高等学校化学学报

高等学校化学学报 ›› 1992, Vol. 13 ›› Issue (2): 209.

• 论文 • 上一篇    下一篇

烷基-全氟酰氧基氮氧自由基——全氟酰基过氧化物与脂肪族伯、仲胺单电子转移反应的EPR研究

赵成学, 曲延玲, 彭以元   

  1. 华中理工大学化学系, 武汉, 430074
  • 收稿日期:1991-03-27 出版日期:1992-02-24 发布日期:1992-02-24
  • 通讯作者: 赵成学
  • 基金资助:

    国家自然科学基金

AlkyI Perfluoroacyloxyl Nitroxides ——EPR Studies on SET Reactions Between Perfluorodiacyl Peroxides and Aliphatic Amines

ZHAO Cheng-xue, QU Yan-ling, PENG Yi-yuan   

  1. Department of Chemistry, Huazhong University of Science and Technology, Wuhan, 430074
  • Received:1991-03-27 Online:1992-02-24 Published:1992-02-24

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摘要： EPR研究表明,全氟酰基过氧化物在室温下可将脂肪族仲胺氧化成相应的稳定双烷基氮氧自由基。它们与RNH2的氧化反应是单电子转移过程,生成烷基-全氟酰氧基氮氧自由基RN(O·)OCORF;当R为叔烷基时,还生成RN(O·)R、RN(O·)H、RN(O·)RF和RN(O·)RF′(RF′=RF-CF2)等4种稳定性差别很大的氮氧自由基。EPR研究结果揭示了该反应机理的重要信息。

关键词: 全氟酰基过氧化物, 脂肪胺, 单电子转移, EPR, 烷基-全氟酰氧基氮氧自由基

Abstract: Perfluorodiacyl peroxides, (RFCO2)2[R2= n-C3F7, n-C7F15 and H(CF2)4], oxidize secondary aliphatic amines into bis-alkyl nitroxides, RN (O·)R, which are stable in F113 (CClF2-CCl2F) solutions at roon temperatureIn one-electron oxidation reactions of the primary amines, RNH2(R = primary, secondary, as well as tertiary, such as t-butyl) with (RFCO2)2 under the similar conditions, alkyl perfluoroacyloxyl nitroxides RN(O·)OCORF, are always formed and detected by EPRIn the case of t-butyl amine, four more nitroxides of quite different life times, RN(O·)R, RN(O·)H, RN(O·)RFand RN(O·)RF′(RF′=RF-CF2), are observedOur EPRand product studies have revealed the dependence of the reaction patterns on the nature of the Rgroups, of the one-electron oxidation of the primary amines.

Key words: Perfluorodiacyl peroxides, Aliphatic amines, Single electron transfer (SET), EPR, Alkyl perfluoroacyloxyl nitroxides

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