Monofluorination of fluorinated oxolanes with high-valency metal fluorides

Article abstract of DOI:10.1016/S0022-1139(97)00130-9

Fluorinated oxolanes were fluorinated by high-valency metal fluorides (HVMFs) such as AgF₂,MnF₃,CoF₃,HgF₂ and KCoF₄ in a batch system. The fluorination reactivities of these reagents with 3,3,4,4-tetrafluoro-oxolane (4F) and 2,3,3,4,4-pentafluoro-oxolane (5F) follow the order CoF₃ > AgF₂ > MnF₃, KCoF₄ Gt; HgF₂. The order of fluorination reactivities with 4F and 5F agrees with that of oxidation hypothesis [R.D. Fowler et al., Industrial and Engineering Chemistry, 39 (3) 1947, 343; J. Burdon, I.W. Parsons, J.C. Tatlow, Tetrahedron, 28 (1972) 43]. In monofluorination of 5F with CoF₃, AgF₂ and MnF₃, fluorination of -CH₂-unit was major. In a flow system, monofluorination of 4F with CoF₃ was successfully achieved by diluting CoF₃ with CoF₂.