The preparative cathodic reductions of benzo[ ]thiophene and diphenyl ether were investigated. Aqueous and mixed organic-aqueous solutions of tetrabutylammonium salts served as electrolytes, and the cathode was a mercury pool. Experiments were carried out at a constant current and the products were isolated and identified.It was found that benzo [b]thiophene is initially reduced to 2,3-dihydrobenzo[b]thiophene, which is subsequently reductively cleaved to 2-ethylbenzenethiol. If the amount of charge transferred is controlled, it is possible to form the dihydro derivative or the cleaved benzenethiol as major product. The cathodic product of diphenyl ether was found to be a mixture of bis(2,5-dihydrophenyl) ether (~50%) and phenol (~30%). The first product is of particular interest since phenol and benzene are the only products of diphenyl ether obtained by reductions involving solvated electrons. The mechanism of reduction of the two reactants is discussed, and possible pathways for the formation of the various products are proposed.
The behavior of geminate and diffusive radical caged-pairs arising from the photolysis of dicumyl ketone in conventional and supercritical carbon dioxide (SC--CO(2)) solvents has been examined. The results suggest that locally enhanced solvent density about a solute (solvent/solute clustering) can lead to an enhanced cage effect near the critical pressure in supercritical fluid solvents. This enhanced cage effect is similar in magnitude for both diffusive and geminate caged-pairs.
0-, m-, and p-terphenyls (la-c) as well as biphenyl undergo, during alkali metal-hexamethylphosphoric triamide reduction, C-C reductive cleavage, the terphenyls giving 3-phenylcyclohexa-1,4-diene (2) and cyclohexa-1,3-diene (3) and biphenyl giving cyclohexa-1,3-cliene (3).
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