The Kinetics of the Permanganate Oxidation of Alkenes<sup>1</sup>

Wiberg, Kenneth B.; Geer, Richard D.

doi:10.1021/ja00976a025

Cited by 51 publications

(36 citation statements)

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“…The above mechanism involves two competitive rate-determining steps (3,4) The observed rapid growth of the blue color and then gradual fading supports that suggestion. Again, the Mn(VI) green intermediate was decomposed much more slowly to the final products of the keto derivative (colorless solution) and MnO 2 .…”

Section: Effect Of Ionic Strength On the Reaction Ratesupporting

confidence: 73%

“…Table I. This result, together with the linear first-order plots (ln(absorbance) vs. time), inferred a first-order rate dependence on MnO 4 − concentration. …”

Section: Stoichiometrysupporting

confidence: 53%

“…The kinetic measurements were carried out by tracing either the decay of absorbance at λ max = 525 nm (the absorption maximum belonging to KMnO 4 ) or the initial growth of absorbance at λ max = 610 nm (the absorption maximum belonging to [CMC Mn (VI) O 4 2− ]) after subtracting the absorbance of MnO 4 − at 610 nm at the same MnO 4 − concentration used in the experiment or both (cf. Fig.…”

Section: Kinetic Measurementsmentioning

confidence: 99%

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Kinetics and mechanism of formation of manganate(VI) and hypomanganate(V) coordination polymer intermediates during the base‐catalyzed oxidation of carboxymethyl cellulose polymer by permanganate, Part 1

Shaker

2001

Int J of Chemical Kinetics

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Section: Effect Of Ionic Strength On the Reaction Ratesupporting

confidence: 73%

“…Table I. This result, together with the linear first-order plots (ln(absorbance) vs. time), inferred a first-order rate dependence on MnO 4 − concentration. …”

Section: Stoichiometrysupporting

confidence: 53%

Section: Kinetic Measurementsmentioning

confidence: 99%

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Kinetics and mechanism of formation of manganate(VI) and hypomanganate(V) coordination polymer intermediates during the base‐catalyzed oxidation of carboxymethyl cellulose polymer by permanganate, Part 1

Shaker

2001

Int J of Chemical Kinetics

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“…In the oxidation of unsaturated compounds in alkaline medium Wiberg and Geer [21 and Simandi and Jaky [3] suggested cis attack of MnO; on the double bond in the rate-determining step. In general, manganate {Mn(VI)} oxidations are slower than those of permanganate (Mn(VI1)).…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese in aqueous alkaline medium

Sreenivasulu

Adinarayana

Sethuram

et al. 1985

Int J of Chemical Kinetics

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Kinetics of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese has been studied in aqueous alkaline medium. The order in [oxidant] was unity while that in [substrate] was fractional. The order of reactivity of anions is fumarate -+ acrylate --f cinnamate + maleate. The reactions followed Michaelis-Menten kinetics suggesting the formation of a cyclic intermediate between Mn(V1) and the substrate followed by its disproportionation in a slow step. The equilibrium constant ( K ) for the preequilibrium step and the rate constant (k) for the slow disproportionation step have been calculated from the intercept and the slope values of the linear plot of l/kOb, versus l/[substrate]. Activation parameters are also presented and discussed. A convenient iodometric method is reported for the estimation of Mn(V1).

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“…By eqs. [4] and [5], 2 m OH-result from 3 m cyclohexene. 'Thus upon assuming 100% consumption of the cyclohexene with adipic acid as the exclusive by-product, 2/3 X 0.0492 = 0.0328 m OHformed.…”

Section: Manganese Dioxide Analysismentioning

confidence: 99%

Permanganate peroxidation of cyclohexene. III. Hydroxide ion and salt effect studies

Taylor¹,

Green²

1985

Can. J. Chem.

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. Good yields of cis-l,2-cyclohexanediol were formed by the reaction of cyclohexene and aqueous potassium permanganate under turbulent stirring conditions only in the presence of low concentrations of sodium hydroxide. Larger amounts had no further benefit or were deleterious. The lack of sensitivity to low concentrations of hydroxide ion indicated that its benefit is to inhibit acid promoted oxidations. There was no indication of its participation in the mechanism of glycol formation. The addition of the neutral salts, sodium sulfate or sodium nitrate, caused a decrease in glycol yields presumably due to a positive salt effect on a secondary negative ion -negative ion reaction, which formed other oxidation products. Stoichiometric amounts of hydroxide and potassium ions were not isolated as reaction products due to interaction with the hydrated manganese dioxide in a 1 : 2 ratio. The mechanisms in acidic and basic solutions appear to be quite different. A mechanism for basic solutions is suggested.JAY E. TAYLOR et RENEE GREEN. Can. J. Chem. 63, 2777Chem. 63, (1985. I1 se forme de bons rendements de cyclohexanediol-l,2-cis lors de la rtaction du cyclohexbne et du permanganate de potassium, soumis une agitation tumultueuse et seulement en presence de faibles concentrations d'hydroxyde de sodium. Des concentrations plus fortes d'hydroxyde n'amtliorent pas la reaction; elles peuvent m&me avoir un effet contraire. Le manque de sensibilitC 2 la presence de faibles concentrations d'ions hydroxydes indique que ces derniers inhibent les oxydations favorisees par les milieux acides. On n'a aucune preuve de leur participtation au mCcanisme de formation du glycol. L'addition de sels neutres, comme le sulfate de sodium ou le nitrate de sodium, provoque une diminution du rendement en glycol et cet effet est probablement cause par un effet de sel positif sur une reaction secondaire entre ions nCgatifs qui forme d'autres produits d'oxydation. A cause de l'interaction avec le dioxyde de manganbse hydrate, dans un rapport de 1 :2, on n'a pas is016 des produits de la riaction des quantites stoechiomCtriques d'ions potassium et hydroxyde. Les mkanismes de reaction en solutions acide et basique semblent &tre trbs difftrents. On suggbre un mecanisme pour les reactions en solutions basiques.[Traduit par le journal]

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The Kinetics of the Permanganate Oxidation of Alkenes¹

Cited by 51 publications

References 0 publications

Kinetics and mechanism of formation of manganate(VI) and hypomanganate(V) coordination polymer intermediates during the base‐catalyzed oxidation of carboxymethyl cellulose polymer by permanganate, Part 1

Kinetics and mechanism of formation of manganate(VI) and hypomanganate(V) coordination polymer intermediates during the base‐catalyzed oxidation of carboxymethyl cellulose polymer by permanganate, Part 1

Kinetics and mechanism of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese in aqueous alkaline medium

Permanganate peroxidation of cyclohexene. III. Hydroxide ion and salt effect studies

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The Kinetics of the Permanganate Oxidation of Alkenes1

Cited by 51 publications

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Kinetics and mechanism of formation of manganate(VI) and hypomanganate(V) coordination polymer intermediates during the base‐catalyzed oxidation of carboxymethyl cellulose polymer by permanganate, Part 1

Kinetics and mechanism of formation of manganate(VI) and hypomanganate(V) coordination polymer intermediates during the base‐catalyzed oxidation of carboxymethyl cellulose polymer by permanganate, Part 1

Kinetics and mechanism of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese in aqueous alkaline medium

Permanganate peroxidation of cyclohexene. III. Hydroxide ion and salt effect studies

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The Kinetics of the Permanganate Oxidation of Alkenes¹