Kinetics and Mechanism of the Oxidation of Dl-Methionine by Benzimidazolium Dichromate

Pandey, D S; Kothari, Seema

doi:10.3184/146867809x466221

Cited by 7 publications

(5 citation statements)

References 11 publications

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“…No effect of added benzimidazolium ion on the rate of oxidation also supports the postulation that BIDC remain as nonionised. 5 The crystal structure study of BIDC, reported by Meng et al 15 supports the non-ionic nature of the oxidant in the reaction system. The dichromate ion connects two benzimidazolium rings via.…”

Section: Discussionmentioning

confidence: 96%

“…The dependence of k obs on the concentration of aldehyde was studied at different temperatures and the values of K and k 2 were evaluated from the double reciprocal plots using equation (5). The thermodynamic parameters for the complex formation and the activation parameters for the decomposition of complexes were calculated from the values of K and k 2 respectively, at different temperatures (Tables 3 and 4).…”

Section: Rate Lawsmentioning

confidence: 99%

“…There seems to be only two reports available on the kinetic and mechanistic aspects of the oxidation by BIDC. 4,5 These are published from our laboratory. In the continuation of our studies, we report here the kinetics of the oxidation of six aliphatic aldehydes viz.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics and Mechanism of the Oxidation of Aliphatic Aldehydes by Benzimidazolium Dichromate

Kumar¹,

Panday²,

Kothari³

2011

Croat. Chem. Acta

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Abstract. Kinetic and mechanistic studies of the oxidation of aliphatic aldehydes, (in organic non-aqueous solvents), were discussed with an emphasis of correlation of structure and reactivity. The reactions were of first order with respect to BIDC and hydrogen-ion. However, Michaelis-Menten type kinetics were observed with respect to aldehyde. The deuterium isotope effect for the oxidation of acetaldehyde (k H /k D = 6.36 at 298 K) indicated an α-C-H bond cleavage in the rate-determining step. Based on kinetic data, analyses of the solvent effect and results of structure-reactivity correlation along with some nonkinetic parameters suggested a mechanism involving rate-determining oxidative decomposition of a aldehyde-BIDC complex via a cyclic transition state to give a carbocationic species through hydride-ion transfer from the aldehyde to the oxidant. (doi: 10.5562/cca1694)

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Section: Discussionmentioning

confidence: 96%

Section: Rate Lawsmentioning

confidence: 99%

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Kinetics and Mechanism of the Oxidation of Aliphatic Aldehydes by Benzimidazolium Dichromate

Kumar¹,

Panday²,

Kothari³

2011

Croat. Chem. Acta

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“…We have been interested in the kinetics and mechanism of the oxidation by newer complexes of Cr(VI). We have published a few reports on the kinetic www.prkm.co.uk and mechanistic aspects of the oxidation by BIDC [3][4][5][6][7][8][9][10]. In continuation of our earlier studies, we report here the kinetics and mechanism of the oxidation of mandelic acid (MA) and nine monosubstituted MAs by BIDC in dimethyl sulfoxide (DMSO), a non-aqueous solvent.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Correlation Analysis of Reactivity in the Oxidation of Some α-Hydroxy Acids by Benzimidazolium Dichromate

Panday¹,

Kachawa²,

Kothari

2018

Progress in Reaction Kinetics and Mechanism

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Kinetic and mechanistic studies of the oxidation of mandelic acid and nine monosubstituted mandelic acids by benzimidazolium dichromate (BIDC) in dimethyl sulfoxide are discussed with an emphasis on correlation of structure and reactivity. The reactions were of first order with respect to BIDC. However, Michaelis-Menten type kinetics were observed with respect to hydroxy acids. The reactions are catalysed by protons. The deuterium isotope effect for the oxidation of mandelic acid ( kH/ kD = 5.91 at 298 K) indicated an α-C-H bond cleavage in the rate-determining step. An analysis of the solvent effect showed that the role of cationsolvation is major. The reaction showed an excellent correlation with the Hammett σ values, the reaction constant being negative. Based on the kinetic data, analysis of the solvent effect and results of structure-reactivity correlation along with some non-kinetic parameters, a mechanism involving rate-determining oxidative decomposition of the complex through hydride-ion transfer via a cyclic transition state to give the corresponding oxoacid is suggested.

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“…14,15 a two electron transfer mechanism leading to the formation of Cr(IV) intermediate; 16 the mechanism involving the formation of a chromate thioester 17 and its disproportionation in a slow step; 18 the S N 2 mechanism involving a nucleophilic attack of sulfur on chromium followed by ligand coupling between S and O; 15,19,20 the mechanism which follows Michalies-Menten kinetics with complex formation 21 and slow decomposition of the complex. 22 The present study of oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) will be of particular interest owing to the application of PSAA in pharmaceutical preparations and in the synthesis of several organic compounds.…”

Section: Introductionmentioning

confidence: 99%

Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)

Subramaniam¹,

Selvi²,

Devi³

2014

Journal of the Korean Chemical Society

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ABSTRACT. The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile − 80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta-and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log k2 and Hammett σ constants with a negative value of reaction constant. The ρ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.

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Kinetics and Mechanism of the Oxidation of Dl-Methionine by Benzimidazolium Dichromate

Cited by 7 publications

References 11 publications

Kinetics and Mechanism of the Oxidation of Aliphatic Aldehydes by Benzimidazolium Dichromate

Kinetics and Mechanism of the Oxidation of Aliphatic Aldehydes by Benzimidazolium Dichromate

Kinetics and Correlation Analysis of Reactivity in the Oxidation of Some α-Hydroxy Acids by Benzimidazolium Dichromate

Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)

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