Kinetics and mechanism of oxidation of d-erythrose and dL-glyceraldehyde by chromium(VI) and vanadium(V) in perchloric acid medium

Gupta, Kalyan Kali Sen; Basu, Srinka

doi:10.1016/s0008-6215(00)84576-0

Cited by 25 publications

(6 citation statements)

References 25 publications

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“…Since either glyceraldehyde (11,26) or lower sugars without possibility of cyclic forms (15), under the same experimental conditions, do not show kinetic evidence of chromic-ester formation, we propose cyclic hemiacetal forms as the reactive forms for aldohexoses, where hydroxyl groups are better disposed to bind Cr(V1) (27). This is in agreement with the great stability observed for Cr(V)/aldohexose complexes at higher pH (23): oxidation rates of both aldose/Cr(VI) and aldose/ Cr(V) complexes (as can be deduced from epr measurements) are strongly pH dependent; so, at higher pH, oxidation is negligible and aldohexoses coordinate to Cr(V1) or Cr(V) without reducing them.…”

Section: Discussionmentioning

confidence: 99%

“…It was considered worthwhile to revise the degradative oxidation of aldoses by action of Cr(V1) (10)(11)(12)(13)(14)(15) in order to determine: (a) the extension of ester chromate formation; (b) the detection of Cr (V) (not yet reported for the oxidation of aldoses); ( c ) the availability of the hydroxyl groups to bind Cr(V1).…”

Section: Introduction Stabilize Cr(v) Intermediates After Further Intmentioning

confidence: 99%

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Oxidation of L-rhamnose and D-mannose by Cr(VI) in perchloric acid. A comparative study

Sala¹,

Signorella²,

Rizzotto³

et al. 1992

Can. J. Chem.

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LUIS F. SALA, SANDRA R. SIGNORELLA, MARCELA RIZZOT~O, M A R~A I. FRASCAROLI, and FABIO GANDOLFO. Can. J. Chem. 70, 2046Chem. 70, (1992.The oxidation of L-rhamnose and D-mannose by Cr(V1) in perchloric acid follows the rate law: M -~ S-I pour le L-rhamnose. Cette equation de vitesse correspond a la reaction conduisant a la formation de la L-1 ,4-rhamnonelactone et de la D-1 ,4-mannonelactone. I1 ne se produit pas de clivage en dioxyde de carbone lorsque la quantite d'aldose utilisee depasse de 20 fois ou plus la quantite de Cr(V1). On interprkte les valeurs relatives des constantes cinktiques en fonction d'une participation du groupe hydroxyle primaire dans 1.kster chromique qui se forme au cours de la premikre Ctape de la reaction. Les radicaux libres qui se forment au cours de la reaction reagissent avec le Cr(V1) pour former du Cr(V). On attribue deux signaux (gi,, = 1,977 et gi,, = 1,970) observes par resonance paramagnetique Clectronique (rpe) sur des solutions de 0,25 1 N de HC10, saturees en L-rhamnose et en c~,o,'-, aux complexes du Cr(V) intermediaire. A des pH supkrieurs (3-7), on n'a detecte que le signal a g = 1,977. Pour le D-mannose, on n'observe que le signal a g = 1,978 ti toutes les concentrations de HC104.[Traduit par la redaction]

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Section: Discussionmentioning

confidence: 99%

Section: Introduction Stabilize Cr(v) Intermediates After Further Intmentioning

confidence: 99%

Oxidation of L-rhamnose and D-mannose by Cr(VI) in perchloric acid. A comparative study

Sala¹,

Signorella²,

Rizzotto³

et al. 1992

Can. J. Chem.

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“…This is attributed to the economic and biological importance of carbohydrates to living organisms. The oxidations have been carried out in both acidic and alkaline media using such oxidants as transition metal ions, inorganic acids, organometallic complexes and enzymes [1][2][3][4][5][6][7][8]. The results of these experiments have revealed that in some cases the mechanism is proposed based on the formation of intermediate complexes while in others the results are analyzed on the basis of formation of free radicals.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of oxidation of some simple reducing sugars by permanganate ion in alkaline medium

Odebunmi

Owalude

2008

JICS

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The kinetics of oxidation of glucose, galactose, fructose, maltose and sucrose by alkaline permanganate anion has been studied. The reactions studied spectrophotometrically over a wide range of experimental conditions show that the rate of the reactions is enhanced by increase in pH, ionic strength, and temperature as well as the reactant concentrations. The mechanism has been proposed to proceed via the formation of enediol intermediate complexes and the order of reactivities of the sugars is fructose > glucose § galactose > maltose > sucrose. The activation parameters were evaluated and lend further support to the proposed mechanism.

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“…Nonetheless, these findings do not conclusively dismiss the possibility of the proposed complex. It was hypothesized that the rate constants governing the complex formation step are very small, explaining the absence of observable kinetic and spectrophotometric evidence (34,(39)(40)(41). Previous studies on the oxidation process of various organic compounds using Cr(VI)-based oxidants have reported an ester complex formation mechanism (40)(41)(42)(43).…”

Section: Mechanism Of the Reactionmentioning

confidence: 99%

Insight into D-galactose Oxidation: Kinetic and Mechanistic Analysis with Imidazolium Fluorochromate

Tomar,

Arora,

Singh

2024

Journal of the Turkish Chemical Society Section A: Chemistry

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In a 50% (v/v) aqueous acetic acid medium, a study on the oxidation kinetics of D-galactose by imidazolium fluorochromate (IFC) was conducted. The study revealed unit-order dependence on [D-galactose], [IFC], and [perchloric Acid]. The reaction was catalyzed by perchloric acid, and followed a 1:1 stoichiometric ratio. Adding sodium hyperchlorate (VII) salt did not affect the reaction. Polymerization of acrylonitrile was not observed in the oxidation process. The oxidation rates were retarded on adding Mn2+ ions in the mixture, and rates increased as the reaction medium’s dielectric constant (D) decreased. The observed results follow the Amis and Kirkwood plots {log k1 vs. (1/D) and ((D-1/2D+1))}. Several thermodynamic variables were determined by analyzing the kinetic data across a temperature range. Arabinose and formic acid were formed as the products of the reaction. A mechanistic path involving the formation of an ester followed by hydride ion transfer was proposed.

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Kinetics and mechanism of oxidation of d-erythrose and dL-glyceraldehyde by chromium(VI) and vanadium(V) in perchloric acid medium

Cited by 25 publications

References 25 publications

Oxidation of L-rhamnose and D-mannose by Cr(VI) in perchloric acid. A comparative study

Oxidation of L-rhamnose and D-mannose by Cr(VI) in perchloric acid. A comparative study

Kinetics and mechanism of oxidation of some simple reducing sugars by permanganate ion in alkaline medium

Insight into D-galactose Oxidation: Kinetic and Mechanistic Analysis with Imidazolium Fluorochromate

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