Kovalenko V. Reactions of dimethylcarbamoyl group transfer between pyridines and pyridine N-oxides

The reactions 108 in number of dimethylcarbamoyl group transfer between pyridines and pyridine N-oxides in acetonitrile solutions have been studied. The rate constants vary from 10-5 to 10+3 l/(mol·с). The equilibrium constants of acetyl and dimethylcarbamoyl group transfer vary from 10-8 to 10+8 and do not depend on nature of acyl groups. The reactions of dimethylcarbamoyl group transfer between pyridines and pyridine N-oxides in acetonitrile solutions proceed through concerted mechanism. The structure of TS and its position on the reaction coordinate for identity reactions have been considered with the help of More-O'Ferral-Jencks diagram.The Marcus equation is enable to describe symmetrical reactions of dimethylcarbamoyl group transfer. It is received modified Marcus equation, which allows to describe nonsymmetrical reactions of dimethylcarbamoyl group transfer.