Electron transfer with aliphatic substrates. Oxidations of cycloaliphatic substrates with cobalt(III) and manganese(III) ions alone and in the presence of oxygen

Onopchenko, Anatoli; Schulz, Johann G. D.

doi:10.1021/jo00911a006

Cited by 28 publications

(4 citation statements)

References 8 publications

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“…Apart from this there is an entirely different class of hydrocarbon oxidations wherein induction period is eliminated by using the potent oxidizing agent Co(III), even when hydroperoxides have initially been excluded carefully. In these cases initiation is caused by direct electron transfer from C−H bonds to Co(III). − However, mechanisms for such initiations cannot be similar for saturates (paraffins and naphthenes) − and aromatics: − Saturates RH + Co false( III false) → R • + Co false( II false) + H + Aromatics RH + Co false( III false) ↔ RH + + Co false( II false) RH + → R • + H …”

Section: Theoretical Detailsmentioning

confidence: 99%

Selective Homogeneous Oxidation System for Producing Hydroperoxides Concentrate: Kinetics of Catalytic Oxidation of Gas Oils

Naqvi

Khan

2009

Ind. Eng. Chem. Res.

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A selective and mild (55 °C and 50 psig) homogeneous oxidation system has been described to produce hydroperoxides from a narrow cut made from typical gas oil. During this process oil, dissolved in wet acetic acid, is treated with air in the presence of the redox couple Co(III)/Co(II) (partially oxidized catalyst, POC). A straightforward route to POC consists of oxidizing Co(II) in wet acetic acid with calculated aqueous potassium chlorate. Initiation is the manifestation of the potent oxidizing ability of Co(III) toward generating alkyl radicals from hydrocarbons in the oil. Classical propagation then leads to assorted hydroperoxides, simultaneously decomposed by POC. Kinetics of the simultaneous formation and decomposition of hydroperoxides, under varying sets of process and composition variables, was studied in an isothermal, mechanically agitated, semibatch reactor, operating in the pure kinetic regime. A unique kinetic model, based on a rare irreversible consecutive reaction network (pseudo-first-order formation of hydroperoxides followed by their second-order decomposition), has been found to reasonably describe the kinetic data (R 2 = 0.9214). This kinetic model allowed the evaluation of the formation and decomposition rate constants that permitted the estimation of conversion of oil and selectivity to hydroperoxides. On average 15.12 ± 3.23% conversion was achieved in 9.3 ± 4.0 min with 99.86 ± 0.23, 92.88 ± 7.95, and 28.77 ± 11.67% selectivities for 0.10, 1.00, and 10.0% conversions, respectively.

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Section: Theoretical Detailsmentioning

confidence: 99%

Selective Homogeneous Oxidation System for Producing Hydroperoxides Concentrate: Kinetics of Catalytic Oxidation of Gas Oils

Naqvi

Khan

2009

Ind. Eng. Chem. Res.

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“…Back in the 1960's and 1970's, a stoichiometric amount of manganese(III) acetate (Mn 3 O(OAc) 9 ) was used to oxidise various hydrocarbons in acetic acid, the major oxidation products mostly being acetates of the substrates. [21][22][23][24] Reactions which require Mn 3 O(OAc) 9 in equivalent amounts are alcohol oxidations with a 2,3-dichloro-5,6-dicyano-1,4-benzoquinone oxidant, 25 oxidative free-radical cyclizations, [26][27][28][29][30] conversion of oximes to ketones and aldehydes 31 as well as radical reactions of C 60 with various esters and ketones. [32][33][34] Studies on manganese salt catalysed reactions are much scarcer including Mn 3 O(OAc) 9 in oxidation of alkenes with tert-butylhydroperoxide (tBuOOH) 35 and sulfides with H 2 O 2 .…”

Section: Introductionmentioning

confidence: 99%

Mn(ii) acetate: an efficient and versatile oxidation catalyst for alcohols

Räisänen

Al‐Hunaiti

Atosuo

et al. 2014

Catal. Sci. Technol.

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“…Isolation of 9 was not attempted. Distillation of 3,3-dimethylcyclohexanol from p -toluenesulfonic acid has been reported to give 9 and 10 in the ratio 35:65 …”

Section: Methodsmentioning

confidence: 99%

Radical Formation in the Oxidation of 2,2‘-Azo-2-methyl-6-heptene by Thianthrene Cation Radical

Chen

Shine

1996

J. Org. Chem.

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Reaction of 2,2'-azo-2-methyl-6-heptene (1) with thianthrene cation radical perchlorate (Th(*)(+)ClO(4)(-)) in CH(2)Cl(2) solution containing 2,6-di-tert-butyl-4-methylpyridine (DTBMP) gave a mixture of nine C(8) hydrocarbons, namely, 1,1,2-trimethylcyclopentane (4, 2.2%), 6-methyl-1-heptene (5, 2.2%), 2-methyl-1,6-heptadiene (6, 9.8%), 2,2-dimethyl-1-methylenecyclopentane (7, 2.9%), 6-methyl-1,5-heptadiene (8, 39%), 3,3-dimethyl- (9, 7.6%), 4,4-dimethyl- (10, 11%), 1,2-dimethyl- (11, 5.4%), and 1,6-dimethylcyclohexene (12, 1.5%). The amounts of acyclic dienes (6, 8) fell and of cyclohexenes (9, 10) rose when DTBMP was omitted from or diminished in the solution. The results provide firm evidence (products 4, 5, and 7) for the formation of the 2-methyl-6-hepten-2-yl radical (2), although the major fate of 2 is its oxidation to the corresponding cation 13, the origin of the bulk of the other products.

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Electron transfer with aliphatic substrates. Oxidations of cycloaliphatic substrates with cobalt(III) and manganese(III) ions alone and in the presence of oxygen

Cited by 28 publications

References 8 publications

Selective Homogeneous Oxidation System for Producing Hydroperoxides Concentrate: Kinetics of Catalytic Oxidation of Gas Oils

Selective Homogeneous Oxidation System for Producing Hydroperoxides Concentrate: Kinetics of Catalytic Oxidation of Gas Oils

Mn(ii) acetate: an efficient and versatile oxidation catalyst for alcohols

Radical Formation in the Oxidation of 2,2‘-Azo-2-methyl-6-heptene by Thianthrene Cation Radical

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