meso-焦脱镁叶绿酸-a的化学反应及其叶绿素类二氢卟吩衍生物的合成
收稿日期: 2013-11-23
修回日期: 2013-12-30
网络出版日期: 2014-01-22
基金资助
国家自然科学基金（No. 21272048）和山东省黄金工程技术研究中心（2011年度）资助项目.
Reaction of meso-Pyropheophorbide-a and Synthesis of Chlorophyllous Chlorin Derivatives
Received date: 2013-11-23
Revised date: 2013-12-30
Online published: 2014-01-22
Supported by
Project supported by the National Natural Science Foundation of China (No. 21272048) and the Project of Shandong Applied Reaearch Centre of Gold Nanotechnology (2011).
以meso-焦脱镁叶绿酸-a甲酯为起始原料，利用其二氢卟吩大环上的活性反应区域，选用不同的亲电试剂进行卤化和硝化反应，分别在20-meso-位上选择性地引进了氯、溴、碘和硝基；通过空气氧化和胺解等反应，对其五元E-环实施了结构改造，并在外接环上稠并了不同的含氮杂环，完成了13个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-Vis，IR，1H NMR及元素分析予以证实，同时讨论了meso-焦脱镁叶绿酸-a的化学反应机理和相应的光谱性质.
关键词： 叶绿素-a; 二氢卟吩; meso-焦脱镁叶绿酸; 化学反应; 合成
徐希森 , 姚楠楠 , 刘洋 , 殷军港 , 祁彩霞 , 王进军 . meso-焦脱镁叶绿酸-a的化学反应及其叶绿素类二氢卟吩衍生物的合成[J]. 有机化学, 2014 , 34(5) : 938 -947 . DOI: 10.6023/cjoc201311039
meso-Pyropheophorbide-a methyl ester was used as a starting material, and the halogenation and nitration were carried out with different electrophilic reagents making use of active regions in chlorin macrocycle selectively to introduce chlorine, bromine, iodine and nitryl group at 20-meso-position, respectively. The reconstructions for five-membered exocyclic E-ring by allomerization and aminolysis were completed to fuse different azo-heterocycle with the exocyclic ring. The synthesis of 13 unreported chlorins related to chlorophyll was accomplished and their chemical structures were characterized by elemental analysis, UV-Vis, IR and 1H NMR spectra. The reaction mechanisms of meso-pyropheophorbide-a and corresponding spectral properties were discussed.
Key words： chlorophyll-a; chlorin; meso-pyropheophorbide; chemical reaction; synthesis
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