Synthesis and Characterization of 2,3-Dibromopropyl-2,4,6-tribromophenyl Ether (DPTE) and Structurally Related Compounds Evidenced in Seal Blubber and Brain

Abstract

The unknown compound UBC-1 previously described as the major organobromine contamination in the blubber extract of a hooded seal (Cystophora cristata) from the Barents Sea was identified as 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE). DPTE, which is the main component of the brominated flame retardant (BFR) Bromkal 73-5 PE, was synthesized by electrophilic addition of bromine to allyl-2,4,6-tribromophenyl ether (ATE). The chirality of DPTE was proven by gas chromatographic enantioseparation of the synthesized racemate. On the basis of GC/ECNI-MS ion chromatograms (m/z79 and 81), DPTE was the dominating organobromine compound in blubber and brain samples of hooded seals and harp seals (Phoca groenlandica) from the Barents and Greenland Seas. The concentrations of DPTE in blubber and brain were up to 470 and 340 microg/kg wet weight. Next to DPTE, the natural dibromo-trichloromonoterpene (MHC-1), the anthropogenic BDE 47 and BDE 99, as well as ATE, 3,5-dibromo-2-(2',4'-dibromo)-phenoxyanisole (6-MeO-BDE 47), 2-bromoallyl-2,4,6-tribromophenyl ether (BATE), and 4,6-dibromo-2-(2',4'-dibromo)-phenoxyanisole (2'-MeO-BDE 68) were present with decreasing relevance. BATE, which was detected for the first time in environmental samples, was synthesized from DPTE by E2 elimination. In brain samples of the harp seals, DPTE, ATE, and BATE were the most abundant organobromine compounds, whereas polybrominated diphenyl ethers (PBDEs) and MHC-1 were virtually absent. This indicated that DPTE, ATE, and BATE were able to penetrate the blood-brain barrier. The general co-occurrence of ATE and BATE in samples contaminated with DPTE support the hypothesis that these compounds are biotransformation products of DPTE. Anaerobic transformation studies of DPTE with super-reduced corrinoids resulted in the formation of ATE. Furthermore, 2,4,6-tribromophenol (TBP) and two other unknown minor transformation products were detected.