title: Effects of counter cations of base catalysts on nitrosation mechanisms.
abstract: Reaction of 2-butanone (1) with tert-butyl nitrite (tert-BuONO) was performed using base catalysts (RO-M+: R=CH3, C2H5; M+=Li+, Na+, K+) in alcohols (CH3OH or C2H5OH). In this report, the effects of M+ of RO-M+ on the nitrosation mechanisms were investigated. The yield of E-hydroxyimino compound (5E) increases much better in the reaction using Na+ or K+ as M+ compared with that using Li+. It is also observed that the yield of 5E increases by addition of crown ether as a cation-capturing agent. The experimental results suggested that under the conditions lowering the effects of M+ of RO-M+ on the nitrosation mechanisms, because the reactivity of naked enolate of I increases and the reaction in the C-N bond formation process tends to proceed via open-chain transition state without M+, the yield of 5E tends to increase.
authors.affiliation: Faculty of Pharmaceutical Sciences, Fukuoka University, Japan. ikeda@fukuoka-u.ac.jp
authors.forename: H
authors.initials: H
authors.lastname: Ikeda
authors.forename: M
authors.initials: M
authors.lastname: Yukawa
authors.forename: T
authors.initials: T
authors.lastname: Niiya
authors.forename: Y
authors.initials: Y
authors.lastname: Goto
mesh_terms: D002384:Catalysis; D002412:Cations; D004583:Electrons; D004988:Ethers, Cyclic / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry; D009603:Nitroso Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D002412:Cations; D004988:Ethers, Cyclic; D009603:Nitroso Compounds