具有氮杂环并叶绿素色基结构的二氢卟吩衍生物的合成  

Synthesis of Chlorins with Chlorophyllous Chromophore Fused with Nitrogenous Heterocycle

作　　者：杨泽[1] 王振[1] 徐希森[1] 刘洋[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11期2099-2107,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：采用一锅法从叶绿素-a制得132-氧代焦脱镁叶绿酸-a甲酯,再与邻苯二胺反应生成四种含氮杂环并二氢卟吩衍生物,再经硝酸铊或者四氧化锇氧化将其3-位乙烯基转化成高反应性的甲酰基和甲酰甲基.C3-甲酰甲基与邻氨基苯甲醛的Friedl nder缩合顺利地环合成喹啉结构,与重氮甲烷和氧化苯甲腈的1,3-偶极环加成反应在3-位上构建了五元杂环.首次报道的具有叶绿素基本碳架的二氢卟吩衍生物的化学结构均经UV,IR,1H NMR及元素分析得以证实.Methyl 13^2-oxopyropheophorbide-a was prepared using one pot method from chlorophyll-a, and subsequently reacted with o-diaminobenzene to produce four chlorins fused with nitrogenous heterocycle derivatives. The hyperactive functional groups such as formyl and formymethyl groups were introduced at 3-position by oxidation with thallium nitrate or osmium tetroxide. Friedlainder condensation of C3-formymethyl group with o-aminobenzaldehyde was carried out smoothly to build quinolinic structure. The five-membered heterocyclic rings were established at 3-position via the 1,3-dipolar cycloaddition reaction of C-vinyl group with diazomethane and benzonitrile oxide. The structures of new chlorins with chlorophyllous basic skeleton were characterized by UV, IR, 1H NMR and elemental analysis.

关 键 词：叶绿素 二氢卟吩 氮杂环并二氢卟吩 合成 

分 类 号：O626[理学—有机化学]