Ab Initio Molecular Orbital Study of Reactivity of Active Alkyl Groups. II. Deprotonation of Some Acyclic Carbonyl Compounds with Methoxide Anion

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The present report describes sudies on the reaction mechanisms of an α-proton abstraction from acetone (MMK), methyl ethyl ketone (MEK), methyl isopropyl ketone (MIPK) and methyl tert-butyl ketone (MTBK) using CH_3ONa in CH_3OD solution. The activation energies for the deuterium exchange reaction of active methyl group of the ketones MMK, MEK, MIPK and MTBK were 11.87,12.14,12.29 and 13.14 kcal・mol^<-1>, respectively. The deprotonation reaction mechanisms of the methyl alkyl ketones with methoxide anion were studied by ab initio molecular orbital method. Optimized geometries and energies of all complexes consisting of two molecules were calculated by 6-31+G basis set. The correlation between the activation energies and the differences in calculated energies of the transition state (E_TS) and the H-bonded encounter complex I (E_1) was fairly good. It is shown that the mechanisms of the deprotonation reactions can be explained with a simple model consisting of a methyl alkyl ketone and a methoxide anion.
公益社団法人日本薬学会の論文
1991-10-25