THE PREPARATION OF ARYL DIFLUOROMETHYL ETHERS
THE PREPARATION OF ARYL DIFLUOROMETHYL ETHERS
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DOI：
10.1021/jo01081a048
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发表时间：
1960-01-01
影响因子：
3.6
通讯作者：
THANASSI, JW
中科院分区：
文献类型：
--
作者：
MILLER, TG;THANASSI, JW
芳基二氟甲基醚可以通过氯二氟甲烷与酚在含水二氧六环溶剂中和在过量氢氧化钠存在下的反应以可接受的产率制备。原甲酸芳基酯作为副产物形成。与在Reimer-Tiemann中制备α-氟代醚的二氯亚甲基相比，合成中的反应性中间体二氟亚甲基仅提供芳氧基离子的O-烷基化。先前制备α-氟代醚的方法涉及用氟取代醚中的氯和溴，将金属醇化物加成到含氟烯烃上，醚的电化学还原，以及金属醇化物与饱和的，含氟碳化合物。1 2
Aryl difluoromethyl ethers may be prepared in acceptable yieldsby the reaction of chlorodifluoromethane with phenols in an aqueous dioxane solvent and in the presence of an excess of sodium hydroxide. Aryl orthoformates are formed as byproducts. Difluoromethylene, the reactive intermediate in the synthesis, affords only O-alkylation of the aryloxide ion in contrast to dichloromethylene which, in the Reimer-TiemannPrevious methods for the preparation of a-fluoroethers have involved replacement of chlorine and bromine in ethers by fluorine, addition of metal alcoholates to fluorine-containing olefins, electrochemical fluorination of ethers, and thereaction of metal alcoholates with saturated, fluorinecontaining carbon compounds. 1 2