焦脱镁叶绿酸-a甲酯的溴化反应  

Bromination Reaction of Methyl Pyropheophorbide-a

作　　者：王进军[1] 韩光范 邬旭然[1] 王鲁敏[1] 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科学与工程学院,镇江212003 [3]仁济大学

出　　处：《有机化学》2004年第5期537-542,共6页Chinese Journal of Organic Chemistry

基　　金：国家科技部中韩政府间合作研究 (2 0 0 2 )资助项目

摘　　要：以焦脱镁叶绿酸 a甲酯为起始原料 ,通过与各种溴化剂的加成和取代反应 ,在 3 位和meso 位上引进溴原子 ,分别得到单取代、三取代和四取代的溴化卟吩 ;其 3 位乙烯基与溴化氢的加成则分别生成正常溴代产物和水解产物及其酯化产物 .用四氧化锇和高碘酸钠将焦脱镁叶绿酸甲酯的 3 位乙烯基氧化成醛 ,进而与四溴化碳和三苯基磷反应 ,生成 3 位偕二溴取代焦脱镁叶绿酸衍生物 .所合成的叶绿酸溴代衍生物均经UV ,IR 。Methyl pyropheophorbide-a (MPP-a) was used as starting material for the synthesis of new bromine-substituted chlorin compounds. The bromines were introduced into 3-position and meso-position of the chlorin chromophore by addition reaction and substitution reaction with the bromide reagents to give mono-bromine- and tri-bromine-substituted chlorines. The formal addition product, hydrolyzate and esterified product were obtained by addition reaction with 30% hydrogen bromide in acetic acid. MPP-a was oxidized with OsO4 in THF containing catalytic pyridine at 0 degreesC and followed by glycol cleavage with sodium periodate in aqueous THF to give the methyl pyropheophorbide-d (MPP-d) which was reacted with carbon tetrabromide and triphenylphosphine to generate gem-dibromine substituted product at 3(b)-position. The structures of all new compounds were characterized by elemental analysis, UV, IR and H-1 NMR spectra.

关 键 词：焦脱镁叶绿酸-a甲酯 溴化反应 光动力疗法 光敏剂 抗癌药物 

分 类 号：O621.25[理学—有机化学]