The role of the Baeyer–Villiger reaction in the liquid-phase oxidation of organic compounds

Perkel, A. L.; Voronina, S. G.; Borkina, G. G.

doi:10.1007/s11172-018-2137-0

Cited by 16 publications

(8 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1) 40 and cyclohexyl acetate oxidation initiated with azobisisobutyronitrile at 333 К (Fig. 2) 42 together with the data on the composition of products of neopentyl heptano- (7), and hexanoic acid (8).…”

Section: Methodsmentioning

confidence: 79%

“…The reliable procedure to obtain the k p gr values consists in the use of the conditions of the Howard-Ingold method. Introduction into the reaction mixture of a hydroperoxide (for example, Bu t OOH) ensures the replacement of ester peroxyl radicals by tert-butyl peroxyl radicals (Scheme 8) and, in addition, the suppression of the reaction of types (7) and (8).…”

Section: Reactivity Of the Ester с-н Bondsmentioning

confidence: 99%

“…Esters of secondary and primary alcohols are formed as side products of the liquid-phase oxidation of cyclo-hexane, other saturated hydrocarbons, and their oxygencontaining derivatives. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Monocarboxylic, dicarboxylic acids, and ω-hydroxycarboxylic acids, aldehydes, and diols can be obtained by a direct oxidation of esters. 11,16 The use of esters as solvents, softeners, and components of lubricating oils is accompanied by a loss of operational properties due to thermal oxidative destruction of these compounds.…”

Section: Introductionmentioning

confidence: 99%

“…Kinetics of product accumulation (after reduction with Ph 3 P) in the methyl hexanoate oxidation initiated with cumene peroxide in the presence of tert-butyl hydroperoxide at 373 К; 40 initial concentrations are 6.46 for methyl hexanoate, 0.006 for cumene peroxide, and 0.5 mol L -1 for tert-butyl hydroperoxide; С is a product concentration, and τ is the reaction time (here and in other fi gures). The shown kinetic dependences correspond to methyl 2,3-dihydroxyhexanoate (1), methyl 6-hydroxyhexanoate (2), methyl 2,3-epoxyhexanoate (3), methyl 2-hexenoate (4), methyl 2-hydroxyhexanoate (5), methyl 4-hydroxyhexanoate (6), methyl 5-hydroxyhexanoate(7), and hexanoic acid(8).…”

mentioning

confidence: 98%

See 3 more Smart Citations

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

Perkel

Voronina

2020

Russ Chem Bull

Self Cite

View full text Add to dashboard Cite

Data on kinetics, reactivity, and mechanisms of formation of destruction products of the liquid-phase oxidation of saturated esters by molecular oxygen have been systematized and discussed. The ester group has both an activating and deactivating eff ects on the reactivity of the СН bonds of the alkoxyl (α´-, β´-, γ´-, and δ´-) and acyl (α-, β-, and γ-) groups. The activating eff ect in esters is weaker than in alcohols, ketones, and ethers and extends to the αand α´-CH bonds. The reactivity of the β-, β´-, and γ´-СН bonds is signifi cantly lower than that of the secondary СН bonds of hydrocarbons. Oxidation of the β-СН bonds of the acyl moieties of esters leads to НОО • radical, α,β-epoxy-, α,β-dihydroxy-, and α,β-unsaturated esters, but not to hydroperoxides. Upon the oxidation of esters, the highly active α-carboxyalkylperoxy-, α-acyloxyperoxy-, and НОО • -radicals are formed. The recombination reactions involving these radicals occur both with and without chain termination. The specifi city of the decomposition of ester hydroperoxides are due to intra-and intermolecular interactions of the hydroperoxide groups with the ester groups. Labile peroxide intermediates (α-hydroxyperoxyesters, peroxyesters, and peroxylactones) are formed through the corresponding tetrahedral intermediates and decay predominantly by the non-radical pathway. The recombination of the peroxyl radicals and the decay of labile peroxides result in the parallel accumulation of per oxide and non-peroxide products during the oxidation of esters.

