the benzylic series. Thus, ben zyl, 1- and 2-naphthylmethyl derivatives belong to a class of compound s which react with aniline nucleophiles through a relatively loose S(N )2 TS. Kinetic secondary deuterium isotope effects indicated that a st ronger nucleophile and nucleofuge lead to a later TS as the definition of rho(XZ) requires.