Cross effects of structure and temperature in the reactions of trans-2,3-diaryloxiranes with 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 accordance with the regularities of isoparametric dependencies at this IPP substituents Y in the acidic reagent should not influence on the rate of these reactions (qY ХT = 0). This is illustrated by a decrease in the sensitivity coefficient qY XT to the effects of the substituents Y practically to zero in the reactions of oxirane 1d with a decrease in temperature: 17 qY XT (T K) = 1.01 ± 0.09 (298 K), 0.50 ± 0.04 (281 K), 0.10 ± 0.05 (265 K).…”

“…At this point the effects of the substituents Y should not appear, which is confirmed by a decrease in qY XT (T = 265 K) = 1.57 ± 0.02, 1.00 ± 0.04, 1.50 ± 0.03, 0.10 ± 0.05 with an increase in the electron-withdrawing properties of the substituents X in oxiranes 1a, 1b, 1c, and 1d. 17 In terms of activation parameters, the second-order interactions of the effects of structure and temperature can be described by a PLE:…”

“…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.…”