Base-induced instability of fluorotelomer alcohols

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. •The instability of fluorotelomer alcohol...

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Bibliographic Details
Published in:Journal of fluorine chemistry 2013-12, Vol.156, p.26-29
Main Authors: Tucker, William B., Mecozzi, Sandro
Format: Article
Language:English
Subjects:
Alcohols
Determinants
Fluorine
Fluorotelomer alcohols
Fluorous synthesis
HF-elimination
Hydrogen bonds
Instability
Solubility
Solvation
Stability
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Summary: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. •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.
ISSN:0022-1139
1873-3328
DOI:10.1016/j.jfluchem.2013.08.010