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本文报道将先前合成的双多氟和全氟烷基氮氧自由基1与多氟和全氟亚硝基烷烃2混合溶液的技术应用于烷烃、芳烃3自由基攫氢反应的研究。氮氧自由基1由烷烃,芳烃迅速攫氢转变为羟胺,生成的烷基自由基中间体立即被2截捕得到稳定的自旋加合物4和5。由自旋加合物ESR参数,可以确定自由基结构并由此来研究攫氢反应机理。本文也提供了一个产生大量含氟烷基氮氧自由基并研究其结构的有效而简单的方法。
This paper reports the application of the previously synthesized bis-fluorene and perfluoroalkyl nitroxide 1 mixed with polyfluoro and perfluoro-nitrosoalkanes 2 to the hydrogen-abstraction reaction of alkanes and arenes 3 free radicals. Nitroxyl radical 1 was rapidly converted from alkane and aromatic hydrocarbon to hydroxylamine. The resulting alkyl radical intermediate was immediately intercepted by 2 to obtain stable spin adducts 4 and 5. From the spin adduct ESR parameters, we can determine the free radical structure and thus study the mechanism of hydrogen grab reaction. This article also provides an efficient and simple method of generating large amounts of fluoroalkyl nitroxides and studying their structure.