化学学报 ›› 1988, Vol. 46 ›› Issue (9): 924-927. 上一篇    下一篇

研究论文

脂族酰基过氧化物分解动力学的研究X: 过氧化酰热分解反应的自旋捕获ESR研究

郭庆祥;邢丽梅;刘有成   

  1. 兰州大学化学系
  • 出版日期:1988-09-15 发布日期:1988-09-15

Studies on the kinetics of decomposition of diacyl peroxides X: An ESR study of the trapping experiment of thermal decomposition products

GUO QINGXIANG;XING LIMEI;LIU YOUCHENG   

  • Online:1988-09-15 Published:1988-09-15

用亚硝基丁烷(TNB)、亚硝基苯和C-苯基-N-叔丁基硝酮作为自旋捕获剂来捕获和检出一些二酰基过氧化物类化合物分解时形成的短命烷基自由基. 报导了烷基自由基对自旋捕获剂加成的氮氧化物自由基的电子自旋共振谱, 并观察到2,4,4-三甲基戊基自由基中α-CH2的氢是非对映和非等价的. 据此, 认为与这一类自由基的加合物产生的电子自旋共振谱与其它类型自由基是不同的.

关键词: 亚硝基化合物, 热分解法, 反应动力学, 苯, 四氯化碳, 游离基, 自由基反应, 电子自旋共振, 酰化合物, 过氧化物

C-Phenyl-N-tert-butylnitrone (PBN), nitrosobenzene (NB), and tert-nitrosobutane (TNB) have been used as spin-trapping agents for the trapping and detection of short-lived alkyl radicals formed during the decomposition of several diacyl peroxides RC(O)OOC(O)R (R = n-C11H23, n-C9H19, n-C8H17, n-C7H15, n-C5H11, Me2CH(CH2)3, Me2CHCH2, Me3CCH2, Me3CCH2CHMeCH2) in benzene or carbon tetrachloride. The ESR spectra of the nitroxide radicals produced by the addition of alkyl radicals to spin-trapping agents have been recorded. It is observed that the hydrogens of a-CH2 in 2,4,4-trimethylpentyl radical are diastereotopic and nonequivalent and, on account of this, the ESR spectrum produced from the adduct with this radical is different from that with the other radicals.

Key words: NITROSO COMPOUNDS, THERMAL DECOMPOSITION METHOD, REACTION KINETICS, BENZENE, CARBON TETRACHLORIDE, FREE RADICAL, FREE RADICAL REACTION, ELECTRON SPIN RESONANCE, ACYL COMPOUND, PEROXIDE

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