title: Amino effect on the protonation of beta-aminoacrylonitrile.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211, USA.
authors.forename: Hong
authors.initials: H
authors.lastname: Wu
authors.forename: Rainer
authors.initials: R
authors.lastname: Glaser
mesh_terms: D000181:Acrylonitrile / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011522:Protons; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D011522:Protons; D000644:Quaternary Ammonium Compounds; D000181:Acrylonitrile