Free radical reactions in hydrocarbon mixtures

Brook, J. H. T.; Glazebrook, R. W.

doi:10.1039/tf9605601014

Cited by 11 publications

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“…and therefore the relative ease of oxidation of different substrates can be correlated with the relative rates of reaction 18 (54,55). Peroxy radicals can also abstract a hydrogen atom, particularly one in the ,&position, by an intramolecular process (278) and can add to olefinic double bonds (187, 223, 224, 231, 272).…”

Section: B Propagationmentioning

confidence: 99%

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Inhibition of the Autoxidation of Organic Substances in the Liquid Phase.

Ingold¹

1961

Chem. Rev.

387

249

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Section: B Propagationmentioning

confidence: 99%

“…can react with hydroperoxides to produce free radicals (12, 65, 318). The metallic ion can act either as a reductant: (55) or as an oxidant:…”

Section: R R"mentioning

confidence: 99%

Inhibition of the Autoxidation of Organic Substances in the Liquid Phase.

Ingold¹

1961

Chem. Rev.

387

249

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“…This suggests that the free radical induced decomposition of the peroxide is relatively unimportant compared with reaction [3]. The composition of the main products varies slightly with the initial peroxide concentration and with the extent of its decomposition (see Table I).…”

Section: Resultsmentioning

confidence: 99%

“…This may be due to a direct reaction between the phenol and the peroxide (29) or to some indirect solvation pheilomena. However, it is also possible that the increased rate is due to a reduction in the rate of recon~bination of t-butoxy radicals to re-form the peroxide (i.e., the reverse of reaction [3]) since the phenol will reduce the steady-state concentration of these radicals. The major products under varying conditions are given in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The ratio, [t-butanol]/[acetone], produced in different substrates therefore gives a measure of the relative rates of hydrogen abstraction fro-m the substrates. These radicals are readily prepared by the decomposition of di-t-butyl peroxide and the reactions can be represented by, This technique has been employed by a number of workers in recent years to measure the relative rates of hydrogen abstraction by t-butoxy radicals from a variety of substrates such as hydrocarbons (2)(3)(4)(5)(6)(7)(8)(9), ethers, (10, l l ) , alcohols (12), and amiiles (13,14). As a part of our general program for studying the inhibition of autoxidation by phenols (15)(16)(17) we considered that an examination of the reaction of t-butoxy radicals with phenols might throw considerable light on the overall mechanism of inhibition.…”

Section: P Imentioning

confidence: 99%

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THE REACTION OF tert-BUTOXY RADICALS WITH 2,6-Di-tert-BUTYL-4-METHYLPHENOL AND 2,6-Di-tert-BUTYLPHENOL

Ingold¹

1963

Can. J. Chem.

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The products of the reaction of t-butowy radicals with 2,6-di-t-butyl-4-meth~lphei101 and 2,6-di-t-butplphenol ill carbon tetrachloride have been analyzed quantitatively. There is a satisfactory agreement between the measured and calculated yields of t-butanol u i t h both phenols. The deuterium isotope effect ( k~l k~) for abstraction of the pheilolic hydrogen from 2,6-di-t-butyl-4-methylphenol is about 6.4.The abstraction of hydrogen atoms by alkoxy radicals from substrates in the liquid phase is of particular interest in relation to autoxidation phenomena (1). These radicals are produced in the chain branching deco~llposition of the initially formed hydroperoxides and are therefore responsible for the autocatalytic nature of most autoxidations.The t-bu toxy radical is particularly suitable for studying the relative rates of reaction [2] with different substrates since it may either abstract a hydrogen to give t-butanol o r decdmpose t o give acetone and a methyl radical. The ratio, [t-butanol]/[acetone], produced in different substrates therefore gives a measure of the relative rates of hydrogen abstraction fro-m the substrates. These radicals are readily prepared by the decomposition of di-t-butyl peroxide and the reactions can be represented by, This technique has been employed by a number of workers in recent years to measure the relative rates of hydrogen abstraction by t-butoxy radicals from a variety of substrates such as hydrocarbons (2-9), ethers, (10, l l ) , alcohols (12), and amiiles (13,14). As a part of our general program for studying the inhibition of autoxidation by phenols (15-17) we considered that an examination of the reaction of t-butoxy radicals with phenols might throw considerable light on the overall mechanism of inhibition. In particular, we were interested to see whether the phenolic hydrogen was abstracted by the t-butoxy radical in the rate-determining step.In view of the comparative ease with which an isotope effect was detected in the reaction of peroxy radicals with 2,6-di-t-butyl-4-methylphenol (BLIP) (15, 16) this compound was chosen for the present investigation. There have also been numerous studies in recent years of the products of oxidation of this pl~enol by a variety of oxidizing agents (18)(19)(20)(21)(22)(23)(24)(25). Some results on the reaction of t-butoxy radicals with 2,6-di-t-butylphenol (BP) are also reported.

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Reaktionen mit tert.‐Butoxyradikalen. V. Der Deuteriumisotopeneffekt bei der Reaktion von tert.‐Butoxyradikalen mit aliphatischen Ketonen

Schwetlick

Spitz

1965

J. Prakt. Chem.

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IrihaltsubersichtDie Reaktit itat \ o n .\veton, Uiathyllwton, Cyclohrxanori und cier cntsprechenderi \-deuterierten Ketone bei dor H-,ihspaltung durch tert.-Rutoxyradikalo w ird bestimmt. Die ,s-CH,-Gruppen drs Dikthylketoris xirtd 13mal realitiver rils die P-CH,-Gruppen ; die Keaktionsfihigkeit, der beidrn n-CH,-Gruppen des Cyrlohesanons ist lOmal grofier als d i e der drei /Iund ;)-C:H,-Gruppcn. Der Deiiteriumisotopcnefft,kt bei der H-Abspsltung durch tort.-Butoxyradiliale c t i i~ drr 2-Stc.llung hctraqt 5.4 hci Xcrton, 3.9 hei Tliiithylketon und 1,4 bci Cyclohcsmon. Die Reaktivitkt voii CH-Verbindiingen gegeniiber tert.-Butoxpradikalen (CH3), (CH,),COH -1 R . (1) Dnlrtei zeigte sich, daB die meisten Substituenten die Reaktivitlit der ihnen benachbarten CH-Gruppen infdge von Hybridisierungs-und Konjugatioiiseffekten erhohen. Dariiber hinaiis wirken sich polare Substituenteneffekte aus: -1-1und 4-M-Gruppen steigwn die Reaktivitat, --Iund -M-Substituenten senkeii sie. Die HAMMETT-Gleichung wird sowohl bei substituierten Toluolen 3, 4, und Phenolen 9, als aiich bei siibstituierten Methanen (3966).(GI. 1) wurde von versehiedenen Autoren untersucht l-l0).

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Free radical reactions in hydrocarbon mixtures

Cited by 11 publications

References 0 publications

Inhibition of the Autoxidation of Organic Substances in the Liquid Phase.

Inhibition of the Autoxidation of Organic Substances in the Liquid Phase.

THE REACTION OF tert-BUTOXY RADICALS WITH 2,6-Di-tert-BUTYL-4-METHYLPHENOL AND 2,6-Di-tert-BUTYLPHENOL

Reaktionen mit tert.‐Butoxyradikalen. V. Der Deuteriumisotopeneffekt bei der Reaktion von tert.‐Butoxyradikalen mit aliphatischen Ketonen

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