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有机化学
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有机化学 ›› 2011, Vol. 31 ›› Issue (10): 1653-1661. 上一篇    下一篇

研究论文

叶绿素-b的结构修饰及其二氢卟吩类衍生物的合成

武进1，殷军港2，张千2，孙传民2，李付国2，裴文3，王进军*,2   

  1. (1烟台大学药学院 烟台 264005)
    (2烟台大学化学化工学院 烟台 264005)
    (3浙江工业大学 绿色化学合成技术国家重点实验室培育基地 杭州 310032)
  • 收稿日期:2011-04-16 修回日期:2011-06-07 发布日期:2011-06-10
  • 通讯作者: 王进军 E-mail:wjj1955@163.com

Structure Modifications of Chlorophyll-b and Synthesis of Chlorin De-rivatives

Wu Jin1 Yin Jungang2 Zhang Qian2 Sun Chuanmin2 Li Fuguo2 Pei Wen3 Wang Jinjun*,2   

  1. (1 College of Pharmacy, Yantai University, Yantai 264005)
    (2 Colledge of Chemistry and Chemical Engineering, Yantai University, Yantai 264005)
    (3 State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310032)
  • Received:2011-04-16 Revised:2011-06-07 Published:2011-06-10

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1266

被引次数

23 | 13

在含有5%的硫酸甲醇溶液中, 通过去除金属镁离子和酯交换反应将叶绿素-b降解为脱镁叶绿酸-b甲酯, 在二苯醚中的热裂解进一步将其转化为焦脱镁叶绿酸-b甲酯. 通过乙酸中的空气氧化得到132-羟基脱镁叶绿酸-b甲酯和132-羟基焦脱镁叶绿酸-b甲酯, 前者和脱镁叶绿酸-b甲酯在碱性条件下继续与空气中氧分子作用均给出相应的氧化产物. C3-乙烯基与重氮甲烷1,3偶极环加成及热裂解反应生成C3-吡唑啉基和环丙基取代的二氢卟吩衍生物|C7-甲酰基与溴化三苯基苄基鏻的Wittig反应给出C7-苯亚甲基取代的二氢卟吩衍生物. 所合成新的二氢卟吩类衍生物均经UV, IR, 1H NMR光谱及元素分析证明其结构. 与此同时, 对相应的反应提出了可能的反应机理.

关键词: 叶绿素-b, (焦)脱镁叶绿酸, 红紫素-18, 化学修饰, 二氢卟吩衍生物, 合成

In the methanol solution containing 5% sulfuric acid chlorophyll-b was degraded to produce methyl pheophorbide-b which was converted into methyl pyropheophorbide-b by pyrolysis in diphenyl ether. The methyl 132-hydroxylpheophorbide-b and methyl 132-hydroxylpyropheophorbide-b were obtained by allomerization in acetic acid from methyl pheophorbide-b. In alkaline condition, pheophorbide-b continued to react with air to give relevant oxidized products. The 1,3-dipolar cycloaddition of C3-vinyl group with diazomethane and pyrolysis produced C3-pyrazolinyl- or C3-cyclopropyl-substituted chlorines. The Wittig reaction of C7-formyl group with benzyltriphenylphosphonium bromide formed C7-styrylchlorin derivatives. The structures of all new chlorin derivatives were charac-terized by elemental analysis, UV, IR and 1H NMR spectra. The possible mechanisms about corresponding reactions were tentatively proposed.

Key words: chlorophyll-b, (pyro)pheophorbide, purpurin-18, chemical modification, chlorin, synthesis