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有机化学
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有机化学 ›› 2007, Vol. 27 ›› Issue (12): 1547-1551. 上一篇    下一篇

研究论文

“黑洞型”缺电子联吡啶环蕃的合成

席海涛a,b，孙小强*,b，魏海林b，孟启b，潘毅a，胡宏纹a   

  1. (a南京大学化学化工学院 南京 210093)
    (b江苏工业学院精细石油化工重点实验室 常州 213164)
  • 收稿日期:2007-03-14 修回日期:2007-08-20 发布日期:2007-12-04
  • 通讯作者: 孙小强

Synthesis of “Black Hole” 4,4'-Bipyridinium Cyclophane

XI Hai-Taoa,b, SUN Xiao-Qiang*,b, WEI Hai-Linb, MENG Qia,
PAN Yia, HU Hong-Wena   

  1. (a Department of Chemistry, Nanjing University, Nanjing 210093)
    (b Key Laboratory of Fine Chemical Engineering, Jiangsu Polytechnic University, Changzhou 213164)
  • Received:2007-03-14 Revised:2007-08-20 Published:2007-12-04
  • Contact: SUN Xiao-Qiang

PDF

1069

被引次数

3

利用2,3,5,6-四氟-1,4-苯二甲酸为原料, 经过酯化、还原及溴代, 合成1,4-二溴甲基-2,3,5,6-四氟苯. 以其为原料在低温下利用模板效应合成高度缺电子的“黑洞型”缺电子联吡啶环蕃化合物, 经过连续液液萃取及离子交换得到“黑洞型”缺电子联吡啶环蕃单体. 产品经1H NMR, 13C NMR, MS表征. 利用变温核磁共振技术研究“黑洞型”缺电子联吡啶环蕃与经典的双环(百草枯-对苯撑)型缺电子联吡啶环蕃在溶液中的变化.

关键词: 2,3,5,6-四氟-1,4-苯二甲酸, 变温核磁共振, 1,4-二溴甲基-2,3,5,6-四氟苯, 模板效应, 环蕃, 黑洞型

The 4,4'-bipyridinium-based cyclophane cyclo(paraquat-2,3,5,6-tetrafluoro-p-phenylene- paraquat) was prepared by the template-directed synthesis in a 21% yield, of which the starting material 1,4-bis(bromomethyl)-2,3,5,6-tetrafluorobenzene was prepared by the esterification of 2,3,5,6-tetrafluoro-p- phthalic acid with methanol, reduction with LiAlH4 to give 1,4-bis(hydroxymethyl)-2,3,5,6-tetrafluorobenzene, and then bromination with toluene and 48% HBr. The free cyclophane was characterized by MS, 1H NMR and 13C NMR spectra. The influence of fluorine on the cyclophane in solution was studied by dynamic 1H NMR spectroscopy.

Key words: 1,4-bis(bromomethyl)-2,3,5,6-tetrafluorobenzene, template, cyclophane, black hole, dynamic 1H NMR spectroscopy, 2,3,5,6-tetrafluoro-p-phthalic acid