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有机化学
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有机化学 ›› 2010, Vol. 30 ›› Issue (11): 1716-1720. 上一篇    下一篇

研究论文

4-异丁氧基-10-羟基-1,7-二氮杂菲-2,8-二羧酸甲酯的合成、表征及晶体结构

朱恒衡1,2，管自生*,1，詹传郎2   

  1. (1南京工业大学材料科学与工程学院 南京 210009)
    (2中国科学院化学研究所北京分子科学国家实验室 中国科学院光化学重点实验室 北京 100190)
  • 收稿日期:2009-11-24 修回日期:2010-04-02 发布日期:2010-06-20
  • 通讯作者: 管自生 E-mail:zishengguan@163.com
  • 基金资助:

    国家级.国家自然科学基金

Synthesis, Characterization and Single Crystal Structure of 4-iso-Butoy-10-hydroxy-1,7-phenanthroline- 2,8-dicarboxylic Acid Dimethyl Ester

Zhu Hengheng1,2 Guan Zisheng*,1 Zhan Chuanlang2   

  1. (1 College of Materials Science and Eegineering, Nanjing University of Technology, Nanjing 210009)
    (2 Beijing National Laboratory for Molecular Sciences (BNLMS), Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190)
  • Received:2009-11-24 Revised:2010-04-02 Published:2010-06-20

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报道了4-异丁氧基-10-羟基-1,7-二氮杂菲-2,8-二羧酸甲酯(1)的选择性合成. 化合物1是以间苯二胺(3)为起始原料, 经三步反应合成得来. 间苯二胺和1,4-二羧酸二甲酯丁炔(4)反应生成了1,3-二-(1,2-二甲氧羰基-乙烯氨基)苯(5), 随后化合物5在二苯醚中加热回流, 生成4,10-二羟基-1,7-邻二氮杂菲-2,8-二羧酸甲酯(6)和4,5-二羟基-1,8-二氮杂蒽- 2,7-二羧酸甲酯(7). 从核磁共振氢谱中可以估算出, 化合物6的产率是化合物7的7～9倍. 化合物6和7的混合物通过Mitsunobu反应生成了化合物1和4,5-二异丁氧基-1,8-二氮杂蒽-2,7-二羧酸甲酯(2), 其中化合物1的产率是化合物2的5～7倍. 晶体结构清楚地表明化合物1中10位上的羟基与1位上的氮原子之间形成了六元环分子内氢键, 而在化合物2中却没有发现分子内氢键, 此现象很好的说明了氢键的形成与选择性合成之间存在着重要的联系.

关键词: 选择性合成, 分子内氢键, Mitsunobu反应, 晶体结构

In this article, the selective synthesis of 4-iso-butoy-10-hydroxy-1,7-phenanthroline-2,8-dicar- boxylic acid dimethyl ester (1) was reported. Compound 1 was synthesized via three steps from m-phenylenedi- amine (3). Reaction of m-phenylenediamine and dimethyl acetyleneducarboxylate (4) yielded 1,3-bis-(1,2-di-methoxycarbonyl-vinylamino)benzene (5), which was refluxed in diphenyl ether to yield 4,10-dihydroxy-1,7-phenanthroline-2,8-dicarboxylic acid dimethyl ester (6) and 4,5-dihydroxy- 1,8-diaza anthracene-2,7-dicarboxylic acid dimethyl ester (7). The yield of 6 was about 7～9 times higher than that of 7, estimated from the 1H NMR spectrum. The mixture of 6 and 7 was then converted into 1 and 4,5-di-iso-butoy-1,8-diaza anthracene-2,7-dicarboxylic acid dimethyl ester (2) via Mitsunobu reaction. The purified yield of 1 was about 5～7 times of that of 2. Crystal structure of compound 1 revealed formation of a six-member intramolecular hydrogen-bond between the 10-hydroxyl-hydrogen atom and 1-nitrogen atom, while no intramolecular hydrogen-bonds can be formed in molecule 2. This strongly suggested a deep relationship between formation of the hydrogen bond and synthetic selectivity.

Key words: synthetic selectivity, intramolecular hydrogen-bond, Mitsunobu reaction, crystal structure

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