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  

Synthesis of C-3-isoxazolyl Chlorins with Basic Skeleton of Chlorophyll-a

作　　者：王进军[1] 李韵伟[1] 李家柱[1] 殷军港[1] 

机构地区：[1]烟台大学化学生物理工学院,烟台264005

出　　处：《有机化学》2011年第12期2074-2081,共8页Chinese Journal of Organic Chemistry

基　　金：山东省自然科学基(No.Y2008B49)资助项目

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，1HNMR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．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-p6 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 chlorophyll derivatives were characterized by UV, IR, 1H NMR spectra and elemental analysis. The possible mechanisms about corresponding oxidation, substitution and rearrangement reactions were tentatively proposed.

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) 

分 类 号：O626[理学—有机化学]