Trinitrotoluene compounds

In comparison with the production of dinitrotoluene compounds, the production of trinitrotoluene is of relatively little importance today. Either toluene or surplus 2-nitrotoluene can be used as raw materials. 

The manufacture of 2,4,6-trinitrotoluene (TNT), a traditionally important explosive, is mainly continuous, with units of 4 to 6 nitration reactors and separators for the separation of sparingly soluble nitrotoluenes in the nitration mixture. The reactants toluene and nitrating acid (16.5% HNO3, 83.5% H2SO4) are fed counter-currently into the cascade reactor. In the first reactor, mononitrotoluene is the predominant product, while in subsequent reactors further nitration takes place. The reaction proceeds with an increase in temperature from 50 to 100 °C. 

The crude trinitrotoluene is worked up by washing with water and soda solution or with sodium sulfite solution to remove the less stable asymmetric isomers which lower the crystallizing point of 2,4,6-TNT. The electron-withdrawing effect of the nitro groups of the asymmetric isomers facilitates nucleophilic substitution by OH or HSO3 groups, even at ambient temperature, so that the reaction products are water-soluble. The crystallizing point of the purified TNT should be at least 80.6 °C. When mixed with 20% aluminum, TNT is marketed under the trade name Tritonal , and when mixed with 50% ammonium nitrate, it is sold under the trade name Amatol . 

---

Organic Reactions. Nitric acid is used extensively ia iadustry to nitrate aHphatic and aromatic compounds (21). In many iastances nitration requires the use of sulfuric acid as a dehydrating agent or catalyst the extent of nitration achieved depends on the concentration of nitric and sulfuric acids used. This is of iadustrial importance ia the manufacture of nitrobenzene and dinitrotoluene, which are iatermediates ia the manufacture of polyurethanes. Trinitrotoluene (TNT) is an explosive. Various isomers of mononitrotoluene are used to make optical brighteners, herbicides (qv), and iasecticides. Such nitrations are generally attributed to the presence of the nitronium ion, NO2, the concentration of which iacreases with acid strength (see Nitration). 

Industrial. Nitric acid is itself the starting material for ammonium nitrate, nitroglycerin [55-63-0] trinitrotoluene [118-96-7]., nitroceUulose [9004-70-0] and other nitrogen compounds used in the manufacture of explosives (see Explosives and propellants). Nitric acid is made by oxidation of ammonia to nitrogen dioxide [10102-44-0] which is subsequently absorbed by water. 

Toxic Effects on the Blood-Forming Tissues Reduced formation of erythrocytes and other elements of blood is an indication of damage to the bone marrow. Chemical compounds toxic to the bone marrow may cause pancytopenia, in which the levels of all elements of blood are reduced. Ionizing radiation, benzene, lindane, chlordane, arsenic, chloramphenicol, trinitrotoluene, gold salts, and phenylbutazone all induce pancytopenia. If the damage to the bone marrow is so severe that the production of blood elements is totally inhibited, the disease state is termed aplastic anemia. In the occupational environment, high concentrations of benzene can cause aplastic anemia. 

The action of hydroxylamine and sodium acetate in ethanol upon picryl chloride was stated to give 4,6-dinitrobenzofuroxan, and probably some of this compound was formed, although it was later shownthat much of the original work was faulty. A report that hydroxylamine and 2,4,5-trinitrotoluene give 5-methyl-6-nitro-benzofuroxan has been found to be incorrect. Benzofuroxan has not been prepared by V-oxidation of benzofurazan, and it seems unlikely that this could be achieved, since benzofuroxan itself is oxidizable by powerful reagents to o-dinitrobenzene (Section VI, B). A report of the oxidation by nitric acid of anthraceno[l,2-c]furazan to the furoxan is incorrectlv abstracted. 

Of the eight nonmetals listed in Table 21.1, nitrogen is by far the least reactive. Its inertness is due to the strength of the triple bond holding the N2 molecule together (B.E. N=N = 941 kj/mol). This same factor explains why virtually all chemical explosives are compounds of nitrogen (e.g., nitroglycerin, trinitrotoluene, ammonium nitrate,... 

C04-0139. Compounds that undergo explosions typically produce large quantities of hot gases from much smaller volumes of highly reactive solids or liquids. Balance the reaction for the decomposition of trinitrotoluene (TNT), a violent explosive C7 H5 N3 Og(/) N2(g) + C02(g) + H2 0(g) + C(,3 )... 

C05-0138. In an explosion, a compound that is a solid or a liquid decomposes very rapidly, producing large volumes of gas. The force of the explosion results from the rapid expansion of the hot gases. For example, TNT (trinitrotoluene) explodes according to the following balanced equation ... 

Effects of functional group repetition and close groups. The presence of a sole site with an unstable characteristic often leads to more or less stable molecule. Nevertheless, its repetition puts an end to this stability. Thus, if nitrobenzene is a satisfactorily stable compound, this is not the case for m-dinitrobenzene, trinitrotoluene (TNT) or trinitrophenol, which are all strong explosives, especially TNT. 

The temperature of explosive decomposition of trinitrotoluene very much depends on the compound purity. The table below shows the influence of various impurities on this compound. 

TNT The abbreviation for trinitrotoluene. It is a much more stable compound than nitroglycerine but still capable of producing a powerful explosion when detonated. 

Several nitro compounds are soluble in chlorine trifluoride, but the solutions are extremely shock-sensitive. These include trinitrotoluene, hexanitrobiphenyl, hexanitrodiphenyl-amine, -sulfide or -ether. Highly chlorinated compounds behave similarly. 

