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2015 , Vol. 35 >Issue 9: 1929 - 1938

DOI: https://doi.org/10.6023/cjoc201503050

研究论文

脱镁叶绿酸-aC-吡咯子环连带基团的结构转换及其叶绿素类二氢卟吩衍生物的合成

  • 张珠 ,
  • 姜齐永 ,
  • 张千 ,
  • 武进 ,
  • 王进军
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  • a 烟台大学文经学院食品与生物工程系 烟台 264005;
    b 烟台大学化学化工学院 烟台 264005

收稿日期: 2015-03-31

  修回日期: 2015-05-15

  网络出版日期: 2015-05-26

基金资助

国家自然科学基金(No. 21272048)资助项目.

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Structure Transformations on the Groups Linked with C-Pyrrol Subring of Pheophorbide-a and Synthesis of Chlorin Derivatives

  • Zhang Zhu ,
  • Jiang Qiyong ,
  • Zhang Qian ,
  • Wu Jin ,
  • Wang Jinjun
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  • a Department of Food & Biological Engineering, Wenjing College, Yantai University, Yantai 264005;
    b College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005

Received date: 2015-03-31

  Revised date: 2015-05-15

  Online published: 2015-05-26

Supported by

Project supported by the National Natural Science Foundation of China (No. 21272048).

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摘要

以脱镁叶绿酸-a甲酯为起始原料, 利用C-吡咯子环所连带的活性反应区域进行空气氧化、与甲醛的羟醛缩合、环酮的亲核加成以及与重氮甲烷的Tiffeneau-demjanov重排等化学反应, 在五元外接环和12-位上建立了不同的羰基结构. 新形成的活性基团与邻苯二胺、邻氨基苯甲醛的缩合, 与甲醛和肌氨酸的1, 3-偶极环加成以及其他结构转换, 在外接环上和12-位上形成包括含氮杂环和螺环在内的新颖结构, 完成了一系列未见报道的叶绿素类二氢卟吩衍生物的合成, 其化学结构均经UV、IR、1H NMR及元素分析予以证实.

关键词： 叶绿素-a; 二氢卟吩; C-吡咯子环; 化学修饰; 合成

本文引用格式

张珠 , 姜齐永 , 张千 , 武进 , 王进军 . 脱镁叶绿酸-aC-吡咯子环连带基团的结构转换及其叶绿素类二氢卟吩衍生物的合成[J]. 有机化学, 2015 , 35(9) : 1929 -1938 . DOI: 10.6023/cjoc201503050

Abstract

Methyl pheophorbide-a ester was used as starting material, and the chemical reactions, including allomerization, aldol condensation with formaldehyde, nucleophilic addition on the cycloketone, Tiffeneau-demjanov rearrangement with diazomethane, were carried out making use of active reaction regions linked with C-pyrrol subring to establish different carbonyl structures on the exocyclic ring and 12-position. From these new-formed active groups, the novel structures such as nitrogenous heterocycle and spirocycle were formed by condensations with o-phenylenediamine or o-aminobenzaldehyde, 1,3-dipolar cycloaddition with formaldehyde and sarcosine, and other structure transformations. A series of unreported chlorins related to chlorophyll were synthesized and their chemical structures were characterized by elemental analysis, UV, IR and 1H NMR spectra.

Key words： chlorophyll-a; chlorin; C-pyrrol subring; chemical modification; synthesis

参考文献

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