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Methods for synthesis of nonabromodiphenyl ethers and a chloro-nonabromodiphenyl ether
Stockholm University, Faculty of Science, Department of Environmental Chemistry.
Stockholm University, Faculty of Science, Department of Environmental Chemistry.
Stockholm University, Faculty of Science, Department of Environmental Chemistry.
Stockholm University, Faculty of Science, Department of Environmental Chemistry.
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2006 (English)In: Chemosphere, Vol. 63, no 4, 562-569 p.Article in journal (Refereed) Published
Abstract [en]

Polybrominated diphenyl ethers (PBDEs) have been used extensively as brominated flame retardants (BFRs) in textiles, upholstery and electronics. They are ubiquitous contaminants in wildlife and humans. A low concentration of nonabrominated diphenyl ethers (nonaBDEs) is present in commercial DecaBDE and they are also abiotic and biotic debromination products of decabromodiphenyl ether (BDE-209). The objective of the present work was to develop methods for synthesis of the three nonaBDEs, 2,2',3,3',4,4',5,5',6-nonabromodiphenyl ether (BDE-206), 2,2',3,3',4,4',5,6,6'-nonabromodiphenyl ether (BDE-207) and 2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (BDE-208), with the intention of making them available as authentic standards for analytical, toxicological and stability studies, as well as studies regarding physical-chemical properties. Two methods were developed, one based on perbromination of phenoxyanilines and the other via reductive debromination of BDE-209 by sodium borohydride followed by chromatographic separation of the three nonaBDE isomers formed. An additional nonabrominated compound, 4'-chloro-2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (Cl-BDE-208), was also synthesized in the present work. Cl-BDE-208, prepared by the perbromination of 4-chlorodiphenyl ether, may be used as an internal standard in analysis of highly brominated diphenyl ethers. BDE-206, BDE-207, BDE-208 and Cl-BDE-208 were characterized by 1H NMR, 13C NMR, electron ionization mass spectra and by their melting points. The structures of all three nonaBDEs have been characterized previously by X-ray crystallography.

Place, publisher, year, edition, pages
2006. Vol. 63, no 4, 562-569 p.
Research subject
Environmental Chemistry
Identifiers
URN: urn:nbn:se:su:diva-24736PubMedID: 16297962OAI: oai:DiVA.org:su-24736DiVA: diva2:198216
Note
Part of urn:nbn:se:su:diva-7410Available from: 2008-03-07 Created: 2008-03-06 Last updated: 2010-01-25Bibliographically approved
In thesis
1. Synthesis and characterization of highly polybrominated diphenyl ethers
Open this publication in new window or tab >>Synthesis and characterization of highly polybrominated diphenyl ethers
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polybrominated diphenyl ethers (PBDEs) make up an important class of brominated flame retardants. The present production is mainly concentrated to DecaBDE but until recently also a significant production of PentaBDE and OctaBDE took place, leaving us with a large number of different PBDE congeners. The PBDEs have become widespread pollutants abiotically and in biota, particularly in high trophic level wildlife and in humans. Accordingly, pure authentic reference standards have been required to promote high quality exposure assessments of wildlife and humans and analysis of abiotic matrices, to study both chemical and physical properties of the PBDEs and to allow toxicological studies. The objective of this thesis was to develop methods for synthesis of polybrominated diphenyl ether (PBDE) congeners and to characterize them. Further, some octabrominated DEs were determined with x-ray crystallography. Main focus has been to prepare highly brominated PBDE congeners, i.e. PBDEs substituted with six to nine bromine atoms.

A total number of twenty-three PBDE congeners were synthesized via reduction of decabromodiphenyl ether receiving nonaBDEs; perbromination and bromination of mono- and diaminodiphenyl ethers followed by diazotization of the amino group(s) and reduction of the diazonium ion(s) receiving octaBDEs and nonaBDEs; selective bromination of diaminodiphenyl ethers followed by diazotization of the amino groups and insertion of bromine receiving hexaBDEs and heptaBDEs; bromination of the latter PBDEs giving octaBDEs; and an improved coupling of symmetrical diphenyliodonium salts with bromophenols yielding tetraBDEs to octaBDEs. To enable these compounds to be synthesized three hexabromodiphenyl iodonium salts were prepared: 2,2’,3,3’,4,4’-, 2,2’,4,4’,5,5’- and 2,2’,4,4’,6,6’ - hexabromodiphenyliodonium salts. These iodonium salts are described for the first time which made it possible to synthesize PBDE congeners with 2,3,4-, 2,4,5- and 2,4,6-tribromo substitution in the phenyl rings originating from the diphenyliodonium salts. Among the PBDE congeners 18 are synthesized for the first time. The thesis includes an improved methodology for synthesis of polybromodiphenyl iodonium salts which is based on improved solubilization of both one of the reactants and the product formed. The present work on PBDE synthesis adds useful methods for synthesis of the most highly brominated diphenyl ether congeners.

Place, publisher, year, edition, pages
Stockholm: Institutionen för miljökemi, 2008. 73 p.
National Category
Environmental Sciences
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-7410 (URN)978-91-7155-561-8 (ISBN)
Public defence
2008-04-04, sal G, Arrheniuslaboratorierna, Svante Arrhenius väg 14-18, Stockholm, 13:00
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Supervisors
Available from: 2008-03-07 Created: 2008-03-06Bibliographically approved

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