13^2-氧代焦脱镁叶绿酸的化学反应及其叶绿素类二氢卟吩衍生物的合成  

Chemical Reactions of 13^2-Oxo-pyropheophorbide and Synthesis of Chlorophyllous Chlorins Derivatives

作　　者：杨晓英[1] 张善国[2] 张朋[2] 张千[2] 王振[2] 金英学[1] 祁彩霞 王进军[2,3] 

机构地区：[1]哈尔滨师范大学化学化工学院,哈尔滨150025 [2]烟台大学文经学院,烟台264005 [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》2015年第1期181-190,共10页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21272048);山东省黄金工程技术研究中心(2011年度)资助项目~~

摘　　要：以焦脱镁叶绿酸-a甲酯及其12-氧代衍生物为起始原料,利用试剂氧化和空气氧化在周环上构建了不同的含氧官能团,再通过E-环羰基的Wittig和Grignard反应、20-meso-位的亲电取代反应和3-位乙烯基的1,3-偶极环加成等经典反应进行官能团转换,讨论了132-氧代焦脱镁叶绿酸的分子结构、反应位点及其化学选择性,完成了一系列未见报道的叶绿素类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.Pyropheophorbide-a methyl ester and its 13^2-oxoed derivatives were used as starting material, and the oxygen-containing functional groups were established on the chlorin periphery by oxygenation with agent and allomerization. The functional group transformation was carried out by classic reactions including Wittig and Grignard reactions in E-ring, electrophilic substitution at 20-meso-position and 1,3-dipolar cyclocaddition with C（3）-vinyl group. The molecule structure, reactive site and chemical selectivity of 13^2-oxopyropheophorbide-a were also discussed. The syntheses of a series of unreported chlorins related to chlorophyll were accomplished and their chemical structures were characterized by elemental analysis, UV, IR and 1^H NMR spectra.

关 键 词：叶绿素-A 二氢卟吩 13^2-氧代焦脱镁叶绿酸 化学反应 合成 

分 类 号：O621.3[理学—有机化学]