有机化学 ›› 2015, Vol. 35 ›› Issue (9): 1929-1938.DOI: 10.6023/cjoc201503050 上一篇    下一篇

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a, 姜齐永a, 张千b, 武进b, 王进军a,b   

  1. 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 出版日期:2015-09-25 发布日期:2015-05-26
  • 通讯作者: 王进军 E-mail:wjj1955@163.com
  • 基金资助:

    国家自然科学基金(No. 21272048)资助项目.

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

Zhang Zhua, Jiang Qiyonga, Zhang Qianb, Wu Jinb, Wang Jinjuna,b   

  1. a Department of Food & Biological Engineering, Wenjing College, Yantai University, Yantai 264005;
    b College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005
  • Received:2015-03-31 Revised:2015-05-15 Online:2015-09-25 Published:2015-05-26
  • Supported by:

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

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

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