高等学校化学学报

高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (11): 2052.

• 研究论文 • 上一篇    下一篇

“魔蓝”试剂由对位取代苯甲醛区域选择攫氢反应的EPR研究──全氟(1-丙氧基乙基)-对位取代苯甲酰氮氧自由基的合成及其αN,αFβ与取代基参数的相关分析

李晋, 林正欢, 窦红岩, 赵成学   

  1. 上海交通大学化学系, 上海200240
  • 收稿日期:2004-10-08 出版日期:2005-11-10 发布日期:2005-11-10
  • 基金资助:

    国家博士培养基金(批准号:20020248003);国家高新技术研究“八六三”计划基金(批准号:2002AA323040)资助

EPR Study on Regioselective Hydrogen Abstraction from p-Substituted Benzaldehydes by“Magic Blue”──The Generation of Perfluoro[(1-propoxyl)ethyl]p-Substituted Benzoyl Nitrooxides andthe Correlation Analyses of TheirαN,αFβValues with Substituent C

LI Jin, LIN Zheng-Huan, DOUHong-Yan, ZHAO Cheng-Xue   

  1. Department ofChemistry,Shanghai Jiaotong University,Shanghai200240,China
  • Received:2004-10-08 Online:2005-11-10 Published:2005-11-10

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摘要： 由全氟(2-丙氧基丙酰)过氧化物[n-C3F7OCF(CF3)COO]2与亚硝酸钠制得新型的“魔蓝”试剂[n-C3F7OCF(CF3)]2N(O)(1)和n-C3F7OCF(CF3)NO2的F113(CCl2FCClF2)溶液,在室温下与一系列对位取代苯甲醛(3)发生攫氢/自旋截捕反应,生成稳定的全氟(1-丙氧基乙基)对位取代苯甲酰基氮氧自由基(4).由自由基4的超精细偶合常数αN和αFβ与取代基的Hammett极性参数和自旋离域参数的相关分析得知,虽然自旋离域因素影响αN值,但取代基的极性是决定αN值的主要因素.

关键词: 魔蓝, 攫氢, 全氟烷基对位取代苯甲酰基氮氧自由基, 相关分析

Abstract: New“magic blue”reagent containing bis(perfluoroalkyl) nitrooxide [n-C3F7OCF(CF3)]2.N(O.)(1) and perfluoronitrosoalkanen-C3F7OCF(CF3) NO2 in F113(CCl2FCClF2) solution whichwere both generated in the reaction of perfluoro[(2-propoxy)propyonyl] peroxide(n-C3F7OCF(CF3)COO)2with NaNO2,reacted with a series ofp-substituted benzaldehydes(3)viaregioselective abstraction of the for-myl hydrogen followed with spin trapping ofp-substituted benzoyl radical leading to the stable adducts perflu-oroalkylp-substituted benzoyl nitrooxides4.The correlation analyses ofαNandαβFwith all kinds of Hammettpolar and spin delocalization substituent constants disclose that the polar factor is the major factor varying spindensity on the nitrogen atom of the nitrooxides though the spin delocalization affects theαNvalue slightly.

Key words: Magic blue, Hydrogen abstraction, p-Substituted benzoyl perfluoroalkyl nitrooxides, Correlationanalysis

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