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  

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

作　　者：王振[1] 杨泽[1] 刘洋[1] 徐希森[1] 祁彩霞 王进军[1,2] 

机构地区：[1]烟台大学化学化工学院,烟台264005 [2]山东省黄金工程技术研究中心(工业应用),烟台264005

出　　处：《有机化学》2012年第12期2300-2308,共9页Chinese Journal of Organic Chemistry

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

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.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 car- bonyl groups on E-ring were modified by allomerization, Knoevenagel reaction, Hener reaction, Tiffeneau-Demjano rear- rangement, 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.

关 键 词：叶绿素-A 二氢卟吩 焦脱镁叶绿酸-d甲酯 化学修饰 

分 类 号：O626[理学—有机化学]