Monofluorinated analogues of polybrominated diphenyl ethers as analytical standards: synthesis, NMR, and GC-MS characterization and molecular orbital studies

Gregor Luthe; Pim E G Leonards; Gaby S Reijerink; Huling Liu; Jon E Johansen; Larry W Robertson

doi:10.1021/es052410z

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Monofluorinated analogues of polybrominated diphenyl ethers as analytical standards: synthesis, NMR, and GC-MS characterization and molecular orbital studies

Journal article

Peer reviewed

Monofluorinated analogues of polybrominated diphenyl ethers as analytical standards: synthesis, NMR, and GC-MS characterization and molecular orbital studies

Gregor Luthe, Pim E G Leonards, Gaby S Reijerink, Huling Liu, Jon E Johansen and Larry W Robertson

Environmental science & technology, Vol.40(9), pp.3023-3029

05/01/2006

DOI: 10.1021/es052410z

PMID: 16719106

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Abstract

Polybrominated diphenyl ethers (PBDEs), a group of 209 individual congeners distinguishable by the number and position of bromines, are produced for use as flame retardants in consumer goods. PBDEs have become ubiquitous environmental contaminants, present in increasing levels in the environment and humans. In the present study, 10 individual monofluorinated analogues of PBDEs (F-PBDEs) and one difluorinated PBDE (FF-PBDE) were synthesized and characterized, and their gas chromatographic (GC) and mass spectrometric (MS) characteristics determined. The synthesis method utilized a nucleophilic reaction of bromophenols with diphenyliodonium salts and the perbromination of fluorosubstituted diphenyl ethers. Reaction yields were between 10% and 59% with > or = 98% purity. Apart from the aromatic ring carrying the fluorine atom, only minor chemical nuclear magnetic resonance (NMR) shift changes were observed in comparison to the corresponding parent PBDEs, with the exception that the J(F,H) coupling was stronger. Our preliminary data show that F-PBDEs and PBDEs have comparable retention times in gas chromatography with F-PBDEs demonstrating in general shorter or identical retention times, depending on the pattern of fluorine substitution. We also calculated the torsion angles and the dipole moments for both and report that there is a good correlation between GC retention times and the torsion angles but not with dipole moments. In MS, the difference of the ion peaks of the F-PBDE/ PBDE pairs is m/z 19 (F), which allows a simultaneous MS detection without separation. On the basis of GC separation, simultaneous MS detection, and the stability of fluorine due to its generally resistance to nucleophilic displacement, we propose that F-PBDEs may function as valuable potential standards, markers, and tracers in environmental analysis.

Onium Compounds - analysis

Chemistry Techniques, Analytical - standards

Gas Chromatography-Mass Spectrometry

Magnetic Resonance Spectroscopy

Models, Chemical

Ethers - analysis

Chemistry Techniques, Analytical - methods

Biphenyl Compounds - analysis

Chromatography

Fluorine - analysis

Reference Standards

Animals

Spectrometry, Mass, Electrospray Ionization

Time Factors

Polybrominated Biphenyls - analysis

Mass Spectrometry

Environment

Fluorine - chemistry

Details

Title: Subtitle: Monofluorinated analogues of polybrominated diphenyl ethers as analytical standards: synthesis, NMR, and GC-MS characterization and molecular orbital studies
Creators: Gregor Luthe - Institute of Chemistry, Norwegian University of Science and Technology, N-7041 Trondheim, Norway. gregor-luthe@uiowa.edu
Pim E G Leonards
Gaby S Reijerink
Huling Liu
Jon E Johansen
Larry W Robertson
Resource Type: Journal article
Publication Details: Environmental science & technology, Vol.40(9), pp.3023-3029
DOI: 10.1021/es052410z
PMID: 16719106
NLM abbreviation: Environ Sci Technol
ISSN: 0013-936X
eISSN: 1520-5851
Publisher: United States
Grant note: P42 ES013661 / NIEHS NIH HHS
Language: English
Date published: 05/01/2006
Academic Unit: Occupational and Environmental Health; Iowa Superfund Research Program
Record Identifier: 9984002416102771

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