On the Michaelis–Menten behavior of pyridinium chloro chromate oxidations: Oxidation of dimethyl, dipropyl, and diphenyl sulfide in chlorobenzene–nitrobenzene mixtures

Panigrahi, G. P.; Mahapatro, Debasish

doi:10.1002/kin.550130108

Cited by 26 publications

(14 citation statements)

References 6 publications

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“…But the facts that the reaction solutions fail to initiate polymerization of vinyl monomer and the reaction rates are not suppressed by the addition of acrylamide rule out the possibility of radical mechanism. Panigrahi and Mahapatro 26 postulated the PCC oxidation of organic sulfides as a two‐electron transfer process. Hence the chromium(VI) oxidation of diethyl sulfide may involve a two‐electron process with the formation of chromium(IV) in the rate‐determining step (Scheme ) 19–21, 26.…”

Section: Discussionmentioning

confidence: 99%

Kinetic evidence of a common mechanism in the oxidations of diethyl sulfide by dichromates and halochromates of heterocyclic bases

Karunakaran

Karuthapandian

Suresh

2002

Int J of Chemical Kinetics

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The oxidations of diethyl sulfide by potassium dichromate, pyridinium dichromate, quinolinium dichromate, imidazolium dichromate, nicotinium dichromate, isonicotinium dichromate, pyridinium fluorochromate, quinolinium fluorochromate, imidazolium fluorochromate, pyridinium chlorochromate, quinolinium chlorochromate, and pyridinium bromochromate follow identical kinetic orders-first-order each with respect to the chromium(VI) reagents, sulfide and hydrogen ion, and moderately inhibited by manganese(II) ion. The energy of activation varies linearly with the logarithm of frequency factor and so does the enthalpy of activation with the entropy of activation. Also, the activation free energies do not differ significantly. The dichromates and halochromates of heterocyclic bases oxidize diethyl sulfide via a common mechanism. C

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Section: Discussionmentioning

confidence: 99%

Kinetic evidence of a common mechanism in the oxidations of diethyl sulfide by dichromates and halochromates of heterocyclic bases

Karunakaran

Karuthapandian

Suresh

2002

Int J of Chemical Kinetics

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“…Recently we [4,5] have favored the second mechanism over the first, based on certain experimental evidence, the main evidence being the detection of a stable intermediate complex in the oxidation of alkyl sulfides [5] kinetically.…”

Section: Mechanismmentioning

confidence: 99%

Pyridiniumchlorochromate oxidations: Studies on the kinetics and substituent effect in the oxidation of aniline in nonaqueous systems

Panigrahi

Mahapatro

1982

Int J of Chemical Kinetics

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Pyridiniumchlorochromate (PCC) oxidizes aniline and substituted anilines except nitro anilines smoothly in chlorobenzene-nitrobenzene mixtures in the presence of dichloroacetic acid. The reaction has unit dependence on each of the aniline, PCC, and dichloroacetic acid concentrations. Electron-releasing substituents accelerate the reaction, whereas electronwithdrawing groups retard the reaction, and the rate data obey Hammett's relationship. The reaction constant p is -3.75. Azobenzene and p-benzoquinone have been obtained as products. The observed experimental data have been rationalized in terms of the formation of an intermediate complex involving PCC-amine undergoing a rapid decomposition to products.

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“…[27][28][29][30][31][32][33] A mechanism involving oxygen-atom transfer steps has also been proposed for the periodate oxidation of the iodide ion. [34][35][36] b) Mechanisms involving the nucleophilic addition of the sulfur atom of the sulfide to the central heteroatom of the oxidizing agents were proposed for the reactions of sulfides with pyridinium chlorochromate, [37] iodosylbenzene diacetate [38] and with complexes of permanganate [39,40] and chromate ions. [41][42][43] c) The oxidations of sulfides with peroxydisulfates, [44] and peroxydiphosphates [45] are thought to proceed via the formation of an acyloxysulfonium intermediate of sulfuric and phosphoric acids, respectively.…”

Section: Introductionmentioning

confidence: 99%

Mechanism for the Oxidation of Sulfides and Sulfoxides with Periodates: Reactivity of the Oxidizing Species

et al. 2009

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DFT computations have been performed at different levels of theory to identify the mechanism for the oxidation of sulfides and sulfoxides with periodates. The periodate ion (IO 4 -), periodic acid (HIO 4 ) and their hydrated derivatives all oxidize sulfides to sulfoxides in one-step oxygen-transfer reactions and the relative reactivities are HIO 4 ϾϾ H 5 IO 6 Ͼ IO 4 -Ͼ H 4 IO 6 -ϾϾ H 3 IO 6 2-. The hydration and dissociation equilibria of the periodates are shifted towards IO 4 -in neutral and moderately acidic solutions, and sulfides are oxidized mainly with IO 4 -under normal experimental conditions. The oxygen atoms of the periodates attack the sulfides perpendicularly to the plane of the C-S-C atoms and the S···O···I atoms are in a linear arrangement in the very early transition state (TS). The sulfides are the electron donors and periodates are the

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On the Michaelis–Menten behavior of pyridinium chloro chromate oxidations: Oxidation of dimethyl, dipropyl, and diphenyl sulfide in chlorobenzene–nitrobenzene mixtures

Cited by 26 publications

References 6 publications

Kinetic evidence of a common mechanism in the oxidations of diethyl sulfide by dichromates and halochromates of heterocyclic bases

Kinetic evidence of a common mechanism in the oxidations of diethyl sulfide by dichromates and halochromates of heterocyclic bases

Pyridiniumchlorochromate oxidations: Studies on the kinetics and substituent effect in the oxidation of aniline in nonaqueous systems

Mechanism for the Oxidation of Sulfides and Sulfoxides with Periodates: Reactivity of the Oxidizing Species

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