Kinetics of the oxidation of organic compounds by potassium permanganate. III. Formic acid

Mann, D. R.; Tompkins, F. C.

doi:10.1039/tf9413700201

Cited by 13 publications

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“…Rigby (113) has carried out experiments designed to test this point, but finds that although potassium manganate is an effective hydroxylating agent, his results do not provide any conclusive evidence in favor of the above hypothesis. Tompkins (133) and his coworkers (62,63,97) have made detailed studies of the oxidation of benzaldehyde and formate ions by potassium permanganate in dilute alkaline solution and have suggested that the pentavalent manganese ion, , is formed as an intermediate. Tompkins postulates subsequent reaction of this ion with water to produce the hexavalent ion and tetravalent, hydrated manganese dioxide.…”

Section: Oxidation By Alkaline Permanganatementioning

confidence: 99%

“…One of the principal aims of many workers in the field of acid permanganate oxidations has been the attempt to formulate modes of oxidation and to classify reactions between permanganate and organic compounds by the mechanism according to which the oxidation proceeds. Tompkins and his collaborators (16,17,62,64,97,132,133) have attempted to show that there are two principal mechanisms by which organic compounds are oxidized by acid permanganate; one mechanism proceeds by direct oxidation by the permanganate ion, and the second involves the prior formation of the Mn4+ ion and subsequent oxidation by hydroxyl radicals produced from this ion and water. It is postulated that the radical mechanism is characterized by an initial induction period, while the direct oxidation by the permanganate ion is of the second order throughout.…”

Section: Mnc2oímentioning

confidence: 99%

“…In agreement with Just and Kauko, they suggest a reaction mechanism involving the intermediate formation of some species containing Mn(V) which may perhaps be MnO®or ; the existence of Mn(V) in solution is now wrell established (108, but cf. reference 40), and species derived from this valence state of manganese have been postulated in the reaction of permanganate with various organic compounds including benzaldehvde (133,144) and the formate ion (97,145).…”

Section: B Hydrogenmentioning

confidence: 99%

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Kinetics And Mechanism Of Oxidation By Permanganate

Ladbury¹,

Cullis²

1958

Chem. Rev.

162

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Section: Oxidation By Alkaline Permanganatementioning

confidence: 99%

Section: Mnc2oímentioning

confidence: 99%

Section: B Hydrogenmentioning

confidence: 99%

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Kinetics And Mechanism Of Oxidation By Permanganate

Ladbury¹,

Cullis²

1958

Chem. Rev.

162

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“…he formation of CrIV (as in CrOgH-, Cr03~, or Cr02) as the first reduction product of CrVI has been postulated8 in the oxidation of secondary alcohols (29,30,38). Similarly, Mnv in the ion MnO¡" has previously been proposed as the immediate reduction product of MnVI1 in the oxidation of formate (32)(33)(34).…”

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confidence: 96%

THE COMMON BASIS OF ORGANIC OXIDATIONS IN ACIDIC SOLUTION¹

Levitt¹

1955

J. Org. Chem.

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The view is prevalent that oxidation in organic chemistry is very often the equivalent of dehydrogenation (1), and this has led to the belief that the intimate mechanistic representation of such reactions should portray the removal of a pair of neutral hydrogen atoms per se from the substance oxidized and their transfer to the substance reduced (2-6). Theories of organic oxidation founded on the free-radical thesis (2-6), which require hemolytic cleavage of valence bonds with the accompanying unpairing of electron spins fail to take into account the fact that the great majority of oxidations brought about by the common strong inorganic oxidants exhibit little of the character of radical reactions,2 and are most effective in strongly polar media where the intermediate formation of ions and their incipient solvolysis is a process requiring a considerably smaller expenditure of energy ( 9) than formation of a radical pair.3A cursory consideration of the simple fact that paraffin hydrocarbons are the most oxidatively resistant organic compounds known suffices to reveal immediately that the abstraction of hydrogen atoms (of which the paraffins have the most) has little if, indeed, anything to do with the process of oxidation.The organic compounds most easily oxidized, such as olefins, acetylenes, alcohols, phenols, aldehydes, amines, alkyl halides, thiols, sulfides, disulfides, and sulfoxides, all have one thing in common, namely-an excess of valence electrons over and above those needed for bonding. This, of course, suggests at once that the true mechanism of organic oxidation may well be identical with the well-recognized fundamental definition of oxidation, i.e., a loss of electrons.But if this be the case, how, then, can there be a plausible explanation for the fact that the partially oxidized terminal carbon atom of RCH2OH or RCH2NH2 is more susceptible to oxidation than the corresponding C atom in the paraffin RCH3; for, based on a consideration of the relative electronegativities of the atoms involved, one would necessarily reach the conclusion that, by reason of «+ a-j+ athe inductive effect, the resulting polarities are RCH2OH and RCH2NH2, (both having C's with a lower electron density than in RCH3) and that consequently, the alcohol and amine should be less susceptible to oxidative attack at

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“…accepts an electron or combines with an H atom. It is suggested that the catalytic activity of Ag+ in this reaction is due to its fulfilling this role, and that the rate-determining step of the catalyzed reaction is Ag+ + MnO4-+ H2 -+ AgH+ + Mn042-+ H+, (18) AgMn04 + H2 +-AgH+ + Mn04-+ H+, (19)…”

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confidence: 99%

Kinetics of the reduction of permanganate in aqueous solution by molecular hydrogen

Webster¹,

Halpern²

1957

Trans. Faraday Soc.

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In aqueous solutions of composition ranging from 1.0 M H+ to 0.6 M OH-, the kinetics of the homogeneous reaction between MnO4-and HZ are represented byThe reaction is catalyzed by silver salts, the catalytic contribution having the kinetic form,where k, = 7.5 x 107 exp [-9300/RT] 1.2 mole-2 sec-1. Mechanisms are proposed for the uncatalyzed and catalyzed reactions which involve the formation of Mn(V) and Mn(VI), respectively, as intermediates.

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Kinetics of the oxidation of organic compounds by potassium permanganate. III. Formic acid

Cited by 13 publications

References 0 publications

Kinetics And Mechanism Of Oxidation By Permanganate

Kinetics And Mechanism Of Oxidation By Permanganate

THE COMMON BASIS OF ORGANIC OXIDATIONS IN ACIDIC SOLUTION¹

Kinetics of the reduction of permanganate in aqueous solution by molecular hydrogen

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Kinetics of the oxidation of organic compounds by potassium permanganate. III. Formic acid

Cited by 13 publications

References 0 publications

Kinetics And Mechanism Of Oxidation By Permanganate

Kinetics And Mechanism Of Oxidation By Permanganate

THE COMMON BASIS OF ORGANIC OXIDATIONS IN ACIDIC SOLUTION1

Kinetics of the reduction of permanganate in aqueous solution by molecular hydrogen

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THE COMMON BASIS OF ORGANIC OXIDATIONS IN ACIDIC SOLUTION¹