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Phosphine functionalized polyphosphazenes: soluble and re-usable polymeric reagents for highly efficient halogenations under Appel conditions

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Abstract

In this paper we present the preparation and application of a novel soluble phosphine functionalized polyphosphazene (poly[3-(diphenylphosphino)propylamino]phosphazene) and investigate its application as a polymeric reagent. Upon chlorination of the pendant phosphine groups, the polymer was found to facilitate the rapid and efficient transformation of alcohols to the corresponding chlorides and bromides under Appel-type conditions. Reaction times followed by 31P NMR spectroscopy are shown to be rapid (several minutes) and the yields for the transformation of alcohols to the corresponding halides are in the range 80–99 %. The facile recovery of the oxidized polymeric agent by precipitation is also described, offering a significant advantage over notoriously difficult to remove small molecule phosphine oxide by-products. Furthermore the regeneration of the reactive phosphine chloride pendant groups is demonstrated, which could be efficiently re-used in a further chlorination reaction.

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Acknowledgments

We thank Dr. Wolfgang Schoefberger for his help with the NMR measurements and Wolfgang Gnong for his assistance with the GC–MS measurements. A.L. thanks the Springer Verlag, the Austrian Academy of Sciences (ÖAW) and the Gesellschaft Österreichischer Chemiker (GÖCH) for Chemical Monthly Fellowship for 3 months research abroad.

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Authors and Affiliations

  1. Institute of Polymer Chemistry, Johannes Kepler University, Linz, Austria

    Michael König, Anne Linhardt, Oliver Brüggemann & Ian Teasdale

Authors
  1. Michael König
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  2. Anne Linhardt
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  3. Oliver Brüggemann
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  4. Ian Teasdale
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Corresponding author

Correspondence to Ian Teasdale.

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König, M., Linhardt, A., Brüggemann, O. et al. Phosphine functionalized polyphosphazenes: soluble and re-usable polymeric reagents for highly efficient halogenations under Appel conditions. Monatsh Chem 147, 1575–1582 (2016). https://doi.org/10.1007/s00706-016-1791-x

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  • DOI: https://doi.org/10.1007/s00706-016-1791-x

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