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有机化学
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有机化学 ›› 2011, Vol. 31 ›› Issue (01): 68-74. 上一篇    下一篇

研究论文

C(3)-乙烯基的化学修饰与含氧基团取代的叶绿素-a衍生物的合成

王进军*,1,2，李付国2，李韵伟2   

  1. (1烟台大学化学生物理工学院 烟台 264005)
    (2烟台大学药学院 烟台 264005)
  • 收稿日期:2010-03-02 修回日期:2010-07-13 发布日期:2010-08-12
  • 通讯作者: 王进军 E-mail:wjj1955@163.com
  • 基金资助:

    国家科技部中匈政府间合作项目;山东省自然科学基资助项目

Modification of C(3)-Vinyl Group and Synthesis of Oxygenic Group-Substituted Chorophyll-a Derivatives

Wang Jinjun*,1,2 Li Fuguo2 Li Yun-wei2   

  1. (1 Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005)
    (2 College of Pharmacy, Yantai University, Yantai 264005)
  • Received:2010-03-02 Revised:2010-07-13 Published:2010-08-12

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以焦脱镁叶绿酸-a甲酯为起始原料, 通过加成和氧化反应将其3-位上的乙烯基转化为羟乙基、溴乙基、二羟乙基、二溴乙基和溴羟乙基, 再经过二甲亚砜/乙酸酐或者高钌酸四丙基铵(TPAP)/N-甲基吗啉-N-氧化物所组成的混合氧化剂的氧化反应, 得到多种C(3)-多酮基取代的二氢卟吩衍生物. 其单羟基作为离去基团与不同的活泼亚甲基化合物经过重排过程, 得到相应的酮基取代的二氢卟吩衍生物. 所得新叶绿素衍生物的化学结构均经UV, IR, 1H NMR及元素分析得以证实, 并对相应的反应提出可能的反应机理.

关键词: 叶绿素-a, 焦脱镁叶绿酸-a甲酯, 二氢卟吩衍生物, 化学修饰, 反应机理, 光动力疗法(PDT)

The vinyl group at 3-position of methyl pyropheophorbide-a, used as starting material, was converted into hydroxyethyl, bromoethyl, dihydroxyethyl, dibromoethyl and bromo-hydroxyethyl groups by addition and oxidation reactions. The multi-keto groups-substituted chlorin derivatives were obtained by oxidations with dimethyl sulfoxide/acetic anhydride or tetrappropylammonium perruthenate/N-methylmor- pholine N-oxide as a mixing oxidant. The nucleophilic substitution of the mono-hydroxyl group as a leaving group with active methlene derivatives produced many unexpected processes to give corresponding keto-substituted chlorin derivatives. The structures of new chlorophyll derivatives were characterized by UV, IR, 1H NMR spectra and elemental analysis. The possible mechanisms about corresponding oxidation, substitution and rearrangement reactions were tentatively proposed.

Key words: chlorophyll-a, methyl pyropheophorbide-a, chlorin derivative, chemical modification, chemical mechanism, photodynamic therapy (PDT)