Synthesis of Chlorins with Chlorophyllous Chromophore Fused with Nitrogenous Heterocycle

Ze Yang, Zhen Wang, Xisen Xu, Yang Liu, Caixia Qi, Jinjun Wang
2012 Youji huaxue  
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) 摘要 采用一锅法从叶绿素-a 制得 13 2 -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. C 3 -甲酰甲基与邻氨基苯甲 醛的 Friedländer 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, 1 H NMR 及元素分析得以证实. Abstract 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
more » ... 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. Friedländer condensation of C 3 -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 3 -vinyl group with diazomethane and benzonitrile oxide. The structures of new chlorins with chlorophyllous basic skeleton were characterized by UV, IR, 1 H NMR and elemental analysis.
doi:10.6023/cjoc201206021 fatcat:abw422ubeveufdi4pqovhdjo7u