Abstract
The kinetics of reactions between α,β-unsaturated compounds (UCs) (acrylonitrile (AN), acryl-amide (AA), and methacrylamide (MAA)) and secondary amines (As) (piperidine, morpholine, diethanolamine, diethylamine, and dipropylamine) in water, as well as in DMF, DMSO, formamide, and 1,4-dioxane for acrylonitrile, was studied. It was found that w= k[HC]0[A]0for all of the test pairs. Viscosity, permittivity, and solvation characteristics, such as solvent polarity, nucleophilicity, and electrophilicity, were taken into account in considering the solvent effect on the overall reaction rate. The electrophilicity (acidity) of a medium was found to exert the greatest effect on the reaction rate. It is believed that an increase in the electrophilicity is favorable for the rapid protonation of the UC–amine intermediate complex. The effects of amine basicity, ionization potential, and dipole moment and the steric parameters of substituents in amine molecules on the rates of reactions between the unsaturated compounds and secondary amines were considered.
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Simonyan, G.S., Beileryan, N.M., Pirumyan, E.G. et al. Effects of Solvents and the Structure of Amines on the Rates of Reactions of α,β-Unsaturated Nitriles and Amides with Secondary Amines. Kinetics and Catalysis 42, 474–478 (2001). https://doi.org/10.1023/A:1010513320364
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DOI: https://doi.org/10.1023/A:1010513320364