On the isolation of neat allylic fluorides

Neat cinnamyl fluoride, geranyl fluoride, 5-carbomethoxy-3-fluorocyclohexene and parent 3-fluorocyclohexene undergo spontaneous decomposition on contact with borosilicate glass or catalytic quantities of moderately strong acids that consists in polycondensation with elimination of HF initiated by electrophilic abstraction of F−. Acid sensitivity of these allylic fluorides correlates with stability of respective allylic cations, exceeds that of parent benzyl fluoride, yet can be mitigated by the use of Teflon and PFA containers that permit their isolation and handling in the neat state.

Graphical abstractCommon allylic fluorides undergo spontaneous decomposition on contact with borosilicate glass and catalytic quantities of moderately strong acids that consists in polycondensation with elimination of HF initiated by electrophilic abstraction of F−. Use of fluorinated equipment enables their isolation in the neat state.Figure optionsDownload full-size imageDownload as PowerPoint slide