Photostimulated Reaction of Carboanions from α,β-Unsaturated Nitriles with Aryl Halides by the SRN1 Mechanism

Article abstract of DOI:10.1021/jo00261a015

The photostimulated reaction of p-bromoanisole, p-iodoanisole, and 1-iodonaphthalene with the carbanion 2 of the cyclohexylideneacetonitrile 1 gave good yields of the isomeric substitution products 2-(p-anisyl)-1-cyclohexenylacetonitrile (3a), 2-(p-anisyl)cyclohexylideneacetonitrile (3b), 2-(1-naphthyl)-1-cyclohexenylacetonitrile (8a), and 2-(1-naphthyl)cyclohexylideneacetonitrile (8b).The substitution occured exclusively in the C_γ.These reactions do not occur in the dark, and the photostimulated reactions are inhibited by 1,4-dinitrobenzene.Thus it is proposed that these reactions occur by the S_RN1 mechanism of nucleophilic substitution.