Chemistry of Halogenoperfluoroalkanes> Synthesis of Fluorinated Ethers and Thioethers via Radical or Anionic Intermediates

Article abstract of DOI:10.1021/jo00221a017

Condensation of bromotrifluoromethane with potassium thiophenoxides in DMF is performed under pressure (2-3 atm) in a glass apparatus.Inhibition by nitrobenzene shows that a S_RN1 mechanism is involved in the formation of aryl trifluoromethyl sulfides.Dichlorodifluoromethane itself reacts through a similar process to give aryl chlorodifluoromethyl sulfides.Condensation of 1,1,2-trichlorotrifluoroethane with potassium thiophenoxide or phenoxide occurs even in the presence of nitrobenzene.The formation of aryl 2,2-dichloro-1,1,2-trifluoroethyl sulfides or ethers can be explained by a chain carbanionic mechanism.