title: Ab initio molecular orbital study of the reactivity of active alkyl groups. V. Nitrosation mechanism of acetone with syn-form of methyl nitrite.
abstract: The mechanisms of nitrosation of acetone through sodium enolate [CH3CO1CH2]-Na+ (1) or naked enolate [CH3CO1CH2]- (2) with methyl nitrite CH3O3NO2 (3), and the reactivity of the syn-form of 3 (syn-3) during the C-N bond formation process were investigated using ab initio molecular orbital (MO) methods. Our results have demonstrated the predominant formation of E-1-hydroxyimino-2-oxo-propane CH3COCH=NOH (4E) when the complex [CH3CO1CH2NO2(O3CH3)]-Na+ was produced kinetically via a metal-chelated pericyclic transition state (TS(CHELATED)), in which the O3 atom of syn-3 was coordinated to the Na+ atom of 1.
authors.affiliation: Faculty of Pharmaceutical Sciences, Fukuoka University, Japan. niiya@fukuoka-u.ac.jp
authors.forename: Tokihiro
authors.initials: T
authors.lastname: Niiya
authors.forename: Hirohito
authors.initials: H
authors.lastname: Ikeda
authors.forename: Miho
authors.initials: M
authors.lastname: Yukawa
authors.forename: Yoshinobu
authors.initials: Y
authors.lastname: Goto
mesh_terms: D000096:Acetone / Q000737:chemistry / Q000378:metabolism*; D009573:Nitrites / Q000737:chemistry / Q000378:metabolism*; D015538:Nitrosation; D013237:Stereoisomerism
chemical_list: D009573:Nitrites; D000096:Acetone; C037538:methyl nitrite