Abstract
Forty-three (including eight identical) reactions of acetyl transfer from N-acetyloxypyridinium salts to pyridine N-oxides in acetonitrile solutions were studied. The rate constants k 2 vary in the range 107-10- 1 l mol- 1 s- 1; the equilibrium constants K, in the range 107-10- 7; the activation enthalpy ΔH ≠, in the range 17-30 kJ mol- 1; the activation entropy -ΔS ≠, in the range 60-85 J mol- 1 K- 1; and the heat of reaction -ΔH 0, within ±50 kJ mol- 1. All reactions occur in a single stage by the concerted SN2 mechanism with a low degree of bond cleavage in the transition state. The rate and equilibrium of the acetyl exchange are satisfactorily described by the Brönsted equation. The quality of predicting the reactivity is substantially improved by introducing into the correlation equation a second parameter, the rates of identical reactions.
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Rybachenko, V.I., Schroeder, G., Chotii, K.Y. et al. Acetyl Exchange between Pyridine N-Oxides in Acetonitrile Solutions: An Attempt to Apply the Marcus Equation to Acetyl Transfer. Russian Journal of General Chemistry 71, 1608–1615 (2001). https://doi.org/10.1023/A:1013919523997
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DOI: https://doi.org/10.1023/A:1013919523997