Explosives 4-nitrotoluene

Mixtures of HNO, H2SO4, and SO also result in high concentrations of NO/, and toluene can be readily nitrated at —40 to — 10°C as a result (6). At these low temperatures, the formation of the meta-isomer of mononitrotoluene (MNT) is greatiy reduced. Such a reduction is highly desired in the production both of dinitrotoluenes (DNTs) employed to produce intermediates for polyurethane production and of trinitrotoluene (TNT), which is a high explosive. > -MNT results in the production of undesired DNT and TNT isomers (see Nitrobenzene and nitrotoluenes). 

Bis(2,4,6-trinitrophenyl)methane when treated with NaAc in acetic acid produced (580) as a thermostable explosive (80MIP41600). The conversion of o-nitrotoluene into 2,1-benzisoxazole was effected by mercury(II) oxide catalysis. A mercury containing intermediate was isolated and was demonstrated to be converted into 2,1-benzisoxazole (67AHC(8)277). The treatment of o-nitrotoluene derivative (581) with sulfuric acid gave (582) in 35% yield (72MI41607). 

Folis Explosive. A mixt contg Nitrotoluene and Pb nitrate as basic ingredients, which could be expld by heating... 

Basic Explosives Manufacture. The major quantities and the toughest problems are here. They include a) acid waters, treated with lime or soda ash, chemical washes, spills, washdowns b) Red Water from TNT purification. A complex, brick-red soln of Na nitrate, Na sulfate, Na sulfite, Na nitrite, and about 17% organics which include sulfonated nitrotoluene isomers and complex, unidentified dye-bodies c) dissolved expls, eg, Pink Water which is approx lOOppm TNT in w d) suspended expl particles — dust and chips and e) sometimes solvents such as acet, benz, and dimethyl aniline... 

Nitrotoluenes including 2,4,6-trinitrotoluene (TNT) are important components of explosives and several nitroarenes including the antibacterial nitrofurans have established mntagenicity (Purohit and Basu 2000). Substantial effort has been directed to the degradation of nitroarenes, and to their reduction to amines. Although nitroarene reductases, noted in Chapter 3, Part 3, are distribnted in a range of biota, the products may not necessarily represent intermediates in the degradation... 

Methyl and ethyl nitrates are promoters of the combustion of hydrocarbons. Nitrobenzene and aromatic nitrated explosives are mostly insensitive to impact. They become sensitive when potassium or Na-K alloy is present. 4-Nitrotoluene with sodium in diethyl ether medium forms a black residue that combusts spontaneously in air. 

Mixtures with nitrobenzene, 1- or 4-nitrotoluene, 1,3-dinitrobenzene or 1-nitronaphthalene were found to be high explosives of high sensitivity and detonation velocities [1]. Those with nitrobenzene are spark-detonable [2],... 

Industrial preparation of 4-cyano-3-nitrotoluene by heating the reaction components at around 170°C for 6 h led to an explosion in 1976. Subsequent investigation by DSC showed that the cyano compound in presence of the starting materials exhibited an exotherm at 180°C. After 6 h reaction, this threshold temperature fell to 170°C. Isothermal use of a safety calorimeter showed that a large exotherm occurred dining the first hour of reaction and that, in absence of strong cooling,... 

Crude 2-nitrotoluene, containing some hydrochloric and acetic acids, was charged into a vacuum still with flake sodium hydroxide to effect neutralisation prior to distillation. An explosion occurred later. Similar treatments had been used uneventfully previously, using the weaker bases lime or sodium carbonate for neutralisation. It seems likely that the explosion involved formation and violent decomposition of the sodium salt of an aci-nitro species, possibly of quinonoid type. 

Solutions of 4-nitrotoluene in 93% sulfuric acid decompose very violently if heated to 160°C. This happened on plant-scale when automatic temperature control failed [1], but the temperature was erroneously abstracted as 135°C [2], The explosion temperature of 160°C for the mixture (presumably containing a high proportion of 4-nitrotoluene-2-sulfonic acid) is 22°C lower than that observed for onset of decomposition when 4-nitrotoluene and 93% sulfuric acid are heated at a rate of 100°C/h [3], Mixtures of 4-nitrotoluene with 98% acid or 20% oleum begin to decompose at 180 and 190°C, respectively [3,4], Thereafter, decomposition accelerates (190-224° in 14 min, 224-270 in 1.5 min) until eruption occurs with evolution of much gas [4],... 

A series of mixtures of nitric acid with one or more of mono- and di-nitrobenzenes, di- and tri-nitrotoluenes have been shown to possess high-explosive properties [1]. Critical detonation diameters for mixtures of nitric acid with dinitrotoluene and TNT have been determined [2],... 

Mixtures with nitrobenzene were formerly used as liquid high explosives, with addition of carbon disulfide to lower the freezing point, but high sensitivity to mechanical stimulus was disadvantageous [1], Dining the recovery of acids from nitration of toluene, mixtures of the oxide with nitrotoluene or dinitrotoluene may... 

