Elemental fluorine. Part 14. Electrophilic fluorination and nitrogen functionalisation of hydrocarbons
Elemental fluorine. Part 14. Electrophilic fluorination and nitrogen functionalisation of hydrocarbons
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DOI：
10.1039/b204776b
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发表时间：
2002-01-01
期刊：
影响因子：
--
通讯作者：
Moilliet, JS
中科院分区：
文献类型：
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作者：
Chambers, RD;Kenwright, AM;Moilliet, JS
通过与元素氟或 N-F 类亲电子氟化试剂 Selectflu™ 反应，实现了一系列碳氢化合物的选择性氟化。设想了亲电机制。在长时间的反应中，当使用Selectflu TM 作为氟化试剂时，氢被氟取代时形成的强酸性反应介质会促进初始氟化产物中氟化物的损失。在里特型工艺中，乙腈溶剂捕获随后的碳正离子，得到烃类的整体氮官能化。烃的酰胺化也可以通过烃与氟和路易斯酸(例如三氟化硼-乙醚)在乙腈中反应而以一步法实现。
Selective fluorination of a range of hydrocarbons was achieved by reaction with either elemental fluorine or Selectfluor(TM), an electrophilic fluorinating reagent of the N-F class. An electrophilic mechanism is envisaged. On prolonged reaction, the strongly acidic reaction medium that is formed upon substitution of hydrogen by fluorine when Selectfluor(TM) is used as the fluorinating reagent, promotes loss of fluoride from the initial fluorinated product. Trapping of the subsequent carbocation by the acetonitrile solvent in a Ritter type process gives overall nitrogen functionalisation of hydrocarbons. Amidation of hydrocarbons could also be achieved in a one-stage process by reaction of the hydrocarbon with fluorine and a Lewis acid, such as boron trifluoride-diethyl ether, in acetonitrile.