Intrinsic reactivities of some carbanions in σ-adduct forming reactions

Abstract

Kinetic and equilibrium data are reported for nucleophilic attack in methanol at unsubstituted ring-positions of 1,3,5-trinitrobenzene, 2,4,6-trinitrotoluene and 1-chloro-2,4,6-trinitrobenzene by carbanions derived from dimethyl malonate, ethyl cyanoacetate and 4-nitro-, 4-cyano- and 2-cyanobenzyl cyanides. The results are used to determine intrinsic reactivities for the carbanions in these σ-adduct forming reactions and are discussed in terms of the electronic and solvent reorganisation occurring during reaction.