- Phenolic hydrogen abstraction by the triplet excited state of thiochromanone: A laser flash photolysis study
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Triplet ketones are known to oxidize biological substrates which can lead to damage of several biomolecules such as amino acids, nucleosides and DNA. As part of our systematic study on the interaction between carbonyl compounds and phenols, the triplet reactivity of thiochromanone (1) towards substituted phenols, in acetonitrile, was investigated employing the laser fash photolysis technique. The quenching rate constants ranged from (1.1 ± 0.1) × 108 L mol-1 s-1 (4-cyanophenol) to (5.8 ± 1.0) × 109 L mol-1 s-1 (hydroquinone). A Hammett plot for the reaction of triplet 1 with phenols containing polar substituents resulted in a reaction constant ρ =-0.90. This negative value observed for the reaction constant ρ is in accord with a mechanism in which the hydrogen transfer from phenols to the triplet carbonyl involves a coupled electron/proton transfer.
- Ribeiro, Alessandra M.,Bertoti, Ada Ruth,Netto-Ferreira, Jose? Carlos
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scheme or table
p. 1071 - 1076
(2010/10/21)
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- Oxidation of phenols employing polyoxometalates as biomimetic models of the activity of phenoloxidase enzymes
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A kinetic study of the oxidation of substituted phenols with either vanadium(v) polyoxotungstate, [α-SiVVW11O 40]5- (viz. SiW11V), or manganese(iii) polyoxotungstate, [α-SiMnIIIW11/su
- Galli, Carlo,Gentili, Patrizia,Nunes Pontes, Ana Sofia,Gamelas, Jose A. F.,Evtuguin, Dmitry V.
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p. 1461 - 1467
(2008/02/13)
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- Reactivity of substituted phenols toward alkyl radicals
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The rate constants for the reaction of primary alkyl radicals with substituted phenolic compounds have been measured in benzene or toluene at room temperature by using the radical clock technique. With three representative phenols, containing in the ortho positions substituents of different size, the kinetics of the hydrogen transfer to alkyl radicals was studied at different temperatures to obtain the corresponding Arrhenius parameters. The kinetic solvent effect on the reaction with α-tocopherol was also investigated in six different solvents behaving as hydrogen bond acceptors, while the reaction with 2,4,6-trimethylphenol and 2,6-di-tert-butylphenol was studied in toluene and γ-valerolactone. For some phenols, the effect of self-aggregation on the kinetic parameters was also studied.
- Franchi, Paola,Lucarini, Marco,Pedulli, Gian Franco,Valgimigli, Luca,Lunelli, Bruno
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p. 507 - 514
(2007/10/03)
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- Radiolytic decomposition of 4-bromophenol and 4-chlorophenol in dilute aqueous solution
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The pH dependence of azide radical, hydroxyl radical and hydrated electron induced decomposition of 4-chloro- and 4-bromophenol was investigated by pulse radiolysis in airfree solutions under reducing and oxidizing conditions and also in air saturated sol
- Kovacs, Andras,Gonter, Katalin,Foeldiak, Gabor,Gyoergy, Istvan,Wojnarovits, Laszlo
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p. 453 - 475
(2007/10/03)
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- Iodine Atoms and Iodomethane Radical Cations: Their Formation in the Pulse Radiolysis of Iodomethane in Organic Solvents, Their Complexes, and Their Reactivity with Organic Reductants
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Pulse radiolysis of iodomethane in various organic solvents leads to formation of iodine atoms or iodomethane radical cations, which in turn form complexes with iodomethane or with the solvent.Radiolysis in cyclohexane gives CH3I*I, which exhibits an absorption peak at 390 nm, whereas radiolysis in benzene forms the solvent complex, C6H6*I, which exhibits an intense broad absorption centered at 490 nm.Radiolysis of iodomethane in acetone, benzonitrile, and halogenated hydrocarbons results in formation of the radical cation CH3I.+.In the former two solvents, this species forms a complex with another molecule of iodomethane to give (CH3))2+, which absorbs at 420 nm, in agreement with previous results in aqueous solutions, but in halogenated hydrocarbons it forms complexes with the solvents, absorbing at 320-360 nm, i.e. near the absorption of monomeric CH3I.+ in water.Complexes of I atoms oxidize phenol and triphenylamine relatively slowly whereas complexes of CH3I.+ react more rapidly.The reactivity of the CH3I.+*RX complexes increases in the order of RX = CH2Cl2, CHCl3, CH2Br2, CCl4, CH3I, and for each complex the reactivity with phenol increases with increase in electron donating power of substituents.Replacing the methyl group of iodomethane radical cation with ethyl or isopropyl decreases the reactivity, whereas trifluoromethyl increases the reactivity.These oxidation reactions proceed via an intermediate complex between the iodine species and the organic reductant.
- Shoute, Lian C. T.,Neta, P.
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p. 4411 - 4414
(2007/10/02)
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- The one-electron reduction potential of 4-substituted phenoxyl radicals in water
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By means of pulse radiolysis the one-electron reduction potentials of twelve 4-substituted phenoxy radicals have been determined. The main reference used was the ClO2./ClO2- couple. By combining the redox potentials of phenoxyl radicals with the aqueous acidities of phenols the bond strength of the phenolic O-H bond was calculated. These values were found to be in good agreement with O-H bond dissociation enthalpies measured in the gas phase.
- Lind,Shen,Eriksen,Merényi
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p. 479 - 482
(2007/10/02)
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- Substituent Effects on Rates of One-Electron Oxidation of Phenols by the Radicals ClO2, NO2, and SO3(1-)
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Rate constants for the reactions of ClO2, NO2, and SO3(1-) radicals with several substituted phenoxide ions have been measured by pulse radiolysis.They vary from the immeasurably slow (4) to almost diffusion-controlled rates (>109 M-1 s-1) and depend on the redox potentials of the phenoxide ions and the inorganic radicals.With the weak oxidant SO3(1-) reverse reactions were observed in certain cases; i.e., the phenoxyl radical oxidizes sulfite ions.An attempt is made to correlate the rate constants with Hammett's substituent constants and the results are compared with those obtained previously for the reactions of various inorganic radicals with phenols and phenoxide ions.
- Alfassi, Zeev B.,Huie, Robert E.,Neta, P.
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p. 4156 - 4158
(2007/10/02)
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- Reaction of tert-Butoxy Radicals with Phenols. Comparison with the Reactions of Carbonyl Triplets
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Tert-butoxy radicals generated in the photodecomposition of di-tert-butyl peroxide react efficiently with phenols to yield the corresponding phenoxy radicals.Typical rate constants in benzene at 22 deg C are 3.3x108 and 1.6x109 Msup
- Das, P. K.,Encinas, M. V.,Steenken, S.,Scaiano, J. C.
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p. 4162 - 4166
(2007/10/02)
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