A theoretical study on the pyrolysis of perfluorobutanoic acid as a model compound for perfluoroalkyl acids

Mohammednoor Altarawneh

doi:10.1016/j.tetlet.2012.05.109

A theoretical study on the pyrolysis of perfluorobutanoic acid as a model compound for perfluoroalkyl acids

Mohammednoor Altarawneh

Research output: Contribution to journal › Article › peer-review

26 Citations (Scopus)

Abstract

The potential energy surface is mapped out for all plausible reactions in the self-decomposition of perfluorobutanoic acid (CF₃CF ₂CF₂COOH) as a model compound for the notoriously toxic and bio-accumulative perfluoroalkyl acids. Initial decomposition of perfluorobutanoic acid is found to be controlled by HF elimination and the formation of an α-lactone intermediate. The fate of this intermediate is predicted to be dominated by two competing channels, namely formation of pentafluoropropanoyl fluoride (CF₃CF₂COF) and the closed-shell singlet CF₃CF₂CF:. Direct elimination of CO₂ through decarboxylation is found to be retarded by strong hyperconjugation effects induced by fluorine atoms on the carbon chain. The results presented herein provide insightful information towards a comprehensive understanding of the decomposition of perfluoroalkyl acids in thermal systems.

Original language	English
Pages (from-to)	4070-4073
Number of pages	4
Journal	Tetrahedron Letters
Volume	53
Issue number	32
DOIs	https://doi.org/10.1016/j.tetlet.2012.05.109
Publication status	Published - Aug 8 2012
Externally published	Yes

Keywords

Decarboxylation
Perfluorobutanoic acid
Pyrolysis
Reaction rate constants

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2012.05.109

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title = "A theoretical study on the pyrolysis of perfluorobutanoic acid as a model compound for perfluoroalkyl acids",

abstract = "The potential energy surface is mapped out for all plausible reactions in the self-decomposition of perfluorobutanoic acid (CF3CF 2CF2COOH) as a model compound for the notoriously toxic and bio-accumulative perfluoroalkyl acids. Initial decomposition of perfluorobutanoic acid is found to be controlled by HF elimination and the formation of an α-lactone intermediate. The fate of this intermediate is predicted to be dominated by two competing channels, namely formation of pentafluoropropanoyl fluoride (CF3CF2COF) and the closed-shell singlet CF3CF2CF:. Direct elimination of CO2 through decarboxylation is found to be retarded by strong hyperconjugation effects induced by fluorine atoms on the carbon chain. The results presented herein provide insightful information towards a comprehensive understanding of the decomposition of perfluoroalkyl acids in thermal systems.",

keywords = "Decarboxylation, Perfluorobutanoic acid, Pyrolysis, Reaction rate constants",

author = "Mohammednoor Altarawneh",

note = "Funding Information: This study was supported by a grant of computing time from the National Computational Infrastructure (NCI) , Australia (Project Id = De3).",

year = "2012",

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doi = "10.1016/j.tetlet.2012.05.109",

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T1 - A theoretical study on the pyrolysis of perfluorobutanoic acid as a model compound for perfluoroalkyl acids

AU - Altarawneh, Mohammednoor

N1 - Funding Information: This study was supported by a grant of computing time from the National Computational Infrastructure (NCI) , Australia (Project Id = De3).

PY - 2012/8/8

Y1 - 2012/8/8

N2 - The potential energy surface is mapped out for all plausible reactions in the self-decomposition of perfluorobutanoic acid (CF3CF 2CF2COOH) as a model compound for the notoriously toxic and bio-accumulative perfluoroalkyl acids. Initial decomposition of perfluorobutanoic acid is found to be controlled by HF elimination and the formation of an α-lactone intermediate. The fate of this intermediate is predicted to be dominated by two competing channels, namely formation of pentafluoropropanoyl fluoride (CF3CF2COF) and the closed-shell singlet CF3CF2CF:. Direct elimination of CO2 through decarboxylation is found to be retarded by strong hyperconjugation effects induced by fluorine atoms on the carbon chain. The results presented herein provide insightful information towards a comprehensive understanding of the decomposition of perfluoroalkyl acids in thermal systems.

AB - The potential energy surface is mapped out for all plausible reactions in the self-decomposition of perfluorobutanoic acid (CF3CF 2CF2COOH) as a model compound for the notoriously toxic and bio-accumulative perfluoroalkyl acids. Initial decomposition of perfluorobutanoic acid is found to be controlled by HF elimination and the formation of an α-lactone intermediate. The fate of this intermediate is predicted to be dominated by two competing channels, namely formation of pentafluoropropanoyl fluoride (CF3CF2COF) and the closed-shell singlet CF3CF2CF:. Direct elimination of CO2 through decarboxylation is found to be retarded by strong hyperconjugation effects induced by fluorine atoms on the carbon chain. The results presented herein provide insightful information towards a comprehensive understanding of the decomposition of perfluoroalkyl acids in thermal systems.

KW - Decarboxylation

KW - Perfluorobutanoic acid

KW - Pyrolysis

KW - Reaction rate constants

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ER -

A theoretical study on the pyrolysis of perfluorobutanoic acid as a model compound for perfluoroalkyl acids

Abstract

Keywords

ASJC Scopus subject areas

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