Electrolytic Partial Fluorination of Organic Compounds. Part 41: Highly Selective Electrolytic Fluorination of Dimethoxyethane, its Homologues, and Crown Ethers

The anodic fluorination of dimethyoxyethane (DME), and diethylene glycol dimethyl ether in acetonitrile containing a fluoride salt as a supporting electrolyte and a fluoride ion source using an undivided cell provided the corresponding monofluoromethyl ethers as a main product in good yields. On the other hand, anodic fluorination of crown ethers resulted in carbon–carbon bond cleavage which led to the selective production of α,ω-difluoro products with high yields. A carbon anode as well as a platinum anode was found to be effective for the electrolytic fluorination when Et3N·5HF was used as the supporting electrolyte.