Ozonization of organic substrates. Hydrotrioxide formation and decomposition to give singlet oxygen

Stary, Frank E.; EMGE, DALE E.; Murray, Robert W.

doi:10.1021/ja00423a039

Cited by 71 publications

(40 citation statements)

References 14 publications

(14 reference statements)

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“…Price and co-workers [68] proposed the so-called "insertion" mechanism, according to which ozone is inserted into the α-C-H bonds at the first step through 1,3-dipolar addition, thus forming unstable HTO. This mechanism was also supported by the data of Erickson and Bailey [2,67,69], Murray and coworkers [70], who measured the activation parameters of the decomposition of a series of HTO, obtained by the ozonolysis of some ethers. Giamalva and co-workers [71] summarized the possible mechanisms known today, i.e.…”

Section: Etherssupporting

confidence: 61%

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: Etherssupporting

confidence: 61%

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

Rakovsky¹,

Anachkov²,

Belitskii³

et al. 2016

ChChT

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“…[27][28][29][30] This splitting was previously assigned to the presence of two hydrotrioxide forms with OOOH bonded either intramolecularly or intermolecularly 9-12:…”

Section: Resultsmentioning

confidence: 99%

Formation of hydrotrioxides during ozonation of hydrocarbons on silica gel. Decomposition of hydrotrioxides

Avzyanova

Timerghazin

Khalizov

et al. 2000

J. Phys. Org. Chem.

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Hydrotrioxides (HT), ROOOH, from isopentane, 1,4-dimethylcyclohexane, 1,3-dimethylcyclohexane, decalin and triphenylmethane were synthesized for the first time by low-temperature ozonation of the corresponding hydrocarbons on a silica surface. Thermal decomposition of hydrotrioxides is accompanied by the formation of radicals and by infrared and visible chemiluminescence (CL). In solution the HTs form self-associates and react reversibly with the solvent (acetone) producing Bayer-Villiger type intermediates (unsymmetrical dialkyl trioxides). These reactions cause a complex character of the decomposition kinetics of HTs, as evidenced by monitoring the dependence of CL intensity on time. Activation parameters of thermal decomposition of HTs show a compensation effect (logA vs E A ) which describes well the available experimental and theoretical data for the homolysis of organic trioxides.

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“…Erickson et al (1968) identified tert-butyl acetate, tert-butyl formate and tert-butyl alcohol as ETBE ozonation byproducts. According to Bailey and Lerdal (1978), two types of initial attack of ozone on ethers take place and lead to the formation of hydrotrioxide intermediates (identified by Stary et al, 1976). The most important, the 1,3-dipolar insertion would be activated by the least acidic hydrogen in the alphaposition from the ether group (Price and Tumolo, 1964;Bailey and Lerdal, 1978;Giamalva et al, 1986).…”

Section: And the Year 2000 By A Quadrupling Of The American Consumptmentioning

confidence: 99%

Oxidation of Methyl tert-Butyl Ether (MTBE) and Ethyl tert-Butyl Ether (ETBE) by Ozone and Combined Ozone/Hydrogen Peroxide

Leitner¹,

Papailhou²,

Croué³

et al. 1994

Ozone: Science & Engineering

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The aim of this work was to study the reaction of ozone and combined ozone/hydrogen peroxide on oxygenated additives such as methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE) in dilute aqueous solution using controlled experimental conditions. Experiments conducted in a semi-continuous reactor with MTBE and ETBE in combination (initial concentration: 2 mmol/L of each) showed that ETBE was better eliminated than MTBE with both ozone and combined 0j/H 2 0 2 . Batch experiments led to the determination of the ratio of the kinetic constants for the reaction of OH°-radical with MTBE and ETBE [KH°/nit/Kt<"mu = 1-7). Tert-butyl formate and tert-butyl acetate were identified as the ozonation byproducts of MTBE and ETBE, respectively, while tert-butyl alcohol was found to be produced during the ozonation of both compounds.

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Ozonization of organic substrates. Hydrotrioxide formation and decomposition to give singlet oxygen

Cited by 71 publications

References 14 publications

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

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

Formation of hydrotrioxides during ozonation of hydrocarbons on silica gel. Decomposition of hydrotrioxides

Oxidation of Methyl tert-Butyl Ether (MTBE) and Ethyl tert-Butyl Ether (ETBE) by Ozone and Combined Ozone/Hydrogen Peroxide

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