Synthesis of polychlorinated biphenyls and their metabolites with a modified Suzuki-coupling.
A modified procedure for the synthesis of polychlorinated biphenyls (PCBs) utilizing the Suzuki-coupling, a palladium-catalyzed cross-coupling reaction, is described. The coupling of (chlorinated) benzene boronic acids with bromochlorobenzenes, using Pd(dppf)(2)Cl(2) (dppf = 1,1'-bis(diphenylphosphino)ferrocene) as the catalyst and aqueous sodium carbonate as the base, gave the desired PCB congeners in moderate to good yields. Eleven PCB congeners, including environmentally important PCB congeners and metabolites, were synthesized using this modified procedure. This new catalyst Pd(dppf)(2)Cl(2) offers the advantage of being less air-sensitive and has a longer shelf life compared to Pd(PPh(4))(4). Three new (di-)methoxylated PCB congeners were synthesized using the same procedure by either coupling a chlorinated benzene boronic acid with a bromo (di-)methoxybenzene or by coupling a (di-)methoxy benzene boronic acid with a chlorinated bromobenzene. The dimethoxylated PCB congeners were readily converted into the respective dihydroxylated PCB derivatives using boron tribromide in dichloromethane. This approach offers the advantage of high selectivity and moderate to good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.
Kania-Korwel
Izabela
I
Department of Occupational and Environmental Health, College of Public Health, University of Iowa, Iowa City, IA 52242, USA.
Parkin
Sean
S
Robertson
Larry W
LW
Lehmler
Hans-Joachim
HJ
D001555:Benzene Derivatives / Q000737:chemistry; D001897:Boronic Acids / Q000737:chemistry; D002384:Catalysis; D004785:Environmental Pollutants / Q000138:chemical synthesis*; D008956:Models, Chemical; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry; D011078:Polychlorinated Biphenyls / Q000138:chemical synthesis*
D001555:Benzene Derivatives; D001897:Boronic Acids; D004785:Environmental Pollutants; D010165:Palladium; D011078:Polychlorinated Biphenyls