Summary
The kinetics of the oxidation of sixp-substituted phenethyl alcohols (PEA, R=−H, −Cl, −Br, −CH3, −OCH3, and -NO2) by sodium-N-chloro-p-toluene sulfonamide (chloramine-T,CAT) in the presence of HCl was studied at 35°C. The rate shows a first order dependence on [CAT]0 and [H+]0 and a fractional order in [PEA]0 and [Cl−]0. Ionic strength variations, addition of reaction product toluene sulfonamide, and variation of the dielectric constant of the medium have no effect on the rate. The solvent isotope effect\(k_{H_2 0}^\prime /k_{D_2 0}^\prime \) amounts to about 0.90. Proton inventory studies have been made in H2O-D2O mixtures. The rates correlate satisfactorily withHammett's relationship. The reaction constant ρ was −3.3 for electron releasing substituents and −0.25 for electron withdrawing groups at 35°C. The activation parameters ΔH #, ΔS #, ΔG #, and logA were derived. ΔH # and ΔS # are linearly related, and an isokinetic relationship is observed with β=166.7K, indicating entropy as a controlling factor.
Zusammenfassung
Die Kinetik der Oxidation von sechsp-substituierten Phenethylalkoholen (PEA), R=−H, −Cl, −Br, −OCH3 und NO2) mit Natrium-N-chlor-p-toluolsulfonamid (Chloramin-T,CAT) in Gegenwart von HCl bei 35°C wurde untersucht. Die Reaktionsgeschwindigkeit ist in bezug auf [CAT]0 und [H+]0 ester und hinsichtlich [PEA]0 und [Cl]0 gebrochener Ordnung. Variation der Ionenstärke, Zusatz von Reaktionsprodukt oder Toluolsulfonamid und Variation der Dielektrizitätskonstante des Mediums haben keinen Einfluß auf die Reaktionsgeschwindigkeit Der Lösungsmittel-Isotopeneffekt\(k_{H_2 0}^\prime /k_{D_2 0}^\prime \) beläuft sich auf etwa 0.90. Die Protonenbilanz wurde in H2O-D2O Mischungen untersucht. Die Geschwindigkeiten korrelieren zufriedenstellend nach derHammettschen Beziehung. Die Reaktionskonstante wurde mit ρ=−3.3 für elektronenabgebende und ρ=−0.25 für elektronenanziehende Substituenten bei 35°C bestimmt. Die Aktivierungsparameter ΔH #, ΔG #, ΔG # und logA wurden abgeleitet; ΔH # und ΔS # korrelieren linear, und eine isokinetische Beziehung mit β=166.7K weist auf die Entropie als kontrollierenden Faktor hin.
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Ramachandra, H., Rangappa, K.S., Mahadevappa, D.S. et al. Oxidation of substituted phenethyl alcohols by sodium-N-chloro-p-toluene sulfonamide: A kinetic study. Monatsh Chem 127, 241–255 (1996). https://doi.org/10.1007/BF00813789
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DOI: https://doi.org/10.1007/BF00813789