叶绿素降解产物的羟(烷)基化及其二氢卟吩衍生物的合成

doi:10.6023/cjoc201210053

有机化学 ›› 2013, Vol. 33 ›› Issue (03): 581-589.DOI: 10.6023/cjoc201210053 上一篇下一篇

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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^a, 张千^a, 刘洋^a, 徐希森^a, 祁彩霞^b, 王进军^a,b

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 发布日期:2012-12-06
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 )和山东省自然科学基金(No. Y2008B49)资助项目.

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

Yin Yifan^a, Zhang Qian^a, Liu Yang^a, Xu Xisen^a, Qi Caixia^b, Wang Jinjun^a,b

a College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
b Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264005

Received:2012-10-31 Revised:2012-12-01 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/Abstract

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.

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

引用此文

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.

Yin Yifan, Zhang Qian, Liu Yang, Xu Xisen, Qi Caixia, Wang Jinjun. Hydroxy(alky)lation of Chlorophyllous Degradation Products and Synthesis of Their Chlorin Derivatives[J]. Chin. J. Org. Chem., 2013, 33(03): 581-589.

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叶绿素降解产物的羟(烷)基化及其二氢卟吩衍生物的合成

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

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