叶绿素降解产物的环丙基化及其二氢卟吩衍生物的合成有机化学.pdfVIP

DOI: 10.6023/cjoc201310002 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 叶绿素降解产物的环丙基化及其二氢卟吩衍生物的合成 刘 洋a 徐希森a 李家柱a 殷军港a 祁彩霞b 王进军*,a,b a ( 烟台大学化学化工学院 烟台 264005) (b 山东省黄金工程技术研究中心(工业应用) 烟台 264005) 摘要 以叶绿素降解产物脱镁叶绿酸-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, 沿着N21-N23 轴向进 行官能团修饰, 通过 1,3-偶极环加成反应、Grignard 反应和外接环的结构改造, 在周环上的不同位置上引进了三元环烷 基结构, 完成了一系列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, IR, 1H NMR, MS 及元素分析 予以证实, 同时也讨论了环丙基的引进对二氢卟吩的理化性质所产生的各种影响, 并对部分新化合物的体外光动力活 性进行了测试. 关键词 叶绿素-a; 二氢卟吩; 化学修饰; 环丙基化; 合成 Cyclopropylation of Chlorophyllous Degradation Products and Synthesis of Chlorin Derivatives Liu, Yanga Xu, Xisena Li, Jiazhua Yin, Junganga Qi, Caixiab Wang, Jinjun*,a,b (a College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005) (b Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264005) Abstract Pheophorbide-a methyl ester, as a degraded product from chlorophyll-a, was used as a starting material, and the modifications for functional groups along N21-N23-axis were completed by making use of reactive regions. The tri-membered ring structures were introduced to the macrocyclic chromophore in different position by 1,3-polar cycloaddition, Grignard reaction and reconstructions for exocyclic ring. A series of unreported chlorins related to chlorophyll were synthesized and their chemical structures were characterized by UV, IR,