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  

Acetylation of Chlorophyll-a Degradation Products and Synthesis of Chlorin Derivatives

作　　者：王鲁敏[1] 姚楠楠 杨泽[1] 王振[1] 沈荣基[3] 王进军[1,2] 

机构地区：[1]烟台大学化学化工学院,烟台264005 [2]山东省黄金工程技术研究中心(工业应用),烟台264005 [3]仁济大学纳米工程学院

出　　处：《有机化学》2012年第10期1899-1907,共9页Chinese Journal of Organic Chemistry

基　　金：中匈政府间科技合作项目(No.2008-333-4-32);山东黄金工程技术研究中心(No.2011)资助项目~~

摘　　要：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.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~/--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 conbi- nation 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.

关 键 词：叶绿素-A 脱镁叶绿酸-a甲酯 二氢卟吩 酰化反应 

分 类 号：O621.3[理学—有机化学]