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

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.

Synthesis of fluorinated polybrominated diphenyl ethers (F-PBDEs) as internal standards for environmental analysis.

Polybrominated diphenyl ethers (PBDEs) have become widely distributed as environmental contaminants due to their wide-spread use as flame retardants. Their structural similarity to other halogenated organic pollutants, for example polychlorinated biphenyls (PCBs), has led to speculation that they may have similar toxicological properties and effects. Recent focus on PBDEs as possible priority pollutants has also led to an increasing need for reference standards of PBDEs for toxicological studies and for environmental analysis. In this work we synthesized a series of fluorinated PBDEs (F-PBDEs) which can be used as possible internal standards, as an alternative to high-cost alternatives, such as the (13)C-labelled analogues. F-PBDEs have been synthesized by using different coupling reactions and by bromination of fluorinated starting materials.