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

摘要

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(N)2 mechanism determined by enhanced donor-acceptor and acid-base properties of amine complexes with alcohol associates in comparison to amines.