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- W2015184499 abstract "The reactions of the title substrates with alicyclic secondary amines and pyridines are subject to a kinetic study in water [25 °C, ionic strength 0.2 mol dm–3(KCl)]. The Brønsted-type plots obtained for all reaction series are non-linear, indicating the existence of a tetrahedral intermediate (T±) in the reaction pathway and a change in the rate-limiting step involving formation and breakdown of T±. Calculated curves based on the above hypothesis fit the experimental data well. From estimations of both the pKa of the T± formed in the reactions with secondary amines and the rate of arylthiolate ion expulsion from T±(k2) it is deduced that the rate coefficient for proton transfer from T± to a base is lower than k2. The centre of the Brønsted-type curvature for the reactions of the dinitro derivative lies at pKa= pKa°= 8.9 (alicyclic amines) and 6.6 (pyridines). For 2,4,6-trinitrophenyl thiolacetate, pKa°= 7.8 (alicyclic amines) and 4.9 (pyridines). These figures show that pyridines leave T± at a rate (k–1) slower than isobasic secondary amines (the k2 value is independent of the amine nature). From estimations of k–1 and k2 based on the aminolysis of other aryl thiolacetates the pKao values of both reaction series are predicted. These show reasonable agreement with the experimental values. Comparison of these reactions with the aminolyses of aryl acetates indicates that the ‘push’ provided by ArO (to expel a given amine) from an analogous oxy-T± is slightly stronger than that exerted by an isobasic ArS group in T±." @default.
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- W2015184499 date "1991-01-01" @default.
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- W2015184499 title "Kinetics and mechanism of the aminolysis of 2,4-dinitrophenyl and 2,4,6-trinitrophenyl thiolacetates" @default.
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- W2015184499 doi "https://doi.org/10.1039/p29910000063" @default.
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