Kinetics of oxidation of aliphatic alcohols by ozone in aqueous solutions

Gerchikov, A. Ya.; Zimin, Yu. S.; Trukhanova, N. V.; Evgrafov, V. N.

doi:10.1007/bf02475510

Cited by 7 publications

(2 citation statements)

References 6 publications

(9 reference statements)

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“…A number of authors have tried to elucidate the kinetics and mechanism of the ozonolysis of alcohols and their application to the selective preparation of ketones and aldehydes in high yields under mild conditions [3,[39][40][41][42][43][44][45][46]. The basic concepts of such reactions are discussed in several references [1,2,25,34,35,39].…”

Section: Alcoholsmentioning

confidence: 99%

Kinetics and Mechanism of the Ozone Reaction with Alcohols, Ketones, Ethers and Hydroxybenzenes

Rakovsky¹,

Anachkov²,

Belitskii³

et al. 2016

ChChT

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Abstract. The review, based on 92 references, is focused on degradation of organics by ozonation and it comprises various classes of oxygen-containing organic compounds -alcohols, ketones, ethers and hydroxybenzenes. The mechanisms of a multitude of ozone reactions with these compounds in organic solvents are discussed in details, presenting the respective reaction schemes. The corresponding kinetic parameters are given and some thermodynamic parameters are also listed. The dependences of the kinetics and the mechanism of the ozonation reactions on the structure of the compounds, on the medium and on the reaction conditions are revealed. Various possible applications of ozonolysis are specified and discussed. All these reactions have practical importance for the protection of the environment.

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Section: Alcoholsmentioning

confidence: 99%

Kinetics and Mechanism of the Ozone Reaction with Alcohols, Ketones, Ethers and Hydroxybenzenes

Rakovsky¹,

Anachkov²,

Belitskii³

et al. 2016

ChChT

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“…Thus, this inhibition effect could be evidence that the assumed intermediate shared by acetone and tert -butyl alcohol formation is likely to be tert -butyl hydrotrioxide or its derivative. As suggested by the observations during the ozonation of butanone and isobutane, dioxygen potentially inhibits other reactions involving H-atom abstraction during the initiation steps, such as the ozonation of 2-butanol , and n -butane.…”

Section: Resultsmentioning

confidence: 99%

Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

Zhu

Jackson

Subramaniam

2023

JACS Au

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We have demonstrated the oxidation of mixed alkanes (propane, nbutane, and isobutane) by ozone in a condensed phase at ambient temperature and mild pressures (up to 1.3 MPa). Oxygenated products such as alcohols and ketones are formed with a combined molar selectivity of >90%. The ozone and dioxygen partial pressures are controlled such that the gas phase is always outside the flammability envelope. Because the alkane−ozone reaction predominantly occurs in the condensed phase, we are able to harness the unique tunability of ozone concentrations in hydrocarbon-rich liquid phases for facile activation of the light alkanes while also avoiding over-oxidation of the products. Further, adding isobutane and water to the mixed alkane feed significantly enhances ozone utilization and the oxygenate yields. The ability to tune the composition of the condensed media by incorporating liquid additives to direct selectivity is a key to achieving high carbon atom economy, which cannot be achieved in gas-phase ozonations. Even in the liquid phase, without added isobutane and water, combustion products dominate during neat propane ozonation, with CO 2 selectivity being >60%. In contrast, ozonation of a propane+isobutane+water mixture suppresses CO 2 formation to 15% and nearly doubles the yield of isopropanol. A kinetic model based on the formation of a hydrotrioxide intermediate can adequately explain the yields of the observed isobutane ozonation products. Estimated rate constants for the formation of oxygenates suggest that the demonstrated concept has promise for facile and atom-economic conversion of natural gas liquids to valuable oxygenates and broader applications associated with C−H functionalization.

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