3-位苯并含氮杂环取代的焦脱镁叶绿酸-a甲酯的合成

有机化学 ›› 2004, Vol. 24 ›› Issue (8): 906-911. 上一篇下一篇

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3-位苯并含氮杂环取代的焦脱镁叶绿酸-a甲酯的合成

王进军^*,a, 邬旭然^a, 王鲁敏^a, 韩光范^b, 沈荣基^c

^a烟台大学应用化学系烟台 264005
^b华中船舶工业学院材料与工程学院镇江 212003
^c仁济大学微工程学院釜山韩国

收稿日期:2003-10-08 修回日期:2004-02-20 接受日期:2004-02-20 发布日期:2022-09-20
通讯作者: * E-mail: wjj1955@163.com
基金资助:
科技部中韩政府间合作项目(No. 2002)资助项目.

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

WANG Jin-Jun^*,a, WU Xu-Ran^a, WANG Lu-Min^a, HAN Guang-Fan^b, SHIM Yong Key^c

^aDepartment of Applied Chemistry, Yantai University, Yantai 264005
^bSchool of Materials Science and Engineering, East China Shipbulding Institute, Zhenjiang 212003
^cSchool of Nano Engineering, Inji University, Pusan, Korea

Received:2003-10-08 Revised:2004-02-20 Accepted:2004-02-20 Published:2022-09-20

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摘要/Abstract

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, ¹H NMR及元素分析证明其结构.

关键词: 叶绿素-a衍生物, 焦脱镁叶绿酸-a甲酯, 杂环取代卟吩衍生物, 光动力疗法(PDT)

Methyl pyropheophorbide-a (MPP-a) (1) was usedas starting material for the synthesis of chlorin compounds. Zinc(II) methyl pyropheophorbide-a (2) was obtained by refluxing with zincacetate in CH₂Cl₂. 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 ethyleniclinkage of 3 was oxidized with OsO₄ and TPAP/N-methylmorphline N-oxide to afford diketone (4). The condensation of 4 with o-phenylenediamine by TFA catalyzed to givemethyl 3-quinoxalynyl pyropheophorbide-a (5). MPP-a (1) was oxidized by OsO₄ and NaIO₄ to generate methylpyropheophorbide-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 and¹H NMR spectra.

Key words: chlorophyll-a, methyl pyropheophorbide-a, chlorin derivatives substituted with heterocycle, photo~dynamic therapy (PDT)

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王进军, 邬旭然, 王鲁敏, 韩光范, 沈荣基. 3-位苯并含氮杂环取代的焦脱镁叶绿酸-a甲酯的合成[J]. 有机化学, 2004, 24(8): 906-911.

WANG Jin-Jun, WU Xu-Ran, WANG Lu-Min, HAN Guang-Fan, SHIM Yong Key. Synthesis of Methyl Pyripheophorbide-a Substituted at 3-Position by Benzo-heterocycle with Nitrogen Atom[J]. Chinese Journal of Organic Chemistry, 2004, 24(8): 906-911.

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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

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