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Substituent effects on the activation parameters of pyridine acylation with esters and thioesters in solution

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Abstract

Variation of the activation parameters in the acylation of pyridine with esters and thioesters may be used as a tool for studying mechanisms of acyl transfer reactions in solution. Here, the effect of substituents in benzene and pyridine derivatives on the activation parameters ΔX ≠ (where X stands for enthalpy H, entropy S, or Gibbs energy G) in terms of an equation analogous to the Hammett equation is used to estimate the reaction constant δΔX ≠. The linear dependence of the reaction constant δΔH ≠int on δΔG ≠ provides an alternative way of assessing variations in the pyridine acylation mechanism when one step of the process is the only rate-determining step.

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Authors and Affiliations

  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, pr. Akademika Lavrent’eva 9, Novosibirsk, 630090, Russia

    V. M. Vlasov

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  1. V. M. Vlasov
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Correspondence to V. M. Vlasov.

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Dedicated to Full Member of the Russian Academy of Sciences I.P. Beletskaya on her jubilee

Original Russian Text © V.M. Vlasov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 3, pp. 405–411.

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Vlasov, V.M. Substituent effects on the activation parameters of pyridine acylation with esters and thioesters in solution. Russ J Org Chem 49, 391–397 (2013). https://doi.org/10.1134/S1070428013030135

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  • DOI: https://doi.org/10.1134/S1070428013030135

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