具有叶绿素-a基本骨架的20-meso-位取代二氢卟吩衍生物的合成  

Synthesis of 20-meso-Substituted Chlorins with the Basic Skeleton of Chlorophyll-a

作　　者：王鲁敏[1] 王振[1] 杨泽[1] 金英学[2] 王进军[1,3] 

机构地区：[1]烟台大学化学化工学院,烟台264005 [2]哈尔滨师范大学化学化工学院,哈尔滨150025 [3]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2154-2161,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.20972036);山东省自然科学基金(No.Y2008B49)资助项目~~

摘　　要：以脱镁叶绿酸-a甲酯(MPa)为起始原料,分别与氯化、溴化和硫酸重氮苯进行偶联反应,其主要产物为20-卤素取代或者亚硝基取代的二氢卟吩,仅以微量产率的得到期待的产物.焦脱镁叶绿酸的锌配合物与3-N,N-二甲胺基丙烯醛的Vilsmeier反应生成20-甲酰乙烯基焦脱镁叶绿酸.焦脱镁叶绿酸-d与N-溴代丁二酰亚胺(NBS)的溴代反应生成单一的20-溴代产物,再经Wittig反应恢复乙烯基而得到20-溴代焦脱镁叶绿酸-a甲酯.其它叶绿素降解产物的亲电取代反应均以较好的产率得到生成的20-meso-位取代的二氢卟吩衍生物.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 pheophorbide-a （MPa） was used as starting material. The coupling reaction of MPa with diazobenzene hydrochloride, hydrobromide and sulfate was carded out to give traces of expected product, while major products were 20-halogenated and nitroso-substituted chlorins. Zinc methyl pyropheophorbide-a reacted with 3-N,N-dimethylacrolein to give Vilsmeier product. The bromination of pyropheophorbide-d with N-bromosuccinimide （NBS） formed single 20-brominated product, the vinyl group of which was resumed by Wittig reaction to give 20-bromopyropheophorbide-a. The electrophilic substitution of other chlorphyllous degradation products afforded corresponding 20-meso-substituted chlorin derivatives in better yields, respectively. The structures of all the new chlorins with basic skeleton of chlorophyll were characterized by UV, IR, 1H NMR spectra and elemental analysis.

关 键 词：叶绿素-A 脱镁叶绿酸-a 焦脱镁叶绿酸-a 二氢卟吩 亲电反应 

分 类 号：O626[理学—有机化学]