Ab Initio Molecular Orbital Study of Reactivity of Active Alkyl Groups. III. Nitrosation of Acyclic Carbonyl Compound with Methyl Nitrite via Na+ Chelated Transition State.

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The mechanism of the nitrosation of sodium enolate of acetone [CH3COCH2]-Na+ (1) with methyl nitrite CH3ONO (2) to give 1-hydroxy-imino-2-oxo-propane CH3COCH=NOH (3) was studied by the ab initio molecular orbital (MO) method. The complex [CH3COCH2NO(OCH3)]-Na+ (C-II) was first formed from the adduct (C-I) of 1 and 2 through the pericyclic transition state (TS1). Finally, Z-hydroxyimino compound (3Z) was obtained through demethoxylation of 2 moiety and abstraction of an active hydrogen atom in C-II with a base. In the final formation of 3Z, two leaving groups, the methoxy group and the active hydrogen atom in C-II, should be situated in positions with respect to each other which permit their elimination, i.e., they are antiperiplanar to one another. It has become apparent that 3Z tends to be formed predominantly when a countercation of a base coordinates to the oxygen atom of the enolate of acetone.

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