Chin. J. Org. Chem. ›› 2012, Vol. 32 ›› Issue (10): 1936-1943.DOI: 10.6023/cjoc201205002 Previous Articles     Next Articles



殷军港a, 王振a, 杨泽a, 金英学b, 王进军a,c   

  1. a 烟台大学化学化工学院 烟台 264005;
    b 哈尔滨师范大学化学化工学院 哈尔滨 150025;
    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:2012-05-02 修回日期:2012-05-29 发布日期:2012-06-05
  • 通讯作者: 王进军
  • 基金资助:

    国家自然科学基金(No. 20972036 )和山东省自然科学基金(No. Y2008B49)资助项目.

Alkynylation of Pyropheophorbide-a and Synthesis of Chylorophyllous Chlorin Derivatives

Yin Junganga, Wang Zena, Yang Zea, Jin Yingxueb, Wang Jinjuna,c   

  1. a College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    b College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025;
    c Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264005
  • Received:2012-05-02 Revised:2012-05-29 Published:2012-06-05
  • Supported by:

    Project supported by the National Natural Science Foundations of China (No. 20972036) and the Natural Science Foundation of Shandong Province of China (No. Y2008B49).

Methyl pyropheophorbide-a was used as starting material and converted into 3-formyl or 3-acetyl substituted and E-ring protected reactive precursors. The Grignard reactions of these carbonyl groups introduced alkynyl groups at 3-position to build the tert-alcohol or sec-alcohol structures. Further dehydrations and oxidations produced terminal eneyne and ketyne substituted chlorins, respectively. The pyropheophorbide-a with long chain alkyl group at 3-position was obtained by Grignard reaction with decyl magnesium bromide, protection for E-ring and oxidation of C(3)-hydroxyl group from 3-formylpyropheo- phorbide-a, converted into chlorin containing eneyne moiety in chain by acid-catalyzed dehydration. The structures of all new chlorin derivatives were characterized by elemental analysis, UV, IR and 1H NMR spectra. The possible mechanisms about corresponding reactions were tentatively proposed.

Key words: chlorophyll-a, pyropheophorbide, chlorin, alkynylation, chemical modification