具有长波吸收的(焦)脱镁叶绿酸衍生物的合成及其电子光谱
收稿日期: 2012-09-06
修回日期: 2012-09-23
网络出版日期: 2012-10-11
基金资助
中匈政府间科技合作(No. 2008-333-4-32 )和山东黄金工程技术研究中心(2011年度)资助项目.
Synthesis of (Pyro)pheophorbide Derivatives with Long Wavelength Absorption and Their Electronic Spectra
Received date: 2012-09-06
Revised date: 2012-09-23
Online published: 2012-10-11
Supported by
Project supported by the Technology Cooperation between Governments of China and Hungary and the Shandong Applied Research Centre of Gold Nanotechnology (2011).
以脱镁叶绿酸-a甲酯和脱镁叶绿酸-b甲酯为起始原料, 通过3-位乙烯基、外接E-环和20-meso-位的化学修饰, 在脱镁叶绿酸-a甲酯周环上建立了不同的羰基结构. 利用脱镁叶绿酸-a甲酯的所建羰基和脱镁叶绿酸-b甲酯的原有7-位甲酰基分别与丙二睛进行Knoevenagel缩合反应, 在二氢卟吩的不同位置引进了β, β-二氰亚甲基结构, 完成一系列具有长波吸收的叶绿素类二氢卟吩衍生物的合成, 讨论了β,β-二氰亚甲基的引入对大环分子的化学活性和电子光谱的影响, 并对相应的化学反应提出可能的反应机理. 未见报道的10个叶绿素-a衍生物均经UV, IR, 1H NMR及元素分析证明其结构.
杨泽 , 王振 , 刘洋 , 徐希森 , 祁彩霞 , 王进军 . 具有长波吸收的(焦)脱镁叶绿酸衍生物的合成及其电子光谱[J]. 有机化学, 2013 , 33(01) : 116 -124 . DOI: 10.6023/cjoc201209009
Methyl pheophorbide-a and b were used as starting material. The different carbonyl groups were built along the periphery of methyl pheophorbide-a by modifing for C(3)-vinyl group, exocyclic E-ring and 20-meso-position. Making use of these carbonyl groups or original C(7)-formyl group of pheophorbide-b introduced β,β-dicyanomethylene moiety at different positions by Knoevenagel condensation with malononitrile to synthesize a series of chlorophyllous chlorin derivatives with long wavelength absorption. The effect on the electronic spectra and chemical activities of macrocycle molecule due to introduction of β,β-dicyanomethylene moiety were discussed, and the possible mechanisms about corresponding reactions were tentatively proposed. The structures of all new chlorin derivatives were characterized by 1H NMR, UV, IR spectra and elemental analysis.
Key words： chlorophyll; (pyro)pheophorbide; chlorin; synthesis; electronic spectra
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