Palladium(II)-Catalyzed Oxidation of α-Hydroxy Acids with Sodium N-Chlorobenzenesulfonamide in Perchloric Acid Solution: A Kinetic and Mechanistic Study

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Title:Palladium(II)-Catalyzed Oxidation of α-Hydroxy Acids with Sodium N-Chlorobenzenesulfonamide in Perchloric Acid Solution: A Kinetic and Mechanistic Study
Creators:
Revathi, Somanalli K.
Ananda, Sannaiah
Mohana, Kikkeri N.
Rangaswamy,
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 69, 8, pp. 1577-1589
Uncontrolled Keywords:Kinetics, Mechanism, Palladium(II), α-Hydroxy acids, Oxidation, Chloramine B, Substituent effects

Abstract

Kinetics of oxidation of glycolic acid (GA), lactic acid (LA) and 2-hydroxybutanoic acid (BA) with Chloramines B (CAB) catalyzed by Pd(II) in a HClO<sub>4</sub> solution has been studied at 30 °C. The reaction rate shows first-order dependence each on [CAB], [hydroxy acid] and [Pd(II)] and a fractional-order dependence on [H<sup>+</sup>]. Additions of chloride ions, perchlorate ions and the reduction product of CAB, benzenesulfonamide (BSA), have no effect on the reaction rate. Variations of ionic strength and dielectric permittivity of the medium have no effect on the rate. Activation parameters have been evaluated. A mechanism consistent with kinetic data is proposed. A Taft linear free-energy relationship is observed for the reaction with ρ* = -3.593, indicating an increase in the rate with the presence of electron-donating substituents. An isokinetic relationship is observed with β = 376 K, indicating the effect of enthalpy factors on the rate. <p>

Title:Palladium(II)-Catalyzed Oxidation of α-Hydroxy Acids with Sodium N-Chlorobenzenesulfonamide in Perchloric Acid Solution: A Kinetic and Mechanistic Study
Creators:
Revathi, Somanalli K.
Ananda, Sannaiah
Mohana, Kikkeri N.
Rangaswamy,
Uncontrolled Keywords:Kinetics, Mechanism, Palladium(II), α-Hydroxy acids, Oxidation, Chloramine B, Substituent effects
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:69
Number:8
Page Range:pp. 1577-1589
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20041577UNSPECIFIED
ID Code:2295
Item Type:Article
Deposited On:06 Feb 2009 17:17
Last Modified:06 Feb 2009 16:17

Citation

Revathi, Somanalli K.; Ananda, Sannaiah; Mohana, Kikkeri N.; Rangaswamy, (2004) Palladium(II)-Catalyzed Oxidation of α-Hydroxy Acids with Sodium N-Chlorobenzenesulfonamide in Perchloric Acid Solution: A Kinetic and Mechanistic Study. Collection of Czechoslovak Chemical Communications, 69 (8). pp. 1577-1589. ISSN 0010-0765

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