Isoparametricity and related phenomena in reactions of trans-2,3-diaryloxiranes with arenesulfonic acids

Abstract

This article is a continuation of a series of publications devoted to the systematic study of the still poorly investigated unique isoparametricity phenomenon in chemistry. Quantitative evidence for all variants of the second-order interaction structure-structure and structure-temperature types were obtained in the reactions between X-substituted trans-2,3-diaryloxiranes and Y-substituted arenesulfonic acids. Experimental evidence for the reality of isoparametric points with respect to the parameters of variable factors was obtained. Of particular importance is the proof of the physical reality of such an aspect of isoparametricity as the widely discussed enthalpy-entropy compensation effect. Important information was obtained about the intriguing properties of the three-parameter relationships with cross terms, concerning such attributes as the critical values of the parameters of the variable factors. At these critical values corresponding terms in threeparameter regressions disappear.

Non-additive Effects of Structural Factors in Pyridine Catalyzed Reactions of Phenyloxirane with N-aroylbenzenesulfonamides

“…In reactions of aryloxiranes with arenesulfonic and arenecarboxylic acids the interactions structure-structure and structure-temperature types were clearly manifested, [7][8][9][10] which made it possible to obtain convincing experimental evidence of the isoparametricity phenomenon. Of particular importance is the proof of the physical reality of such an aspect of isoparametricity as the widely discussed enthalpy-entropy compensation effect.…”

“…Of particular importance is the proof of the physical reality of such an aspect of isoparametricity as the widely discussed enthalpy-entropy compensation effect. [8][9][10] Our recent study [11] showed that in the catalyzed by Z-substituted pyridines reaction of phenyloxirane with such representative of NH acids as N-benzoylbenzenesulfonamide, there was no interaction between the effects of substituents Z and temperature. This reaction turned out to be isoenthalpic with respect to variation of substituents Z (ΔHZ ‡ = const, δZΔH ‡ = 0).…”