Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (10): 2047-2056.DOI: 10.6023/cjoc201402041 Previous Articles     Next Articles

Articles

焦脱镁叶绿酸-a的C(12)-位非甲基化及其叶绿素类二氢卟吩衍生物的合成

纪建业a, 殷军港b, 张千b, 刘超b, 祁彩霞c, 王进军b,c   

  1. a. 通化师范学院化学系 通化 134002;
    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:2014-02-28 修回日期:2014-04-04 发布日期:2014-06-09
  • 通讯作者: 王进军 E-mail:jj1955@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.

C(12)-Nomethylation of Pyropheophorbide-a and Synthesis of Chlorophyllous Chlorins Derivatives

Ji Jianyea, Yin Jungangb, Zhang Qianb, Liu Chaob, Qi Caixiac, Wang Jinjuncb,c   

  1. a. Department of Chemistry, College of Teachers, Tonghua 134002;
    b. College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    c. Shandong Applied Research Centre of Gold nanotechnology Au-SDARC, Yantai 264005
  • Received:2014-02-28 Revised:2014-04-04 Published:2014-06-09
  • 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).

Pyropheophorbide-a methyl ester, as a degradation product from chlorophyll-a, was used as a starting material, and the formyl group was introduced at 12-position by allomerization. The transformations of C(12)-functional group, including the structural rebuilding of E-ring, were carried out by classic reactions such as oxygenation, reduction, Grignard reaction, Knoevenagel reaction, Cannizzaro reaction and 1,3-dipolar cyclocaddition. The acyl, ester and substituted alkyl groups, which could conjugated with macrocyclic chromophore at various degrees, were established at 12-position. The synthesis of a series of unreported chlorins related to chlorophyll was accomplished and their chemical structures were characterized by elemental analysis, UV, IR and 1H NMR spectra. The different fluences on the chlorophyllous tetrapyrrole molecule by C(12)-nomethylation were also discussed.

Key words: chlorophyll-a, chlorin, chemical modification, C(12)-nomethylation, synthesis