N-OXIDATION OF THE QUINOLINE BY PEROXY ACIDS IN THE ORGANIC SOLVENTS

V. Dutka, G. Midyana, Y. Dutka, O. Pal’chikova
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Abstract

The rate oxidation reaction of quinoline with peroxy acid in warious organic solvents was studded. It has been found effective rate constants (k) and activation energy (Ea) studded process. Between the parameters of the transition state ΔН≠ and ΔЅ≠ is a linear relationship, indication the presence of counteraction effect in our series of experiments. The rate of oxidation and activation energy inflation of solvation peroxyacids and quinoline. 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 303 K has the form lg k = 0.2103 + (11.2719 ±1.7750)f(n) + (1.2126 ± 0.3906)f (ε) + +(0.0002 ± 0.0008)B – (0.0209 ± 0.0079)ET – (0.0019 ± 0.0007)δ2 – – (0.0130 ± 0.0018)Vм ( 1) N = 9; R = 0,9899; S = 0.0591; F = 119.4348, N = 9; R = 0,9737; S = ±0.0950; F = 30.3963. 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 lg Eак = 4.8998 – (18.7772 ± 0.4915) f(n) + (1.8883 ± 0.1038) f(ε) – – (0.0077 ± 0.0002)B – (0.0304 ± 0.0014)Eт + (0.0050 ± 0.0001) δ2 + + (0.0108 ± 0.0005)Vм (2) N = 8; R = 0.9982; S = ±0.0103; F = 1513.94. The proposed correlation equations relate the parameters of the transition state of the oxidation process and the physic-chemical parameters of solvents.
喹啉在有机溶剂中被过氧酸氧化
研究了喹啉与过氧酸在不同有机溶剂中的氧化反应速率。得到了反应的有效速率常数k和活化能Ea。跃迁态的参数ΔН≠与ΔЅ≠之间呈线性关系,说明在我们的一系列实验中存在着反作用。溶剂化过氧酸和喹啉的氧化速率和活化能膨胀。反应介质影响氧化速率。建立了反应速率常数与溶剂的理化参数之间的相关方程。303 K下溶剂的有效速率常数与基本理化参数的相关方程为:lg K = 0.2103 +(11.2719±1.7750)f(n) +(1.2126±0.3906)f (ε) + +(0.0002±0.0008)B -(0.0209±0.0079)ET -(0.0019±0.0007)δ2 - -(0.0130±0.0018)vm (1) n = 9;R = 0,9899;S = 0.0591;F = 119.4348, n = 9;R = 0,9737;S =±0.0950;F = 30.3963。其他温度下的有效速率常数的相关方程是相似的。活化有效能(Ea)与溶剂基本物化参数的相关方程为:lg e伺服= 4.8998 -(18.7772±0.4915)f(n) +(1.8883±0.1038)f(ε) - -(0.0077±0.0002)B -(0.0304±0.0014)exe +(0.0050±0.0001)δ2 + +(0.0108±0.0005)vm (2) n = 8;R = 0.9982;S =±0.0103;F = 1513.94。建立了氧化过程过渡态参数与溶剂理化参数之间的关联方程。
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