Advances in the application of N2O4/NO2 in organic reactions

Shiri, Morteza; Zolfigol, Mohammad Ali; Kruger, Hendrik G.; Tanbakouchian, Zahra

doi:10.1016/j.tet.2010.09.057

Cited by 75 publications

(40 citation statements)

References 347 publications

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“…In our present system, the NO 2 used for nitration is also regarded as an equilibrium mixture between N 2 O 4 (b.p. 21.3°C at 760 mm Hg) and NO 2 , and the dimer predominates at low temperatures [27]. Metal salts with highly electronegative cations have strong electron-withdrawing ability which is the driving force for the heterolytic disproportionation of dinitrogen tetroxide to [ [24].…”

Section: Catalytic Performance Of Various Metal Saltsmentioning

confidence: 99%

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene

Zhou

You

et al. 2017

Front. Chem. Sci. Eng.

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Metal salts with highly electronegative cations have been used to effectively catalyze the liquid-phase nitration of benzene by NO 2 to nitrobenzene under solventfree conditions. Several salts including FeCl O, Fe 2 (SO 4 ) 3 , and CuSO 4 were examined and anhydrous FeCl 3 exhibited the best catalytic performance under the optimal reaction conditions. The benzene conversion and selectivity to nitrobenzene were both over 99%. In addition, it was determined that the metal counterion and the presence of water hydrates in the salt affects the catalytic activity. This method is simple and efficient and may have potential industrial application prospects.

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Section: Catalytic Performance Of Various Metal Saltsmentioning

confidence: 99%

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene

Zhou

You

et al. 2017

Front. Chem. Sci. Eng.

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“…[9b] It is suggested that the reactiond oes not directly involve NO 2 C,but insteadthe dimer N 2 O 4 , [12] whichisaknown non-radical nitrosating agent in solution,i sp resenta nd exists in both the covalent (ONONO 2 )a nd the ionic form (NO + NO 3 À ). [13][14][15] Thus, in the initial step, a( likelyr eversible) [16] nitrosation of the N-acetyl terminus in dipeptide 1 produces N-nitrosamide 2. The electron-withdrawing effect of the N-nitroso group [9a] leads to activation of the adjacent acyl moiety and enables nucleophilic, intramolecular cyclization of the peptiden itrogen atom.…”

Section: Introductionmentioning

confidence: 99%

Fragmentation–Rearrangement of Peptide Backbones Mediated by the Air Pollutant NO₂^.

Gamon

Nathanael

Taggert

et al. 2015

Chemistry A European J

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The fragmentation-rearrangement of peptide backbones mediated by nitrogen dioxide, NO2 (.) , was explored using di-, tri-, and tetrapeptides 8-18 as model systems. The reaction, which is initiated through nonradical N-nitrosation of the peptide bond, shortens the peptide chain by the expulsion of one amino acid moiety with simultaneous fusion of the remaining molecular termini through formation of a new peptide bond. The relative rate of the fragmentation-rearrangement depends on the nature of the amino acids and decreases with increasing steric bulk at the α carbon in the order Gly>Ala>Val. Peptides that possessed consecutive aromatic side chains only gave products that resulted from nitrosation of the sterically less congested N-terminal amide. Such backbone fragmentation-rearrangement occurs under physiologically relevant conditions and could be an important reaction pathway for peptides, in which sections without readily oxidizable side chains are exposed to the air pollutant NO2 (.) . In addition to NO2 (.) -induced radical oxidation processes, this outcome shows that ionic reaction pathways, in particular nitrosation, should be factored in when assessing NO2 (.) reactivity in biological systems.

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“…47 • NO 2 is also known to dimerize into N 2 O 4 at moderate concentrations which effectively hides its radical character. 48 …”

Section: Introductionmentioning

confidence: 99%

Reactive Nitrogen Species Reactivities with Nitrones: Theoretical and Experimental Studies

Nash¹,

Rockenbauer

Villamena³

2012

Chem. Res. Toxicol.

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Reactive nitrogen species (RNS) such as nitrogen dioxide (•NO2), peroxynitrite (ONOO–), and nitrosoperoxycarbonate (ONOOCO2–) are among the most damaging species present in biological systems due to their ability to cause modification of key biomolecular systems through oxidation, nitrosylation and nitration. Nitrone spin traps are known to react with free radicals and non-radicals via electrophilic and nucleophilic addition reactions, and have been employed as reagents to detect radicals using electron paramagnetic resonance (EPR) spectroscopy, and as pharmacological agents against oxidative stress-mediated injury. This study examines the reactivity of cyclic nitrones such as 5,5-dimethylpyrroline N-oxide (DMPO) with, •NO2, ONOO–, ONOOCO2–, SNAP and SIN-1 using EPR. The thermochemistries of nitrone reactivity with RNS, and isotropic hfsc's of the addition products were also calculated at the PCM(water)/B3LYP/6-31+G**//B3LYP/6-31G* level of theory with and without explicit water molecules in order to rationalize the nature of the observed EPR spectra. Spin trapping of other RNS such as azide (•N3), nitrogen trioxide (•NO3), amino (•NH2) radicals, and nitroxyl (HNO) were also theoretically and experimentally investigated by EPR spin trapping and mass spectrometry. This study also shows other spin traps such as AMPO, EMPO and DEPMPO can react with radical and non-radical RNS, thus, making spin traps suitable probes as well as antioxidants against RNS mediated oxidative damage.

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Advances in the application of N2O4/NO2 in organic reactions

Cited by 75 publications

References 347 publications

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene

Fragmentation–Rearrangement of Peptide Backbones Mediated by the Air Pollutant NO₂^.

Reactive Nitrogen Species Reactivities with Nitrones: Theoretical and Experimental Studies

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Advances in the application of N2O4/NO2 in organic reactions

Cited by 75 publications

References 347 publications

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene

Fragmentation–Rearrangement of Peptide Backbones Mediated by the Air Pollutant NO2.

Reactive Nitrogen Species Reactivities with Nitrones: Theoretical and Experimental Studies

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Fragmentation–Rearrangement of Peptide Backbones Mediated by the Air Pollutant NO₂^.