Postulated intermediates and activated complexes in the permanganate ion oxidation of organic compounds

Freeman, Fillmore

doi:10.1007/bf03155668

Cited by 44 publications

(10 citation statements)

References 140 publications

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“…Two different pathways, both of which lead to the manganese(V) intermediate 1 , have been proposed . The (3 + 2) pathway a in Scheme involves concerted attack of the oxygen atoms to the unsaturated carbons and proceeds via a five-membered cyclic transition state 2 . , This mechanism was also suggested by theoretical speculations based on the frontier molecular orbital (FMO) theory and the Zimmerman treatment . The other mechanism, pathway b ,1e in which a four-membered organometallic intermediate 3 is formed first via [2 + 2] cycloaddition and then rearranges to 1 , is based on the general proposal by Sharpless and co-workers 11 for the reactions between alkenes and oxo transition-metal species.…”

Section: Introductionmentioning

confidence: 99%

Semiquantitative FMO Analysis of Substituent Effect on the Reaction of Permanganate Ion with Unsymmetrical Alkenes

et al. 1998

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The substituent effects on the reactions of permanganate ion with unsymmetrical alkenes are analyzed on the assumption of a concerted (3 + 2) cycloaddition model by using an equation obtained by approximation based on the FMO theory in which development and localization of the frontier molecular orbitals at the reaction sites with progress of the reaction are considered. The Hammett plots are successfully reproduced with the newly obtained rate data for the reactions of trans-chalcone and its derivatives and the data for methyl cinnamates, cinnamate ions, and alkyl vinyl ethers taken from the literature using FMO energies and orbital coefficients calculated by the PM3 method. It was indicated that a factor introduced to the basic equation in order to estimate the extent of localization of the molecular orbitals at the transition state is closely related to the position of the transition state along the reaction path.

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Section: Introductionmentioning

confidence: 99%

Semiquantitative FMO Analysis of Substituent Effect on the Reaction of Permanganate Ion with Unsymmetrical Alkenes

et al. 1998

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“…Reaction kinetics determines the best way to achieve desirable products in the least possible time as well as optimum temperature, pressure, concentrations and quantity and quality of catalyst. [25][26][27][28][29][30][31][32]…”

Section: Introductionmentioning

confidence: 99%

Experimental Determination of the Kinetic Rate Law for the Oxidation of Acetone in Aqueous Environment by Potassium Permanganate and Sulfuric Acid at 25°C and Proposed Mechanism for the Reaction

Rasa¹,

Badri²

2019

Orient. J. Chem

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This research paper aims to determine of the rate equation for the reaction that is described in this article.Experiments carried out by using iodometric method for determine the concentration of potassium permanganate at different times. The results are very similar to the results of the UV-Visible spectrophotometric method. These results showed that order of reaction for acetone, potassium permanganate and sulfuric acid were 1, 1 and 1, respectively. Therefore, the rate equation is according to the chemical equation. In addition, it was demonstrated that there was no relationship between products concentration and rate of reaction. A suitable mechanism is also suggested. Thus, the reaction rate law implies a complicated reaction mechanism with low acetone concentrations. In addition, elevated temperature and reactants concentrations are required for a fast acetone oxidation. A reaction mechanism in good consistent with the kinetic results will be suggested and discussed.

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“…Wiberg, 1965;Freeman, 1976;Lee, 1980;Lee and Tranhanovsky, 1982;Simandi et al, 1983;Lee et al, 1987) especially since the introduction of phase transfer catalysis (Lee, 1980;Lee and Tranhanovsky, 1982;Lee et al, 1987) which permits the use of solvents like methylene chloride and benzene. Kinetic studies are vital sources of mechanistic information on these reactions, as validated by result stating to unsaturated acids in both aqueous (Fatiadi, 1987;Stewart and Wiberg, 1965;Freeman, 1976;Lee, 1980;Lee and Tranhanovsky, 1982;Simandi et al, 1983;Lee et al, 1987;Wiberg et al 1973) and non-aqueous media (Wiberg et al 1973). As is known, in aqueous alkaline medium the permanganate ion oxidizes a number of organic compounds, which are not, or only very slowly, attacked in acidic or neutral medium (Ladbury and Cullis, 1958;William, 1958), (Drummond and Waters, 1935).…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of permanganate oxidation of nalidixic acid in aqueous alkaline medium

Jain¹,

Tazwar²,

Devra³

2017

J App Pharm Sci

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The kinetics and mechanism of oxidation of nalidixic acid (NA) by permanganate ion in alkaline medium have been studied at 40 ± 1 o C. The Stoichiometry was observed to be 2:1 in terms of mole ratio of permanganate ion and nalidixic acid consumed. The reaction shows first order with respect to oxidant and fractional order in both the substrate and alkali concentration. The oxidation reaction proceeds via an alkali permanganate species that forms a complex with nalidixic acid and the complex then decomposes to give the product. The effects of added products and ionic strength have also been investigated. The main products identified were hydroxylated NA and Mn(VI). A mechanism was proposed on the basis of experimental results. Investigation of the reaction at different temperature allowed the determination of the activation parameters with respect to the slow step of the proposed mechanism.

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Postulated intermediates and activated complexes in the permanganate ion oxidation of organic compounds

Cited by 44 publications

References 140 publications

Semiquantitative FMO Analysis of Substituent Effect on the Reaction of Permanganate Ion with Unsymmetrical Alkenes

Semiquantitative FMO Analysis of Substituent Effect on the Reaction of Permanganate Ion with Unsymmetrical Alkenes

Experimental Determination of the Kinetic Rate Law for the Oxidation of Acetone in Aqueous Environment by Potassium Permanganate and Sulfuric Acid at 25°C and Proposed Mechanism for the Reaction

Kinetics and mechanism of permanganate oxidation of nalidixic acid in aqueous alkaline medium

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