有机化学 ›› 2015, Vol. 35 ›› Issue (1): 181-190.DOI: 10.6023/cjoc201406047 上一篇    下一篇

研究论文

132-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

杨晓英a, 张善国b, 张朋b, 张千b, 王振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 烟台大学文经学院 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:2014-06-28 修回日期:2014-09-09 出版日期:2015-01-25 发布日期:2015-01-28
  • 通讯作者: 金英学, 王进军 E-mail:wjj1955@163.com
  • 基金资助:

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

Chemical Reactions of 132-Oxo-pyropheophorbide and Synthesis of Chlorophyllous Chlorins Derivatives

Yang Xiaoyinga, Zhang Shanguob, Zhang Pengb, Zhang Qianb, Wang Zhenb, Jin Yingxuea, Qi Caixiac, Wang Jinjunb,c   

  1. a College of Chemistry & Chemical Engineering, Harbin Normal University, Harbin 150025;
    b Wenjing College, Yantai University, Yantai 264005;
    c Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264005
  • Received:2014-06-28 Revised:2014-09-09 Online:2015-01-25 Published:2015-01-28
  • Supported by:

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

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.

关键词: 叶绿素-a, 二氢卟吩, 132-氧代焦脱镁叶绿酸, 化学反应, 合成

Pyropheophorbide-a methyl ester and its 132-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 132-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 1H NMR spectra.

Key words: chlorophyll-a, chlorin, 132-oxopyropheophorbide-a, chemical reaction, synthesis