For onsite analysis, the examination of the vast number of samples necessitates the use of quick, reliable, field portable equipment that can rapidly, quantitatively verify the many chemically different types of ammunition, explosives, and pyrotechnics. The most common suite of analytes to detect is large, consisting of very chemically different compounds and usually occurs at trace levels in complex environmental matrices. This suite encompasses smokeless powders, black powders, and numerous propellant and energetic formulations. Detection should also be sought for common decomposition products of these explosives such as the methylanalines, aminonitrotoluenes, nitrotoluenes, mono- and dinitoroglycerines, and the nitrobenzenes under on-site conditions. 

The 60 still base was a 45.5 m3 horizontal, cylindrical, mild steel tank 7.9 m long and 2.7 m diameter. The still was used to separate a mixture of the isomers of mononitrotoluene (MNT), two of which (o-nitrotoluene and m-nitrotoluene) are liquids at room temperature and third (p-nitrotoluene) a solid. Other byproducts were also present, principally dinitrotoluene and nitrocresols. It is well known in the industry that these nitro compounds can be explosive in the presence of strong alkali or strong acid, but in addition explosions can be triggered if they are heated to high temperatures or held at moderate temperatures for a long period. 

Nitration reactions are mostly substitution type, forming a wide variety of products including nitrobenzene, nitrotoluenes, nitroglycerine, nitrocellulose, trinitrotoluene, nitrophenols and nitroparaffins, many of which are known chemical explosives. Some examples are ... 

Jones Blasting Explosives. Jones patented the following compn chlorates such as NaC103 are used with finely divided carbonaceous substances the o-isomer of nitrotoluene, which-keeps the mixt plastic. The chlorate may be mixed with a powdered carbonaceous absorbent material such as sawdust a liq mixt of o-nitrotoluene melted TNT Ref L.T.W. Jones, USP 1820567 1820568 (1931) CA 25, 5771 (1931)... 

Kinetite (Kinetit or Kinenite-Swiss). One of the earliest gelatinous (plastic) expls which contd no NG. It was patented in 1884 by Petry and Fallenstein and was used extensively at the end of the last century in Ger and other European countries. It was prepd by gelatinizing Nitrobenzene or Nitrotoluene with Collodion Cotton, and impregnating this plastic mass with sulfur, K chlorate and other ingredients. Sulfur was later replaced by Sb penta-sulfide. Its compn was NB 16.0 to 21.0, Collodion Cotton 0.75 to 1.0, K chlorate 82.5 to 75.0, Sb2Ss and/or K nitrate 3.0 to 1.0%. The function of the Sb pentasulfide was to render the explosion more regular and more complete... 

T. Urbanski, Influence of Non-Explosive liquids on the Detonation Rate of Solid Explosives , ArchProcesouSpalania 3 (2), 117—32 (1972) CA 78, 99944 (1973) [The author discusses the effect on the deton rate of adding w to PETN, RDX, p-Nitrotoluene or TNT in concns of from 5 to 40%. He reports that at low w concns the deton rate is minimized. As the w content increases the deton rate curve passes thru a maximum to reach a second minimum at the higher ( V 40%) level of w concn. The author concludes that the increase in deton rate can be attributed to three factors, the existence of a covolume, a phlegmatizing factor, and the result of mixing of two components, at least one of which is expl] 9) T.V. Ferris, Expansion of Methanol-Air Mixtures at Above Atmospheric Conditions , LossPrevn 8,15—19 (1974) CA 82, 45989 (1975) [Upper flammability limits were detd for various mixts of methanol with air, or a 30/70 02—N2 mixt with and without w. A rise of 12 vol % in the flammability limit above the nominal value of 36 vol % methanol in w-free air mixts is reported in the presence of liq w]... 

Nitrosyl perchlorate, N0C104, is generally considered stable at room temperature and,by itself, should be completely safe. Decomposition begins just below 100 t, above IOOt (II5°-120ct) low order explosions occur (Ref 103) p-Nitrotoluene - HzSO4 mixtures explode when heated to 160°C... 

Reinsdorf Explosion. The spent acid from the trinitration step in the manuf of TNT has been the cause of several disasters, although it had been considered safe to handle. The most noteworthy example of this occurred in the Reinsdorf factory in Ger in 1935. The hot spent add flowed down to open iron tanks, where, as the liq cooled, a mixt of di- and tri-nitrotoluenes rose to the surface. It was skimmed off from time to time and transferred to a washing tank, where it was washed with w. On skimming, a rubber glove and a shelf left on the edge of the tank with some cotton wool on it- fell into the tank. The reaction between the spent acid and the rubber and cotton wool initiated violent decompn and fire. An attempt to extinguish the flames failed, and soon the nitro compds on the surface of the spent acid expld. The expln... 

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