Enthalpy-entropy compensation effect and other aspects of isoparametricity in reactions between trans-2,3-bis(3-bromo-5-nitrophenyl)oxirane and arenesulfonic acids

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

“…To quantify the effects of the cross-varied factors on the rate and free activation energy of reactions shown in Scheme, their kinetic and activation parameters taken from recent papers [16][17][18] were subjected to a regression analysis.…”

“…In this context, the experimental evidence of isoparametricity is an actual phenomenological task. Our previous studies have shown that nucleophilic substitution reactions at carbonyl, benzyl, and benzhydryl carbon atoms, [9][10][11][12] along with nucleophilic reactions of oxirane ring opening, [13][14][15][16][17][18] are very promising for the experimental investigation of isoparametricity in all its aspects. The systematic study of multifactor effects on the kinetics of these reactions revealed a wide variety of IPPs in cross correlations of the structure-structure, structure-solvent, structure-temperature, and solvent-temperature types.…”

“…It should be noted that the oxirane ring opening reactions are of particular interest because they clearly demonstrate such a special aspect of isoparametricity as an enthalpy-entropy compensation effect (EECE), which has been the subject of hot debate by scientists for many decades. [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] Earlier, [16][17][18] we have studied the joint effects of structure and temperature on the rates and activation parameters of the reactions of symmetrically X-substituted trans-2, 3- Since in the reaction series three factors were cross-varied (substituents X, Y, and temperature T), this allowed us to test the manifestation of various combinations of the second-order interactions of their effects, as well as the third-order interaction. A part of the results of cross correlation analysis of a kinetic experiment © ARKAT USA, Inc was presented in the publications mentioned above.…”

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).…”