Fluoride-catalyzed hydroalkoxylation of hexafluoropropene with 2,2,2-trifluoroethanol

Trifluoroethoxylation of hexafluoropropene with 2,2,2-trifluoroethanol (TFE) were conducted using an alkali metal fluoride catalyst to produce CF3CHFCF2OCH2CF3. KF exhibited the highest yield and selectivity of CF3CHFCF2OCH2CF3, whereas LiF and NaF were inactive for the trifluoroethoxylation reaction. The same reaction also proceeded well in the presence of RbF or CsF, but yielded large amounts of olefinic and high molecular weight side products, implying that the size of alkali metal cation or the degree of MF dissociation plays an important role in determining the activity and the product composition. FT-IR and NMR experiments revealed that CsF interacts with TFE more strongly than KF through a hydrogen bonding. The experimental and spectroscopic results suggest that the degree of MF dissociation should be in the medium range for the selective production of CF3CHFCF2OCH2CF3 in high yield and selectivity.

Graphical abstractMechanistic investigation was conducted for the synthesis of CF3CHFCF2OCH2CF3 from the hydroalkoxylation of hexafluoropropene and 2,2,2-trifluoroethanol in the presence of an alkali metal fluoride (MF).Figure optionsDownload full-size imageDownload as PowerPoint slide