Quantum Chemical Study of Addition–Elimination Reactions of Dimethyl Carbonate with Methylamine

详细

The mechanisms of noncatalytic and autocatalytic addition–elimination reactions of dimethyl carbonate with methylamine have been studied in terms of wB97XD/6-311++G(df,p), M06/6-311++G(df,p), and PBE0/6-311++G(df,p) quantum chemical methods, and thermodynamic and activation parameters of these reactions have been calculated. The rate-determining stage is the formation of tetrahedral carbon intermediate. The addition–elimination mechanism is preferred over the autocatalytic S_N2 mechanism determined by enhanced donor–acceptor and acid–base properties of amine complexes with alcohol associates in comparison to amines.