摘要
从脱镁叶绿酸-a甲酯开始, 先行通过1,3-偶极环加成、游离基取代和Wittig成烯等经典反应、在二氢卟吩周环的3-, 12-和20-位上构建了能与色基形成不同共轭效应的含芳取代基团, 再利用空气氧化、缩合和重排反应实现外接环的结构转化而形成其他各种叶绿素降解结构, 完成了一系列未见报道的新型二氢卟吩衍生物的合成, 其化学结构均经UV, IR, 1H NMR及元素分析予以证实, 同时, 讨论了周环的化学反应历程、含芳取代基团的共轭效应和大环分子电子光谱的变化规律.
关键词 ： 叶绿素-a, 二氢卟吩, 外接环转换, 叶绿素降解产物, 化学反应
Abstract：
From pheophorbide-a methyl ester, the substituted groups with aromatic ring, which can conjugated with chromophore in different forms, were established at 3-, 12- and 20-position on the chlorin periphery by some classic reactions such as 1,3-dipolar cycloaddition, radical substitution and Wittig olefin-forming. The transformations in the exocyclic ring to other chlorophyllous degradation structures were carried out making use of allomerization, condensation and rearrangement reac-tions. A series of unreported new chlorins were synthesized and their chemical structures were characterized by elemental analysis, UV, IR and 1H NMR spectra. In the same time the chemical reaction process around the periphery, the conjugated effect about the aromatic substitutes and the varying law about electronic spectra of the macrocyclic molecule were also discussed.
张善国, 李家柱, 张朋, 祁彩霞, 王进军. 脱镁叶绿酸的外接环转换与芳环取代叶绿素降解衍生物的合成[J]. 有机化学, 2015, 35(5): 1060-1068
