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有机化学 ›› 2007, Vol. 27 ›› Issue (12): 1594-1599. 上一篇    下一篇

研究简报

氢氧化锂存在下(焦)脱镁叶绿酸-a甲酯的空气重排反应

李家柱a,b,c， 刘万卉c，李付国b，
王进军a,b，索有瑞a，刘永军*,a   

  1. (a中国科学院西北高原生物研究所 西宁 810001)
    (b烟台大学化学生物理工学院 烟台 264005)
    (c烟台大学药学院 烟台 264005)
  • 收稿日期:2007-01-27 修回日期:2007-04-13 发布日期:2007-12-04
  • 通讯作者: 刘永军

Air Oxidation and Rearrangement Reactions of Methyl(pyro)-pheophorbide-a in the Presence of Lithium Hy-droxide

LI Jia-Zhub,c, LIU Wan-Hui c, LI Fu-Guob, WANG Jin-Juna,b
SUO You-Ruia, LIU Yong-Jun*,a   

  1. (a Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Xining 810001)
    (b Science and Engineering College of Chemistry and Biology, Yantai Univer-sity, Yantai 264005)
    (c Pharmacy College, Yantai University, Yantai 264005)
  • Received:2007-01-27 Revised:2007-04-13 Published:2007-12-04
  • Contact: LIU Yong-Jun

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被引次数

48 | 16

在氢氧化锂存在下, 脱镁叶绿酸-a甲酯(1a)发生空气氧化和重排反应, 经盐酸酸化和重氮甲烷甲基化, 得到由紫红素-7三甲酯(2)、紫红素-18甲酯(3)、卟吩-p6三甲酯(4)、地质卟啉衍生物(5)和3-环氧乙基-3-去乙烯基紫红素-18甲酯(6)所组成的混合物. 用相同的方法处理焦脱镁叶绿酸-a甲酯(1b), 则分离出132-氧代焦脱镁叶绿酸-a甲酯(7)、15-甲酰基紫红素-5二甲酯(8)、紫红素-18甲酯(3)和3-环氧乙基-3-去乙烯基紫红素-18甲酯(6). 所得新叶绿素衍生物5, 6和8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, 空气氧化, 光动力疗法, 重排反应

In the presence of lithium hydroxide, air oxidation and rearrangement reactions of methyl pheo- phorbide-a (1a) followed by acidification with hydrochloric acid and methylation with diazomethane to give a mixture including purpurin-7 trimethyl ester (2), purpurin-18 methyl ester (3), chlorine-p6 trimethyl ester (4), geoporphyrin derivatives (5) and 3-epoxyvinyl-3-devinylpurpurin-18 ester (6) were performed. Methyl pyropheophorbide-a (1b) was oxidized in the same reaction as chlorin 1a followed by chromatography isola- tion to obtain methyl 132-oxopyropheophorbide-a (7), 15-formylpurpurin-5 dimehyl ester (8), purpurin-18 methyl ester (3) and 3-epoxyvinyl-3-devinylpurpurin-18 ester (6), respectively. The structures of new chlorophyll derivatives 5, 6 and 8 were characterized by UV, IR, 1H NMR spectra and elemental analysis. The possible mecha-nisms for the air oxidation and rearrangement reaction were tentatively proposed.

Key words: methyl(pyro)pheophorbide-a, air oxidation, rearrangement reaction, photodynamic therapy, chlorophyll-a