Benzene, acylation radical anion

Acyl radicals and acyl anions are proposed intermediates in the reduction of phenylacetyl chloride and hydrocinnamoyl chloride at mercury in MeCN [223]. Among the products obtained from the reduction of phenylacetyl chloride are 1,4-diphenyl-2-butene-2,3-diol diphenylacetate, phenylacetaldehyde, toluene, 1,3-diphenyl-acetone, and l,4-diphenyl-2,3-butanediol, as well as phenylacetic acid and phenylacetic acid anhydride. Analogous products arise from the reduction of hydrocinnamoyl chloride l,6-diphenyl-3-hexene-3,4-diol dihydrocinnamate, hydrocinnamaldehyde, ethyl benzene, l,6-diphenyl-3,4-hexanediol, hydrocinnamic acid, and hydrocinnamic acid anhydride. 

Manganese(III) can oxidize carbonyl compounds and nitroalkanes to carboxy-methyl and nitromethyl radicals [186]. With Mn(III) as mediator, a tandem reaction consisting of an intermolecular radical addition followed by an intramolecular electrophilic aromatic substitution can be accomplished [186, 187). Further Mn(III)-mediated anodic additions of 1,3-dicarbonyl and l-keto-3-nitroalkyl compounds to alkenes and alkynes are reported in [110, 111, 188). Sorbic acid precursors have been obtained in larger scale and high current efficiency by a Mn(III)-mediated oxidation of acetic acid acetic anhydride in the presence of butadiene [189]. Also the nitromethylation of benzene can be performed in 78% yield with Mn(III) as electrocatalyst [190]. A N03 radical, generated by oxidation of a nitrate anion, can induce the 1,4-addition of aldehydes to activated olefins. NOj abstracts a hydrogen from the aldehyde to form an acyl radical, which undergoes addition to the olefin to afford a 1,4-diketone in 34-58% yield [191]. 

Resolution (enantiomers), 307-309 Resonance, 43-47 acetate ion and, 43 acetone anion and. 45 acyl cations and, 558 allylic carbocations and, 488-489 allylic radical and, 341 arylamines and, 924 benzene and, 44. 521 benzylic carbocation and, 377 benzylic radical and, 578 carbonate ion and. 47 carboxylate ions and, 756-757 enolate ions and, 850 naphthalene and, 532 pentadienyl radical and. 48 phenoxide ions and, 605-606 Resonance effect, 562 Resonance forms, 43... 

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