有机化学 ›› 2014, Vol. 34 ›› Issue (11): 2279-2287.DOI: 10.6023/cjoc201403067 上一篇    下一篇

研究论文

(焦)脱镁叶绿酸-a的1,3-偶极环加成反应及其叶绿素类二氢卟吩的合成

杨晓英a, 殷军港b, 金英学a, 祁彩霞c, 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 烟台大学化学化工学院 烟台 264005;
    c 山东省黄金工程技术研究中心(工业应用) 烟台 264005
  • 收稿日期:2014-03-31 修回日期:2014-06-05 出版日期:2014-11-25 发布日期:2014-07-11
  • 通讯作者: 金英学;王进军,wjj1955@163.com 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.

1,3-Dipolar Cycloadditions of (Pyro)pheophorbide-a and Synthesis of Chlorophyllous Chlorin Derivatives

Yang Xiaoyinga, Yin Jungangb, Jin Yingxuea, Qi Caixiac, Wang Jinjunb,c   

  1. a College of Chemistry & Engineering, Harbin Normal University, Harbin 150025;
    b College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    c Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264005
  • Received:2014-03-31 Revised:2014-06-05 Online:2014-11-25 Published:2014-07-11
  • Supported by:

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

以脱镁叶绿酸-a甲酯为起始原料, 通过加成、缩合和空气氧化等常见化学反应, 在二氢卟吩色基上构建了新的碳碳双键; 选择不同的1, 3-偶极体与3-位、12-位和外接环烯键进行1,3-偶极环加成反应, 完成了一系列具有五元杂环取代的叶绿素类二氢卟吩衍生物的合成, 其化学结构均经UV-Vis、IR、MS、1H NMR及元素分析予以证实, 并对1,3-偶极环加成反应的区域选择性及其相应的反应机理进行了讨论.

关键词: 叶绿素-a, 二氢卟吩, 1,3-偶极环加成反应, 区域选择性, 合成

Pheophorbide-a methyl ester was used as a starting material, and new carbon-carbon double bonds were built on the chlorin chromophore by addition, condensation and allomerization. 1,3-Dipolar cycloadditions with different 1,3-dipols for the olefinic bonds at 3-position, 12-position and exocyclic E-ring were performed to synthesize a series of chlorophyllous chlorin derivatives substituted with five-membered heterocycle. The chemical structures of the unreported chlorins were characterized by UV-Vis, 1H NMR, IR, MS and elemental analysis. The region selectivity of 1,3-dipolar cycloadditions and corresponding reaction mechanisms were also discussed.

Key words: chlorophyll-a, chlorin, 1,3-dipolar cycloaddition, region selectivity, synthesis