具有叶绿素-a基本碳架的氯代二氢卟吩衍生物的合成有机化学.pdfVIP

2009 年第 29 卷 有 机 化 学 Vol. 29, 2009 第 10 期, 1598～1605 Chinese Journal of Organic Chemistry No. 10, 1598～1605 ·研究论文· 具有叶绿素-a 基本碳架的氯代二氢卟吩衍生物的合成 王进军* 赵丽丽 李家柱 (烟台大学化学生物理工学院 烟台 264005) 摘要 选择脱镁叶绿酸-a 甲酯为起始原料, 经过化学结构修饰转换成其他叶绿素-a 衍生物. 以过氧化氢/盐酸、N-氯代 丁二酰亚胺(NCS)、氯化氢(或者浓盐酸)为氯化剂, 根据 3- 乙烯基和 20-meso-位的不同化学反应活性, 通过亲电加成和 亲电取代反应, 在二氢卟吩环上选择性地引进氯原子, 完成 8 种未见报道的具有叶绿素-a 基本碳架的氯代二氢卟吩衍 生物的合成. 所合成的新化合物均经 UV, IR, 1H NMR 及元素分析证明其结构. 关键词 脱镁叶绿酸-a 甲酯; 亲电反应; 选择性氯代; 氯代二氢卟吩; 光动力治疗 Synthesis of Chloro-substituted Chlorin Derivatives with Basic Skeleton of Chlorophyll-a Wang, Jinjun* Zhao, Lili Li, Jiazhu (Department of Applied Chemistry, Yantai University, Yantai 264005) Abstract Methyl pheophorbide-a was chosen as a starting material and converted into other chlorophyll-a derivatives by chemical modification. Chlorine atoms were selectively introduced into the chlorin ring based on different reactivity between vinyl group at 3-position and 20-meso position by electrophilic addition and electrophilic substitution using hydrogen peroxide/hydrochloric acid, N-chlorosuccinimide (NCS), hydrogen chloride (or concentrated hydrochloric acid) as chlorinating reagent. Eight new chlorosubstituted chlorin de- rivatives with skeleton of chlorophyll-a were synthesized and their chemical structures were characterized by 1 elemental analysis, UV, IR and H NMR spectra. Keywords methyl pyropheophorbide-a; electrophilic reaction; selective chlorination; chlorinated chlorin; photodynamic therapy 某