Kinetics and Correlation Analysis of Reactivity in the Oxidation of Aromatic Aldehydes by Butyltriphenylphosphonium Dichromate

Pandey, D S; Kothari, Seema

doi:10.3184/146867808x340546

Cited by 7 publications

(3 citation statements)

References 20 publications

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“…A review of the values in Table 2 and 3 indicates that the formation constants, K eq , of the substituted Mandelic acid-EDDC complexes are not very responsive to substitution in the aromatic ring. Similar findings have already been reported in the oxidation processes of various Cr(VI) complexes 18,19 . However, the complex rates of decomposition, k d , vary significantly with the substitution.…”

Section: Correlation Analysis Of Reactivitysupporting

confidence: 90%

The Oxidative Transformation of Substituted Mandelic acids by Ethylenediammonium Dichromate in AcOH-H2 O medium: (A Kinetic Study)

Kharetiya,

Panday

2023

Orient. J. Chem

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The oxidation of Mandelic Acids to the corresponding oxoacids with ethylenediammonium dichromate (EDDC) in aqueous acetic acid has been studied. The reaction is first order with respect to [EDDC] and less than two order observed for Mandelic acids and [H+]. The oxidation of α-deuteriomandelic acid shows the presence of a primary kinetic isotope effect (kH/kD = 6.01 at 298K). The reaction has been found to be catalyzed by [H+] ions. The various thermodynamic parameters for the oxidation have been reported and discussed along with the validity of the isokinetic relationship. With a negative reaction constant (ρ), the reaction displayed a strong correlation with the Hammett σ values. All of the chosen Mandelic acids are oxidised by the same process, according to the Exner plot.

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Section: Correlation Analysis Of Reactivitysupporting

confidence: 90%

The Oxidative Transformation of Substituted Mandelic acids by Ethylenediammonium Dichromate in AcOH-H2 O medium: (A Kinetic Study)

Kharetiya,

Panday

2023

Orient. J. Chem

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“…Examination of the values in Tables 3 and 4 shows that the formation constants, K, of the HA-BIDC complexes are not particularly sensitive to substitution in the aromatic ring. Similar observations have been made earlier in the oxidation reactions of other Cr(VI) complexes [25,26]. However, the rates of decomposition of the complexes, k 2 , show considerable variation with the substitution.…”

Section: Correlation Analysis Of Reactivitysupporting

confidence: 87%

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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“…It was observed that the formation constant, K, does not vary appreciably with the hydrogen-ion concentration, however, the rate of decomposition of complex increases linearly. Similar observations have been made in the oxidation of aldehydes 11,12 and oxyacids of phosphorus 13 by butyltriphenylphosphonium dichromate (BTPPD).…”

Section: Effect Of Aciditysupporting

confidence: 56%

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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Kinetics and Correlation Analysis of Reactivity in the Oxidation of Aromatic Aldehydes by Butyltriphenylphosphonium Dichromate

Cited by 7 publications

References 20 publications

The Oxidative Transformation of Substituted Mandelic acids by Ethylenediammonium Dichromate in AcOH-H2 O medium: (A Kinetic Study)

The Oxidative Transformation of Substituted Mandelic acids by Ethylenediammonium Dichromate in AcOH-H2 O medium: (A Kinetic Study)

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

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

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