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关于卤代烃自由基光解生成的电子自旋共振自旋捕集研究。

Electron spin resonance spin trapping studies on the photolytic generation of halocarbon radicals.

作者信息

Davies M J, Slater T F

出版信息

Chem Biol Interact. 1986 May;58(2):137-47. doi: 10.1016/s0009-2797(86)80093-x.

DOI:10.1016/s0009-2797(86)80093-x
PMID:3013435
Abstract

The technique of free radical spin trapping has been used to study the photolytic behaviour of anaerobic solutions of aliphatic halocarbons such as CCl4, CBrCl3 and halothane in either toluene or water at room temperature. Use of the spin traps N-tert-butyl-alpha-phenylnitrone (PBN) and 2-methyl-2-nitrosopropane provides evidence for photolytic cleavage of carbon-halogen bonds yielding radicals such as .CCl3 (from CCl4 and CBrCl3) and .CHClCF3 (from halothane) which are readily trapped; this method of generating biologically important radicals may be of use in studying model reactions of these species. Under aerobic conditions evidence is obtained, by use of the spin trap PBN, for the production of the corresponding halocarbon peroxyl radicals (such as CCl3O2.) by addition of oxygen to the initially produced halocarbon radical. Though the direct detection of the peroxyl radical adducts to the spin trap proved impossible under these experimental conditions, the observed oxidation products of the spin trap (acyl nitroxides) are shown to be indicative of the presence of such species.

摘要

自由基自旋捕集技术已被用于研究室温下在甲苯或水中的脂肪族卤代烃(如四氯化碳、三氯溴甲烷和氟烷)厌氧溶液的光解行为。使用自旋捕集剂N-叔丁基-α-苯基硝酮(PBN)和2-甲基-2-亚硝基丙烷为碳-卤键的光解断裂提供了证据,产生了如·CCl3(来自四氯化碳和三氯溴甲烷)和·CHClCF3(来自氟烷)等容易被捕获的自由基;这种产生具有生物学重要性的自由基的方法可能在研究这些物种的模型反应中有用。在有氧条件下,通过使用自旋捕集剂PBN,获得了证据,证明通过向最初产生的卤代烃自由基中添加氧气会生成相应的卤代烃过氧自由基(如CCl3O2·)。尽管在这些实验条件下无法直接检测到自旋捕集剂与过氧自由基的加合物,但观察到的自旋捕集剂的氧化产物(酰基氮氧化物)表明存在此类物质。

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