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A Study into the Stability of 3,6-Dihydro-2H-thiopyran Rings: Key Linkages in the RAFT Hetero-Diels−Alder Click Concept

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    A Study into the Stability of 3,6-Dihydro-2H-thiopyran Rings: Key Linkages in the RAFT Hetero-Diels−Alder Click Concept
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    • Sebastian Sinnwell
      Sebastian Sinnwell
      Preparative Macromolecular Chemistry, Institut für Technische Chemie and Polymer Chemie, Universität Karlsruhe (TH)/Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany, and Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
      More by Sebastian Sinnwell
    • Christopher V. Synatschke
      Christopher V. Synatschke
      Preparative Macromolecular Chemistry, Institut für Technische Chemie and Polymer Chemie, Universität Karlsruhe (TH)/Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany, and Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
      More by Christopher V. Synatschke
    • Tanja Junkers
      Tanja Junkers
      Preparative Macromolecular Chemistry, Institut für Technische Chemie and Polymer Chemie, Universität Karlsruhe (TH)/Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany, and Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
      More by Tanja Junkers
    • Martina H. Stenzel*
      Martina H. Stenzel
      Preparative Macromolecular Chemistry, Institut für Technische Chemie and Polymer Chemie, Universität Karlsruhe (TH)/Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany, and Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
      * Corresponding authors. (C.B-K.) Fax: +49 721 6085740. E-mail: [email protected]. (M.H.S.) Fax: +61 2 93856250. E-mail: [email protected]
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    • Christopher Barner-Kowollik*
      Christopher Barner-Kowollik
      Preparative Macromolecular Chemistry, Institut für Technische Chemie and Polymer Chemie, Universität Karlsruhe (TH)/Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany, and Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney NSW 2052, Australia
      * Corresponding authors. (C.B-K.) Fax: +49 721 6085740. E-mail: [email protected]. (M.H.S.) Fax: +61 2 93856250. E-mail: [email protected]
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    Macromolecules

    Cite this: Macromolecules 2008, 41, 21, 7904–7912
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    https://doi.org/10.1021/ma8013959
    Published October 14, 2008
    Copyright © 2008 American Chemical Society
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    Abstract

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    The combination of RAFT chemistry and hetero-Diels−Alder (HDA) cycloaddition provides a convenient conjugation tool for the construction of macromolecular architectures. The actual conjugation linkage, which is formed in the RAFT HDA approach, consists of a 3,6-dihydro-2H-thiopyran ring. Herein, a careful study into the stability of polymer linked by 3,6-dihydro-2H-thiopyran rings under different thermal and pH conditions is performed. As polymeric model system, a 3,6-dihydro-2H-thiopyran functionalized poly(ethylene glycol) (PEG) obtained after a HDA cycloaddition between a diene functionalized PEG and 1-phenylethyl (diethoxyphosphoryl)dithioformate or 1-phenylethyl pyridin-2-yldithioformate is used. Electrospray ionization mass spectrometry (ESI-MS) is employed to map the generated products. The stability tests under thermal conditions showed for the diethoxyphosphoryl derivative the preservation of the polymer end-groups after 24 h at temperatures up to 80 °C. At higher temperatures degradation reactions of the 3,6-dihydro-2H-thiopyran ring including the retro HDA reaction occurred. A complete fragmentation was observed after 24 h at 160 °C. The pyridinyl derivative was found to be slightly more temperature stable since its structure was unaffected at conditions up to 24 h at 120 °C and full cleavage was only observed after 24 h at 180 °C. In this case the fragmentation mechanism occurred exclusively via the retro HDA reaction and the resulting diene functionalized polymer was the only detected product species. Both conjugates showed an excellent stability toward hydrolysis in aqueous media under strong acidic (0.1 and 1 m HCL) and strong basic (0.1 and 1 M NaOH) conditions.

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    Macromolecules

    Cite this: Macromolecules 2008, 41, 21, 7904–7912
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ma8013959
    Published October 14, 2008
    Copyright © 2008 American Chemical Society
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