有机化学 ›› 2015, Vol. 35 ›› Issue (6): 1294-1301.DOI: 10.6023/cjoc201410047 上一篇    下一篇

研究论文

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

李晶华a, 程建军a, 张朋c, 武进c, 金英学a, 王进军b,c   

  1. a 哈尔滨师范大学化学化工学院 哈尔滨 150025;
    b 烟台大学文经学院 烟台 264005;
    c 烟台大学化学化工学院 烟台 264005
  • 收稿日期:2014-10-31 修回日期:2015-01-20 发布日期:2015-02-02
  • 通讯作者: 金英学 E-mail:wjj1955@163.com
  • 基金资助:

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

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

Li Jinghuaa, Cheng Jianjuna, Zhang Pengc, Wu Jinc, Jin Yingxuea, Wang Jinjunb,c   

  1. a College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025;
    b Wenjing College, Yantai University, Yantai 264005;
    c College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005
  • Received:2014-10-31 Revised:2015-01-20 Published:2015-02-02
  • Supported by:

    Project supported by the National Natural Science Foundations of China (No. 21272048) and the Project of Shandong Applied Research Centre of Gold Nanotechnology (2011).

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.

关键词: 叶绿素-a, 焦脱镁叶绿酸, 二氢卟吩, 化学反应, 合成

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.

Key words: chlorophyll-a, pyropheophorbide, chlorin, chemical reaction, synthesis