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有机化学
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有机化学 ›› 2006, Vol. 26 ›› Issue (04): 482-486. 上一篇    下一篇

研究论文

杯芳烃与NO2硝化反应的研究

于付江，杨海军，李勇*   

  1. (清华大学化学系 生命有机磷化学及化学生物学教育部重点实验室 北京 100084)
  • 收稿日期:2005-08-17 修回日期:2005-10-08 发布日期:2006-03-31
  • 通讯作者: 李勇

Study on the Nitration of Calix[n]arenes with Nitrogen Diox-ide

YU Fu-Jiang,YANG Hai-Jun,LI Yong*   

  1. (Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology of Ministry of Educa-tion,
    Department of Chemistry, Tsinghua University, Beijing 100084)
  • Received:2005-08-17 Revised:2005-10-08 Published:2006-03-31
  • Contact: LI Yong

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系统地研究了羟基杯[n]芳烃、甲氧基杯[n]芳烃和对特丁基杯[n]芳烃(n＝4, 6, 8)与NO2气体的硝化反应, 发现可以成功地得到25,26,27,28-四羟基杯[4]芳烃、37,38,39,40,41,42-六羟基杯[6]芳烃以及25,26,27,28-四甲氧基杯[4]芳烃的对位全硝化产物, 产率分别为90%, 70%和40%; 尤其是25,26,27,28-四羟基杯[4]芳烃与NO2的反应20 min即可完成. 认为共振式酚氧负离子结构是影响该类硝化反应的关键, 并对反应机理进行了探讨.

关键词: NO2, 硝化反应, 杯芳烃

Syntheses of p-nitrocalix[n]arenes were carried out under different reaction conditions by using nitrogen dioxide as nitration agent. It was found that only p-nitrocalix[4]arene, p-nitrocalix[6]arene and 25,26,27,28-tetramethoxy-5,11,17,23-tetranitrocalix[4]arene were obtained from the corresponding calix[4]- arene, calix[6]arene and 25,26,27,28-tetramethoxycalix[4]arene in yields of 90%, 70% and 40% respectively. Especially, the reaction of calix[4]arene with NO2 could be finished in 20 min. The reaction mechanism based on resonance structures of phenoxy anion in calixarene is discussed.

Key words: nitration, nitrogen dioxide, calix[n]arene