3-位苯并含氮杂环取代的焦脱镁叶绿酸-a甲酯的合成  

Synthesis of Methyl Pyripheophorbide-a Substituted at 3-Position by Benzo-heterocycle with Nitrogen Atom

作　　者：王进军[1] 邬旭然[1] 王鲁敏[1] 韩光范 沈荣基[3] 

机构地区：[1]烟台大学应用化学系,烟台264005 [2]华中船舶工业学院材料与工程学院,镇江212003 [3]仁济大学微工程学院

出　　处：《有机化学》2004年第8期906-911,共6页Chinese Journal of Organic Chemistry

基　　金：科技部中韩政府间合作项目 (No.2 0 0 2 )资助项目

摘　　要：以焦脱镁叶绿酸 a甲酯 (MPP a) ( 1)为起始原料 ,在二氯甲烷中与醋酸锌共回流得锌配合物 2 ,在四氯钯锂催化下 ,通过与苯基氯化汞的偶联反应生成 3 b 苯基焦脱镁叶绿酸 a甲酯 ( 3 ) .分别选用四氧化锇、高钌酸四丙基铵 (TPAP)和N 甲基吗啉N 氧化物将环外烯键氧化成邻二酮 ( 4 ) .在酸性条件下 ,4与邻苯二胺的缩合形成了 3 位喹喔啉取代的焦脱镁叶绿酸 a甲酯 ( 5 ) .用四氧化锇和高碘酸钠将 1的 3 位碳碳双键氧化 ,则生成焦脱镁叶绿酸 d甲酯 ( 6) .所得卟吩醛与环己二酮和萘胺进行一锅法反应 ,得到 3 位苯并吖啶取代的焦脱镁叶绿酸 a甲酯 ( 7) .所合成的新卟吩化合物均经UV ,IR 。Methyl pyropheophorbide-a (MPP-a) (1) was used as starting material for the synthesis of chlorin compounds. Zinc(II) methyl pyropheophorbide-a (2) was obtained by refluxing with zinc acetate in CH 2Cl 2. The palladium-catalyzed coupling reaction of complex 2 with phenylmercuric chloride was carried out to give methyl 3 b-phenyl pyropheophorbide-a (3). The exocyclic ethylenic linkage of 3 was oxidized with OsO 4 and TPAP/N-methyl morphline N-oxide to afford diketone (4). The condensation of 4 with o-phenylenediamine by TFA catalyzed to give methyl 3-quinoxalynyl pyropheophorbide-a (5). MPP-a (1) was oxidized by OsO 4 and NaIO 4 to generate methyl pyropheophorbide-d (MPP-d) (6). The one pot reaction of 6 with cyclohexadione and naphthylamine was completed to form methyl 3-benzoacridinyl pyropheophorbide-a (7). The structures of the compounds were characterized by elemental analysis, UV, IR and 1H NMR spectra.

关 键 词：焦脱镁叶绿酸-a甲酯 合成 杂环取代卟吩衍生物 叶绿素-a衍生物 光动力疗法 抗癌药物 

分 类 号：TQ26[化学工程—有机化工] TQ463