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Synthesis of polybrominated diphenyl ethers via unsymmetrical diaryliodonium triflates
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Environmental Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Environmental Chemistry.
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental pollutants due to theirpersistent character and extensive use as additive flame retardants. In order to assess theirbiological effects, fate, environmental concentrations and other parameters related to riskassessment, authentic PBDE congers are needed for research purposes. In the present work anew general method for the preparation of individual PBDE congeners is presented. Themethodology used is based on recent advances in unsymmetrical diaryliodonium saltsynthesis as well as advances in O-arylation of phenols with these types of salts. Accordingly,three brominated diphenyliodonium triflates were prepared i.e. phenyl(2,4,5-tribromophenyl)iodonium triflate, phenyl(2,4,6-tribromophenyl)iodonium triflate andphenyl(2,3,4,6-tetrabromophenyl)iodonium triflate from 1,2,4-tribromo-5-iodobenzene, 1,3,5-tribromo-2-iodobenzene and 1,2,3,5-tetrabromo-4-iodobenzene, respectively. Yields indiaryliodonium salt syntheses ranged from 69-96%. These salts were further used to O-arylatevarious brominated phenols giving individual tetra- to octa-BDE congeners in yields rangingfrom 64-98%. The O-arylation method used was given after a minor optimisation study, regarding reaction time and temperature, which is reported herein. In addition, this O-arylationmethod was also used with two brominated methoxyphenols in the syntheses of twomethoxylated PBDEs.

National Category
Other Chemistry Topics Organic Chemistry
Research subject
Environmental Chemistry
Identifiers
URN: urn:nbn:se:su:diva-95826OAI: oai:DiVA.org:su-95826DiVA: diva2:661739
Funder
Formas, 2009-1309Formas, 2009-1303
Available from: 2013-11-04 Created: 2013-11-04 Last updated: 2013-11-08
In thesis
1. Synthesis of organobromines as a tool for their characterisation and environmental occurrence assessment
Open this publication in new window or tab >>Synthesis of organobromines as a tool for their characterisation and environmental occurrence assessment
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polybrominated diphenyl ethers (PBDEs) have been intensively used as flame retardants (FRs) and have become ubiquitous environmental pollutants. PBDEs form hydroxylated PBDEs (OH-PBDEs) as metabolites. Further, some OH-PBDEs and methoxy-PBDEs (MeO-PBDEs) are natural products. These are all compounds of environmental and health concern and it is therefore important to confirm their identity and to assess their environmental levels and toxicities. Hence, it is vital to obtain authentic reference standards of individual PBDEs and OH/MeO-PBDEs. The thesis main aim was to develop synthesis methods of congener specific PBDEs, OH- and MeO-PBDEs. The second aim was to identify and quantify PBDEs, OH- and MeO-PBDEs in environmental samples. The third was to propose an abbreviation system for FRs.

O-Arylation of brominated phenols, using either symmetrical or unsymmetrical brominated diphenyliodonium salts, was selected for synthesis of PBDEs and OH-/MeO-PBDEs. A total of 16 MeO-PBDEs, 11 OH-PBDEs, 1 diMeO-PBDE and 1 EtO-MeO-PBDE were synthesised. Three novel unsymmetrical diaryliodonium triflates were synthesised and used in synthesis. Optimisations were made to construct a reliable general method for congener specific PBDE synthesis, which was used in the synthesis of 8 representative PBDE congeners. The products were generally characterised by electron ionisation mass spectrometry (EIMS) and nuclear magnetic resonance (NMR) spectroscopy.

Identification of PBDEs and OH-PBDEs in various matrixes was based on gas chromatographic and mass spectrometric analyses. Fourteen OH-PBDE congeners were identified in a pooled human blood sample. One previously uncharacterised natural PBDE analogue was identified as 6-OH-6’-MeO-BDE-194, and quantified in Swedish blue mussels. PBDE congeners and other BFRs were identified and quantified in workers and dust from a smelter in Sweden.

A structured and practical abbreviation system was developed for halogen- and phosphorus containing FRs.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2013. 85 p.
Keyword
Polybrominated diphenyl ethers, Brominated diphenyliodoniums salts, PBDEs, OH-PBDEs, MeO-PBDEs, Synthesis, Analysis, Abbreviations, Metabolites, Marine natural products, E-waste, Brominated flameretardants
National Category
Other Chemistry Topics
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-95649 (URN)978-91-7447-800-6 (ISBN)
Public defence
2013-12-12, Stora hörsalen, Naturhistoriska riksmuseet, Frescativägen 40, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Formas, 2009-1297Formas, 2009-1309Formas, 2009-1303
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Submitted. Paper 4: Manuscript.

Available from: 2013-11-20 Created: 2013-10-31 Last updated: 2013-11-08Bibliographically approved

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