有机化学 ›› 2012, Vol. 32 ›› Issue (01): 149-155.DOI: 10.6023/cjoc1106303 上一篇    下一篇

研究简报

β,β-二氰亚甲基取代的叶绿素类二氢卟吩衍生物的合成及其可见光谱

武进a, 殷军港b, 刘冉冉b, 杨泽b, 王振a, 王进军a,b   

  1. a 烟台药学院 烟台 264005;
    b 烟台大学化学化工学院 烟台 264005
  • 收稿日期:2011-06-30 修回日期:2011-08-24 发布日期:2011-09-28
  • 通讯作者: 王进军 E-mail:wjj1955@163.com
  • 基金资助:

    山东省自然科学基(No. Y2008B49)资助项目.

Synthesis of Chlorphyll-a Derivatives Substituted with β,β-Dicyanomethylene and Their Visible Spectra

Wu Jina, Yin Jungangb, Liu Ranranb, Yang Zeb, Wang Zhena, Wang Jinjuna,b   

  1. a Colledge of College of Pharmacy, Yantai University, Yantai 264005;
    b Chemistry and Chemical Engineering, Yantai University, Yantai 264005
  • Received:2011-06-30 Revised:2011-08-24 Published:2011-09-28
  • Contact: Wang Jinjun E-mail:wjj1955@163.com
  • Supported by:

    Project supported by Natural Science Foundation of Shandong Province (No. Y2008B49).

以焦脱镁叶绿酸-a 甲酯为起始原料, 通过对3-位乙烯基的氧化、格氏反应和E-环的空气氧化和重排在二氢卟吩周环的不同位置上构建酰基结构, 利用叶绿素-a 衍生物的烷酰基和叶绿素-b 的原有甲酰基与丙二腈进行Knoevenagel反应, 完成一系列具有长波吸收的β,β-二氰亚甲基叶绿素-a 衍生物的合成, 并对不同取向的共轭取代基团对大环分子的可见光谱所产生的影响进行了相应的讨论. 未见报道的叶绿素-a 衍生物均经UV, IR, 1H NMR 及元素分析证明其结构.

关键词: 焦脱镁叶绿酸-a 甲酯, 叶绿素-a 衍生物, 合成, 可见光谱, 光动力疗法

Using methyl pyropheophorbide-a as starting material, the carbonyl structures were constructed in different positions of the chlorin periphery by oxidition of the 3-vinyl group, Grignard reaction and air oxidation and rearrangement of E-ring. Then the synthesis of chlorphyll-a derivatives substituted with β,β-dicyanomethylene having long wavelength absorption property was accomplished by Knoevenagel reaction of the carbonyl group on the chromophore with malononitrile. The effect of the peripheral conjugated substitutes oriented in different directions on the visible spectra was also discussed. The structures of all new chlorine derivatives were characterized by elemtntal analysis, UV, IR and 1H NMR spectra.

Key words: methyl pyropheophorbide-a, chlorophyll-a derivative, synthesis, visible spectra, photodynamic therapy