Journal article
Synthesis and structure of environmentally relevant perfluorinated sulfonamides
Journal of fluorine chemistry, Vol.128(6), pp.595-607
2007
DOI: 10.1016/j.jfluchem.2007.01.013
PMCID: PMC2394736
PMID: 18516235
Abstract
Alkylated perfluorooctanesulfonamides are compounds of environmental concern. To make these compounds available for environmental and toxicological studies, a series of
N-alkylated perfluorooctanesulfonamides and structurally related compounds were synthesized by reaction of the corresponding perfluoroalkanesulfonyl fluoride with a suitable primary or secondary amine. Perfluoroalkanesulfonamidoethanols were obtained from the
N-alkyl perfluoroalkanesulfonamides either by direct alkylation with bromoethanol or alkylation with acetic acid 2-bromo-ethyl ester followed by hydrolysis of the acetate.
N-Alkyl perfluorooctanesulfonamidoacetates were synthesized in an analogous way by alkylation of
N-alkyl perfluoroalkanesulfonamides with a bromo acetic acid ester, followed by basic ester hydrolysis. Alternatively,
N-alkyl perfluoroalkanesulfonamides can be alkylated with an appropriate alcohol using the Mitsunobu reaction. Perfluorooctanesulfonamide was synthesized from the perfluorooctanesulfonyl fluoride via the azide by reduction with Zn/HCl. All perfluorooctanesulfonamides contained linear as well as branched C
8F
17 isomers, typically in a 10:1 to 30:1 ratio. The crystal structures of
N-ethyl and
N,
N-diethyl perfluorooctanesulfonamide show that the S–N bond has considerable double bond character. This double bond character results in a significant rotational barrier around the S–N bond (Δ
G
≠
=
62–71
kJ
mol
−1) and a preferred solid state and solution conformation in which the
N-alkyl groups are oriented opposite to the perfluorooctyl group to minimize steric crowding around the S–N bond.
Several perfluoroalkanesulfonamides were synthesized from the corresponding perfluoroalkanesulfonylfluorides. The X-ray crystal structures of
N-ethyl-perfluorooctane-1-sulfonamide and two other perfluoroalkanesulfonamides are described.
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Details
- Title: Subtitle
- Synthesis and structure of environmentally relevant perfluorinated sulfonamides
- Creators
- Hans-Joachim Lehmler - Department of Occupational and Environmental Health, The University of Iowa, Iowa City, IA 52242, USAV.V.V.N.S Rama Rao - Department of Occupational and Environmental Health, The University of Iowa, Iowa City, IA 52242, USADhananjaya Nauduri - Department of Anesthesiology, Mitochondrial Research Interest Group, University of Rochester Medical Center, Rochester, NY 14642, USAJohn D Vargo - University Hygienic Laboratory, The University of Iowa, Iowa City, IA 52242, USASean Parkin - Department of Chemistry, University of Kentucky, Lexington, KY 40506, USA
- Resource Type
- Journal article
- Publication Details
- Journal of fluorine chemistry, Vol.128(6), pp.595-607
- DOI
- 10.1016/j.jfluchem.2007.01.013
- PMID
- 18516235
- PMCID
- PMC2394736
- NLM abbreviation
- J Fluor Chem
- ISSN
- 0022-1139
- eISSN
- 1873-3328
- Publisher
- Elsevier B.V
- Language
- English
- Date published
- 2007
- Academic Unit
- Occupational and Environmental Health; Iowa Neuroscience Institute
- Record Identifier
- 9984001077902771
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