The cobalt-catalyzed decomposition of tert.-butyl hydroperoxide

Dean, Matthew; Skirrow, G.

doi:10.1039/tf9585400849

Cited by 36 publications

(10 citation statements)

References 7 publications

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“…(1963) showed that in the cobalt-catalyzed oxidation of tetrali,n, addition of 107% of water by volume reduced the rate by a factor of five. Further support for the hypothesis is seen in k-he work of Dean and Skirrow (1958). Addition of water to a cobalt acetate: t-butyl hydroperoxide : acetic acid system gave a retarding effect of 25-fold, which leveled off at 3% added water.…”

Section: Resultsmentioning

confidence: 79%

Autoxidation of Methyl Linoleate in Freeze‐Dried Model Systems. II. Effect of Water on Cobalt‐Catalyzed Oxidation

Labuza

Maloney

Karel

1966

Journal of Food Science

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SUMMARY The oxidation of methyl linoleate catalyzed by various salts of cobalt was studied in a model system based on microcrystalline cellulose. The freeze‐dried model system was adjusted to various water activities, and the effect of water on the oxidation kinetics was determined using manometric measurements and measurements of diene conjugation. It was found that water had an inhibitory effect on the metal‐catalyzed oxidation of the fatty ester, as well as on oxidation in the absence of added metals. The kinetics of the reactions were evaluated in terms of the previously established hydroperoxide decomposition mechanisms. The effect of water on the metal‐catalyzed oxidation was found to exist in the monomolecular decomposition period as well as in the more rapid phase of the reaction, during which the hydroperoxide decomposition is known to follow bimolecular decomposition kinetics. The inhibition of the reaction by water is interpreted as due to deactivation of added, as well as of originally present, metal catalysts by hydration of the coordination shells; and also possibly as due to hydrogen bonding between hydroperoxides and water, and therefore to interference with the normal bimolecular decomposition reaction.

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Section: Resultsmentioning

confidence: 79%

Autoxidation of Methyl Linoleate in Freeze‐Dried Model Systems. II. Effect of Water on Cobalt‐Catalyzed Oxidation

Labuza

Maloney

Karel

1966

Journal of Food Science

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“…The products are 0 2 , dibutyl peroxide, tertiary-butyl alcohol, and tertiary-butoxy radical formed by the following competing reactions, the former being more important than the latter by a factor of 3 :1 (25).…”

Section: Discussionmentioning

confidence: 99%

Reactions of ozonides. VII. Isolation and oxidation of ozonolysis products from 1-decene

Diaper¹

1968

Can. J. Chem.

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1-Decene ozonide (1) was isolated by column chromatography of the mixed products of ozonation of 1-decene (2) in several nonpolar solvents. 1-Methoxy- (3) and 1-tertiary butoxynonane-1-hydroperoxide (4) were similarly obtained. The thin-layer chromatographic separation of these products from each other and from other ozonation products was examined. Compounds 3 and 4 were smoothly oxidized to di-(1-alkoxyalkyl)peroxides by Ce(IV). The stoichiometry of this reaction, examined by isothermal calorimetry, was 1:1. Compounds 1,3, and 4 were oxidized by CF3CO3H and by other oxidizing agents to nonanoic acid with chain degradation loss of 2–30%.

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“…The consumption of hydroperoxide. Two important conclusions can cyclohexene in process [6] is : be drawn: (i) the initial rates of the product accumulations exceed essentially the rates of [7] -(dC: y21) = k6[HRO;][RfH2] initiation for both products, and (ii) the initial 6 rates of the accumulalion depend linearly on The left side of [7] can be easily obtained from [HROOH],. These experimental facts indicate Fig.…”

mentioning

confidence: 99%

On the induced decomposition of α-phenylethylhydroperoxide by peroxy radicals

Hajdú¹,

Nemes²,

Gál³

et al. 1977

Can. J. Chem.

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The induced decomposition of α-phenylethylhydroperoxide (HROOH) has been investigated in three different systems: hydroperoxide + cyclohexene + AIBN + O2 (I); cyclohexene substituted by isooctane (II), and cyclohexene substituted by chlorobenzene (III). The decomposition products of the HROOH were in all cases acetophenone (RO) and methylphenylcarbinol (HROH).It was established that peroxy radicals induced the decomposition. The considerable material balance deficit in I is due to the addition of the peroxy radicals to cyclohexene the rate constant of which was estimated from the experimental data. No material balance deficit was observed with II. Experiments supported the assumption that both RO and HROH were formed simultaneously in the interaction between peroxy radicals and HROOH.The rate constant of the reaction HRO2• + HROOH → HROH + O2 + HRO• was measured as k = 1.03 × 109 exp (−13 100/RT). It is suggested that in the autoxidation of ethylbenzene the induced decomposition of HROOH is fast enough to be the main source of RO and HROH.

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The cobalt-catalyzed decomposition of tert.-butyl hydroperoxide

Cited by 36 publications

References 7 publications

Autoxidation of Methyl Linoleate in Freeze‐Dried Model Systems. II. Effect of Water on Cobalt‐Catalyzed Oxidation

Autoxidation of Methyl Linoleate in Freeze‐Dried Model Systems. II. Effect of Water on Cobalt‐Catalyzed Oxidation

Reactions of ozonides. VII. Isolation and oxidation of ozonolysis products from 1-decene

On the induced decomposition of α-phenylethylhydroperoxide by peroxy radicals

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