The chemistry of diacyl peroxides. VI: Electron transfer reactions between benzoyl peroxide and carbanions derived from nitroalkanes for synthesis of aldehydes, ketones

Acta Chimica Sinica ›› 1987, Vol. 45 ›› Issue (1): 83-86. Previous Articles Next Articles

Original Articles

酰基过氧化物的化学 VI:过氧化苯甲酰与硝基烷烃阴离子间的单电子转移反应一种合成醛、酮的新反应

赵成学;曲延玲;蒋锡夔

中国科学院上海有机化学研究所

发布日期:1987-01-15

The chemistry of diacyl peroxides. VI: Electron transfer reactions between benzoyl peroxide and carbanions derived from nitroalkanes for synthesis of aldehydes, ketones

ZHAO CHENGXUE;QU YANLING;JIANG XIKUI

Published:1987-01-15

Abstract

The carbanions R1R2C-NO2 (R1, R2 = e.g. Me, H; Me, Me; Et, Me) derived from nitroalkanes can be easily oxidized into R1R2CO by benzoyl peroxide (BPO) in acetonitrile at 50癈. Product studies combined with ESR and IR detns. strongly support that the reactions involve an initial electron-transfer step from carbanions to BPO. The major products-aldehydes or ketones as well as benzoyl nitrites, come from fragmentation of the unstable nitroalkyl benzoate intermediates formed in cage combination of nitroalkyl and benzoyloxy radicals produced in collapse of ion-radical pair. These new reactions may serve as a synthetic route to aldehydes or ketones from nitroalkanes.

Key words: GAS CHROMATOGRAPHY, ALKANE P, ALDEHYDES, KETONE, ACYL COMPOUND, PEROXIDE, ACYL GROUP, CARBANION, NITRO HYDROCARBON, SINGLE ELECTRON TRANSFER REACTION

CLC Number:

O621.16

Cite this article

ZHAO CHENGXUE;QU YANLING;JIANG XIKUI. The chemistry of diacyl peroxides. VI: Electron transfer reactions between benzoyl peroxide and carbanions derived from nitroalkanes for synthesis of aldehydes, ketones[J]. Acta Chimica Sinica, 1987, 45(1): 83-86.

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酰基过氧化物的化学 VI:过氧化苯甲酰与硝基烷烃阴离子间的单电子转移反应一种合成醛、酮的新反应

The chemistry of diacyl peroxides. VI: Electron transfer reactions between benzoyl peroxide and carbanions derived from nitroalkanes for synthesis of aldehydes, ketones

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