J. Tousek et al., STUDY OF THE ELECTROCHEMICALLY INITIATED CYANOMETHYLATION OF AZOMETHINES BY MEANS OF THE MNDO AND AM1 SEMIEMPIRICAL METHODS, Collection of Czechoslovak Chemical Communications, 60(12), 1995, pp. 2028-2038
The semiempirical methods (MNDO and AM1) have been used in the quantum
chemical study of electrochemically initiated cyanomethylation of azo
methines. Reaction steps leading to the main product of the studied re
action, beta-aminonitrile, have been described. The stationary points
on the reaction path have been found and the activation enthalpies of
reaction steps have been determined. Three possible mechanisms for the
abstraction of a proton from acetonitrile have been described (by azo
methine radical anion, by beta-aminonitrile anion, and by hydrogenated
azomethine anion). At the MNDO level, the abstraction of a proton by
azomethine radical anion has the highest activation enthalpy (Delta H
= 197 kJ mol(-1)) and the abstraction of a proton by hydrogenated azom
ethine anion has the lowest activation enthalpy (Delta H = 146 kJ mol(
-1)). The activation enthalpy of the next reaction step (the reaction
of acetonitrile anion with azomethine) is low compared to the activati
on enthalpies of the previous reation steps (Delta H = 12 kJ mol(-1)).