摘要
过氧化环丙基甲酰(CPP)能将硝基仲烷烃阴离子氧化成相应的酮.产物分析和ESR研究揭示该反应经过由硝基烷烃阴离子向CPP的单电子转移引发步骤及随后的一系列自由基反应步骤,生成主要产物酮和典型的自由基副产物,如双环丙基、硝基烷基二聚体和能被ESR直接检测的双环丙基氮氧自由基等.
The carbanions derived from secondary nitroalkanes can be oxidized into ketones by cyclopropylformyl peroxide(CPP)in acetonitrile at 70℃.Both product studies and ESR observations support a mechanism that involves an initial electron-transfer step from the carbanions to CPP.The major product,ketone,originates from the fragmentation of the unstable cage combination product,nitroalkyl cyclopropylformate.The minor products,bicyclopropyl,gem-dinitroalkane and nitroalkane are coupling products of cyclopropyl and nitroalkyl radicals,and H-abstraction product of nitroalkyl radicals,respectively.The short-lived di-cyclopropyl nitroxide is the spin adduct of cyclopropyl radical to nitrosocyclopropane generated from decarboxylation of the unstable fragmentation product,cyclopropylformyl nitrite.
出处
《化学学报》
SCIE
CAS
1988年第4期349-352,共4页
Acta Chimica Sinica
