具有叶绿素基本碳架的C-3-异噁唑啉基二氢卟吩类衍生物的合成有机化学.pdfVIP

2011 年第 31 卷 有 机 化 学 Vol. 31, 2011 第 12 期, 2074～2081 Chinese Journal of Organic Chemistry No. 12, 2074～2081 ·研究论文· 具有叶绿素基本碳架的 C-3-异噁唑啉基二氢卟吩类衍生物的合成 王进军* 李韵伟 李家柱 殷军港 a ( 烟台大学化学生物理工学院 烟台 264005) 摘要 以脱镁叶绿酸-a 甲酯为起始原料, 通过 3-位乙烯基与氧化苯甲腈和 4-取代氧化苯甲腈的 1,3-偶极环加成反应, 分别得到 3-位异噁唑基取代的二氢卟吩衍生物以及其他形式的加成产物, 对其脱镁叶绿酸的 E-环结构修饰则转换成相 应的二氢卟吩-p6 衍生物; 脱镁叶绿酸-a 甲酯经空气氧化和重排反应形成了红紫素-18- 内酰胺, 再与 4-取代氧化苯甲腈 进行相同的环加成反应, 也以理想的产率生成标题化合物. 所得新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, 并对相应的反应提出可能的反应机理. 关键词 叶绿素-a; 脱镁叶绿酸-a 甲酯; C-3-异噁唑基二氢卟吩; 1,3-偶极环加成; 光动力疗法(PDT) Synthesis of C-3-isoxazolyl Chlorins with Basic Skeleton of Chlorophyll-a Wang, Jinjun* Li, Yunwei Li, Jazhu Yin, Jungang a ( Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005) Abstract Methyl pheophorbide-a was used as starting material, and C-3-isoxazolyl-substituted chlorins and other adducts were obtained by 1,3-dipolar cycloadditions of the vinyl group at 3-position with benzoni- trile oxide and 4-nitrobenzonitrile oxide, respectively. The 3-isoxazolylpheophorbide-a was converted into relevant chlorin-p 6 derivative by the modification for the E-ring. The allomerization and rearrangement of the starting material produced purpurin-18 imide which was converted into title compound in desirable yield via same cycloaddition with 4-subatituted benzonitrile oxide. The structures of new c