On the Synthesis of Arylacetones by the SRN 1 Arylation of Acetone Enolate Ion

概要

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Numerous aryl bromides and iodides react with acetone enolate ion in liquid ammonia under irradiation to form arylacetones in high yield. This synthesis is successful with bromo-or iodobenzene derivatives carrying alkoxy, alkyl, phenyl, halogen, and carboxylate substituents, and with halogen derivatives of polynuclear aromatic hydrocarbons. The method is remarkably insensitive to steric hindrance ; for example, 2,4,6-triethylbromobenzene reacts quite well. With greater steric hindrance, as in 2,4,6-triisopropyliodobenzene, reactivity falls and a side reaction of dehalogenation becomes appreciable, for reasons which are suggested. The synthesis was unsuccessful with the diethylamino, nitro and ionized hydroxy (-O^-) substituents. Potassium metal-stimulated reactions of a few aryl diethyl phosphates with acetone enolate ion give generally lower yields of arylation and larger yields of dephosphation (hydrocarbon) products, compared even to potassium-stimulated reactions with aryl bromides. It is postulated that the lesser formation of hydrocarbon products from the aryl bromides is related to transport effects and solution inhomogeneity.
公益社団法人日本薬学会の論文
1975-11-25