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.

Key words: ANION GROUP, ELECTRON SPIN RESONANCE SPECTROMETRY, ALKANE P, CYCLOPROPANE CARBOXYLIC ACID P, ACYL COMPOUND, NITRO HYDROCARBON, PEROXYACID, SINGLE ELECTRON TRANSFER REACTION