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化学学报
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化学学报 ›› 1987, Vol. 45 ›› Issue (1): 83-86. 上一篇    下一篇

研究论文

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   

  1. 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

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在50℃乙腈溶液中,用苯甲酰过氧化物(BPO)能顺利地转化硝基烷烃钠盐为相应的醛和酮.用ESR和IR研究的结果表明反应包含一个从碳阴离子到BPO的电子转移过程.主要产品醛、酮以及苯甲酰亚硝酸酯均来自不稳定的苯甲酸硝基烷基酯的碎裂反应,后者是在离子-自由基对分裂时产生的硝烷基和过氧化苯甲酰基自由基的笼形复合过程中形成的,这些新反应可用于从硝基烷烃合成醛和酮.

关键词: 气相色谱, 烷烃 P, 醛, 酮, 酰化合物, 过氧化物, 酰基, 阴碳离子, 硝基烃, 单电子转移反应

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

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