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2012 , Vol. 32 >Issue 12: 2300 - 2308

DOI: https://doi.org/10.6023/cjoc201207022

研究论文

焦脱镁叶绿酸-d甲酯的化学修饰与叶绿素类二氢卟吩衍生物的合成

  • 王振 ,
  • 杨泽 ,
  • 刘洋 ,
  • 徐希森 ,
  • 祁彩霞 ,
  • 王进军
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  • a 烟台大学化学化工学院 烟台 264005;
    b 山东省黄金工程技术研究中心工业应用 烟台 264005

收稿日期: 2012-07-17

  修回日期: 2012-08-20

  网络出版日期: 2012-08-22

基金资助

中匈政府间科技合作(No. 2008-333-4-32)和山东黄金工程技术研究中心(2011年度)资助项目.

收起

Chemical Modification of Methyl Pyropheophorbide-d and Synthesis of Chlorophyllous Chlorin Derivatives

  • Wang Zhen ,
  • Yang Ze ,
  • Liu Yang ,
  • Xu Xisen ,
  • Qi Caixia ,
  • Wang Jinjun
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  • a College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    b Shandong Applied Research Centre of Gold Nanotechnology Au-SDARC, Yantai 264005

Received date: 2012-07-17

  Revised date: 2012-08-20

  Online published: 2012-08-22

Supported by

Project supported by the Project of Technology Cooperation between Covernments of China and Hungary (No. 2008-333-4-32) and the Project of Shandong Applied Research Centre of Gold Nanotechnology (2011).

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摘要

叶绿素降解产物是合成光动力治疗药物的理想合成前体. 为了获得新型叶绿素类光敏剂, 以焦脱镁叶绿酸-d甲酯为起始原料, 通过空气氧化反应、Knoevenagel反应、Hener反应、Tiffeneau-Demjanov重排、Friedlaender缩合和还原等经典化学反应对其甲酰基和外接环羰基实施化学修饰, 在C(3)-位和外接E-上建立了不同的化学结构, 合成出一系列具有叶绿素基本碳架结构的二氢卟吩衍生物, 讨论了分子结构与其紫外-可见光谱之间的联系, 并对相应的化学反应提出了可能的反应机理. 新报道的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.

关键词： 叶绿素-a; 二氢卟吩; 焦脱镁叶绿酸-d甲酯; 化学修饰

本文引用格式

王振 , 杨泽 , 刘洋 , 徐希森 , 祁彩霞 , 王进军 . 焦脱镁叶绿酸-d甲酯的化学修饰与叶绿素类二氢卟吩衍生物的合成[J]. 有机化学, 2012 , 32(12) : 2300 -2308 . DOI: 10.6023/cjoc201207022

Abstract

Chlorophyllous degraded products are ideal synthetic precursors for the synthesis of photodynamic therapy drugs. To obtain chlorophyllous photosensitizer, methyl pyropheophorbide-d was used as starting material, and its formyl and carbonyl groups on E-ring were modified by allomerization, Knoevenagel reaction, Hener reaction, Tiffeneau-Demjano rearrangement, Friedlaender condensation and reduction to build different chemical structures at 3-position and exocyclic E-ring. A series of chlorins with basic skeleton of chlorophyll were synthesized, and the relations between the molecular structures and their UV-Vis spectra were discussed. The possible mechanisms about corresponding reactions were tentatively proposed. The structures of new-reported chlorophyll derivatives were characterized by UV, IR, 1H NMR and elemental analysis.

Key words： chlorophyll-a; chlorin; methyl pyropheophorbide-d; chemical modification

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