Synthesis of hydroxylated and methoxylated polybrominated diphenyl ethers - Natural products and potential polybrominated diphenyl ether metabolites
Synthesis of hydroxylated and methoxylated polybrominated diphenyl ethers - Natural products and potential polybrominated diphenyl ether metabolites
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DOI：
10.1002/ejoc.200300081
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发表时间：
2003-07-14
影响因子：
2.8
通讯作者：
Bergman, A
中科院分区：
文献类型：
--
作者：
Marsh, G;Stenutz, R;Bergman, A
羟基化和甲氧基化多溴联苯醚（OH-PBDEs和MeO-PBDEs）可能是天然产物，也可能是多溴联苯醚（PBDEs）的代谢物，常用作阻燃剂。这项工作的目的是合成用于分析和毒理学研究的真实OH-和MeO-PBDE参比标准品。通过2，4-二溴苯酚与各种氟代苯甲醛的偶联或溴代羟基苯甲醛与2，2 '，4，4'-四溴二苯基氯化碘鎓的偶联制备溴代苯氧基苯甲醛。以溴代苯氧基苯甲醛为原料，经Baeyer-Villiger氧化和酸催化水解合成了羟基多溴二苯醚。这些羟基多溴二苯醚被三溴化苄基三甲基铵邻位和对位溴化（相对于羟基）和/或被溴/叔丁胺邻位溴化，在一种情况下还被溴溴化。通过对制备的OH-PBDEs进行甲基化得到MeO-PBDEs。溴代甲氧基苯酚与2，2 '，4，4'-四溴二苯基碘鎓盐偶联，脱甲基后得到相应的羟基多溴二苯醚，也可制得MeO-PBDEs。所制备的大多数OH-/MeO-PBDEs在二苯醚键的邻位具有羟基/甲氧基。所制备的所有OH-/MeO-PBDE在不含羟基/甲氧基的环中都具有2，4-二溴取代模式（相对于二苯醚键）。((C)Wiley-VCH Verlag GmbH & Co. KGaA，69451魏因海姆，德国，2003）。
Hydroxylated and methoxylated polybrominated diphenyl ethers (OH-PBDEs and MeO-PBDEs) may be natural products or they may be formed as metabolites of polybrominated diphenyl ethers (PBDEs), frequently used as flame retardants. The aim of this work was to synthesize authentic OH-and MeO-PBDE reference standards for analytical and toxicological studies. Brominated phenoxybenzaldehydes were prepared either by coupling of 2,4-dibromophenol with various fluorobenzaldehydes or by coupling of brominated hydroxybenzaldehydes with 2,2',4,4'-tetrabromodiphenyliodonium chloride. OH-PBDEs were synthesized via the brominated phenoxybenzaldehydes by Baeyer-Villiger oxidation and acid-catalyzed hydrolysis. These OH-PBDEs were ortho- and para-brominated (relative to the hydroxy group) with benzyltrimethylammonium tribromide and/or ortho- brominated with bromine/tert-butylamine, and were also brominated with bromine in one case. MeO-PBDEs were obtained by methylation of the prepared OH-PBDEs. MeO-PBDEs were also prepared through the coupling of brominated methoxyphenols with 2,2',4,4'-tetrabromodiphenyliodonium salts, the corresponding OH-PBDEs being obtained after demethylation. A majority of the OH-/MeO-PBDEs prepared have the hydroxy/methoxy group in the ortho position relative to the diphenyl ether bond. All OH-/MeO-PBDEs prepared have 2,4-dibromo substitution patterns (relative to the diphenyl ether bond) in the non-hydroxy-/non-methoxy-containing ring. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).