Generation and Trapping of Ketenes in Flow.

Generation and Trapping of Ketenes in Flow.
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DOI:
10.1002/ejoc.201403603
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发表时间:
2015-03
影响因子:
2.8
通讯作者:
Whitby, Richard J.
Whitby, Richard J.
中科院分区:
化学3区
文献类型:
--
作者:
Henry, Cyril;Bolien, David;Ibanescu, Bogdan;Bloodworth, Sally;Harrowven, David C.;Zhang, Xunli;Craven, Andy;Sneddon, Helen F.;Whitby, Richard J.

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在流动条件下,烷氧基炔经热分解生成烯酮,然后与胺和醇捕集,干净地得到酰胺和酯。对于10分钟的反应时间,对于EtO、iPrO和tBuO烷氧基炔的> 95%转化率,分别需要180、160和140 °C的温度。通过IR光谱法在线监测输出的温度和流速的变化允许容易地估计1-乙氧基-1-辛炔转化的动力学参数(Ea = 105.4kJ/mol)。通过醇捕获原位生成的烯酮以得到酯需要添加叔胺催化剂以防止烯酮与烷氧基炔前体的竞争性[2+2]加成。
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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