2-(N-methylanilino)-2-phenylsulfanylacetonitrile, a reagent tested for electrophilic, nucleophilic and radical reactions

Abstract

2-(N-Methylanilino)-2-phenylsulfanylacetonitrile 1 has been readily prepared from 2-(N-methylanilino)acetonitrile and diphenyl disulfide. Alkylation of the anion of 1 with halogenoalkanes resulted in concurrent elimination of benzenethiol to give conjugated α-aminoalkenenitriles of 2E-configuration. Autoxidation of 1 in the presence of alkoxide ions afforded alkyl N-methyl-Nphenylcarbamates. Nucleophilic substitution of 1 with Grignard reagent or appropriate silyl compounds were promoted by Cul or Lewis acids to give varied α-amino nitriles. The 4-oxo-2-amino nitriles 9 obtained by condensation of 1 and titanium enolates can be considered as derivatives of 1, 3-dicarbonyl compounds with the aldehyde group being activated to give an amino nitrile umpolung. When 1 was treated with tributylstannane, the corresponding amino nitrite α-radical was formed and the self-coupling product was isolated.