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

Abstract

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 − .

Authors:
 [1];  [1];  [1];  [1];  [2];  [2];  [1]; ORCiD logo [1]
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  1. University of Southern California Loker Research Institute LHI 106 837 Bloom Walk Los Angeles California 90089-1661 USA
  2. University of Alabama Department of Chemistry &, Biochemistry Tuscaloosa Alabama 35487 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1477129
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Name: Chemistry - A European Journal Journal Volume: 24 Journal Issue: 63; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Baxter, Amanda F., Schaab, Jonas, Hegge, Joachim, Saal, Thomas, Vasiliu, Monica, Dixon, David A., Haiges, Ralf, and Christe, Karl O. α‐Fluoroalcohols: Synthesis and Characterization of Perfluorinated Methanol, Ethanol and n ‐Propanol, and their Oxonium Salts. Germany: N. p., 2018. Web. doi:10.1002/chem.201804306.
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Baxter, Amanda F., Schaab, Jonas, Hegge, Joachim, Saal, Thomas, Vasiliu, Monica, Dixon, David A., Haiges, Ralf, & Christe, Karl O. α‐Fluoroalcohols: Synthesis and Characterization of Perfluorinated Methanol, Ethanol and n ‐Propanol, and their Oxonium Salts. Germany. https://doi.org/10.1002/chem.201804306
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Baxter, Amanda F., Schaab, Jonas, Hegge, Joachim, Saal, Thomas, Vasiliu, Monica, Dixon, David A., Haiges, Ralf, and Christe, Karl O. Thu . "α‐Fluoroalcohols: Synthesis and Characterization of Perfluorinated Methanol, Ethanol and n ‐Propanol, and their Oxonium Salts". Germany. https://doi.org/10.1002/chem.201804306.
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@article{osti_1477129,
title = {α‐Fluoroalcohols: Synthesis and Characterization of Perfluorinated Methanol, Ethanol and n ‐Propanol, and their Oxonium Salts},
author = {Baxter, Amanda F. and Schaab, Jonas and Hegge, Joachim and Saal, Thomas and Vasiliu, Monica and Dixon, David A. and Haiges, Ralf and Christe, Karl O.},
abstractNote = {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 − .},
doi = {10.1002/chem.201804306},
journal = {Chemistry - A European Journal},
number = 63,
volume = 24,
place = {Germany},
year = {Thu Oct 11 00:00:00 EDT 2018},
month = {Thu Oct 11 00:00:00 EDT 2018}
}
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https://doi.org/10.1002/chem.201804306
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