Permanganate oxidation of crotonic acid.  Spectrometric detection of an intermediate

Wiberg, Kenneth B.; Deutsch, Carol; Rocek, Jan

doi:10.1021/ja00790a061

Cited by 57 publications

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“…The fact that the spectra recorded for this species are quite similar to the ones shown in Fig. 3 could support a Mn(IV) species, as suggested by some authors (4,12,13), rather than the widely accepted cyclic manganate(V) diester (16)(17)(18)(19)(20)(21)(22)(23)(24).…”

Section: Discussionsupporting

confidence: 77%

Identification of the product from the reduction of permanganate ion by trimethylamine in aqueous phosphate buffers

Mata-Pérez¹,

Perez‐Benito²

1985

Can. J. Chem.

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The product obtained from the reduction of potassium permanganate by trimethylamine in aqueous phosphate buffers has been identified as a soluble form of colloidal manganese dioxide which is stabilized in solution by adsorption of phosphate ions on its surface. The dependence of the rate of flocculation on several experimental variables has been studied. Phosphate ions have been found to increase the solubility of the colloid by increasing the apparent energy of activation of the flocculation process. This could explain the well-known capacity of those ions for retarding the precipitation of manganese dioxide.

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Section: Discussionsupporting

confidence: 77%

Identification of the product from the reduction of permanganate ion by trimethylamine in aqueous phosphate buffers

Mata-Pérez¹,

Perez‐Benito²

1985

Can. J. Chem.

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“…Although the oxidation is somewhat faster than the exchange at lower pH, the general agreement between the two rates is very close, suggesting that the reactive intermediates in the oxidation are the enolate anion for p H > 3. 5 The principal results for the oxidation of 1 by the permanganate-independent path above p H 3.5 are: (i) The reaction produces formaldehyde and the 7-keto lumazine. (ii) The reaction is first order in 1 and is subject to general base catalysis.…”

Section: Permangunate-independent Pathmentioning

confidence: 99%

Acid and Base Catalysis in the Oxidation of 6,7,8-Trimethyllumazine. II. Kinetics and Mechanism

Stewart¹,

Oyama²

1974

Can. J. Chem.

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Ross STEWART and K I Y~T A K A OYAMA. Can. J. Chem. 52,3884 (1974). The kinetics of the oxidation of 6,7,8-trin1ethyllunlazine, 1, by permanganate in aqueous solution is examined. The pH-rate plot shows a minimum at p H 3.5 and there is catalysis by buffers. Above p H 3.5 the 7-keto compound, 5, is produced by a general base catalyzed route the rate of which is identical to that of the reaction that causes exchange at the 7-methyl group. The kinetic isotope effect for oxidation of the 7-CD, compound is 6.89 at 31.4".Below p H 3.5 scission of the pyrazine ring occurs, there is a small isotope effect, and the rate is somewhat faster than that observed for exchange of the 7-methyl group. There appear to be three route3 leading to product; one, a permanganate-independent reaction catalyzed by general acids, a second which is also permanganate independent and involves hydration of the substrate, and a third which is permanganate dependent and involves attack by permanganate on the conjugate acid of the substrate.The utility of oxidation as a means of locating hydration sites in heterocyclic compounds is discussed and some comments are made on the mechanism of the enzymic oxidation of the ribityl analog of 1. Chem. 52,3884(1974). On a examine la cinetique de I'oxydation du trimethyl-6,7,8 lumazine, 1, par le permanganate en solution aqueuse. La relation entre la vitesse et le p H montre un minimum a un p H 3.5 et il y a catalyse par les tampons. Au-dessus du p H 3.5, il y a formation du compose cetonique en position 7, 5, par un processus impliquant une catalyse basique generale dont la vitesse de laquelle est identique a celle de la reaction qui produit l'echange du groupe methyle en position 7. veffet isotopique cinetique pour l'oxydation du compose contenant un CD3 en position 7 est de 6.89 a 31.4". En-dessous du p H de 3.5, il y a coupure du cycle pyrazine; ceci s'effectue avec un petit effet isotopique et la vitesse est passablement plus rapide que celle observee pour l'echange du groupe mCthyle en position 7. I1 semble que trois routes peuvent conduire a ce produit: la premiere, une reaction independante du permanganate catalyske d'une maniere gtnerale par les acides; une seconde qui est aussi independante du permanganate et qui implique une hydratation du substrat; une troisieme est dependante du permanganate et implique une attaque du permanganate sur I'acide conjugue du substrat.On discute de l'utilite de l'oxydation comnle nlethode de determiner les sites d'hydratation dans les htttrocycles et on fait quelques commentaires sur le mecanisme de I'oxydation enzymatique de I'analogue ribityle de 1.[Traduit par le journal] Kinetics The reaction of 6,7,8-trimethyllurnazine, 1, with permanganate in unbuffered aqueous solution is extremely slow, except under strongly acidic or strongly basic conditions. The rate of the oxidation is dependent on p H and, at a given pH. is more rapid in buffered than in unbuffered solutions. Outside the region p H 1-6 the reaction in phosphate buffer ([Na,HPO,] = 0.1 M) is too rapid t...

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“…Oxidations by permanganate ion find widespread applications in organic syntheses 1,[6][7][8][9][10][11] especially as the introduction of phase transfer catalysis 8,9,11 which permits the use of solvents like methylene chloride and benzene. An important sources of mechanistic information on these reactions are kinetic studies, as certified by result stating to unsaturated acids in both aqueous 1,[6][7][8][9][10][11][12] and non-aqueous media. 12 Previous studies reveals that the permanganate ion oxidizes a number of organic compounds in aqueous alkaline medium, which are very slowly, attacked in acidic or neutral medium.…”

Section: Introductionmentioning

confidence: 99%

“…An important sources of mechanistic information on these reactions are kinetic studies, as certified by result stating to unsaturated acids in both aqueous 1,[6][7][8][9][10][11][12] and non-aqueous media. 12 Previous studies reveals that the permanganate ion oxidizes a number of organic compounds in aqueous alkaline medium, which are very slowly, attacked in acidic or neutral medium. 2,3,[13][14][15] The oxidation mechanism depends on the nature of the substrate and pH of the reaction mixture.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Mechanism of Permanganate Oxidation of Enrofloxacin in Aqueous Alkaline Medium

Jain¹,

Devra²

2017

J. Pharm. Sci. Innov.

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The reaction kinetics of oxidation of enrofloxacin by potassium permanganate has been investigated in aqueous alkaline medium using spectrophotometric technique at 30 ± 1°C at constant ionic strength of 0.10 mol L -1 . The reaction exhibits 2:1 stoichiometry (2 KMnO4:1 Enrofloxacin). The order with respect to oxidant and substrate is found to be unity in each, whereas fractional order with re spect to alkali concentration. The oxidation products were identified by using FTIR, LCMS spectral studies. The effects of added products, ionic strength and dielectric constant have been studied on the rate of reaction. Based on the experimental results a suitable mechanism is proposed. There is no evidence of intermediate complex formation, thus, the outer-sphere mechanism is proposed as the mechanism for this reaction.

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Permanganate oxidation of crotonic acid. Spectrometric detection of an intermediate

Cited by 57 publications

References 0 publications

Identification of the product from the reduction of permanganate ion by trimethylamine in aqueous phosphate buffers

Identification of the product from the reduction of permanganate ion by trimethylamine in aqueous phosphate buffers

Acid and Base Catalysis in the Oxidation of 6,7,8-Trimethyllumazine. II. Kinetics and Mechanism

Kinetics and Mechanism of Permanganate Oxidation of Enrofloxacin in Aqueous Alkaline Medium

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