Nitroaromatic compounds reduction

Aromatic nitroso compounds usually are considered to be intermediates in the hydrogenation of a nitroaromatic compound to the aromatic hydroxyl-amine or amine. However, nitroso compounds do not accumulate in these reductions, suggesting that they are reduced more easily than are nitro compounds. Catalysts effective for the nitro group should also be effective for nitroso. 

Two important examples of reductive metabolism of xenobiotics are the reductive dehalogenation of organohalogen compounds, and the reduction of nitroaromatic compounds. Examples of each are shown in Figure 2.13. Both types of reaction can take place in hepatic microsomal preparations at low oxygen tensions. Cytochrome P450 can catalyze both types of reduction. If a substrate is bound to P450 in the... 

Glaus M A, CG Heijman, RP Schwarzenbach, J Zeyer (1992) Reduction of nitroaromatic compounds mediated by Streptomyces sp. exudates. Appl Environ Microbiol 58 1945-1951. 

Schwarzenbach RP, R Stierliu, K Lanz, J Zeyer (1990) Quinone and iron porphyrin mediated reduction of nitroaromatic compounds in homogeneous aqueous solution. Environ. Sci. Technol. 24 1566-1574. 

Rafii F, W Franklin, RH Hetlich, CE Cerniglia (1991) Reduction of nitroaromatic compounds by anaerobic bacteria isolated from the human gastrointestinal tract. Appl Environ Microbiol 51 962-968. 

Other bacteria. Intestinal bacteria may play a critical role in the metabolic activation of certain nitroaromatic compounds in animals (119) and several reports have appeared on the metabolism of nitro PAHs by rat and human intestinal contents and microflora (120-123). Kinouchi et al. (120) found that 1-nitropyrene was reduced to 1-aminopyrene when incubated with human feces or anaerobic bacteria. More recently, Kinouchi and Ohnishi (121) isolated four nitroreductases from one of these anaerobic bacteria (Bacteroides fragilis). Each nitroreductase was capable of converting 1-nitropyrene into 1-aminopyrene, and one form catalyzed the formation of a reactive intermediate capable of binding DNA. Howard ej al. (116) confirmed the reduction of 1-nitropyrene to 1-aminopyrene by both mixed and purified cultures of intestinal bacteria. Two additional metabolites were also detected, one of which appeared to be 1-hydroxypyrene. Recently, similar experiments have demonstrated the rapid reduction of 6-nitro-BaP to 6-amino-BaP (123). 

Rafii F, Cemiglia CE (1995) Reduction of azo dyes and nitroaromatic compounds by bacterial enzymes from the human intestinal tract. Env Health Persp 103 17-19... 

Schwarzenbach, R. P., R. Stierli, and J. Zeyer (1990), "Quinone and Iron Porphyrine Mediated Reduction of Nitroaromatic Compounds in Homogeneous Aqueous Solution , Env. Sci. Technol. 24/10, 1566-1574. 

Although most color tests for polynitroaromatic explosives are based on their reaction with bases, a completely different approach involves the reduction of nitroaromatic compound to the corresponding aromatic amine. Zn, SnCl2, and TiCls in acidic medium were used as reducing agents [23—26]. The aromatic amine is then identified by one of two methods ... 

This relationship also conveys one of the reasons why the sensing of explosives can be so effective with this method. Most explosives, especially TNT and other nitroaromatic compounds, are highly electron deficient and have favorable reduction potentials. For instance, the reduction potential of TNT and DNT are only —0.7 and—1.0 V (versus SCE) respectively, quite favorable when compared with other electron acceptors, such as 1,4-dicyanobenzene (—1.7 V versus SCE). This means that if the sensory material emits hght, for example, at 460 nm, the oxidation... 

Nitroaromatic Reduction Nitroaromatics constitute an important class of potential environmental contaminants, because of their wide use in agrochemicals, textile dyes, munitions, and other classes of industrial chemicals. Reduction of nitroaromatics produces amines, throngh a series of electron transfer reactions with nitroso and hydroxylamines as intermediates (Fig. 13.1). Compared to the parent nitroaromatic compound, all intermediates typically reduce readily (Larson and Weber 1994). 

Klupinski et al. (2004) conclude that the reduction of nitroaromatic compounds is a surface-mediated process and suggest that, with lack of an iron mineral, reductive transformation induced only by Fe(II) does not occur. However, when C Cl NO degradation was investigated in reaction media containing Fe(II) with no mineral phase added, a slow reductive transformation of the contaminant was observed. Because the loss of C Cl NO in this case was not described by a first-order kinetic model, as in the case of high concentration of Fe(II), but better by a zero-order kinetic description, Klupinski et al. (2004) suggest that degradation in these systems in fact is a surface-mediated reaction. They note that, in the reaction system, trace amounts of oxidize Fe(II), which form in situ suspended iron oxide... 

Sanders PF, Wolfe NL. 1985. Reduction of nitroaromatic compounds in anaerobic sediment/water systems. Amer Chem Soc 25 225-226. 

The required A-arylhydroxylamines may also be generated in situ by treatment of the corresponding nitrobenzenes with mild reductive metals in liquid hydrogen fluoride323 (former reports324-325). Examples of the reduction of nitroaromatic compounds 12 to fluoroaromatic amines 11 arc given below.323... 

Illustrative Example 14.5 Estimating Rates of Reduction of Nitroaromatic Compounds by DOM Components in the Presence of Hydrogen Sulfide... 

P 14.6 Evaluating the Effect of Substituents on the One-Electron Reduction Potentials of Nitroaromatic Compounds... 

Haderlein, S. B., and R. P. Schwarzenbach, Environmental processes influencing the rate of abiotic reduction of nitroaromatic compounds in the subsurface . In Biodegradation of Nitroaromatic Compounds, J. C. Spain, Ed., Plenum Press, New York, 1995, pp. 199-225. 

Heijman, C. G., E. Grieder, C. Holliger, and R. P. Schwarzenbach, Reduction of nitroaromatic compounds coupled to microbial iron reduction in laboratory aquifer columns , Environ. Sci. Technol., 29, 775-783 (1995). 

Nivinskas, H., R. L. Koder, Z. Anusevicius, J. Sarlauskas, A.-F. Miller, and N. Cenas, Quantitative structure activity relationships in two-electron reduction of nitroaromatic compounds by Entrobacter cloacae NAD(P)H nitroreductase , Arch. Biochem. Biophys., 385, 170-178 (2001). 

Knowledge of the enzymes used by microorganisms in the transformation of nitroaromatic compounds is limited. Blasco Castillo (1993) characterized an inducible nitrophenol reductase from Rhodobacter capsulatus that catalyzed the reduction of 2,4-dinitrophenol (DNP) to 2-amino-4-nitrophenol. This enzyme was a dimer that contained flavin mononucleotide and possibly nonheme iron as... 

The enteric bacterium Enterobacter cloacae produces a nitroreductase that reduces nitrofurans, nitroimidazoles, nitrobenzene derivatives, and quinones (Bryant DeLuca, 1991). This oxygen-insensitive enzyme has been purified and is known to require FMN to transfer reducing equivalents from NAD(P)H to the nitroaromatic compounds, TNT being the preferred substrate. Aerobically, this enzyme reduces nitrofurazone through the hydroxylamine intermediate, which then tautomerizes to yield an oxime end-product. Anaerobically, however, the reduction proceeds to the fully reduced amine adduct. When E. cloacae was grown in the presence of TNT, the nitroreductase activity increased five- to tenfold. 

---