Reactions of o-iodohalobenzenes with carbanions of aromatic ketones.: Synthesis of 1-aryl-2-(o-halophenyl)ethanones

o-Iodohalobenzenes (X = I, Br, Cl) react in DMSO with the enolate ions of acetophenone, propiophenone and 1-(2-naphthyl) ethanone to afford mainly monosubstitution with retention of one halogen. The monosubstituted dehalogenated compounds are formed in low overall yields in the reactions of o-diiodobenzene with the carbanions of 1-(2-naphthyl) ethanone and of acetophenone and in the reaction of o-bromoiodobenzene with the carbanion of propiophenone. The reactions can be performed in the dark, with usually increased yields of substitution under irradiation, as well as under FeBr2 initiation. Treatment of 2-(2-bromophenyl)-1-phenylethanone with Cu bronze affords the ring closure benzofuran product. The degree of dehalogenation is discussed in terms of the energetics of the intramolecular electron transfer (ET) from the ArCO-pi system to the C-halogen bond in the monosubstituted radical anions proposed as intermediates. The lack of ring closure of the radicals formed by dehalogenation of these radical anions is analyzed in terms of geometric factors.