Homolytic decompositions of hydroperoxides. IV. Metal-catalyzed decompositions

Hiatt, R.; Irwin, Katherine C.; Gould, Constance W.

doi:10.1021/jo01268a025

Cited by 122 publications

(38 citation statements)

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“…Lipid radicals are highly reactive species and they can readily undergo propagation reactions either by abstraction of a hydrogen atom (10,12) or by reaction with an oxygen molecule in its ground state (11).…”

Section: Propagation and Termination Of Autoxidationmentioning

confidence: 99%

“…The radical formed by reaction of a phenol with a lipid radical is stabilised by delocalisation of the unpaired electron around the aromatic ring as indicated by the valence bond isomers (20). (20) The stability of the phenoxyl radical (A') reduces the rate of propagation of the autoxidation chain reaction since propagation reactions such as (21)- (23) are very slow compared with (10), (11) and (12),…”

Section: Primary (Chain-breaking) Antioxidantsmentioning

confidence: 99%

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The Mechanism of Antioxidant Action in Vitro

1990

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Section: Propagation and Termination Of Autoxidationmentioning

confidence: 99%

Section: Primary (Chain-breaking) Antioxidantsmentioning

confidence: 99%

The Mechanism of Antioxidant Action in Vitro

1990

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“…It is known that alkoxy and alkyl peroxy radicals generated via hydroperoxide decomposition (Scheme 1) are involved not only in crosslinking and propagation reactions, but also in the formation of carbonyl-containing secondary oxidation products [43,44]. Particularly, alkoxy radicals are capable of undergoing b-scission reaction [11][12][13]18,25,38], leading to the formation of volatile and non-volatile secondary oxidation products.…”

Section: Formation Of Secondary Oxidation Byproductsmentioning

confidence: 99%

Oxidation and oligomerization of ethyl linoleate under the influence of the combination of ascorbic acid 6-palmitate/iron-2-ethylhexanoate

Micciché¹,

Haveren²,

Oostveen³

et al. 2006

Applied Catalysis A: General

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“…These two mechanisms can usually be distinguished by determining the hydroperoxide derived products, e.g., cumene hydroperoxide gives phenol and acetone by a heterolytic decomposition while a-cumyl alcohol, a-methylstyrene, and acetophenone are formed by a radical induced reaction. Furthermore, radical induced decompositions obey a rate law which is firstorder in each reactant (13).…”

mentioning

confidence: 99%

“…Hiatt et al (13) considered that metal ion catalyzed decomposition of tertiary alkyl hydroperoxides can be described by reactions 8 and 9 followed by Several experimental observations, however, indicate that reactions 11 and 12 are not important for the nickel complexes. First, rates of oxygen evolution were less than 1/100th rates of radical production.…”

mentioning

confidence: 99%

Metal complexes as antioxidants. III. Reaction of nickel dialkyldithiocarbamates and nickel dialkyldithiophosphates with alkyl hydroperoxides

Howard¹,

Chenier²

1976

Can. J. Chem.

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. Can. J. Chem. 54,390 (1976). Alkyl hydroperoxides are shown to react with nickel dialkyldithiocarbamates and nickel dialkyldithiophosphates in the liquid-phase a t 30 OC to generate free radicals. These radicals are capable of inducing the decomposition of the hydroperoxide and destroying the nickel complex. Rates of radical generation, as determined from hydrocarbon autoxidation, are similar to rates of complex disappearance and areca. 1/5th rates of hydroperoxide disappearance. Rates of disappearance of both reactants are retarded by the addition of hydrogen atom donating antioxidants, the rate of hydroperoxide disappearance is reduced to the rate of radical generation and the rate of complex disappearance is significantly less than the rate of radical generation. These results are consistent with a mechanism for decomposition which involves cycling of the nickel complex. Decomposition of cumene hydroperoxide to a-cumyl alcohol, a-methylstyrene and acetophenone suggests the intermediacy of curnyloxy radicals in this system while the electron spin resonance spectroscopic method indicates that alkylperoxy radicals are also transient intermediates. Ces radicaux sont capables d'induire la dCcomposition de I'hydroperoxyde et de dCtruire le complexe de nickel. Les taux deformation des radicaux, tels que dCterminCs par I'autooxydation d'hydrocarbures, sont sernblables aux taux de disparition du complexe et sont approximativement 5 fois plus lents que les taux de disparition de I'hydroperoxyde. Les taux de disparition des deux rCactifs sont retardis par addition d'antioxydant pouvant donner des atornes d'hydrogkne; le taux de disparition de I'hydroperoxyde est rCduit au taux de genCration des radicaux et la vitesse de disparition du complexe est beaucoup plus faible que la vitesse de gCnCration des radicaux. Ces rCsultats sont en accord avec un mecanisme pour la dCcornposition qui implique un recyclage du complexe de nickel. La dCcompositiorl de I'hydroperoxyde de cumene en alcool a-cumyle, en a-rnCthylstyrkne et en acCtophCnone suggkre que les radicaux cumyloxy sont des intermidiaires dans ce systkme alors que des Ctudes de spectroscopie de risonance paramagnb tique electronique indiquent que les radicaux alkylperoxy sont aussi des interrnkdiaires de courte duke.[Traduit par le journal]

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Homolytic decompositions of hydroperoxides. IV. Metal-catalyzed decompositions

Cited by 122 publications

References 0 publications

The Mechanism of Antioxidant Action in Vitro

The Mechanism of Antioxidant Action in Vitro

Oxidation and oligomerization of ethyl linoleate under the influence of the combination of ascorbic acid 6-palmitate/iron-2-ethylhexanoate

Metal complexes as antioxidants. III. Reaction of nickel dialkyldithiocarbamates and nickel dialkyldithiophosphates with alkyl hydroperoxides

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