叶绿素-a降解产物的酰基化反应及其二氢卟吩衍生物的合成
收稿日期: 2012-04-03
修回日期: 2012-05-30
网络出版日期: 2012-06-06
基金资助
中匈政府间科技合作项目(No. 2008-333-4-32 )和山东黄金工程技术研究中心(No. 2011)资助项目.
Acetylation of Chlorophyll-a Degradation Products and Synthesis of Chlorin Derivatives
Received date: 2012-04-03
Revised date: 2012-05-30
Online published: 2012-06-06
Supported by
Project supported by the Project of Technology Cooperation between Covernments of China and Hungary (No. 2008-333-4-32) and the Project of Shandong Applied Research Centre of Gold Nanotechnology (No. 2011).
以脱镁叶绿酸-a甲酯(MPa)为起始原料, 经化学结构修饰和中心氮原子金属化后, 与三氯氧磷/3-N,N-二甲基氨基丙烯醛(3-DMA)或者N,N-二甲基甲酰胺进行Vilsmerier反应, 在二氢卟吩周环上区域选择性地引进甲酰基或者甲酰乙烯基; 用硝酸铊对MPa衍生物实施氧化, 将3-位乙烯基顺利地转化为甲酰甲基; 利用3-位乙烯基和E-环酮基的化学反应活性, 在大环上引进羟烷氧基或者羟烷氨基结构, 然后选用高钌酸四丙基铵(TPAP)和N-甲基吗啉-N-氧化物混合氧化剂, 分别将其羟基氧化成甲酰基. 新合成的连有酰基结构的二氢卟吩衍生物的化学结构均经UV, IR, 1H NMR及元素分析得以证实.
王鲁敏 , 姚楠楠 , 杨泽 , 王振 , 沈荣基 , 王进军 . 叶绿素-a降解产物的酰基化反应及其二氢卟吩衍生物的合成[J]. 有机化学, 2012 , 32(10) : 1899 -1907 . DOI: 10.6023/cjoc201204003
Methyl pheophorbide-a (MPa) was used as starting material and converted to Ni(II) complexes by modifying for chemical structures and metallizing with Ni(acac)2. Their Vilsmerier reactions with phosphoryl chloride and 3-(dimethyl- amino)-acrolein or N,N-dimethylformamide were performed regioselectively to introduce formyl or formylvinyl group on the periphery of chlorin. The formylmethyl group also was established by oxidation reaction of the C(3)-vinyl group with thallium nitrate. The hydroxyalkyloxyl or hydroxyalkylamino group on the macrocycle was constructed based on the chemical activities of the vinyl group at 3-position and ketone group in E-ring and subsequently the hydroxyl group was oxidized with the conbination of tetrapropylammonium perruthenate (TPAP) and N-methylmorpholine N-oxide to the corresponding formyl group, respectively. The structures of all the new chlorins containing acyl structure were characterized by UV, IR, 1H NMR spectra and elemental analysis.
Key words： chlorophyll-a; pheophorbide-a; chlorin; acetylation reaction
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