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Reactivity of Cyclanols Towards Quinaldinium Fluorochromate Oxidation.

Sekar KG, Sakthivel RV - J Solution Chem (2013)

Bottom Line: The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations.From the observed kinetic results a suitable mechanism was proposed.The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, National College, Tiruchirappalli, 620001 Tamil Nadu India.

ABSTRACT
The kinetics of oxidation of cyclanols, viz., cyclohexanol, cyclopentanol, cycloheptanol and cyclooctanol by quinaldinium fluorochromate has been studied in aqueous acid medium at 313 K (±0.1 K). The cyclanols were converted to the corresponding cyclic ketones. The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations. Increase in the percentage of acetic acid increases the rate of reaction. The reaction mixture shows the absence of any free radicals in the reaction, which has ruled out the possibility of a one-electron transfer during the addition of acrylonitrile. The reaction has been studied at four different temperatures and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed. The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol. This was explained on the basis of I-strain theory.

No MeSH data available.


Related in: MedlinePlus

Plot of 1/k versus 1/[s]
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Fig1: Plot of 1/k versus 1/[s]

Mentions: The order with respect to substrate was found to be fractional as evidenced by the linear plot of log10 k versus log10 [substrate] with a slope of 0.48. It was further supported by the fact that the plot of 1/k versus 1/[s] gave a straight line (Fig. 1) with a definite intercept, indicating a Michaelis–Menten type of kinetics for the reaction (Table 1).Fig. 1


Reactivity of Cyclanols Towards Quinaldinium Fluorochromate Oxidation.

Sekar KG, Sakthivel RV - J Solution Chem (2013)

Plot of 1/k versus 1/[s]
© Copyright Policy - OpenAccess
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC3824580&req=5

Fig1: Plot of 1/k versus 1/[s]
Mentions: The order with respect to substrate was found to be fractional as evidenced by the linear plot of log10 k versus log10 [substrate] with a slope of 0.48. It was further supported by the fact that the plot of 1/k versus 1/[s] gave a straight line (Fig. 1) with a definite intercept, indicating a Michaelis–Menten type of kinetics for the reaction (Table 1).Fig. 1

Bottom Line: The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations.From the observed kinetic results a suitable mechanism was proposed.The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, National College, Tiruchirappalli, 620001 Tamil Nadu India.

ABSTRACT
The kinetics of oxidation of cyclanols, viz., cyclohexanol, cyclopentanol, cycloheptanol and cyclooctanol by quinaldinium fluorochromate has been studied in aqueous acid medium at 313 K (±0.1 K). The cyclanols were converted to the corresponding cyclic ketones. The order of reaction was found to be one with respect to oxidant and fractional with respect to the substrate and hydrogen ion concentrations. Increase in the percentage of acetic acid increases the rate of reaction. The reaction mixture shows the absence of any free radicals in the reaction, which has ruled out the possibility of a one-electron transfer during the addition of acrylonitrile. The reaction has been studied at four different temperatures and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed. The relative reactivity order was found to be cyclohexanol < cyclopentanol < cycloheptanol < cyclooctanol. This was explained on the basis of I-strain theory.

No MeSH data available.


Related in: MedlinePlus