Synthesis of aryliminoacetonitriles under FVT conditions or by dehydrogenation of arylaminoacetonitriles: an NMR and UV-photoelectron spectroscopy study

The synthesis of [(E)-arylimino]-acetonitriles 3 has been described. It was found that the title compounds can be obtained on the three ways, namely by: (i) dehydrogenation of arylaminoacetonitriles 1, (ii) thermal fragmentation of 1-aryl-4-cyano-β-lactams 4 and (iii) retro-ene reaction of (allyl-p-methoxyphenyl-amino)-acetonitrile (7a) under FVT conditions. 1H and 13C NMR spectra of compounds 3, 5 and 6, and all their precursors 1 and 4, were recorded and analysed in detail using chemical shifts δH and δC [from GIAO DFT B3LYP/6-31(d) calculations] and J-couplings predicted at the DFT B3LYP/IGLO-II level. Also, UV-photoelectron spectra of 4a,d and 3a,d were measured and analysed considering the theoretical evaluation of their ionisation potentials.