Synthesis of polybrominated diphenyl ethers via symmetrical tetra- and hexabrominated diphenyliodonium salts

Abstract

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs) which have become widespread environmental pollutants due to their persistence and bioaccumulativeness. Pure authentic PBDE congeners are required for chemical analysis, assessments of their chemical/physical properties and toxicological studies. We here report an improved method for synthesis of authentic PBDE congeners applying bromophenols and symmetrical brominated diphenyliodonium salts as building blocks. Altogether, 13 PBDEs were synthesized of which seven are new. The improved coupling reaction between the bromophenol and the brominated diphenyliodonium salts resulted in enhanced yields for PBDEs substituted with more than six bromine atoms. Also, improvements in iodonium salt synthesis made it possible to synthesize symmetrical hexabromodiphenyliodonium salts for the first time, i.e. 2,2′,3,3′,4,4′-, 2,2′,4,4′,5,5′- and 2,2′,4,4′,6,6′-hexabromodiphenyliodonium salts and they made it possible to prepare octabrominated PBDEs via the actual coupling method. All synthesized compounds were characterized by 1H NMR, 13C NMR spectra and by their melting points. Also, all products except for the diphenyliodonium salts were characterized by mass spectra in electron ionization mode.