The stabilities of Meisenheimer complexes. Part 29. The reactions of 2,4,6-trinitrotoluene and 2,4,6-trinitrobenzyl chloride with aliphatic amines in dimethyl sulphoxide

Abstract

Kinetic and spectroscopic studies have been made of the reactions in dimethyl sulphoxide of 2,4,6-trinitrotoluene (TNT) and 2,4,6-trinitrobenzyl chloride (TNBCl) with the amines n-butylamine, isopropylamine, benzylamine, piperidine, and 1,4-diazabicyclo[2.2.2]octane. Two processes have been identified, σ-adduct formation and transfer of a side-chain proton. Kinetic and equilibrium data relating to the latter reaction show that the rate of the proton transfer from substrate to amine is relatively insensitive to the nature of the reagents, indicating a reactant-like transition state. The σ-adducts formed from TNBCl and the primary amines are thought to result from attack at the 1-position, while those formed from TNBCl and piperidine or from TNT probably involve attack at the 3-position. Equilibrium constants for these reactions have been determined.