KINETICS OF ALKALINE HYDROLYSIS OF N1-METHYLNICOTINAMIDE CATION

The kinetics of the base-catalyzed hydrolysis of N1-methylnicotinamide cation were studied over a wide range of hydroxide ion concentrations and at several different temperatures. The apparent first-order rate constant which characterized the disappearance of substrate exhibited a complex dependence on hydroxide ion concentration. A reaction mechanism which incorporated specific base catalysis, superimposed general base catalysis by hydroxide ion, and ionization of an amide hydrogen is proposed to explain the observed behavior. The influence of temperature on the parameters of the derived rate law indicated the existence, in the reaction pathway, of a stabilized intermediate which required the addition of energy to form either reactants or products. The possibility of an internal electrostatic interaction which contributed to the stability of the intermediate is proposed. © 1968, American Chemical Society. All rights reserved.