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• W2077146404 abstract "The reactions of S-4-nitrophenyl 4-X-substituted thiobenzoates (X = H, Cl, and NO(2): 1, 2, and 3, respectively) with a series of secondary alicyclic amines (SAA) were subjected to a kinetic investigation in 44 wt % ethanol-water, at 25.0 degrees C and an ionic strength of 0.2 M (KCl). The reactions were followed spectrophotometrically by monitoring the release of 4-nitrobenzenethiolate anion at 420-425 nm. Under excess amine, pseudo-first-order rate constants (k(obsd)) are obtained for all reactions. The plots of k(obsd) vs [SAA] at constant pH are linear with the slope (k(N)) independent of pH. The statistically corrected Brønsted-type plots (log k(N)/q vs pK(a) + log p/q) for the reactions of 1 and 2 are nonlinear with slopes at high pK(a), beta(1) = 0.27 and 0.10, respectively, and slopes at low pK(a), beta(2) = 0.86 and 0.84, respectively. The Brønsted curvature is centered at pK(a) (pK(a)(0)) 10.0 and 10.4, respectively. The reactions of SAA with 3 exhibit a linear Brønsted-type plot of slope 0.81. These results are consistent with a stepwise mechanism, through a zwitterionic tetrahedral intermediate (T(+/-)). For the reactions of 1 and 2, there is a change in rate-determining step with amine basicity, from T(+/-) breakdown to products at low pK(a), to T(+/-) formation at high pK(a). For the reactions of 3, breakdown to products of T(+/-) is rate limiting for all the SAA series (pK(a)(0) > 11). The increasing pK(a)(0) value as the substituent in the acyl group becomes more electron withdrawing is attributed to an increasing nucleofugality of SAA from T(+/-). The greater pK(a)(0) value for the reactions of SAA with 1, relative to that found in the pyridinolysis of 2,4-dinitrophenyl benzoate (pK(a)(0) = 9.5), is explained by the greater nucleofugality from T(+/-) of the former amines, compared to isobasic pyridines, and the greater leaving ability from T(+/-) of 2,4-dinitrophenoxide relative to 4-nitrobenzenethiolate." @default.
• W2077146404 created "2016-06-24" @default.
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• W2077146404 date "2003-09-25" @default.
• W2077146404 modified "2023-10-13" @default.
• W2077146404 title "Kinetic Investigation of the Reactions of <i>S</i>-4-Nitrophenyl 4-Substituted Thiobenzoates with Secondary Alicyclic Amines in Aqueous Ethanol" @default.
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• W2077146404 doi "https://doi.org/10.1021/jo0348120" @default.
• W2077146404 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/14535798" @default.
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