title: Ab initio molecular orbital study of reactivity of active alkyl groups. IV. Nitrosation of acyclic carbonyl compound with methyl nitrite via "open-chain" transition state.
abstract: The mechanism of the nitrosation of enolate anion of acetone [CH3COCH2]- (1) with methyl nitrite CH3ONO (2) via an "open-chain" transition state without Na+ in the C-N bond formation process was studied by the ab initio MO method. The complex [CH3COCH2NO(OCH3)]- (C-II) was first formed from the adduct (C-I) of 1 and 2 through the transition state (TSI). Finally, E-1-hydroxyimino-2-oxo-propane CH3COCH=NOH (3E), together with Z-form (3Z), was obtained by way of the elimination process. It has become apparent that 3E is formed when C-II-A is produced in the C-N bond formation process.
authors: Faculty of Pharmaceutical Sciences, Fukuoka University, Japan. niiya@fukuoka-u.ac.jp
authors: T
authors: T
authors: Niiya
authors: H
authors: H
authors: Ikeda
authors: M
authors: M
authors: Yukawa
authors: Y
authors: Y
authors: Goto
mesh_terms: D000096:Acetone; D002614:Chelating Agents; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D007202:Indicators and Reagents; D007659:Ketones / Q000737:chemistry*; D009573:Nitrites / Q000737:chemistry*; D009603:Nitroso Compounds / Q000138:chemical synthesis; D012997:Solvents
chemical_list: D002614:Chelating Agents; D007202:Indicators and Reagents; D007659:Ketones; D009573:Nitrites; D009603:Nitroso Compounds; D012997:Solvents; D000096:Acetone; C037538:methyl nitrite