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Polyurethane- and Polystyrene-Supported 2,2,6,6-Tetramethyl- piperidine-1-oxyl (TEMPO); Facile Preparation, Catalytic Oxidation and Application in a Membrane Reactor

Authors

  • Muhammad Afzal Subhani,

    1. Organische Chemie, Technische Universität Dortmund, Otto-Hahn-Str. 6, 44221 Dortmund, Germany, Fax:(+49)-231-755-5363
    2. Present address: School of Chemical & Material Engineering, National Univerity of Science and Technology, B2 Navy Housing Scheme, F11/1 Islamabad, Pakistan
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  • Maryam Beigi,

    1. Organische Chemie, Technische Universität Dortmund, Otto-Hahn-Str. 6, 44221 Dortmund, Germany, Fax:(+49)-231-755-5363
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  • Peter Eilbracht

    1. Organische Chemie, Technische Universität Dortmund, Otto-Hahn-Str. 6, 44221 Dortmund, Germany, Fax:(+49)-231-755-5363
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Abstract

In this contribution, the facile synthesis of two new polymer-supported 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) catalysts and their application in the catalytic oxidation of alcohols to carbonyl compounds are described. For attachment of the TEMPO group to the polymer an isocyanate functionalized polymer is chosen. This new approach facilitates the synthesis in comparison with previously existing methods which generally require deprotonation of TEMPO prior to reaction with the polymer. Following this approach, polyurethane (PU)- and polystyrene (PS)-based TEMPO catalysts are prepared in a one-step reaction from commercially available compounds. Both polymer-supported catalysts showed promising yields for a variety of substrates using inorganic and/or organic co-oxidants in biphasic and/or monophasic systems. The recyclability of the corresponding catalysts was studied in repetitive batch experiments using filtration or distillation depending on the support type. Furthermore, application of the homogeneous polyurethane-supported TEMPO for the selective oxidation of benzyl alcohol in a continously operated membrane reactor is demonstrated.

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