Amino effect on the protonation of beta-aminoacrylonitrile.
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.
Wu
Hong
H
Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211, USA.
Glaser
Rainer
R
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
D011522:Protons; D000644:Quaternary Ammonium Compounds; D000181:Acrylonitrile