Chin. J. Org. Chem. ›› 2010, Vol. 30 ›› Issue (11): 1716-1720. Previous Articles     Next Articles

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  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
  • 基金资助:


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

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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