On the atmospheric oxidation of liquid toluene

Pritchard, H. O.

doi:10.1039/b608510e

Cited by 6 publications

(7 citation statements)

References 17 publications

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“…Theoretical studies have focused on some of the reactive intermediates, such as 2, [15][16][17] the benzoxyl radical, [18] and the autoxidation of toluene. [19] The combustion and tropospheric oxidation of toluene are highly complex processes involving a very large number of intermediates. Radicals 1 and 2 are clearly the most important primary reactive intermediates; however, the fate of these species is much less clear.…”

Section: Introductionmentioning

confidence: 99%

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The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

Sander

Roy

Bravo-Rodríguez

et al. 2014

Chemistry A European J

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The benzyl radical (1) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix-isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O₂ is the benzylperoxyl radical (2), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]-H migration and subsequent cleavage of the O—O bond to produce a hydrogen-bonded complex between the hydroxyl radical and benzaldehyde (4). Prolonged photolysis produces the benzoyl radical (5) and water, which finally yield the phenyl radical (7), CO, and H₂O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7. Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds

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Section: Introductionmentioning

confidence: 99%

“…20 kcal mol −1 ),14 and thus reversible at higher temperatures. Theoretical studies have focused on some of the reactive intermediates, such as 2 ,15–17 the benzoxyl radical,18 and the autoxidation of toluene 19…”

Section: Introductionmentioning

confidence: 99%

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

Sander

Roy

Bravo-Rodríguez

et al. 2014

Chemistry A European J

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“…In addition to their use in liquid fuels, substituted aromatics play important roles in benzene and soot formation, atmospheric chemistry, and the pyrolysis and oxidation of coal and biomass. As the parent (poly)alkylbenzene, much effort has been directed in the last 4−5 years toward better understanding the oxidation and pyrolysis of toluene and toluene fuel blends, − but significant uncertainties still remain with respect to aspects of the kinetics and mechanism.…”

Section: Introductionmentioning

confidence: 99%

Thermal Decomposition of the Benzyl Radical to Fulvenallene (C₇H₆) + H

2009

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We show that the benzyl radical decomposes to the C7H6 fragment fulvenallene (+H), by first principles/RRKM study. Calculations using G3X heats of formation and B3LYP/6-31G(2df,p) structural and vibrational parameters reveal that the reaction proceeds predominantly via a cyclopentenyl-allene radical intermediate, with an overall activation enthalpy of ca. 85 kcal mol(-1). Elementary rate constants are evaluated using Eckart tunneling corrections, with variational transition state theory for barrierless C-H bond dissociation in the cyclopentenyl-allene radical. Apparent rate constants are obtained as a function of temperature and pressure from a time-dependent RRKM study of the multichannel multiwell reaction mechanism. At atmospheric pressure we calculate the decomposition rate constant to be k [s(-1)] = 5.93 x 10(35)T(-6.099) exp(-49,180/T); this is in good agreement with experiment, supporting the assertion that fulvenallene is the C7H6 product of benzyl decomposition. The benzyl heat of formation is evaluated as 50.4 to 52.2 kcal mol(-1), using isodesmic work reactions with the G3X theoretical method. Some novel pathways are presented to the cyclopentadienyl radical (C5H5) + acetylene (C2H2), which may constitute a minor product channel in benzyl decomposition.

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“…We assume that toluene is first oxidized into benzyl hydroperoxide, which then regioselectively reacts with the C 78 Cl 8 to produce monosubstituted species sharing the same carbon cage and addition pattern. A number of previously reported works have discussed the possible production of benzyl hydroperoxide from toluene through auto-oxidation. , Indeed, in the toluene solvent involved in the present experiment, a trace amount of benzyl hydroperoxide was detected by GC−MS (see the SI). To support the regioselective mechanism, a control experiment starting with cumene hydroperoxide was also conducted.…”

Section: Resultsmentioning

confidence: 70%

Pentagon-Fused Hollow Fullerene in C₇₈ Family Retrieved by Chlorination

Tan

Zhou

et al. 2010

J. Am. Chem. Soc.

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C(78) is one of the most widely investigated higher fullerenes. Among its huge isomer family, only one non-IPR (IPR = isolated pentagon ring) cage, the C(2)-symmetric (#22010)C(78), was previously stabilized by endohedral derivatization. Here we report a new C(1)-symmetric non-IPR hollow isomer, (#23863)C(78), which was captured as (#23863)C(78)Cl(8) and then subjected to a regioselective substitution reaction with benzyl hydroperoxide to form (#23863)C(78)(OOCH(2)C(6)H(5))Cl(7). The structural connectivity of (#23863)C(78), which contains a pair of fused pentagons, was confirmed by single-crystal X-ray diffraction analysis of the (#23863)C(78)(OOCH(2)C(6)H(5))Cl(7) molecule, which shares the same fullerene core with (#23863)C(78)Cl(8); support for the structure is provided by comparable IR measurements and computation. Theoretical studies suggest that the differences in C-Cl bond length, intermediate stability, and steric effects of the involved molecules account for the chemical regioselectivity of the substitution reaction.

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On the atmospheric oxidation of liquid toluene

Cited by 6 publications

References 17 publications

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

Thermal Decomposition of the Benzyl Radical to Fulvenallene (C₇H₆) + H

Pentagon-Fused Hollow Fullerene in C₇₈ Family Retrieved by Chlorination

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On the atmospheric oxidation of liquid toluene

Cited by 6 publications

References 17 publications

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

Thermal Decomposition of the Benzyl Radical to Fulvenallene (C7H6) + H

Pentagon-Fused Hollow Fullerene in C78 Family Retrieved by Chlorination

Contact Info

Product

Resources

About

Thermal Decomposition of the Benzyl Radical to Fulvenallene (C₇H₆) + H

Pentagon-Fused Hollow Fullerene in C₇₈ Family Retrieved by Chlorination