Oxidation of the Acrydine by Peroxydecanic Acid in Various Organic Solvents

Abstract

The rate of oxidation reaction of the acrydine with peroxydecanoic acid in various organic solvents was studied. It has been found the effective rate constants (k) and the activation energy (Ea) of studied process. Between the parameters of the transition state ΔН≠ and ΔЅ≠ is some linear relationship, indicating on the presence of the counteraction effect in our series of experiments. The rate of oxidation and activation energy inflation of solvation peroxyacid and acrydine was calculated. The reaction medium affects the rate of oxidation. Correlation equations between the rate constants of the reactions in study and the physicochemical parameters of the solvents were proposed. The correlation equation for effective rate constants and the basic physicochemical parameters of solvents at 318 K has the form: k = –388.8034 + (1662.9800 ± 313.4735)f(n) – (221.2833 ± 70.3626)f(ε) + (0.8092 ± 0.1145)B N = 8; R = 0.9982; S = 3.0727; F = 5.2713. The polarizability, polarization and basicity, of solvent have effect on the oxidation process. The influence of electrophilicity polarization and molar volume on the rate of oxidation of acrydine decay process is negligible. Correlation equations for effective rate constants for other temperatures are similar. The correlation equation for effective energies (Ea) of activation and the basic physicochemical parameters of solvents has the form: Eа = 104.6924 + (50.3320 ± 12.6429)f(ε) + (0.0557 ± 0.0137)B – (0.1201 ± 0.0188)δ2 – (0.5573 ± 0.0782)Vм N = 9; R = 0.9663; S = 2.8058; F = 1.3842. The polarizability, basicity, molar volume and Hildebrand's function of solvent have effect on the energy of activation process. The proposed correlation equations relate the parameters of the transition state of the oxidation process and the physic-chemical parameters of solvents.

N-Oxidation of the Quinoline by Peroxy Acids in the Organic Solvents

“…Окиснення ароматичних гетероциклічних сполук пероксикислотами (ПК) перебігає м'яко та приводить до утворення відповідних N-оксидів [5][6][7][8][9]. Реакції окиснення піридину та його похідних пероксидними сполуками описані в [10][11][12][13], однак вплив реакційного середовища на ці процеси маловивчені. В останніх працях з вивчення окиснення ХН та інших органічних сполук процес проводили у водних розчинах як окисних, здебільшого застосовували пероксиоцтову кислоту [14][15][16][17].…”