Chin. J. Org. Chem. ›› 2015, Vol. 35 ›› Issue (6): 1320-1329.DOI: 10.6023/cjoc201410003 Previous Articles     Next Articles



刘红瑶a, 朱国华a, 刘冉冉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:2014-10-06 修回日期:2014-12-22 发布日期:2015-01-09
  • 通讯作者: 王进军
  • 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 Modifications of Purpurin-18 and Synthesis of Chlorophyllous Chlorins Derivatives

Liu Hongyaoa, Zhu Guohuaa, Liu Ranranb, Jin Yingxue a, 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:2014-10-06 Revised:2014-12-22 Published:2015-01-09
  • 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 (2011).

Purpurin-18 methyl ester and its imid ester were used as starting materials. The cycloaddition of the 3-vinyl group in purpurin-18 with nitril oxide or azomethine as 1,3-dipole was carried up to established different five-membered heterocyclic structures on the chlorin chromophore. Azadiene, prepared from the condensation of arylamine with aromatic aldehyde, with double bond at 3-position of purpurin-18 conducted hetero-Diels-Alder reaction (Povarov reaction) to generate ring-opening rearranged products substituted with aroyl or aralkyl group. The electrophilic substitution, allomerization and like-Aldol reaction were accomplished making use of the reactivity of C(12)-methyl or 20-meso-hydrogen to introduce various substitutes at 12- and 20-position on the periphery of purpurin-18. 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 reaction mechanisms involved were also discussed accordingly.

Key words: chlorophyll-a, chlorin, purpurin-18, chemical reaction, synthesis