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

Patel, Sabita; Mishra, Bijay K.

doi:10.1002/kin.20198

Cited by 10 publications

(10 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…B). In the oxidation of various alcoholic compounds by CTADC, Mishra and co‐workers found similar decreasing trends in the rate constants at the higher CTADC concentration and have proposed the formation of reverse micellar–type aggregates . In the present study, the decrease in the rate constant at high oxidant concentration is also ascribed to the formation of reverse micellar aggregates of CTADC where dichromate anions are encapsulated by the CTA + aggregates and thus the effective concentration of substrates in the vicinity of the dichromate decreases due to the partition of substrates in two different microheterogeneous phases, i.e., reverse micellar core and the bulk solution.…”

Section: Resultssupporting

confidence: 77%

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

Garnayak

Patel

2015

Int. J. Chem. Kinet.

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Resultssupporting

confidence: 77%

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

Garnayak

Patel

2015

Int. J. Chem. Kinet.

Self Cite

View full text Add to dashboard Cite

show abstract

“…7). Earlier, a similar type of observation was reported during the oxidation of alcohol, and the result was attributed to the reversed micellization of CTAB in organic solvents [24,25]. CTAB is known to form reversed micelle with an inner hydrophilic core.…”

Section: Figurementioning

confidence: 67%

Deoximation by cetyltrimethylammonium dichromate: A kinetic study

Sahu

Patel

Mishra

2011

Int J of Chemical Kinetics

Self Cite

View full text Add to dashboard Cite

The deoximation kinetics of some oximes was studied by using cetyltrimethylammonium dichromate (CTADC) in dichloromethane in the presence of acetic acid and a cationic surfactant. The rate of reaction is highly sensitive to the change in, polarity of the solvents, and reaction temperature. The reaction is found to be catalyzed by acid with an appreciable uncatalytic rate. The reaction is first order with respect to substrate. With increase in CTADC concentration, rate of the reaction increases with a fractional order dependency with respect to oxidant. Consistent to the observation, a mechanism has been proposed in which the substrate forms a complex with CTADC in the rate determining step followed by decomposition with a fast process to yield corresponding carbonyl compounds. The structure of the substituents has also a significant effect on the rate constant. C 2011

show abstract

“…11 Oxidation of Cr(III) by hypochlorite in base has been shown to proceed via hydroxide-dependent and independent pathways, involving hydroxyl-bridged Cr(III) oligomers. 12 The use of chromium(VI) complexes to oxidize organic substrates, [13][14][15] has been reported, where inner-sphere mechanisms were observed. Similar mechanisms were seen in the oxidation of the iminodiacetatochromium(III) cation by periodate.…”

Section: Redox Reactionsmentioning

confidence: 99%

Reaction mechanisms in solution

Haines

2007

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

View full text Add to dashboard Cite

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

Cited by 10 publications

References 21 publications

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

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

Deoximation by cetyltrimethylammonium dichromate: A kinetic study

Reaction mechanisms in solution

Contact Info

Product

Resources

About