酰基过氧化物的化学 VII: 过氧化环丙基甲酰与硝基烷烃阴离子的单电子转移反应

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DN 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 chemistry of diacyl peroxides VII: Electron transfer reactions between cyclopropylformyl peroxide and carbanions derived from secondary nitroalkanes

The carbanions derived from secondary nitroalkanes can be oxidized into ketones by cyclopropylformyl peroxide (I) in acetonitrile at 70? Both product studies and ESR observations support a mechanism that involves an initial electron-transfer step from the carbanions to I. 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, resp. The short-lived dicyclopropyl nitroxide is the spin adduct of cyclopropyl radical to nitrosocyclopropane generated from decarboxylation of the unstable fragmentation product, cyclopropylformyl nitrite.