Endre søk
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
Synthesis of polybrominated diphenyl ethers via unsymmetrical diaryliodonium triflates
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK), Avdelningen för miljökemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK), Avdelningen för miljökemi.
(engelsk)Manuskript (preprint) (Annet vitenskapelig)
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.

HSV kategori
Forskningsprogram
miljökemi
Identifikatorer
URN: urn:nbn:se:su:diva-95826OAI: oai:DiVA.org:su-95826DiVA, id: diva2:661739
Forskningsfinansiär
Formas, 2009-1309Formas, 2009-1303Tilgjengelig fra: 2013-11-04 Laget: 2013-11-04 Sist oppdatert: 2013-11-08
Inngår i avhandling
1. Synthesis of organobromines as a tool for their characterisation and environmental occurrence assessment
Åpne denne publikasjonen i ny fane eller vindu >>Synthesis of organobromines as a tool for their characterisation and environmental occurrence assessment
2013 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2013. s. 85
Emneord
Polybrominated diphenyl ethers, Brominated diphenyliodoniums salts, PBDEs, OH-PBDEs, MeO-PBDEs, Synthesis, Analysis, Abbreviations, Metabolites, Marine natural products, E-waste, Brominated flameretardants
HSV kategori
Forskningsprogram
miljökemi
Identifikatorer
urn:nbn:se:su:diva-95649 (URN)978-91-7447-800-6 (ISBN)
Disputas
2013-12-12, Stora hörsalen, Naturhistoriska riksmuseet, Frescativägen 40, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Forskningsfinansiär
Formas, 2009-1297Formas, 2009-1309Formas, 2009-1303
Merknad

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.

Tilgjengelig fra: 2013-11-20 Laget: 2013-10-31 Sist oppdatert: 2013-11-08bibliografisk kontrollert

Open Access i DiVA

Fulltekst mangler i DiVA

Søk i DiVA

Av forfatter/redaktør
Rydén, AndreasMarsh, Göran
Av organisasjonen

Søk utenfor DiVA

GoogleGoogle Scholar

urn-nbn

Altmetric

urn-nbn
Totalt: 118 treff
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf