Generation and Trapping of Ketenes in Flow

    Cyril Henry1, David Bolien1, Bogdan Ibanescu1, Sally Bloodworth1, David C. Harrowven1, Xunli Zhang2, Andy Craven3, Helen F. Sneddon3, Richard J. Whitby1 *

    • 1 Chemistry, University of Southampton, Southampton, HANTS, SO17 1BJ, UK,
    • 2 Bioengineering Group, Faculty of Engineering and the Environment, University of Southampton, Southampton, HANTS, SO17 1BJ, UK
    • 3 GlaxoSmithKline R&D Ltd., Medicines Research Centre, Gunnels Wood Road, Stevenage, HERTS, SG1 2NY, UK

    Ketenes were generated by the thermolysis of alkoxyalkynes under flow conditions, and then trapped with amines and alcohols to cleanly give amides and esters. For a 10 min reaction time, temperatures of 180, 160, and 140 °C were required for >95 % conversion of EtO, iPrO, and tBuO alkoxyalkynes, respectively. Variation of the temperature and flow rate with inline monitoring of the output by IR spectroscopy allowed the kinetic parameters for the conversion of 1-ethoxy-1-octyne to be easily estimated (Ea = 105.4 kJ/mol). Trapping of the in-situ-generated ketenes by alcohols to give esters required the addition of a tertiary amine catalyst to prevent competitive [2+2] addition of the ketene to the alkoxyalkyne precursor.

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