Nitrite ions, oxidation with

Oxidation. Nitroparaffins are resistant to oxidation. At ordinary temperatures, they are attacked only very slowly by strong oxidi2ing agents such as potassium permanganate, manganese dioxide, or lead peroxide. Nitronate salts, however, are oxidi2ed more easily. The salt of 2-nitropropane is converted to 2,3-dimethyl-2,3-dinitrobutane [3964-18-9], acetone, and nitrite ion by persulfates or electrolytic oxidation. With potassium permanganate, only acetone is recovered. 

Nucleophilic displacement of iodide by the nitrite ion in 1-iodo-17/. l//,2//,2W-perfluoroalkanes affords the 1-nitro analogue (equation 4). Oxidative nitration of the 1-mtro-l//, l//,2//.2//-perfluoroalkane with tetranitromethane yields the ge/n-dinitro compound [4. ... 

Nitrite ion is often used in plutonium solvent extraction systems to oxidize Pu(III) to Pu(IV) and to reduce Pu(VI) to Pu(IV). But HONO, produced in HN03 media, is extractable into TBP-diluent systems and can interfere with subsequent reductive stripping of plutonium. There is thus a need to find a reagent comparable to nitrite ion in its reactions with Pu(III) and Pu(VI), but which does not extract into TBP solutions. 

Cyanide and thiocyanate anions in aqueous solution can be determined as cyanogen bromide after reaction with bromine [686]. The thiocyanate anion can be quantitatively determined in the presence of cyanide by adding an excess of formaldehyde solution to the sample, which converts the cyanide ion to the unreactive cyanohydrin. The detection limits for the cyanide and thiocyanate anions were less than 0.01 ppm with an electron-capture detector. Iodine in acid solution reacts with acetone to form monoiodoacetone, which can be detected at high sensitivity with an electron-capture detector [687]. The reaction is specific for iodine, iodide being determined after oxidation with iodate. The nitrate anion can be determined in aqueous solution after conversion to nitrobenzene by reaction with benzene in the presence of sulfuric acid [688,689]. The detection limit for the nitrate anion was less than 0.1 ppm. The nitrite anion can be determined after oxidation to nitrate with potassium permanganate. Nitrite can be determined directly by alkylation with an alkaline solution of pentafluorobenzyl bromide [690]. The yield of derivative was about 80t.with a detection limit of 0.46 ng in 0.1 ml of aqueous sample. Pentafluorobenzyl p-toluenesulfonate has been used to derivatize carboxylate and phenolate anions and to simultaneously derivatize bromide, iodide, cyanide, thiocyanate, nitrite, nitrate and sulfide in a two-phase system using tetrapentylammonium cWoride as a phase transfer catalyst [691]. Detection limits wer Hi the ppm range. 

It follows from the above that MPO may catalyze the formation of chlorinated products in media containing chloride ions. Recently, Hazen et al. [172] have shown that the same enzyme catalyzes lipid peroxidation and protein nitration in media containing physiologically relevant levels of nitrite ions. It was found that the interaction of activated monocytes with LDL in the presence of nitrite ions resulted in the nitration of apolipoprotein B-100 tyrosine residues and the generation of lipid peroxidation products 9-hydroxy-10,12-octadecadienoate and 9-hydroxy-10,12-octadecadienoic acid. In this case there might be two mechanisms of MPO catalytic activity. At low rates of nitric oxide flux, the process was inhibited by catalase and MPO inhibitors but not SOD, suggesting the MPO initiation. 

An improved HPLC-photohydrolysis-colorimetry method was validated for twenty-eight reference nitrosamines. These were separated by HPLC and photolytically cleaved by UV radiation. The resulting nitric oxide was oxidized and hydrolyzed to nitrite ions, which were derivatized into an azo dye with Griess reagent and measured spectrophoto-metrically. The method was applied to separate and detect hitherto unknown nonvolatile nitrosamines in biological fluids and food extracts591. 

One-electron reduction at the cathode in the presence of cyanide leads to anion-radical of 4-iodonitrobenzene. Like other halide derivatives, 4-iodonitrobenzene in the anion-radical state easily expels the halide ion and converts into 4-nitrophenyl radical. The latter reacts with cyanide ion and produces anion-radical of 4-cyanonitrobenzene. The same anion-radical can be obtained by reducing the 4-cyanobenzenediazonium salt with dithionite in the presence of nitrite. One-electron oxidation with the initial substrate converts this anion-radical into 4-cyanonitrobenzene. 

Aromatic cation-radicals can also react with NOj", giving nitro compounds. Such reactions proceed either with a preliminary prepared cation-radical or starting from nncharged componnd if iodine and silver nitrite are added. As for mechanisms, two of them seem feasible—first, single electron transfer from the nitrite ion to a cation-radical and second, nitration of ArH with the NOj radical. This radical is quantitatively formed when iodine oxidizes silver nitrite in carbon tetrachloride (Neelmeyer 1904). 

