3-位苯并含氮杂环取代的焦脱镁叶绿酸-a甲酯的合成

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3b-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，^1H NMR及元素分析证明其结构．

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

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.