3-amino-2,4,6-trinitrotoluene

Trinitrotoluene (TNT) is reduced by the aquatic plant Myriophyllum spicatum to ami-nodinitrotoluenes (Pavlostathis et al. 1998) and, in axenic root cultures of Catharanthus roseus, the initial metabolites 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dintrotoluene... 

Clostridium bifermentans reduced 2,4,6-trinitrotoluene to 2,4,6-triaminotoluene, and a metabolite was formed by reaction of one of the amino groups with methylglyoxal (Lewis et al. 1996). 

The degradation of 2,4,6-trinitrotoluene under aerobic conditions is strictly dependent on the reduction of one or more nitro groups to amino groups before dioxygenation (Fiorella and Spain 1997 Johnson et al. 2001). 

The choice of solid-phase microextraction sorbent phase was shown to be important especially for the amino metabolities of trinitrotoluene and RDX, which were extracted better on polar phases. Although equilibration times were quite lengthy, on the order of 30 min or greater, a sampling time of only 10 min was shown to be sufficient for achieving low part-per-billion (ppb) to part-per-trillion (ppt) detection limits for trinitrotoluene and the amino metabolities in real seawater samples. Solid-phase microextraction was ideal for rapid screening of explosives in seawater samples. 

Wang, C. J., Thiele, S., and Bollag, J. M., 2002, Interaction of 2,4,6-trinitrotoluene (TNT) and 4-amino-2,6-dinitrotoluene with humic monomers in the presence of oxidative enzymes. Arch. Environ. Contam. Toxicol. 42 1-8. 

Haidour and Ramos (1996) analyzed the degradation products of 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene by the bacterium Pseudomonas sp. clone A under aerobic conditions utilizing 2,4-dinitrotoluene as a source of nitrogen. Two metabolites tentatively identified were 2-amino-4-nitrotoluene and 4-amino-2-nitrotoluene. Also, three azoxytoluenes were identified 4,4 -dinitro-2,2 -azoxytoluene, 2,2 -dinitro-4,4 -azoxytoluene, and 2,4 -dinitro-2, 4-azoxytoluene. 2-Amino-4-nitrotoluene and 4-amino-2-nitrotoluene were also identified as products of 2,4-dinitrotoluene metabolism by Clostridium acetobutylicum via the hydroxyl-aminonitrotoluene intermediates, namely 4-hydroxylamino-2-nitrotoluene and 2-hydroxylamino-4-nitrotoluene (Hughes et al., 1999). 

Amino-4,6-dinitrotoluene, see 2.4.6-Trinitrotoluene 4-Amino-2,6-dinitrotoluene, see 2.4.6-Trinitrotoluene 4-Aminodiphenylamine, see Aniline... 

Chemists at the Naval Air Warfare Center (NAWC), Weapons Division, China Lake, have reported many examples of polynitroarylamine synthesis via Bamberger rearrangements of arylnitramines. " " The nitration of 4-amino-2,5-dinitrotoluene (36) with a mixture of nitric acid and acetic anhydride in glacial acetic acid at room temperature yields the nitramine (37) which on treatment with neat sulfuric acid, provides 4-amino-2,3,5-trinitrotoluene (38) as the sole product. " Nitration of 3,4-dinitroaniline (39) with a solution of nitric acid in acetic anhydride yields A,3,4-trinitroaniline (40) acid-catalyzed rearrangement of the latter in neat sulfuric acid furnishes a 74 % yield of isomeric 2,3,4- (41) and 2,4,5- (42) trinitroanilines in a 4 6 ratio.Accordingly, a mixture of products can be expected when an unsymmetrical arylnitramine has two unsubstituted ortho positions available. 

From a practical point of view, reduction of NACs is of great interest for two reasons. First, the amino compounds formed may exhibit a considerable (eco)toxi-city, and therefore may be of even greater concern as compared to the parent compounds. Additionally, the reduced products may react further with natural matrices, in particular with natural organic matter, thus leading to bound residues (see sections on oxidations below). One prominent example involves the reduction products of the explosive, 2,4,6-trinitrotoluene (TNT see Fig. 14.6), particularly the two isomeric diaminonitrotoluenes (2,4-DA-6-NT and 2,6-DA-4-NT) and the completely reduced triaminotoluene (TAT). These have been found to bind irreversibly to organic matter constituents present in soils (Achtnich et al., 2000) and sediments (Elovitz and Weber, 1999). This process offers interesting perspectives for the treatment of NAC contaminated sites. In fact, a dual step anaerobic/aerobic soil slurry treatment process has been developed for remediation of TNT contaminated soils (Lenke et al., 2000). 

Explosives and related compounds have become widely recognized as serious environmental contaminants. Among the nitrosubstituted aromatic compounds causing particular concern are 2,4,6-trinitrotoluene (TNT), 2,4,6-trinitrophenol (picric acid), and many nitro- and/or amino-substituted aromatics that result from the manufacture and transformation of explosives. The threat posed by the presence of these compounds in soil and water is the result of their toxicity and is compounded by their recalcitrance to biodegradation. 

Stock solutions (1000 mg/L in acetonitrile) of 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB), 2,4-dinitrotoluene (2,4-DNT), and 4-amino-2,6-dinitrotoluene (4-Am-2,6-DNT) (Supelco). Sodium dodecyl sulfate (SDS) and sodium borate 10-hydrate. Standard solutions of the various explosives should be prepared daily (using the proper safety precautions) in an SDS-containing electrophoresis buffer. Platinum and silver wires, 0.1mm diameter. 