show abstract

Section: Methodsmentioning

confidence: 79%

Section: Reactivity Of the Ester с-н Bondsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 98%

See 2 more Smart Citations

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

Perkel

Voronina

2020

Russ Chem Bull

Self Cite

View full text Add to dashboard Cite

show abstract

“…This is interesting since cycloalkanes are moderately resistant to biodegradation (Connan 1984). The degradation of cycloalkanes involves ring cleavage via Baeyer-Villiger oxidation (Perkel et al 2018; Sheng et al 2001), which requires an initial oxidation of cyclohexane to cyclohexanol by cyclohexane monooxygenase, and then a dehydrogenation reaction to cyclohexanone. This step is followed by another monooxygenase attack to form epsilon-caprolactone, followed by ring cleavage that is carried out by gluconolactonase (Figure 5a).…”

Section: Discussionmentioning

confidence: 99%

Diversity and metagenome analysis of a hydrocarbon-degrading bacterial consortium from asphalt lakes located in Wietze, Germany

Eze

Hose

George

et al. 2021

Preprint

View full text Add to dashboard Cite

The pollution of terrestrial and aquatic environments by petroleum contaminants, especially diesel fuel, is a persistent environmental threat requiring cost-effective and environmentally sensitive remediation approaches. Bioremediation is one such approach, but is dependent on the availability of microorganisms with the necessary metabolic abilities and environmental adaptability. The aim of this study was to examine the microbial community in a petroleum contaminated site, and isolate organisms potentially able to degrade hydrocarbons. Through successive enrichment of soil microorganisms from samples of an historic petroleum contaminated site in Wietze, Germany, we isolated a bacterial consortium using diesel fuel hydrocarbons as sole carbon and energy source. The 16S rRNA gene analysis revealed the dominance of Alphaproteobacteria. We further reconstructed a total of 18 genomes from both the original soil sample and the isolated consortium. The analysis of both the metagenome of the consortium and the reconstructed metagenome-assembled genomes show that the most abundant bacterial genus in the consortium, Acidocella, possess many of the genes required for the degradation of diesel fuel aromatic hydrocarbons, which are often the most toxic component. This can explain why this genus proliferated in all the enrichment cultures. Therefore, this study reveals that the microbial consortium isolated in this study and its dominant genus, Acidocella, could potentially serve as an effective inoculum for the bioremediation of sites polluted with diesel fuel or other organic contaminants.

show abstract

Unraveling the mechanism and kinetics of aerobic Baeyer–Villiger oxidation of cyclohexanone

Wang,

Chen,

Sim

et al. 2023

AIChE Journal

View full text Add to dashboard Cite

This study explores the aerobic Baeyer–Villiger oxidation of cyclohexanone into ε‐caprolactone using metalloporphyrin and benzaldehyde, a greener process to replace hazardous concentrated peroxyacid. The reaction mechanism involves a series of free radical reactions, identified through in situ EPR. In this complex three‐component reaction, we developed an intrinsic kinetic model based on the proposed mechanism. Utilizing a hyperbolic equation, the model well fits experimental data, describing biomimetic catalytic behavior of the aerobic Baeyer–Villiger oxidation. The reaction orders for the three reactants corroborate the kinetic model, with the activation energy of oxygen (130.27 kJ/mol) surpassing cyclohexanone (94.85 kJ/mol) and benzaldehyde (40.73 kJ/mol), implying slow initial oxygen activation while rapid subsequent benzaldehyde oxidation, making oxygen transfer and activation key steps. This unified approach to elementary reaction, mechanism, and intrinsic kinetics provides robust forecasts and lays the groundwork for additional studies, such as side reactions control and mass transfer enhancement and reactor design.

show abstract

The role of the Baeyer–Villiger reaction in the liquid-phase oxidation of organic compounds

Cited by 16 publications

References 28 publications

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

Diversity and metagenome analysis of a hydrocarbon-degrading bacterial consortium from asphalt lakes located in Wietze, Germany

Unraveling the mechanism and kinetics of aerobic Baeyer–Villiger oxidation of cyclohexanone

Contact Info

Product

Resources

About