Explosives 1,4-dinitrobenzene

Starr, Explosives FUl Program. Dinitrobenzene Investigation , NTIS AD Rep 743471 (1972)... 

A substance which may explode under the effect of flame or which Explosive is more sensitive to shocks or friction than dinitrobenzene. 

A detonator, in the form of explosive plates made with tetryl then a screen made of cellulose acetate plates is placed in a wooden container. A 26 mm diameter cylinder full of the substance to be analysed is placed on the screen, and finally a steel plate on top of the cylinder is added. If the substance transmits the detonation, the steel plate will be pierced and not projected. Piercing serves as an indicator of detonation transmission. The number of cellulose acetate disks needed between the sample and the detonator to prevent the detonation from being transmitted is found. Only one is needed for most chemical substances, but with m-dinitrobenzene, 240 are required. 

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. 

Mixtures of nitric acid with dinitrobenzenes and trinitrobenzene are very strong and sensitive explosive combinations. 

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],... 

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... 

Dinitrobenzene is an intermediate employed in chemical syntheses of a large number of compounds used in the dye, explosives and plastics industry. The compound is known to induce methemoglobinemia and to cause testicular toxicity with the Sertoli cell being the major target. Nitro reduction was observed in erythrocytes, in rat Sertoli-germ cell cocultures and in rat testicular subcellular fractions, and it was shown that 3-nitrosonitrobenzene was formed that was considerably more toxic. Testicular toxicity was enhanced when the intracellular thiol levels were reduced by pretreatment with diethylmaleate. In turn, pretreatment with cysteamine or ascorbate reduced the toxicity of 1,3-dinitrobenzene and 3-nitrosonitrobenzene. 

Dining investigation after the violent explosion of a 6-chloro-2,4-dinitrobenzene-... 

A,A -Bis(3-aminopicryl)-l,2-ethanediamine (108) (m.p. 275 °C) is prepared from the reaction of ethylenediamine with two equivalents of 3-chloro-2,4,6-trinitroaniline. " The same chemists reported 3,3 -diamino-2,2 4,4, 6,6 -hexanitrodiphenylamine (109), a heat resistant explosive (m.p. 232-237 °C) prepared from the reaction of l,3-dichloro-4,6-dinitrobenzene with 3-chloroaniline followed by mixed acid nitration and subsequent chloro group displacement with ammonia. The potassium salt of 3,3 -diamino-2,2, 4,4, 6,6 -hexanitrodiphenylamine shows very high thermal stability. " ... 

Diamino-4,6-dinitrobenzofuroxan (DADNBF) (82), an impact insensitive high performance explosive (VOD 8050 m/s, d = 1.91 g/cm ), has been prepared in four steps from l,3,5-trichloro-2,4-dinitrobenzene (78), ° and also by treating the Meisenheimer complex (83) with excess hydroxylamine hydrochloride in aqueous base. DADNBF has also been synthesized in five steps starting from 2-nitroaniline. ... 

Pagoria and co-workers synthesized a number of thermally stable explosives from the reaction of the sodium salt of ANTA with chloro-substituted arylenes and A-heterocycles. These include the synthesis of (117) from picryl ehloride, PRAN (118) from 2-chloro-3,5-dinitropyridine, IHNX (119) from 2,4-dichloro-5-nitropyrimidine, (120) from 1,5-dichloro-2,4-dinitrobenzene, and (121) from 4-chloro-6-(3-nitro-l,2,4-triazolyl)-5-nitropyrimidine. Coburn and co-workers " reported the synthesis of the tetrazine (122) and the triazine (123) from the reaction of the sodium salt of ANTA with 3,6-dichlorotetrazine and cyanuric chloride respectively. 

