具有叶绿素碳架的二氢卟吩醛的合成及其与蛋白质的结合作用  

Synthesis of Chlorin Aldehydes with Chlorophyllous Skeleton and Their Interactions with Protein

作　　者：姜齐永[1] 张珠[1] 刘洋[2] 姚楠楠[2] 王进军[1,2] Jiang Qiyong Zhang Zhu Liu Vang Yao Nannan Wang Jinjun(Department of Food ＆ Biological Engineering, Wenjing College, Yantai University, Yantai 264005 College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005)

机构地区：[1]烟台大学文经学院食品与生物工程系,烟台264005 [2]烟台大学化学化工学院,烟台264005

出　　处：《有机化学》2017年第7期1814-1823,共10页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21272048);山东省高校科技计划(No.J15LC51)资助项目~~

摘　　要：以脱镁叶绿酸-a(b)甲酯为起始原料,经外接环修饰和色基金属化形成不同的叶绿素降解产物,再通过Vilsmeier酰基化和Blanc羟甲基化反应,在20-位上引进了新的官能基团.以四氧化锇、硝酸铊和空气为氧化剂,对二氢卟吩周环上的活性结构进行氧化,分别在二氢卟吩周环上的3-,7-和12-位以及外接环上引进了甲酰基和甲酰甲基,合成了一系列未见报道的叶绿素类二氢卟吩醛衍生物,其化学结构均经UV,IR,~1H NMR及元素分析予以证实;同时也讨论了叶绿素类二氢卟吩醛基化的反应机理,并对新化合物与牛血清白蛋白的结合作用进行了研究.Pyropheophorbide-a（b） methyl esters were used as starting materials to form different chlorophyll degradation products by the modification of the exocyclic ring and the metallization of the chromophore. The new functional groups were introduced at 20-position via the Vilsmeier acylation and the Blanc hydroxymethylation. The active structures of chlorin peripheries were oxidized using osmium tetroxide, thaillum nitrate and air as oxidizing agent to introduce the formyl group and the formylmethyl group at 3-, 7-or 12-postion and on the exocyclic ring, respectively. A series of unreported chlorin aldehydes related to chlorophyll were synthesized and their chemical structures were characterized by elemental analysis, UV, IR and ~1H NMR spectra. The reaction mechanisms on the hydroformylation for the chlorophyllous chlorins were discussed and the interactions of new compounds with bovine serum albumins were researched.

关 键 词：叶绿素 二氢卟吩 牛血清白蛋白 化学修饰 荧光淬灭 

分 类 号：O626[理学—有机化学]