Structure and reactivity of heterosubstituted nitriles. Part XIV. Kinetics and mechanisms of cyanogen bromide reactions with N-alkylanilines

Abstract

The third-order, rate constants for formation of N-alkyl-N-arylcyanamides from cyanogen bromide and N-alkyl-N-arylamines in the presence of hydroxylic compounds in acetone have been determined. The slow step of the reaction is nucleophilic attack of amine on cyanogen bromide. This probably implies a six-membered ring transition state, as seems proved by a study of electronic and steric effects, entropy and enthalpy of activation, and solvent effects.