On the basis of an analysis of the reasons for the multiplicity of σ constants for substituents it has been concluded that they are variables, the absolute value and sign of which depend on the nature of the compounds being considered (in particular other substituents), the partner with which reaction occurs, and the medium (the aggregate state of participants of the interaction). The use of modifications of the Hammett equation is caused by the impossibility in principle of only varying the values and sign of ρ to describe universally linear functions of the dependence of rate (or equilibrium) constants of chemical processes from the algebraic sum of the electronic, steric, and other factors, which differ in their nature.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 227-242, February, 2010.
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Andreev, V.P. The effect of electronic factors on the reactivity of heteroaromatic N-oxides. Chem Heterocycl Comp 46, 184–195 (2010). https://doi.org/10.1007/s10593-010-0490-5
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DOI: https://doi.org/10.1007/s10593-010-0490-5