Integrated Study of the Dinitrobenzene Electroreduction Mechanism by Electroanalytical and Computational Methods

Mendkovich, A. S.; Syroeshkin, Mikhail A.; Mikhalchenko, Ludmila V.; Михайлов, М. Н.; Русаков, А. И.; Gul’tyai, V. P.

doi:10.4061/2011/346043

Cited by 17 publications

(10 citation statements)

References 60 publications

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“…This is also consistent with the behaviour observed for dinitroaromatics in conventional organic solvents. [7,8,10] The electron count for the second peak is much harder to deduce, but is likely to be larger than one in most RTILs due to the larger currents and less reversible shapes of the voltammograms for peak 2 observed in Fig. 2, suggesting that follow-up chemistry is occurring.…”

Section: Voltammetry Of Dnt In Different Rtilsmentioning

confidence: 97%

“…In protic solvents, the generally accepted mechanism is the reduction of the nitro groups of DNT to hydroxylamine or amine groups, depending on the pH of the solution. [7][8][9] However, the mechanism is different in aprotic solvents (e.g. acetonitrile or DMF), [7,8,10] where DNT is reduced by one electron to the radical anion in the first step, and in the second step to the dianion.…”

mentioning

confidence: 99%

“…[7][8][9] However, the mechanism is different in aprotic solvents (e.g. acetonitrile or DMF), [7,8,10] where DNT is reduced by one electron to the radical anion in the first step, and in the second step to the dianion. Follow-up chemical reactions are often observed for these highly basic species at more negative potentials.…”

mentioning

confidence: 99%

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Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation

2018

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The reduction mechanism of 2,4-dinitrotoluene (DNT) has been studied in eight room temperature ionic liquids (RTILs) using cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry, and digital simulation. Two distinctive peaks are observed in the voltammetry, corresponding to the stepwise reduction of the two nitro groups on the aromatic ring. Diffusion coefficients (D) and electron counts (n) were calculated from chronoamperometric transients, revealing an electron count of one in most RTILs, and a linear relationship between D and the inverse of viscosity. Focusing on the first reduction only, the peak appears to be chemically reversible at low concentrations. However, as the concentration increases, the current of the reverse peak diminishes, suggesting that one or more chemical steps occur after the electrochemical step. The results from digital simulation of the CVs in one of the RTILs reveal that the most likely mechanism involves a deprotonation of the methyl group of a parent DNT molecule by the electrogenerated radical anion and/or a dimerisation of two electrogenerated radical anions. Elucidation of the reduction mechanism of DNT (and other explosives) is vital if electrochemical techniques are to be employed to detect these types of compounds in the field.

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Section: Voltammetry Of Dnt In Different Rtilsmentioning

confidence: 97%

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confidence: 99%

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Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation

2018

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“…Compounds having such properties can be particularly useful for the development of approaches to the therapy of hypoxic tumors, which are difficult to treat with cytotoxic drugs with other mechanisms of action . The key feature of PI‐ORs examined in the present work is the presence of the relatively weak N―O bond, which is susceptible to cleavage via reductive 1‐electron transfer . These compounds provide an interesting counterpart to organic peroxides, a related class of biologically active antiparasitic and antitumor compounds containing a weak O―O bond.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical behavior of N‐oxyphthalimides: Cascades initiating self‐sustaining catalytic reductive N―O bond cleavage

Syroeshkin

Krylov

Hughes

et al. 2017

J of Physical Organic Chem

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N-oxyphthalimides are stable and easily accessible compounds that can produce oxygen radicals upon 1-electron reduction. We present a systematic study of electrochemical properties of N-oxyphthalimide derivatives (PI-ORs) in DMF by cyclic voltammetry. In all cases, electron transfer to the substrate leads to decomposition of the intermediate radical anion via the N-O bond cleavage. In the case of benzyloxyphthalimide or its derivatives containing electrondonating substituents, reductive electron transfer induces the chain decomposition of the substrate to phthalimide (PI) radical-anion and the corresponding carbonyl compound. The PI radical-anion product is a powerful reductant that can transfer an electron to the reactant PI-OR, thus establishing a catalytic cycle for reductive N-O scission. This self-catalytic process is reflected in a considerable decrease in the reduction current for the substrate (<1e -/molecule). By contrast, reductive fragmentations of benzyl derivatives containing electronwithdrawing substituents in the aromatic ring or at the benzylic position, as well as tosyl and alkyl derivatives, occur via a 1-electron mechanism. A sequence of N-O and C-C scissions was engineered to support the intermediacy of O-centered radicals in these processes.

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“…The RA of compound 2 is formed at the potential 200 mV more negative than the RA of compound 1; hence, bearing in mind the data of [24] on the correlation between the basicity of RA of aromatic compounds and the potential of their formation, we can state that the RA 2 enters into protonation reactions at the higher rate than the RA of compound 1.…”

Section: Resultsmentioning

confidence: 92%

Electroreduction of Derivatives of N,N'-Dioxides of Phenazine and Quinoxaline in Nonaqueous Media and in the Presence of Proton Donors of Medium Strength

et al. 2020

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The electroreduction (ER) of benzo[a]phenazine-7,12-dioxide (1) and 2-ethoxycarbonyl-3methyl-quinoxaline-1,4-dioxide (2) in DMF on a glassy carbon electrode is studied by the methods of cyclic voltammetry, chronoamperometry, and electrolysis at controlled potential. In aprotic medium, these compounds are reduced to form relatively stable complexes as observed in both cyclic voltammetry curves and UV spectra. The deoxygenation of the derivatives of phenazine and quinoxaline N,N′-dioxides proceeds as a result of decomposition of the radical formed either at the ER of complexes of these compounds with СН 3 СООН or as a result of protonation of radical anions. For compound 2, the competition between the reactions of decomposition and ER of this radical is observed.

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Integrated Study of the Dinitrobenzene Electroreduction Mechanism by Electroanalytical and Computational Methods

Cited by 17 publications

References 60 publications

Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation

Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation

Electrochemical behavior of N‐oxyphthalimides: Cascades initiating self‐sustaining catalytic reductive N―O bond cleavage

Electroreduction of Derivatives of N,N'-Dioxides of Phenazine and Quinoxaline in Nonaqueous Media and in the Presence of Proton Donors of Medium Strength

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