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2013 , Vol. 33 >Issue 03: 581 - 589

DOI: https://doi.org/10.6023/cjoc201210053

研究论文

叶绿素降解产物的羟(烷)基化及其二氢卟吩衍生物的合成

  • 殷一樊 ,
  • 张千 ,
  • 刘洋 ,
  • 徐希森 ,
  • 祁彩霞 ,
  • 王进军
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  • 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: 2012-10-31

  修回日期: 2012-12-01

  网络出版日期: 2012-12-06

基金资助

国家自然科学基金(No. 21272048 )和山东省自然科学基金(No. Y2008B49)资助项目.

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Hydroxy(alky)lation of Chlorophyllous Degradation Products and Synthesis of Their Chlorin Derivatives

  • Yin Yifan ,
  • Zhang Qian ,
  • Liu Yang ,
  • Xu Xisen ,
  • Qi Caixia ,
  • Wang Jinjun
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  • a College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    b Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264005

Received date: 2012-10-31

  Revised date: 2012-12-01

  Online published: 2012-12-06

Supported by

Project supported by the National Natural Science Foundations of China (No. 21272048) and the Natural Science Foundation of Shandong Province (No. Y2008B49).

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摘要

以脱镁叶绿酸-a甲酯为起始原料, 利用二氢卟吩大环上的富电子区域的化学反应性对其实施结构修饰, 通过外接E环α-氢的空气氧化、C(3)-乙烯基的亲电加成、羰基的亲核加成和20-meso-氢的亲电取代反应, 在外接E环、C(3)-, C(12)-β-位和20-meso-位上完成了羟基或者羟烷基的引进, 新建羟基的氧化和脱水反应进一步转换成碳氧双键或者碳碳双键. 所合成的11个未见报道的叶绿素类二氢卟吩衍生物的化学结构均经UV, 1H NMR, IR及元素分析得以证实, 对相应的化学反应提出了可能的反应机理.

本文引用格式

殷一樊 , 张千 , 刘洋 , 徐希森 , 祁彩霞 , 王进军 . 叶绿素降解产物的羟(烷)基化及其二氢卟吩衍生物的合成[J]. 有机化学, 2013 , 33(03) : 581 -589 . DOI: 10.6023/cjoc201210053

Abstract

Methyl pheophorbide-a was used as a starting material, and its modifications were carried out making use of the chemical reactivities of electron-richous regions on the chlorin macrocycle. The introdustions of hydroxyl groups or hydroxyalkyl groups at exocyclic E-ring, C(3)(C12)-β-position and 20-meso-position were accomplished by the allomerizations of α-hydrogen of the exocyclic E-ring, the electrophilic addition of C(3)-vinyl group, the nucleophilic addition of the carbonyl groups and electrophilic substitution at C(20)-position. The newly-formed hydroxyl groups were further converted into carbon-oxygen double bonds or carbon-carbon double bonds by oxidation and dehydration reactions. The chemical structures of 11 unreported chlorin derivatives were characterized by UV, 1H NMR, IR spectra and elemental analysis. The possible mechanisms about corresponding reactions were tentatively proposed.

Key words： chlorophyll-a; pheophorbide; chlorin; hydroxy(alky)lation; synthesis

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