The Sundberg indole synthesis using aromatic azides as precursors of nitrenes has been used in synthesis of various indoles. Some kinds of aryl azides are readily prepared by SNAr reaction of aromatic nitro compounds with an azide ion. For example, 2,4,6-trinitrotoluene (TNT) can be converted into 2-aryl-4,6-dinitroindole, as shown in Eq. 10.60.83... 

The most famous explosive is trinitrotoluene, or TNT, which was mainly used in warfare in both world wars, as well as in mining and building. TNT is still widely used and produced. Most of the current problems with TNT and nitroarene compounds are found in sites where ammunition was handled, stored or manufactured. TNT is a persistent contaminant, but its microbial degradation is possible both aerobically [63] and anaerobically [64]. 

An important demonstrated application of this artificial nose system is the high-speed detection of low levels of explosives and explosive-like vapors. Several sensors, based on Nile Red attached to silica microspheres, show high sensitivity to nitroaromatic compounds (NAC) within a mixture12. Different fluorescence response profiles were observed for several NAC s, such as 1,3,5-trinitrotoluene (TNT) and 1,3-dinitrobenzene (DNB), despite their similar structures. These responses were monitored at low concentrations of the NAC vapors (ca. 5 ppb) and at short vapor exposure... 

By further nitration with more concentrated acid o- and p-nitro-phenols are converted into the same 2 4-dinitrophenol, and finally into picric acid. Polynitro-derivatives of benzene, such as picric acid and trinitrotoluene, can be caused to explode by detonation with mercury fulminate or lead azide. (The formulae of these two compounds should be written.) They are endothermic, i.e. the oxygen of the nitro-group can oxidise carbon and hydrogen within the molecule and heat is liberated. This intramolecular combustion is rather considerable in the case of picric acid, which is decomposed in accordance with the equation ... 

This includes bioremediation cases of contaminated sites with several toxic and carcinogenic pollutants, such as petroleum hydrocarbons, PAHs, dichlorobenzene, chlorinated hydrocarbons, carbon tetrachloride, Dicamba, methyl bromide, trinitrotoluene, silicon-based organic compounds, dioxins, alkyl-phenol polyethoxylates, nonylphenol ethoxylates, and polychlorinated biphenyls. The following is a brief summary of each case. 

The most serious contamination was recognized as a result of production as well as use of 2,4,6-trinitrotoluene (TNT), mainly because of vast amount of water necessary for manufacturing of this compound made it necessary to locate the factories near natural sources of water - mostly rivers. The environment around large rivers is usually characterized by sand-rich soil that allows easy seepage of rainwater. NACs are therefore... 

We concentrate our effort to phytoremediation of 2,4,6-trinitrotoluene (TNT) as the main contaminant of former and present ammunition factories and to nitroesters (PETN, NG) in the Czech Republic and in Germany. In our experiments, we studied the uptake, degradation and distribution of these compounds in plants and its degradation products in plant tissues and its subsequent utilisation for real application both for soil and waste-waters cleaning. 

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. The bacterium utilized 2,6-dinitrotoluene as a source of nitrogen yielding two compounds 2-amino-6-toluene and 6,6 -dinitro-2,2 -azoxytoluene. 2-Hydroxylamino-6-nitro-toluene and subsequent formation of 2,6-dihydroxyaminotoluene were reported as intermediate products of 2,6-dinitrotoluene metabolism by Clostridium acetobutylicum. 2,6-Diaminotoluene was reported as the end product (Hughes et al., 1999). 

It has been known for a long time that polynitroaromatic compounds produce colored products in contact with aUcafis [1]. These color reactions have been extensively used for the identification of nitroaromatic explosives. In the Janowski reaction [7], a solution of the polynitroaromatic compound (di- or trinitroaromatic) in acetone is treated with concentrated aqueous KOH solution. 1,3,5-Trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT), treated with 30% aqueous KOH, produced violet-red and red colors, respectively. Many variations of the Janowski reaction were reported, using KOH or NaOH in aqueous or ethanoHc solutions as reagents, and dissolving the explosives in acetone, ethanol or acetone-ethanol mixture [3,8]. The reaction was used both for spot tests and for spraying TLC plates [9]. 

Nitration via diazotisation has been extensively used for the synthesis of isomeric dinitronaphthalenes. Ward and co-workers used nitration via diazotisation to prepare 3,3, 4,4 -tetranitrobiphenyl from 3,3 -dinitrobenzidine, and 3,4,5-trinitrotoluene from 3,5-dinitro-4-toluidine. Ward and Hardy " prepared 1,4,6-trinitronaphthalene from 4,7-dinitro-1-naphthylamine. Korner and Contardi used the nitrate salts of aryldiazonium compounds for the synthesis of polynitro derivatives of benzene " and toluene. " " Accordingly,... 

McCormick NG, Feeherry FE, Levinson HS. 1976. Microbial transformation of 2,4,6-trinitrotoluene and other nitroaromatic compounds. AppI Environ Microbiol 31 949-958. 

Hathaway J A Subclinical effects of trinitrotoluene A review of epidemiology studies. In Richert DE (ed) Toxicity of Nitroaromatic Compounds, pp 255-274. New York, Hemisphere Publishing, 1985... 

Levine BS, et ah Two-year chronic oral toxi-city/carcinogenicity study on the munitions compound trinitrotoluene (TNT) in rats. Toxicohffst 5 (ahstr 697)175, 1985... 

Nitric acid has a 65 25 fertilizer explosive end use ratio. The production of ammonium nitrate makes up nearly all of these two uses. The other 10% is made into miscellaneous compounds adipic acid, nitroglycerin, nitrocellulose, ammonium picrate, trinitrotoluene, nitrobenzene, silver nitrate, and various isocyanates. 

---