Dioxygen-activated Reductive Epoxidation of Cyclohexene Using Mn (III) Porphyrin-viologen Catalytic Systems

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  • TSUDA Yoshihiro
    Department of Chemistry and Biology Engineering, Fukui National College of Technology
  • TAKAHASHI Kohshin
    Department of Chemistry and Chemical Engineering, Faculty of Engineering
  • YAMAGUCHI Takahiro
    Department of Chemistry and Chemical Engineering, Faculty of Engineering
  • MATSUI Syuichi
    Department of Chemistry and Biology Engineering, Fukui National College of Technology
  • KOMURA Teruhisa
    Department of Chemistry and Chemical Engineering, Faculty of Engineering
  • NISHIGUCHI Ikuzo
    Department of Chemistry, Nagaoka University of Technology

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Other Title
  • ビオロゲンを電子媒介体として含むMnポルフィリン系触媒を用いた一酸素原子添加によるシクロヘキセンのエポキシ化
  • ビオロゲン オ デンシ バイカイタイ ト シテ フクム Mn ポルフィリンケイ

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Abstract

When a viologen-linked Mn (III) porphyrin complex as well as a mixed system of Mn (III) porphyrin and hexylviologen were used as a catalyst for a monooxygenation reaction of cyclohexene in an airequilibrated dichloromethane suspension containing insoluble zinc powder as a reductant and benzoiC anhydride as a cleaving reagent of dioxygen O-O bond, cyclohexene oxide (epoxide) was obtained as a single oxidation product of cyclohexene. Cyclic voltammetry was carried out to clarify the role of the molecular dioxygen, hexylviologen, 1-methyl-imidazole (III/II) and benzoic anhydride for the redox characteristics of the Mn porphyrin, and to explain this catalytic mechanism. It was consequently proved that the coordination of 1-MeIm to Mn porphyrins let to vary the redox potential of its couple and also the coordination of 1-MeIm to Mn (II) porphyrin interfered with that of the molecular dioxygen to its porphyrin, and hexylviologen acted as a mediator of electron transfer from zinc powder to Mn (II) porphyrin-O2 adduct. Therefore, the amount of the produced epoxide varied complexly with concentration of 1-MeIm added in this catalytic system. The larger amount of epoxide was obtained in the mixed system using the Mn porphyrin that has more positive redox potential, because the reduction of the Mn porphyrin occurred more easily.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1998 (9), 581-590, 1998-09-10

    The Chemical Society of Japan

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