Amino Effect on the Protonation of β-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. β- Aminoacrylonitriles thus show propinquity to both acrylonitriles and enamines, and mechanistic and toxicological implications are discussed.
H. Wu and R. Glaser, "Amino Effect on the Protonation of β-Aminoacrylonitrile," Chemical Research in Toxicology, vol. 18, no. 2, pp. 111 - 114, American Chemical Society (ACS), Feb 2005.
The definitive version is available at https://doi.org/10.1021/tx049784a
Keywords and Phrases
Acrylonitrile; Beta Aminoacrylonitrile; Enamine; Imine; Nitrile; Unclassified Drug; Chemical Structure; Deamination; Enthalpy; Hydrogen Bond; Proton Transport; Models; Molecular; Molecular Structure; Oxidation-Reduction; Protons; Quaternary Ammonium Compounds; Stereoisomerism
International Standard Serial Number (ISSN)
Article - Journal
© 2005 American Chemical Society (ACS), All rights reserved.
01 Feb 2005