113279-39-3Relevant academic research and scientific papers
Generation and trapping of ketenes in flow
Henry, Cyril,Bolien, David,Ibanescu, Bogdan,Bloodworth, Sally,Harrowven, David C.,Zhang, Xunli,Craven, Andy,Sneddon, Helen F.,Whitby, Richard J.
, p. 1491 - 1499 (2015/03/04)
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.
AN EFFICIENT SYNTHESIS OF tert-ALKOXYETHYNES
Pericas, Miquel A.,Serratosa, Felix,Valenti, Eduard
, p. 2311 - 2316 (2007/10/02)
The synthesis of tert-butoxyethyne (1a) and (1-adamantyloxy)ethyne (1b) has been performed by a three step sequence starting from ethyl vinyl ether.Overall yields are 34 and 67percent, respectively.The process is insensitive to the steric hindrance of the tertiary alcohol used and can be conveniently modified for the preparation of 1-tert-alkoxy-1-alkynes in high yield, without isolation of the intermediate 1-tert-alkoxyethyne.
