α‐Fluoroalcohols: Synthesis and Characterization of Perfluorinated Methanol, Ethanol and n ‐Propanol, and their Oxonium Salts

Baxter, Amanda F.; Schaab, Jonas; Hegge, Joachim; Saal, Thomas; Vasiliu, Monica; Dixon, David A.; Haiges, Ralf; Christe, Karl O.

doi:10.1002/chem.201804306

α‐Fluoroalcohols: Synthesis and Characterization of Perfluorinated Methanol, Ethanol and n ‐Propanol, and their Oxonium Salts

Journal Article · Thu Oct 11 00:00:00 EDT 2018 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201804306· OSTI ID:1477129

Baxter, Amanda F. ^[1]; Schaab, Jonas ^[1]; Hegge, Joachim ^[1]; Saal, Thomas ^[1]; Vasiliu, Monica ^[2]; Dixon, David A. ^[2]; Haiges, Ralf ^[1]; ^[1]

University of Southern California Loker Research Institute LHI 106 837 Bloom Walk Los Angeles California 90089-1661 USA
University of Alabama Department of Chemistry &, Biochemistry Tuscaloosa Alabama 35487 USA

Abstract

The thermally unstable, primary perfluoroalcohols, CF ₃ OH, C ₂ F ₅ OH, and n C ₃ F ₇ OH, were conveniently prepared from the corresponding carbonyl compounds in anhydrous HF solution. Experimental values for the reaction enthalpies and entropies were derived from the temperature dependence of the R _f COF+HF⇄R _f CF ₂ OH ( R _f =F, CF ₃ , CF ₃ CF ₂ ) equilibria by NMR spectroscopy. Electronic structure calculations of the gas‐phase and solution reaction energies, gas‐phase acidities and heats of formation were carried out at the G3MP2 level, showing that these compounds are strong acids. Protonation of these alcohols in HF/SbF ₅ produced the perfluoroalkyl oxonium salts R _f CF ₂ OH ₂ ⁺ SbF ₆ ⁻ .

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1477129

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 63 Vol. 24; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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