高等学校化学学报

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (4): 724.doi:

• 研究论文 • 上一篇    下一篇

偶氮基杯芳烃化合物的合成及其偶氮-醌腙互变异构性质

范平1, 金辄1,2, 潘懿1, 刘光锦1   

    1. 辽宁大学化学院, 沈阳 110036;
    2. 沈阳药科大学制药工程学院, 沈阳 110016
  • 收稿日期:2008-07-23 出版日期:2009-04-10 发布日期:2009-04-10
  • 通讯作者: 范平, E-mail:fpingping2008@sina.com
  • 基金资助:

    辽宁省自然科学基金(批准号: 002082)资助.

Synthesis and Azo-quinoid Tautomerizm of Azocalixarene

FAN Ping1*, JIN Zhe1,2, PAN Yi1, LIU Guang-Jin1   

    1. College of Chemistry, Liaoning University, Shenyang 110036, China;
    2. School of Pharmaceutical Engineering, Shenyang Pharmaceutical University, Shenyang 110016, China
  • Received:2008-07-23 Online:2009-04-10 Published:2009-04-10
  • Contact: FAN Ping, E-mail:fpingping2008@sina.com

PDF (PC)

被引次数

9

摘要：

通过芳胺的重氮化-偶合反应合成了8个偶氮基杯芳烃化合物, 其结构经IR, 1H NMR, ESI-MS和元素分析表征. 通过UV-Vis, 1H NMR和IR考察了溶液pH值对所合成化合物5,11,17,23-四[(2-苯并噻唑基)偶氮基]-25,26,27,28-四羟基杯芳烃(3)和5,17-二[(1-萘基)偶氮基]-25,26,27,28-四羟基杯芳烃(4)的偶氮-醌腙互变异构的影响. 结果表明, 随着溶液pH值增加, 醌腙体在偶氮-醌腙互变异构平衡中的比例增加, 当pH≥10时, 几乎全部转变为醌腙体. 特别当溶液pH=-1时, 化合物4可以形成一种大的共轭体系, 使其λmax由477 nm红移至545 nm.

关键词: 偶氮基杯芳烃, 重氮化-偶合反应, 酸效应, 偶氮-醌腙互变异构

Abstract:

The introduction of chromophoric azo group into calixarene was of great value for the development of functional calixarenes, and the azo-coupled calixarene usually showed large UV-Vis band shifts when base was added. Eight azocalixarene compounds were synthesized by diazo-coupling reaction. These compounds were characterized by IR, 1H NMR, ESI-MS and elemental analysis. The effect of varying pH values upon the absorption ability of both 5,11,17,23-tetra[(2-benzothiazole)azo]-25,26,27,28-tetrahydroxycalixarene and 5,17-di[(1-naphthyl)azo]-25,26,27,28-tetrahydroxycalixarene was tested to study the azo-quinoid tautomerizm phenomena. Observed result exhibit that with the increasing of pH, the proportion of quinoid tautomer in azo-quinoid tautomerizm equilibrium is rised. Unexpectedly an conjugated system may be formed in the condition of pH=-1 for 5,17-di[(1-naphthyl)-azo]-25,26,27,28-tetrahydroxycalixarene, of which the UV absorption spectra show substantial bathochromic shifts(Δλ=477—545 nm).

Key words: Azocalixarene, Diazo-coupling reaction, Acidity effect, Azo-quinoid tautomerizm

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