脱镁叶绿酸-a甲酯的多阶降解与罗多二氢卟吩衍生物的合成  

Multi-steps Degradation Reaction of Methyl Pheophorbide-a and Synthesis of Rhodochlorin Derivatives

作　　者：殷军港[1] 邬旭然[1] 刘春林[1] 赵丽丽[1] 金英学[2] 王进军[1] 

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

出　　处：《有机化学》2011年第11期1870-1877,共8页Chinese Journal of Organic Chemistry

基　　金：山东省自然科学基金(No.Y2008B49);中匈政府间科技合作(No.2008-333-4-32)资助项目

摘　　要：从脱镁叶绿酸-a甲酯开始,经过一系列降解反应完成罗多二氢卟吩的合成.以N-氯代丁二酰亚胺(NCS)或者硝酸作为亲电试剂,对罗多二氢卟吩实施亲电取代反应;选择氧化对氯苯甲腈和重氮甲烷作为1,3-偶极体,与罗多二氢卟吩进行1,3-偶极环加成反应,分别在二氢卟吩色基上构建了吡唑啉和异噁唑啉环系;继续对吡唑啉基取代的二氢卟吩实施热裂解反应,在3-位上形成环丙基结构;在酸性条件下,罗多二氢卟吩可以水解成相应的单酯衍生物.在红紫素-7的20-meso-位上引进氯原子后,再经脱羧反应去除15-位上的取代基团,区域选择性地完成罗多二氢卟吩的单一氯原子的引入.所合成的新化合物均经UV,IR,1H NMR及元素分析证明其结构.与此同时,对相应的空气氧化和重排反应提出了可能的反应机理.The rhodochlorin was synthesized by a series of degradation from pheophorbide-a.The electro-philic substitution of rhodochlorin was performed with N-chlorosuccinimide（NCS） or nitric acid as electro-philic reagent;1,3-polar cycloaddition reactions of C-3-vinyl group of rhodochlorin with p-chloro-benzonitrile oxide or diazomethane constructed isoxazoline and pyrazoline rings on the chlorin chromo-phore,respectively.The pyrolysis reaction of pyrazolinesubstituted chlorin introduced cyclopropyl group at C-3-position.In acid condition rhodochlorin dimethyl was hydrolyzed to its monoester.After introducing chlorine atom at 20-meso-position the purpurin-7 trimethyl was selectively converted into monochloro-substituted rhodochlorin by decarboxylation to remove functional group at 15-position.The structures of all new compounds were characterized by elemental analysis,UV,IR and 1H NMR spectra.In same time,the possible mechanisms in the air oxidation and rearrangement reaction were tentatively pro-posed.

关 键 词：脱镁叶绿酸-a甲酯 降解反应 罗多二氢卟吩 反应机理 合成 

分 类 号：O626[理学—有机化学]