Quinolinium Dichromate Oxidation of Diols:  A Kinetic Study

Kuotsu, Bernadette; Tiewsoh, Enboklin; Debroy, A.; Mahanti, M. K.

doi:10.1021/jo961079m

Cited by 27 publications

(12 citation statements)

References 10 publications

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“…When a pre-equilibrium protonation is involved, the acid-catalyzed rate is faster in D 2 O than in H 2 O [24,25]. The trend, k D 2 O > k H 2 O , indicates that the hydroxyl group is involved neither in pre-equilibrium nor in the rate-determining step.…”

Section: Resultsmentioning

confidence: 99%

A novel lipopathic Cr(VI) oxidant for organic substrates: Kinetic study of oxidation of benzyl alcohol

Patel¹,

Mishra²

2006

Int J of Chemical Kinetics

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A novel lipopathic oxidizing agent, cetyltrimethylammonium dichromate, was used for oxidation of benzyl alcohol in various organic solvents and in surfactant systems. The reaction kinetics was investigated with change in [acid], [substrate], [oxidant], [surfactant], and temperature. The rate constant values led to propose that the reaction occurs in a reversed micellar system produced by the oxidant, akin to an enzymatic environment. The rate variation with variation in [surfactant] and solvent isotope effect suggest that the path of reaction to be through the formation of an ester complex, the decomposition of which is the rate-determining step.

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Section: Resultsmentioning

confidence: 99%

A novel lipopathic Cr(VI) oxidant for organic substrates: Kinetic study of oxidation of benzyl alcohol

Patel¹,

Mishra²

2006

Int J of Chemical Kinetics

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“…The solvent isotope effect k (H 2 O)/ k (D 2 O) was found to be ((3.3 × 10 −3 )/(4.84 × 10 −3 )) = 0.68. The acid‐catalyzed rate is faster in D 2 O than in H 2 O, when a preequilibrium protonation is involved . The inverse solvent kinetic isotope effect, i.e., k (D 2 O) > k (H 2 O), indicates that the NH 2 group is not involved in the rate‐determining step and thus supports the formation of complex “C” in the reaction process.…”

Section: Resultsmentioning

confidence: 99%

Oxidation of Antitubercular Drug Isoniazid by a Lipopathic Oxidant, Cetyltrimethylammonium Dichromate: A Mechanistic Study

Garnayak

Patel

2015

Int. J. Chem. Kinet.

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The oxidation of an antitubercular drug isoniazid by a lipopathic oxidant cetyltrimethylammonium dichromate (CTADC) in a nonpolar medium generates isonicotinic acid both in the presence and the absence of acetic acid. The conventional UV–vis spectrophotometric method is used to study the reaction kinetics. The occurrence of the Michaelis–Menten–type kinetics with respect to isoniazid confirms the binding of oxidant and substrate to form a complex before the rate‐determining step. The existence of the inverse solvent kinetic isotope effect, k(H2O)/ k(D2O) = 0.7, in an acid‐catalyzed reaction proposes a multistep reaction mechanism. A decrease in the rate constant with an increase in [CTADC] reveals the formation of reverse micellar–type aggregates of CTADC in nonpolar solvents. In the presence of different ionic and nonionic surfactants, CTADC forms mixed aggregates and controls the reaction due to the charge on the interface and also due to partition of oxidant and substrate in two different domains. High negative entropy of activation (ΔS‡ = –145 and –159 J K−1 mol−1 in the absence and presence of acetic acid) proposes a more ordered and highly solvated transition state than the reactants. Furthermore, the solvent polarity‐reactivity relationship reveals (i) the presence of less polar and less ionic transition state compared to the reactants during the oxidation, (ii) differential contribution from nonpolar and dipolar aprotic solvents toward the reaction process, and (iii) the existence of polarity/hydrophobic switch at log P = 0.73. A suitable mechanism has been proposed on the basis of experimental results. These results may provide insight into the mechanism of isoniazid oxidation in hydrophobic environment and may assist in understanding the drug resistance in different location.

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“…The use of quinolinium dichromate for the oxidation of non-vicinal diols yielded αhyroxy carbonyl compounds with a mechanistic pathway involving the intermediate formation of a chromate ester, which undergoes decomposition to yield the product [18]. FTIR spectrum analysis of product showed no observable oxidation of the second hydroxyl group in the diol.…”

Section: Mechanism Of Reactionmentioning

confidence: 99%

Oxidation of Propane-1,3-diol (Non-Vicinal) by Potassium Permanganate in Aqueous Medium. A Kinetic Study

Latona

2020

Adv. J. Chem. A

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The oxidation of propane-1,3-diol by potassium permanganate in aqueous solution was investigated at λmax 525 nm. The rate of the reaction was found to increase with increase in [KMnO4] and [Propane-1,3-diol]. The reaction showed first order dependence each in [KMnO4] and [Propane-1,3-diol] and independent on the ionic strength of the solution. The activation parameters were evaluated from Arrhenius and Erying's equations and the values of〖∆H〗 #(kJ mol-1), 〖∆S〗^#(kJK-1 mol-1) and〖∆G〗^#(kJmol-1) were 24.98,-0.22 and 90.50 respectively. Negative entropy of activation revealed an association mechanism and an ordered transition state for the reaction. Stoichiometric study showed 1:1 consumption of KMnO4 and propane-1,3-diol. Spectroscopic studies and FTIR analysis revealed the product of the reaction to be 3-hydroxyl-propanal. A suitable reaction mechanism was proposed for the reaction investigated.

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Quinolinium Dichromate Oxidation of Diols: A Kinetic Study

Cited by 27 publications

References 10 publications

A novel lipopathic Cr(VI) oxidant for organic substrates: Kinetic study of oxidation of benzyl alcohol

A novel lipopathic Cr(VI) oxidant for organic substrates: Kinetic study of oxidation of benzyl alcohol

Oxidation of Antitubercular Drug Isoniazid by a Lipopathic Oxidant, Cetyltrimethylammonium Dichromate: A Mechanistic Study

Oxidation of Propane-1,3-diol (Non-Vicinal) by Potassium Permanganate in Aqueous Medium. A Kinetic Study

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