Three step procedure for the preparation of aromatic and aliphatic difluoromethyl ethers from phenols and alcohols using a chlorine/fluorine exchange methodology
作者:William R. Dolbier、Fei Wang、Xiaojun Tang、Charles S. Thomoson、Linhua Wang
DOI:10.1016/j.jfluchem.2014.01.018
日期:2014.4
Difluoromethyl ethers are prepared from phenols in three steps via their respective formate ester derivatives. The formates are first converted to dichloromethyl ethers by treatment with PCl5. These ethers are then induced to undergo chlorine/fluorine exchange to form the respective difluoromethyl ethers. The chlorine/fluorine exchange is carried out by either a room temperature, solvolytic process using THF-5HF
二氟甲基醚是由苯酚通过它们各自的甲酸酯衍生物分三步制备的。的甲酸盐首先通过用五氯化磷转化为二氯甲基醚。然后,这些醚是诱导经历氯/氟交换,以形成相应的二氟甲基醚。氯/氟交换由或室温,用THF-5HF或Et溶剂化过程中进行3的N- 3HF作为交换介质,其中HF是氟的最终来源,或者通过在环丁砜在125℃,其中KF是氟源的直接位移过程。由一个或另一个这些过程中,几乎所有的酚和电子差富电子,可以在良好的收益率转化为各自的二氟甲基醚。脂族醇也能够被转换为使用的Et它们二氟甲基醚衍生物3的N- 3HF交换介质。