Dissolve 100 grams of 2,4,6-trinitrotoluene into 200 milliliters of p-dioxane, and then place the mixture into a cold-water bath. Then stir the mixture, and add 2 milliliters of 28 - 30% ammonium solution. Then bubble 46 grams of hydrogen sulfide gas into the mixture over a 2-hour period while keeping the reaction temperature at 20 Celsius by means of the cold-water bath, and stir the reaction mixture continuously during the addition. After the addition of the hydrogen sulfide gas, filter off the precipitated sulfur, and then add the filtered reaction mixture to 1000 milliliters of ice water. After which, filter off the yellow precipitated solid, and then wash the solid with 400 milliliters of water. Then vacuum dry or air-dry the solid. The result is a mixture of the desired 4-amino-2,6-dinitrotoluene (61%), and the by-product, 4-hydroxylamino-2,6-dinitrotoluene (39%). 

Anaerobic extracts of Clostridium acetobutylicum reduced 2,4,6-trinitrotoluene to 2,4-dihydroxylamino-6-nitrobenzene that underwent an enzymatic Bamberger-type rearrangement to 2-amino-4-hydrox-ylamino-5-hydroxy-6-nitrotoluene (Hughes et al. 1998). This is especially remarkable since the enzymatic activity was not dependent on the presence of nitroaromatic compounds as growth substrates. 

The other major use of nitric acid is in organic nitration. Nitration using mixtures of sulfuric and nitric acid is the first step in the synthesis of amino-and nitro-compounds such as aniline and trinitrotoluene (TNT). Many important dyes and pharmaceuticals are ultimately derived from these reactions. However, their quantities are quite small. Polyurethane polymers are also ultimately derived from nitrated toluene and benzene and this use accounts for 5—10% of nitric acid end uses. 

Most studies in the microbial metabolism of nitroaromatic compounds used aerobic microorganisms. In most cases no mineralization of nitroaromatics occurs, and only superficial modifications of the structures are reported. However, under anaerobic sulfate-reducing conditions, the nitroaromatic compounds reportedly undergo a series of reductions with the formation of amino compounds. For example, trinitrotoluene under sulfate-reducing conditions is reduced to triaminotoluene by the enzyme nitrite reductase, which is commonly found in many Desulfovibrio spp. The removal of ammonia from triaminotoluene is achieved by reductive deamination catalyzed by the enzyme reductive deaminase, with the production of ammonia and toluene. Some sulfate reducers can metabolize toluene to (X) sub 2. Similar metabolic processes could be applied to other nitroaromatic compounds like nitrobenzene, nitrobenzoic acids, nitrophenols, and aniline. Many methanogenic bacteria can reduce nitroaromatic compounds to amino compounds. 

Sarlauskas J et al., Flavoenzyme-catalyzed redox cycling of hydroxyl-amino and amino metabolites of 2,4,6-trinitrotoluene Implications for their cytotoxicity, Arch. Biochem. Biophys., 425, 184, 2004. 

Trinitrotoluene (TNT) is the most commonly used energetic compound and found in the soils at U.S. Army installations [16,17], Military grades of TNT contain up to 8% DNTs (2,4-dinitrotoluene and 2,6-dinitrotoluene) as manufacturing impurities, and TNT is often degraded to DNT in hydric soils (i.e., wet anaerobic environments) [18,19], Other compounds are also generated when TNT is degraded (e.g., 2-amino-4,6-dinitrotoluene [2-ADNT], 4-amino-2,6-dinitrotoluene [4-ADNT], 1,3,5-trinitrobenzene [TNB], and others). Contamination from TNT, DNTs, and their environmental breakdown products is known to persist in soil for years [20],... 

Composites of PANI-NFs, synthesized using a rapid mixing method, with amines have recently been presented as novel materials for phosgene detection [472]. Chemiresistor sensors with nanofibrous PANI films as a sensitive layer, prepared by chemical oxidative polymerization of aniline on Si substrates, which were surface-modified by amino-silane self-assembled monolayers, showed sensitivity to very low concentration (0.5 ppm) of ammonia gas [297]. Ultrafast sensor responses to ammonia gas of the dispersed PANI-CSA nanorods [303] and patterned PANI nanobowl monolayers containing Au nanoparticles [473] have recently been demonstrated. The gas response of the PANI-NTs to a series of chemical vapors such as ammonia, hydrazine, and triethylamine was studied [319,323]. The results indicated that the PANI-NTs show superior performance as chemical sensors. Electrospun isolated PANI-CSA nanofiber sensors of various aliphatic alcohol vapors have been proven to be comparable to or faster than those prepared from PANI-NF mats [474]. An electrochemical method for the detection of ultratrace amount of 2,4,6-trinitrotoluene with synthetic copolypeptide-doped PANI-NFs has recently been reported [475]. PANI-NFs, prepared through the in situ oxidative polymerization method, were used for the detection of aromatic organic compounds [476]. 

A very flexible way of getting new, simple names for compounds can be to combine a bit of systematic nomenclature with trivial nomenclature. Alanine is a simple amino acid that occurs in proteins. Add a phenyl group and you have phenylalanine, which is a more complex amino acid also in proteins. Toluene, the common name for methylbenzene, can be combined (both chemically and in making names for compounds ) with three nitro groups to give the famous explosive trinitrotoluene or TNT. 

To a flask were added 10 mL cone. H2SO4 and 0.5 g 4-amino-A,2,5-trinitrotoluene (2.06 mmol). The mixture was cooled at 0°C, stirred for 69 h, and then poured into 100 mL ice water. The resulting precipitate was filtered off and washed with water to give 0.44 g... 

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