Abstract
The quantitative kinetics of the reactions of acrylonitrile and methyl vinyl ketone with ethyl acetoacetate and 2,4-pentanedione, and those of acrylonitrile with ethanol and methanol in basic solution were studied as functions of base concentration, temperature, ionic strength, and solvent composition. An expression is obtained which relates the observed rates to the basicity of the solution for the 2,4-pentanedione reactions by the amount of anion in solution. For the other systems, reasonable values of ionization constants obtained empirically, similarly correlate observed rates with the concentration of base in the system. A quantitative correlation with activity coefficients as expressed by the expanded form of the Debye–Hückel equation gave good agreement for most of the experimental data with ionic strength. A derivation for the particular type of system employed indicated that the activity coefficient for the double-bonded compounds appears to have to be treated as an ion with partial ionic charge. On the basis of experimental data reported, the mechanism proposed involves, (i) anion attack on a polarized double bond, (ii) formation of a cyclic intermediate, severely restricted because of π orbital overlap, and (iii) protonation of this intermediate to form product.
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