- Kinetics and mechanism of oxidation of hydroxyurea derivatives with hexacyanoferrate(III) in aqueous solution
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Kinetics and mechanisms of the oxidation of methoxyurea and N-methylhydroxyurea were studied in neutral and basic aqueous solutions. The obtained pH dependences of the oxidation rates indicate that for both hydroxyureas the reactive species are the deprotonated ones. The second order rate constants, the activation enthalpies and the activation entropies for the reactions of methoxyurea (O-methylhydroxyurea) and N-methylhydroxyurea anions with Fe(CN)63- at 25 °C, I = 2 mol dm-3 (NaClO4) were determined as (5.06 ± 0.01) × 10 2 mol-1 dm3 s-1, (1.92 ± 0.02) × 104 mol-1 dm3 s-1, 27 ± 1 kJ mol-1, 16 ± 1 kJ mol-1,.101 ± 2 J mol-1 K-1, and.107 ± 4 J mol-1 K-1, respectively. The pKa value of methoxyurea at 25 oC and 2 mol dm-3 ionic strength was determined kinetically as 12.7 ± 0.1 and the thermodynamic parameters for the deprotonation reaction were determined as ΔaH = 43 ± 1 kJ mol-1, and.aS =.96 ± 4 J mol-1 K-1. When the kinetic results are compared with the data reported for hydroxyurea, an inverse dependence of the rate constants on the pKa of the hydroxyurea derivatives at 25 °C is observed. Such unexpected behaviour has been explained by the ab initio calculations and NBO analysis of HOMOs for all three hydroxyureates.
- Budimir, Ana,Weitner, Tin,Kos, Ivan,Sakic, Davor,Gabrieevic, Mario,Besic, Erim,Birus, Mladen
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- Hydroxylamine as an oxygen nucleophile: Substitution of sulfonamide by a hydroxyl group in benzothiazole-2-sulfonamides
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Benzothiazole-2-sulfonamides react with an excess of hydroxylamine in aqueous solutions to form 2-hydroxybenzothiazole, sulfur dioxide, and the corresponding amine. Mechanistic studies that employ a combination of structure-reactivity relationships, oxygen labeling experiments, and (in)direct detection of intermediates and products reveal that the reaction proceeds via oxygen attack, and that oxygen incorporated in the 2-hydroxybenzothiazole product derives from hydroxylamine. The reaction, which is performed under mild conditions, can be used as a deprotection method for cleavage of benzothiazole-2-sulfonyl-protected amino acids.
- Kamps, Jos J. A. G.,Belle, Roman,Mecinovi?, Jasmin
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p. 1103 - 1108
(2013/03/28)
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