The autoxidation of aliphatic esters. Part 1. The reactions of tert-butoxyl and cumyloxyl radicals with neopentyl esters

Smith, John R. Lindsay; Nagatomi, Eiji; Stead, Angela; Waddington, David; Bévière, Stéphane D.

doi:10.1039/b000507j

Cited by 19 publications

(7 citation statements)

References 8 publications

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“…The chemistry of t BuO· has been used to study mechanisms of oxidative damage in living (e.g., oxidative damage to DNA, − lipids, etc.) and nonliving (e.g., lubricants) systems, and also to predict the oxidative sensitivity of pharmaceuticals . In atmospheric chemistry, t BuO· has been used to study mechanisms of degradation of volatile organic compounds (VOCs) in the stratosphere .…”

Section: Introductionmentioning

confidence: 99%

Chemistry of the t-Butoxyl Radical: Evidence that Most Hydrogen Abstractions from Carbon are Entropy-Controlled

et al. 2004

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Absolute rate constants and Arrhenius parameters for hydrogen abstractions (from carbon) by the t-butoxyl radical ((t) BuO.) are reported for several hydrocarbons and tertiary amines in solution. Combined with data already in the literature, an analysis of all the available data reveals that most hydrogen abstractions (from carbon) by (t) BuO. are entropy controlled (i.e., TdeltaS > deltaH, in solution at room temperature). For substrates with C-H bond dissociation energies (BDEs) > 92 kcal/mol, the activation energy for hydrogen abstraction decreases with decreasing BDE in accord with the Evans-Polanyi equation, with alpha approximately 0.3. For substrates with C-H BDEs in the range from 79 to 92 kcal/mol, the activation energy does not vary significantly with C-H BDE. The implications of these results in the context of the use of (t) BuO. as a chemical model for reactive oxygen-centered radicals is discussed.

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Section: Introductionmentioning

confidence: 99%

Chemistry of the t-Butoxyl Radical: Evidence that Most Hydrogen Abstractions from Carbon are Entropy-Controlled

et al. 2004

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“…Hydrogen atom abstraction reactions from a variety of substrates by alkoxyl radicals have attracted considerable interest. − Among these studies, particular attention has been devoted to the study of solvent effects on these processes. − In a 1993 paper, Ingold and Lusztyk clearly showed the absence of any significant kinetic solvent effect (KSE) for the H-atom abstraction reaction from cyclohexane by the cumyloxyl radical (CumO • ), and the general statement was made that “For alkoxyl radical hydrogen atom abstraction from alkanes (and from other substrates which are not, themselves, solvated to a significantly greater extent in polar relative to nonpolar solvents) we expect the abstraction rate constants to be essentially solvent independent. Of course, this rule will not hold if the substrate itself is strongly solvated by certain solvents...”.…”

mentioning

confidence: 99%

Kinetic Solvent Effects on Hydrogen Abstraction Reactions from Carbon by the Cumyloxyl Radical. The Role of Hydrogen Bonding

Bietti

Salamone

2010

Org. Lett.

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A kinetic study of the H-atom abstraction reactions from 1,4-cyclohexadiene and triethylamine by the cumyloxyl radical has been carried out in different solvents. Negligible effects are observed with 1,4-cyclohexadiene, whereas with triethylamine a significant decrease in rate constant (k(H)) is observed on going from benzene to MeOH. A good correlation between log k(H) and the solvent hydrogen bond donor parameter alpha is observed, indicative of an H-bonding interaction between the amine lone pair and the solvent.

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“…Hydrogen atom abstraction reactions by alkoxyl radicals have attracted considerable interest because of the key role they play in a variety of important chemical and biological processes. − Several aspects of these processes have been studied in detail including the nature of the substrate and of the abstractable hydrogen atom (C−H − or X−H, where X = O, ,− N, , S, Si, Ge, Sn , ) and the role of the solvent. ,,,,− Most recently, a combined model based on the Marcus cross relation and on the analysis of kinetic solvent effects has been developed and successfully applied to H-atom abstraction reactions from carbon by the tert -butoxyl radical ((CH 3 ) 3 CO • , t BuO • ) …”

mentioning

confidence: 99%

Diffusion Controlled Hydrogen Atom Abstraction from Tertiary Amines by the Benzyloxyl Radical. The Importance of C−H/N Hydrogen Bonding

et al. 2010

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The rate constants for H-atom abstraction (k(H)) from 1,4-cyclohexadiene (CHD), triethylamine (TEA), triisobutylamine (TIBA), and DABCO by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals were measured. Comparable k(H) values for the two radicals were obtained in their reactions with CHD and TIBA whereas large increases in k(H) for TEA and DABCO were found on going from CumO(•) to BnO(•). These differences are attributed to the rate-determining formation of BnO(•) C-H/amine N lone-pair H-bonded complexes.

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The autoxidation of aliphatic esters. Part 1. The reactions of tert-butoxyl and cumyloxyl radicals with neopentyl esters

Cited by 19 publications

References 8 publications

Chemistry of the t-Butoxyl Radical: Evidence that Most Hydrogen Abstractions from Carbon are Entropy-Controlled

Chemistry of the t-Butoxyl Radical: Evidence that Most Hydrogen Abstractions from Carbon are Entropy-Controlled

Kinetic Solvent Effects on Hydrogen Abstraction Reactions from Carbon by the Cumyloxyl Radical. The Role of Hydrogen Bonding

Diffusion Controlled Hydrogen Atom Abstraction from Tertiary Amines by the Benzyloxyl Radical. The Importance of C−H/N Hydrogen Bonding

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