脱镁叶绿酸的C(17)-尾端酯基的化学反应及其二氢卟吩衍生物的合成  

Chemical Reaction of C(17)-End Ester Group in Pyropheophorbide and Synthesis of Chlorin Derivatives

作　　者：李晶华[1] 程建军[1] 张朋[2] 武进[2] 金英学[1] 王进军[3,2] 

机构地区：[1]哈尔滨师范大学化学化工学院,哈尔滨150025 [2]烟台大学化学化工学院,烟台264005 [3]烟台大学文经学院,烟台264005

出　　处：《有机化学》2015年第6期1294-1301,共8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甲酯为起始原料,通过化学修饰在五元外接环上构筑活性反应区域,经分子内的酯交换、Michael加成和Claisen缩合等经典化学反应,使得132-与17-位通过不同的碳链相互连接,在C-D环端向上形成了双环和螺环结构.同时,利用17-位尾端酯基的化学活性进行胺解和酰化反应,在二氢卟吩色基的最远端建立了不同的化学结构,完成了9个未见报道的具有新颖碳架结构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 was used as a starting material. The active reaction regions were constructed by chemical modifications on the five-membered exocyclic ring, and the interconnections through different carbon chain between 132- and 17-position were carried out by classic reaction, such as intramolecular interesterification, Michael addition and Claisen condensation, to form bicyclic or spirocyclic structures in the side of C-D ring. The aminolysis and acylation were performed making use of chemical activity of end ester group at 17-position to establish the different chemical structures in the far end of chlorin chromophore. The syntheses of 9 unreported chlorins related to chlorophyll with novel carbon skeleton were accomplished and their chemical structures were characterized by elemental analysis, UV, IR and 1H NMR spectra.

关 键 词：叶绿素-A 焦脱镁叶绿酸 二氢卟吩 化学反应 合成 

分 类 号：O626[理学—有机化学]