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Biphasic and Flow Systems Involving Water or Supercritical Fluids

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Abstract

Two processes are described for improving reaction rates for relatively hydrophobic substrates in aqueous biphasic systems. In the first, 1-octyl-3-methylimidazolium bromide ([Octmim]Br) increases the rate of hydroformylation of 1-octene from 8% conversion in 24 h to full conversion of 1.5 h. Phase separation is fast and catalyst retention is good. 1-Hexyl-3-methylimidazolium bromide gives little rate enhancement, whilst 1-decyl-3-methylimidazolium bromide gives stable emulsions., The mechanism of action of these additives is discussed. In the second approach, functionalising PPh3 with amidine groups allows the rhodium catalysed hydroformylation of 1-octene in toluene with a very high reaction rate. The catalyst can be switched between toluene and water by bubbling CO2 and back into toluene by bubbling N2 at 60 °C. This switching has been used to separate the catalyst from hydrophobic (from 1-octene) or hydrophilic (from allyl alcohol) aldehydes obtained from hydroformylation reactions. CO2 expanded liquids have been shown to be effective media for transporting substrates and catalysts over supported ionic liquid phase (SILP) catalysts. The advantages offered over all gas phase and liquid phase catalysts are discussed.

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Acknowledgements

We thank Sasol Technology (UK) Ltd for a studentship (S. L. D.) and the EC for funding under the IDECAT Network of Excellence CT-2005-011730 (U. H.).

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Authors and Affiliations

  1. EaStCHEM, School of Chemistry, University of St. Andrews, St. Andrews, Fife, KY16 9ST, UK

    Simon L. Desset, Ulrich Hintermair, Zhenxin Gong & David J. Cole-Hamilton

  2. Laboratoire de Chimie Organometallique de Surface, UMR 9986 CNRS, CPE Lyon, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne Cedex, France

    Ulrich Hintermair & Catherine C. Santini

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  1. Simon L. Desset
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  2. Ulrich Hintermair
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  3. Zhenxin Gong
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  4. Catherine C. Santini
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  5. David J. Cole-Hamilton
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Correspondence to David J. Cole-Hamilton.

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Desset, S.L., Hintermair, U., Gong, Z. et al. Biphasic and Flow Systems Involving Water or Supercritical Fluids. Top Catal 53, 963–968 (2010). https://doi.org/10.1007/s11244-010-9515-7

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