Wu Hong, Glaser Rainer
Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211, USA.
Chem Res Toxicol. 2005 Feb;18(2):111-4. doi: 10.1021/tx049784a.
The protonation of acrylonitrile (1) and of Z- and E-3-aminoacrylonitrile (5 and 9) was studied with the Gaussian-2 method. Ammoniumacrylonitrile ion formation is not important. Nitrilium ion formation is preferred in all cases, and the proton affinities are about 80 kJ/mol higher for aminoacrylonitrile. Remarkably, it is found that C2-protonation of 3-aminoacrylonitriles to form iminium ions can compete with nitrilium ion formation. Beta-aminoacrylonitriles thus show propinquity to both acrylonitriles and enamines, and mechanistic and toxicological implications are discussed.
