有机化学 ›› 2018, Vol. 38 ›› Issue (12): 3250-3259.DOI: 10.6023/cjoc201806046 上一篇    下一篇

研究论文

焦脱镁叶绿酸周环结构的杂环化反应及其叶绿素衍生物的合成

张珠a, 李家柱b, 张善国b, 王振b, 王进军a,b   

  1. a 烟台大学文经学院食品与生物工程系 烟台 264005;
    b 烟台大学化学化工学院 烟台 264005
  • 收稿日期:2018-06-30 修回日期:2018-07-28 发布日期:2018-08-23
  • 通讯作者: 王进军 E-mail:wjj1955@163.com
  • 基金资助:

    国家自然科学基金(No.21272048)和山东省高校科技计划(No.J15LC51)资助项目.

Heterocyclization for the Structures on the Periphery of Py-ropheophorbide and Synthesis of Chlorophyll Derivatives

Zhang Zhua, Li Jiazhub, Zhang Shanguob, Wang Zhenb, Wang Jinjuna,b   

  1. a Department of Food & Biological Engineering, Wenjing College, Yantai University, Yantai 264005;
    b College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005
  • Received:2018-06-30 Revised:2018-07-28 Published:2018-08-23
  • Contact: 10.6023/cjoc201806046 E-mail:wjj1955@163.com
  • Supported by:

    Project supported by the National Natural Science Foundations of China (No. 21272048) and the University Science and Technology Plan Projects of Shandong Province (No. J15LC51).

为了拓展叶绿素类二氢卟吩的研究和应用,以焦脱镁叶绿酸-a甲酯为起始原料,通过氧化和缩合反应,对其N21-N23轴向两端的取代基团进行化学修饰和结构转换,在四吡咯大环分子的周环上构建了醛、邻位二酮、烯腈和烯酮等活性受电子官能结构,再与不同的富电子体系实施关环,合成了一系列未见报道的含有多种杂环结构的焦脱镁叶绿酸衍生物,其化学结构均经UV-Vis,IR,1H NMR,MS及元素分析予以证实.同时,对相应杂环的形成过程、立体化学选择性以及电子光谱变化进行了讨论.

关键词: 叶绿素-a, 二氢卟吩, 化学修饰, 杂环化反应, 合成

In order to expand study and application for the chlorophllous chlorins, pyropheophorbide-a methyl ester was used as a starting material. The chemical modifications and structural transformations along the terminals of N21-N23 axis were carried out to build active electron-accepting functional structures such as aldehyde, α-diketone, enenitrile and ketene moieties. The cyclizations with different electron-sufficient systems were accomplished to synthesize a series of unreported chlorins related to chlorophyll with multiple heterocyclic structures. The chemical structures of new compounds were characterized by elemental analysis, MS, UV-Vis, IR and 1H NMR spectra. Meanwhile the relevant formation process of the heterocyclic ring, the stereochemistry selectivity and the change of the electronic spectrum were discussed.

Key words: chlorophyll-a, chlorin, chemical modification, heterocyclization reaction, synthesis