The nitration of l,3,5-trichloro-2-nitrobenzene (8) to l,3,5-trichloro-2,4-dinitrobenzene (9) with dinitrogen pentoxide in absolute nitric acid goes to completion in only 2-4 minutes at 32-35 °C. Further nitration of (9) would yield l,3,5-trichloro-2,4,6-trinitrobenzene (10) which undergoes ammonolysis on treatment with ammonia in toluene to give the thermally stable explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) (11). The same sequence of reactions with l,3-dichloro-2-nitrobenzene provides a route to l,3-diamino-2,4,6-trinitrobenzene (DATE). Such reactions are clean and occur in essentially quantitative yield. 

DNB is often made first. Both 1,3-DNB and 1,3,5-TNB are formed as by-products when another explosive, trinitrotoluene (TNT), is made. 1,3-DNB is also used to make certain dyes, as an intermediate in the synthesis of organic chemicals, and in the plastics manufacturing industry. 1,3,5-TNB is used in making rubber. Other names for 1,3-DNB include m-dinitrobenzene,... 

As discussed previously, military-grade TNT is not a pure material, containing additional nitroaromatic constituents at concentrations of up to several percent by mass [4], Some of these explosive-related compounds (ERCs) have been shown to be significant contributors to the chemical fingerprint of a landmine [5, 7], Of the ERCs found in TNT, those that are most prevalent in the headspace vapor of TNT include 2,4-DNT, 2,6-DNT, 1,3-dinitrobenzene (1,3-DNB), and... 

Mixtures of aromatic nitro compounds with ammonium nitrate were widely used during World War I, when the enormous demand for high explosives could not be met by the output of TNT, trinitronaphthalene, picric acid, trinitroanisole, trinitrophenetole, dinitrobenzene, hexyl etc. 

During World War II Amatols of increased explosive power, in which a part of the ammonium nitrate was replaced by cyclonite, were also used. Thus German Ammonals were evolved from Amatol 50/50. Dinitrobenzene was used in Amatols 39a and 40 (Table 50) as a substitute for TNT. 

The explosives recommended by Hellhoff [8] are also noteworthy. They consist of concentrated nitric acid and dinitrobenzene or a mixture of nitrobenzene with dinitrobenzene. They have not been used very extensively for practical purposes, because their nitric acid content makes them extremely corrosive, but under war-time conditions they were considered to be the cheapest explosives and the simplest to prepare. During World War II they were suggested in Great Britain under the name of Dithekite. According to Cook, Pack and Gay [9] Dithekite-13 or D-13 has the following composition ... 

The stoichiometric mixture (mentioned above) was found to be very sensitive to priming. It was detonated by a primer as weak as 0.6 g of mercury fulminate. The rate of detonation, or more precisely of explosion, was variable (this is typical for liquid explosives) 1300-2000 m/sec. Expansion in the lead block was found to be 85 (picric acid = 100) which is the same value as that of dinitrobenzene (88). 

None of the nitrated naphthalenes is very sensitive to shock. a-Nitronaphthalene is not an explosive at all and cannot be detonated. Dinitronaphthalene begins to show a feeble capacity for explosion, and trinitronaphthalene stands between dinitrobenzene and dinitrotoluene in its explosive power. Tetranitro-naphthalene is about as powerful as TNT, and distinctly less sensitive to impact than that explosive. Vennin and Chesneau report that the nitrated naphthalenes, charged in a manometric bomb at a density of loading of 0.3, gave on firing the pressures indicated below.46... 

Germans used a mine explosive consisting of 56 per cent potassium perchlorate, 32 per cent dinitrobenzene, and 12 per cent dinitronaphthalene.48 Their Tri-Trinal for small-caliber shells was a compressed mixture of 2 parts of TNT (Tri) with 1 of trinitronaphthalene (Trinal), and was used with a booster of compressed picric acid. 

Roburites were also manufd in Engl by the Roburite Explosives Co, Ltd, who had the following formulation on the old permitted list AN 88, dinitrobenzene 11 and chlor-naphthalene 1%. The following compn passed the Rotherham test and was on the permitted list AN 61, TNT 16 and Na chloride 23%. Its limit charge was 18 oz, and its power (by swing of BalPend) was 2.86 inches (Ref 4)... 

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