高等学校化学学报

高等学校化学学报 ›› 1994, Vol. 15 ›› Issue (1): 63.

• 论文 • 上一篇    下一篇

双－全氟烷基氮氧自由基从取代苯甲醛的攫氢反应──用EPR方法建立取代基自旋离域参数σ的新尝试

赵成学1, 曲延玲1, 张维新1, 蒋锡夔2, 陈国飞2   

  1. 1. 华中理工大学化学系, 武汉, 430074;
    2. 上海有机化学研究所, 上海, 200032
  • 收稿日期:1993-03-10 修回日期:1993-07-31 出版日期:1994-01-24 发布日期:1994-01-24
  • 通讯作者: 赵成学,男,53岁,教授.
  • 作者简介:赵成学,男,53岁,教授.
  • 基金资助:

    国家自然科学基金

H-Abstraction from p-Substituted Benzaldehydes by Bis-perfluoroalkyl Nitroxides──A New Attempt for Establishing Substituent Constants of Spin Delocalization σ by EPR Method

ZHAO Cheng-Xue1, QU Yan-Ling1, ZHANG Wei-Xin1, JIANG Xi-Kui2, CHEN Guo-Fei2   

  1. 1. Departmient of Chemistry, Huazhong University of Science and Technology, Wuhan, 430074;
    2. Shanghai Institute of Organic Chemistry, Shanghai
  • Received:1993-03-10 Revised:1993-07-31 Online:1994-01-24 Published:1994-01-24

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摘要： RFN(O )RF和RFNO的F113溶液在室温下与一系列的对位取代苯甲醛反应,得到稳定的对位取代苯甲酰基全氟烷基氮氧自由基。由△aN和△aFβ的σ单参数相关以及△aN与σ和σ 双参数相关表明:极性效应是影响氟烷基酰基氮氧自由基中氮原子自旋密度变化的主要因素,而自旋离域效应的影响是很小的。

关键词: 攫氢, 对位取代苯甲酰基－氟烷基氮氧自由基, 相关分析, 极性效应, 自旋离域

Abstract: RFN(O·)RF and RFNO dissolved in F113 reacted with a series of p-substituted benzaldehydes at r,t.and ended up with very stable p-substituted benzoyl perfluoroalkyl nitroxides.Correlation analysis(△aN or △aFβ vis σ only;△aN vis σand σ both) disclosed that the polar effect is the major factor varying the spin density on the nitrtigen atom of the fluorinated acylnitroxides while the effect through spin delocalization is almost negligible.

Key words: Hydrogen abstraction, p-Substituted benzoyl fluoroalkyl nitroxides, Correlation analysis, Polar effects, Spin delocalization

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