An attempt to combine electrochemical and micellar-catalytic methods is interesting from the point of view of the mechanism of anode nitration of 1,4-dimethoxybenzene with sodinm nitrite (Laurent et al. 1984). The reaction was performed in a mixture of water in the presence of 2% surface-active compounds of cationic, anionic, or neutral nature. It was established that 1,4-dimethoxy-2-nitrobenzene (the product) was formed only in the region of potentials corresponding to simultaneous electrooxidation of the substrate to the cation-radical and the nitrite ion to the nitrogen dioxide radical (1.5 V versus saturated calomel electrode). At potentials of oxidation of the sole nitrite ion (0.8 V), no nitration was observed. Consequently, radical substitution in the neutral substrate does not take place. Two feasible mechanisms remain for addition to the cation-radical form, as follows ... 

A similar mechanism was invoked by Ohshima and Kawabata (2) to account for their results in the nitrosation of tertiary amines and amine oxides. In applying these concepts to the nitrosative dealkylation of tetraalkyltetrazenes, Michejda al. 5) introduced an interesting variant by suggesting that immonium ions could be formed in two successive one-electron oxidation steps (for example by ferric ion oxidation of tertiary amine to the radical cation followed by radical abstraction of a hydrogen atom from the alpha position), rather than exclusively through the one-step removal of a hydride ion as nitroxyl. The resulting immonium ion was again considered to react directly with nitrite to produce the N-nitroso derivative. These reactions are summarized in Fig. 2b. 

When the reaction of methyl 5,6-dideoxy-2,3-di-0-p-tolylsulfonyl-a-L-arafoino-hex-5-enofuranoside with silver nitrite and iodine was performed in more-polar solvents, such as methanol and acetonitrile, a /3-iodo nitrate was produced, in addition to the C-iodo-C-nitro adduct 88 in methanol, the ratio of the two products was130 3 2. The /3-iodo nitrate was identical with the adduct obtained by the reaction of the alkene with silver nitrate and iodine in acetonitrile.132 The formation of the /3-iodo nitrate in the silver nitrite-iodine reaction in polar solvents may be due to the increased solubility of the silver nitrite the available nitrite ions could then be oxidized to nitrates. The positions of the iodo and nitrate groups in the adduct have not yet been established. 

The spontaneous reaction of nitric oxide with thiols is slow at physiological pH and the final product under anaerobic conditions is not a nitrosothiol (Pryor et al., 1982). The reaction is slow because it involves the conjugate base of the thiol (R—S"). At pH 7.0, the oxidation of cysteine by nitric oxide required 6 hr to reach completion and yields RSSR and N 2O as the products. The synthetic preparation of nitrosothiols usually involves the addition of nitrosonium ion from acidified nitrite to the thiol, or oxidation of the thiol with nitrogen dioxide under anaerobic conditions in organic solvents. Nitric oxide will form nitrosothiols by reaction with ferric heme groups, such as found in metmyoglobin or methemoglobin (Wade and Castro, 1990). It is also possible that nitrosyldioxyl radical also reacts with thiols to form a nitrosothiol. 

Four routes to form peroxynitrite from nitric oxide. The reaction of nitric oxide with superoxide is only one mechanism leading to the formation of peroxynitrite. Supetoxide could also reduce the nitrosyidioxyl radical. If nitric oxide is directly reduced to nitroxyl anion, it will react with molecular oxygen to form peroxynitrite. At acidic pH, nitrite may form nitrous acid and nitrosonium ion, which reacts with hydrogen peroxide to form peroxynitrite. 

At low acid concentrations, nitric oxide tends to form. This evidently may attack nitrosophenol to form diazonium compounds directly. The diazonium salts, in turn, may couple with unreacted phenol to give colored products. Nitrous acid may also produce nitrophenols from phenols. The mechanism of this reaction may involve oxidation of initially formed nitrosophenols, homolytic attack by nitrogen dioxide, or nucleophilic attack by nitrite ions [1]. 

Electrochemical oxidation of 2,3,4,5-tetraphenylpyrrole in aqueous media yields 3,3,4,5-tetraphenylpyrrolin-2-one, whereas when the oxidation is conducted in nitromethane, nucleophilic attack by the nitromethyl anion and subsequent rearrangement of the adduct with the extrusion of the nitrite ion lead to the formation of 2,3,4,6-tetraphenylpyridine (B-77MI30507, 81H(15)495>. 

The ability of copper ions to undergo reversible changes in oxidation state permits them to function in a variety of oxidation-reduction processes. Like iron, copper also provides sites for reaction with 02, with superoxide radicals, and with nitrite ions. 

A group of slow-growing denitrifying bacteria obtain energy by oxidizing ammonium ions anaerobically with nitrite ions.613 614... 

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