Base-induced instability of fluorotelomer alcohols

• The instability of fluorotelomer alcohols – a problem widely acknowledged yet not elucidated in the literature – is investigated.
• The mechanism of decomposition relies on formation of an intramolecular hydrogen bond to facilitate HF-elimination.
• The effects of solvent, base and fluorocarbon-chain length are thoroughly investigated and rationalized through solubility.

The stability of fluorotelomer alcohols under basic conditions was studied. HF elimination across the CF2–CH2 junction is shown to be facilitated by an intramolecular hydrogen bond, while solvation is the key determinant in the stability of alcohols of various perfluoroalkyl lengths. Finally, fluorotelomer alcohols can be rendered kinetically stable if either the alcohol or the base has low solubility in the reaction medium.

The decomposition of fluorotelomer alcohols under basic conditions was found to proceed via an intramolecular-hydrogen-bond-assisted HF-elimination pathway. An unstable alkene is formed, which then oligomerizes further to yield a complex mixture of products.Figure optionsDownload as PowerPoint slide