Nucleophilic substitution in carbonic acid derivatives. Part II. Kinetics and mechanism of the solvolyses of NN-dialkylcarbamoyl chlorides

Abstract

The effects of structural changes in NN-dialkylcarbamoyl chlorides and in some hydroxylic compounds as solvolytic agents, of solvent polarity, and of the kinetic mass-law, on the rates of solvolyses have been studied. The pseudounimolecular constants are enhanced by the increase of the electron-releasing effects of N-alkyl groups as well as by increasing solvent polarity, and are sensitive to the presence of chloride ions. These results are in agreement with the assumption of the unimolecular mechanism in all cases. The isokinetic relationships suggest two interaction mechanisms by solvation of the transition states.