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Activation parameter changes as an additive tool for a mechanistic viewpoint in the aromatic nucleophilic substitution reactions in solution

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Abstract

A study was made of the influence of the substituent effects on the activation parameters changes in the SNAr reactions. It involved the analysis of both the free energy of activation ∆G ≠ from the reaction rate constants at single temperature and δ∆G ≠ reaction constants obtained by the Hammett-like equation. The analysis of the internal enthalpy constants δ∆H ≠int and the Hammett ρ constants allowed one to prove the existence of dependence between the δ∆H ≠int and ρ values in which the high magnitudes of these constants indicate a change in the mechanism from a polar SNAr pathway to a SET (single electron transfer).

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Authors and Affiliations

  1. N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Lavrentjev Ave., 9, 630090, Novosibirsk, Russian Federation

    Vladislav M. Vlasov

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  1. Vladislav M. Vlasov
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Correspondence to Vladislav M. Vlasov.

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Vlasov, V.M. Activation parameter changes as an additive tool for a mechanistic viewpoint in the aromatic nucleophilic substitution reactions in solution. Monatsh Chem 148, 1417–1422 (2017). https://doi.org/10.1007/s00706-017-1956-2

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  • DOI: https://doi.org/10.1007/s00706-017-1956-2

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