有机化学 ›› 2013, Vol. 33 ›› Issue (01): 116-124.DOI: 10.6023/cjoc201209009 上一篇    下一篇

研究论文

具有长波吸收的(焦)脱镁叶绿酸衍生物的合成及其电子光谱

杨泽a, 王振a, 刘洋a, 徐希森a, 祁彩霞a, 王进军b   

  1. a 烟台大学化学化工学院 烟台 264005;
    b 山东省黄金工程技术研究中心(工业应用) 烟台 264005
  • 收稿日期:2012-09-06 修回日期:2012-09-23 发布日期:2012-10-11
  • 通讯作者: 王进军 E-mail:wjj1955@163.com
  • 基金资助:

    中匈政府间科技合作(No. 2008-333-4-32 )和山东黄金工程技术研究中心(2011年度)资助项目.

Synthesis of (Pyro)pheophorbide Derivatives with Long Wavelength Absorption and Their Electronic Spectra

Yang Zea, Wang Zhena, Liu Yanga, Xu Xisena, Qi Caixiaa, Wang Jinjunb   

  1. a College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    b Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264005)
  • Received:2012-09-06 Revised:2012-09-23 Published:2012-10-11
  • Supported by:

    Project supported by the Technology Cooperation between Governments of China and Hungary and the Shandong Applied Research Centre of Gold Nanotechnology (2011).

以脱镁叶绿酸-a甲酯和脱镁叶绿酸-b甲酯为起始原料, 通过3-位乙烯基、外接E-环和20-meso-位的化学修饰, 在脱镁叶绿酸-a甲酯周环上建立了不同的羰基结构. 利用脱镁叶绿酸-a甲酯的所建羰基和脱镁叶绿酸-b甲酯的原有7-位甲酰基分别与丙二睛进行Knoevenagel缩合反应, 在二氢卟吩的不同位置引进了β, β-二氰亚甲基结构, 完成一系列具有长波吸收的叶绿素类二氢卟吩衍生物的合成, 讨论了β,β-二氰亚甲基的引入对大环分子的化学活性和电子光谱的影响, 并对相应的化学反应提出可能的反应机理. 未见报道的10个叶绿素-a衍生物均经UV, IR, 1H NMR及元素分析证明其结构.

关键词: 叶绿素, (焦)脱镁叶绿酸, 二氢卟吩, 合成, 电子光谱

Methyl pheophorbide-a and b were used as starting material. The different carbonyl groups were built along the periphery of methyl pheophorbide-a by modifing for C(3)-vinyl group, exocyclic E-ring and 20-meso-position. Making use of these carbonyl groups or original C(7)-formyl group of pheophorbide-b introduced β,β-dicyanomethylene moiety at different positions by Knoevenagel condensation with malononitrile to synthesize a series of chlorophyllous chlorin derivatives with long wavelength absorption. The effect on the electronic spectra and chemical activities of macrocycle molecule due to introduction of β,β-dicyanomethylene moiety were discussed, and the possible mechanisms about corresponding reactions were tentatively proposed. The structures of all new chlorin derivatives were characterized by 1H NMR, UV, IR spectra and elemental analysis.

Key words: chlorophyll, (pyro)pheophorbide, chlorin, synthesis, electronic spectra