Products and mechanism of the gas phase reaction between nitrate radical and arenes

Rindone, Bruno; Cariati, F.; Restelli, G.; Hjorth, J.

doi:10.1007/bf00325558

Cited by 6 publications

(7 citation statements)

References 9 publications

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“…In a second group of control experiments, N2O5 was admitted into the chamber and left to decay to HNO3 because of the presence of moisture in the system. The content of the chamber was then pumped into the carbon trap, which had previously been saturated with p-(3) or o-xylene (4). Only traces of the aldehydes 3-4a were observed in these experiments.…”

Section: Resultsmentioning

confidence: 99%

“…Polar effects combined with kie values can provide useful information on the prevailing mechanism. The following order of reactivity, observed for the gas-phase reaction, was established using measurements of the 4 for the other benzene derivatives:…”

Section: Scheme IImentioning

confidence: 99%

“…A preliminary study of the reaction of NO3 with toluene and with xylenes has been performed by us (3,4). A preliminary study of the reaction of NO3 with toluene and with xylenes has been performed by us (3,4).…”

Section: Introductionmentioning

confidence: 99%

“…Mechanism and product analysis of the reaction between NO3 and aromatic hydrocarbons have been the subject of a limited number of studies, and the results are still a matter for discussion. A preliminary study of the reaction of NOa with toluene and with xylenes has been performed by us (3,4). Benzaldehyde and benzyl nitrate, in the case of toluene, and the methyl-substituted analogues, in the case of xylenes, have been observed as being the main reaction products.…”

Section: Introductionmentioning

confidence: 99%

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Comparison between the gas-phase and the solution reaction of the nitrate radical and methylarenes

Choidini¹,

Rindone²,

Cariati³

et al. 1993

Environ. Sci. Technol.

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Section: Resultsmentioning

confidence: 99%

Section: Scheme IImentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Comparison between the gas-phase and the solution reaction of the nitrate radical and methylarenes

Choidini¹,

Rindone²,

Cariati³

et al. 1993

Environ. Sci. Technol.

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“…A kinetic isotope effect k H /k D ¼ 2.0-2.3 34 was found and is close to the value of 1.5-1.8 found with p-xylene. 35 These values are borderline between being secondary and primary. A similar value (k H /k D ¼ 1.6) was found for the reaction of toluene in acetonitrile with photochemically produced NO 3 and was attributed to an ET mechanism concerted with carbon-hydrogen bond cleavage to give a benzyl radical and a proton.…”

Section: -Promoted Nitration Of Toluenementioning

confidence: 98%

The regiochemistry of the NO₃‐promoted gas phase nitration of toluene and phenol with NO₂

Bolzacchini

Bruschi

Galliani

et al. 2006

J of Physical Organic Chem

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Product studies, kinetic isotope effect measurements, linear free energy relationships and calculations have been used to study the NO 3 -promoted nitration of toluene and phenol in presence of NO 2 . The competition between of a rate-determining hydrogen abstraction of NO 3 to give the benzyl radical and HNO 3 and of a ratedetermining addition-elimination pathway has been evaluated. The preference for the nitration in ortho and para position of toluene and for the ortho position of phenol is suggested to derive from the concerted loss of nitric acid from an intermediate cyclohexadiene.A kinetic analysis suggests reasons for the dependence of the ratio ortho:paranitration from the initial concentration of reactants.

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Kinetics and mechanisms of the gas‐phase reactions of the NO₃ radical with aromatic compounds

Kwok

Atkinson

Arey

1994

Int J of Chemical Kinetics

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The kinetics and nitrated products of the gas-phase reactions of the NO3 radical with methoxybenzene, 1,2-, 1,3-, and 1,4-dimethoxybenzene, dibenzofuran and dibenzo-p-dioxin have been investigated at 297 ? 2 K and in the presence of one atmosphere of air. A relative rate method was used for the kinetic measurements. No reactions of methoxybenzene or dibenzofuran with the NO3 radical were observed. The dimethoxybenzenes were observed to react by H-atom abstraction and NO3 radical addition to the aromatic ring, while dibenzo-p-dioxin reacted by NO3 radical addition to the aromatic rings. For these compounds, the NO3 radical addition pathways were observed to be reversible. At the NO2 concentrations employed, the NO3-aromatic adducts reacted with NO2 and the observed rate constants increased with increasing NO2 concentration. However, for dibenzo-p-dioxin the observed rate constant became independent of the NO2 concentration for concentrations 24.8 X 1013 molecule ~m -~, and under these conditions the rate constant of 6.8 X cm3 molecule-' s-' was taken to be that for addition of the NO3 radical to the aromatic rings. The proposed NO3 radical reaction mechanisms are discussed.

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Products and mechanism of the gas phase reaction between nitrate radical and arenes

Cited by 6 publications

References 9 publications

Comparison between the gas-phase and the solution reaction of the nitrate radical and methylarenes

Comparison between the gas-phase and the solution reaction of the nitrate radical and methylarenes

The regiochemistry of the NO₃‐promoted gas phase nitration of toluene and phenol with NO₂

Kinetics and mechanisms of the gas‐phase reactions of the NO₃ radical with aromatic compounds

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Products and mechanism of the gas phase reaction between nitrate radical and arenes

Cited by 6 publications

References 9 publications

Comparison between the gas-phase and the solution reaction of the nitrate radical and methylarenes

Comparison between the gas-phase and the solution reaction of the nitrate radical and methylarenes

The regiochemistry of the NO3‐promoted gas phase nitration of toluene and phenol with NO2

Kinetics and mechanisms of the gas‐phase reactions of the NO3 radical with aromatic compounds

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Product

Resources

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The regiochemistry of the NO₃‐promoted gas phase nitration of toluene and phenol with NO₂

Kinetics and mechanisms of the gas‐phase reactions of the NO₃ radical with aromatic compounds