Nitrite elimination

Hofmann KW, H-J Knackmuss, G Heiss (2004) Nitrite elimination and hydrolytic ring cleavage in 2,4,6-trinitrophenol (picric acid) degradation. Appl Environ Microbiol 70 2854-2860. 

According to the vendor, this project could provide a compact, low-cost reactor to treat aqueous mixed waste streams containing nitrates or nitrites, eliminate the need for chemical reagents, and minimize or eliminate secondary wastes such as nitrous oxide and secondary products such as ammonia, H2, and O2 that are prevalent with other nitrate destruction processes. By removing nitrates and nitrites from waste streams before they are sent to high-temperature thermal destruction and vitrification, production of NO can be decreased with the attendant decrease in off-gas system requirements. Biocatalytic nitrate destruction is applicable to a wide range of aqueous wastes with a highly variable composition. All information is from the vendor and has not been independently verified. 

Qualitative Analysis. Nitric acid may be detected by the classical brown-ring test, the copper-turnings test, the reduction of nitrate to ammonia by active metal or alloy, or the nitrogen precipitation test. Nitrous acid or nitrites interfere with most of these tests, but such interference may be eliminated by acidifying with sulfuric acid, adding ammonium sulfate crystals, and evaporating to alow volume. 

Experiments in which radical scavengers are added indicate that a chain reaction is involved, because the reaction is greatly retarded in the presence of the scavengers. The mechanism shown below indicates that one of the steps in the chain process is an electron transfer and that none of the steps involves atom abstraction. The elimination of nitrite occurs as a unimolecular decomposition of the radical anion intermediate, and the SrnI mechanistic designation would apply. 

Various side-reactions may complicate the course of the Nef reaction. Because of the delocalized negative charge, the nitronate anion 2 can react at various positions with an electrophile addition of a proton at the a-carbon reconstitutes the starting nitro alkane. 1. The nitrite anion can act as leaving group, thus leading to elimination products. 

Tiazofurine (142) is an antimetabolite with antineoplastic activity. It preferentially affects leukemic lymphocytes over normal cells due to selective activation by formation of its adenine dinucleotide by transformed cells. Of the syntheses available, one starts by conversion of iniidate 138 to methyl 2,5-anhydroallonothioate (139). Next, condensation with ethyl 2-amino-2-cyanoac-etate leads to the thioamide which undergoes thiol addition to the nitrile function to produce the amminothiazolecarboxyester system of 140 directly. Sodium nitrite in aqueous hypophosphorus acid eliminates the superfluous amino group via the diazonium transformation to give 141. This synthesis of tiazofurine (142) concludes by ester amide exchange in methanolic ammonia [48]. 

The reacdon pathways for the pyrrole formadon are summarized In Scheme 10.3. The group that is eliminated at the final stage is a nitrite ion (Barton-Zard reacdoni or a tolnenesnlfinate ion (Xensen reacdoni, depending on the reacdon pattern. 

Calcium, iron, magnesium, alkali metals, and citrates do not affect the analysis. Ammonium salts interfere and must be eliminated by means of sodium nitrite or sodium hypobromite. The hydrochloric acid normally used in the analysis may be replaced by an equivalent amount of nitric acid without any influence on the course of the reaction. Sulphuric acid leads to high and erratic results and its use should be avoided. 

Diazonium ions generated from ordinary aliphatic primary amines are usually useless for preparative purposes, since they lead to a mixture of products giving not only substitution by any nucleophile present, but also elimination and rearrangements if the substrate permits. For example, diazotization of n-butylamine gave 25% 1-butanol, 5.2% 1-Chlorobutane, 13.2% 2-butanol, 36.5% butenes (consisting of 71% 1-butene, 20% trans-2-butene, and 9% cw-2-butene), and traces of butyl nitrites. ... 

Another case of high nitrosamine concentration in chlorinated phenoxy- and benzoic acid herbicides was resolved by the elimination by the manufacturer of nitrite salts in the formu-... 

Elimination of nitrosating agents in formulations (e.g. soditim nitrite as corrosion inhibitor for metal containers) use of plastic-lined containers. 

Examples of these improvements are the packaging of dimethylamine products in plastic-lined containers and the elimination of sodium nitrite in the final product. This change in packaging and formulating makes it hi ly probable that N-dimethylnitrosamine will not form during storage of the product. Another example of the improvement of products is that Treflan products today contain less than 1 ppm of N-dipropylnitrosamine (T.) whereas some of the older products contained levels as high as 115-150 ppm several years ago (i, ). 

Dioxygenation may result in the elimination of nitrite in reactions that are analogous to the elimination of sulfite from aromatic sulfonates, or halogen from 2-halobenzoates. As an alternative to dioxygenation, toluene-3- and toluene-4-monooxygenases can transform nitrobenzene to 4- or 3-nitrophenol, with the former dominating (Fishman et al. 2004) ... 

Denitrification can be affected by free ammonia, but this inhibition does not appear up to 300 to 400 mg/L NH3.46 This high concentration can justify that no inhibition of the denitrification process has been reported for this kind of wastewater.3-4 Eiroa and colleagues37 observed that nitrate was eliminated much faster at higher initial urea concentrations. However, they also found an increase of nitrite accumulation, which was later removed, due to high urea concentrations. 

Photochemical elimination reactions include all those photoinduced reactions resulting in the loss of one or more fragments from the excited molecule. Loss of carbon monoxide from type I or a-cleavage of carbonyl compounds has been previously considered in Chapter 3. Other types of photoeliminations, to be discussed here, include loss of molecular nitrogen from azo, diazo, and azido compounds, loss of nitric oxide from organic nitrites, and loss of sulfur dioxide and other miscellaneous species. 

Gianguzza and Orecchio [147] have carried out comparative trials of various methods for estimating nitrites in seawaters. These workers compared a method using sulfanilic acid/a-naphthylamine complexes with a method using sulfanilamide/N( 1-naphthyl) ethylenediamine complexes for the determination of nitrites in saline waters. The second method has the greater sensitivity and lower detection limits. The former method is subject to interference from chlorides, and this interference can be completely eliminated by the coupling diazotisation procedure of the latter method. 

Bajic and Jaselskis [153] described a spectrophotometric method for the determination of nitrate and nitrite in seawater. It included the reduction of nitrate and nitrite to hydroxylamine by the zinc amalgam reactor (Jones reductor) at pH 3.4 and reoxidation of the product with iron (III) in the presence of ferrozine. Interference by high levels of nitrite could be eliminated with azide treatment. Levels of nitrate of 0.1 mg/1 could be detected with a precision of 3% in the presence of large amounts of nitrite and chloride. 

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