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2020 , Vol. 40 >Issue 9: 2895 - 2903

DOI: https://doi.org/10.6023/cjoc202004054

研究论文

脱镁叶绿酸的硝(烃基)化反应及其叶绿素类二氢卟吩衍生物的合成

  • 张珠 ,
  • 李家柱 ,
  • 王欣悦 ,
  • 马计划 ,
  • 王旭 ,
  • 王进军
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  • a 烟台大学文经学院食品与生物工程系 山东烟台 264005;
    b 烟台大学化学化工学院 山东烟台 264005

收稿日期: 2020-04-30

  修回日期: 2020-05-31

  网络出版日期: 2020-06-13

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.ZR2015BQ012）资助项目.

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Nitration (Nitroalkylation) of Pheophorbide and Synthesis of Chlorophyllous Chlorin Derivatives

  • Zhang Zhu ,
  • Li Jiazhu ,
  • Wang Xinyue ,
  • Ma Jihua ,
  • Wang Xu ,
  • Wang Jinjun
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  • a Department of Food & Biological Engineering, Wenjing College, Yantai University, Yantai, Shandong 264005;
    b College of chemistry and chemical engineering, Yantai University, Yantai, Shandong 264005

Received date: 2020-04-30

  Revised date: 2020-05-31

  Online published: 2020-06-13

Supported by

Project supported by the National Natural Science Foundations of China (No. 21272048) and the Natural Science Foundation of Shandong Province (No. ZR2015BQ012).

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摘要

以脱镁叶绿酸-a甲酯为起始原料，利用其周环上的活性反应基团进行化学修饰，在N21-N23轴向两端构建了甲酰基、烯酮和邻位二酮结构，通过芳香性大环色基的亲电取代、活性羰基的Henry反应以及外接环上作为不同给受体的β-酮酯和烯酮的Michael加成，分别在3-、12-、20-位和外接环上实施硝化和硝烃基化，完成了一系列未见报道的硝（烷）基取代的叶绿素类二氢卟吩衍生物的合成，其化学结构均经UV-Vis、IR、1H NMR及元素分析予以证实.

关键词： 叶绿素; 脱镁叶绿酸; 二氢卟吩; 硝(烷基)化反应; 合成

本文引用格式

张珠 , 李家柱 , 王欣悦 , 马计划 , 王旭 , 王进军 . 脱镁叶绿酸的硝(烃基)化反应及其叶绿素类二氢卟吩衍生物的合成[J]. 有机化学, 2020 , 40(9) : 2895 -2903 . DOI: 10.6023/cjoc202004054

Abstract

Pyropheophorbide-a methyl ester was used as a starting material, and the chemical modification was carried out making use of its active groups attached to the chlorin periphery to establish the formyl group, ketene and α-diketone moieties around the N21-N23 axis. The nitrations or nitroalkylations at 3-, 12-, 20-position and on the exocyclic ring were performed by the electrophilic substitution on the aromatic macrocyclic chromophore, Henry reaction at the active carbonyl groups, and Michael addition to the β-keto ester and the ketene structures on the exocyclic ring as different donor-acceptor. A series of unreported nitro(nitroalkyl) substituted chlorins related to chlorophyll were synthesized and their chemical structures were characterized by elemental analysis, UV-Vis, IR and 1H NMR spectra.

Key words： chlorophyll; pheophorbide; chlorin; nitration(nitroalkylation) reaction; synthesis

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