Trinitrotoluene solutions

Photolysis of 2,4,6-Trinitrotoluene Solutions , PATR 4407 (1972) 15) Encycl Britannica... 

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. 

During the solution of the trinitrobenzoic acid, the temperature should not be below 35°, owing to the slight solubility of trinitrobenzoic acid in cold water. The heat of neutralization raises the temperature to 45-55°, but the latter temperature should not be exceeded, since any trinitrobenzene formed at this point would later be removed with the unreacted trinitrotoluene. 

The product is now mixed with 2 1. of distilled water at 35° in a 5-I. flask provided with a stirrer, and 15 per cent sodium hydroxide solution is dropped in with continuous stirring until a faint red color is just produced. Should this disappear, it is restored by the addition of a few drops more. When it has persisted for five minutes, the color is discharged by the addition of a few drops of acetic acid, and the insoluble unattacked trinitrotoluene filtered off and washed with a little water. The trinitrobenzoic acid is precipitated from the filtrate by the... 

Seliwanoff s test analy chem A color test helpful in the identification of ketoses, which develop a red color with resorcinol in hydrochloric acid. s3 liv3,nofs, test sellite liNORG chem A solution of sodium sulfite (Na2S03) used in the purification of 2,4,6-trinitrotoluene to remove unsymmetrical isomers. se,lTt ... 

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]. 

The carbon-nitrogen bonds of tetranitromethane are very electron deficient and prone to attackby nucleophiles. Consequently, tetranitromethane and its derivatives behave like nitrating agents in alkaline solution. Huorotrinitromethane (98) behaves in a similar way and has been used for the nitration of the acidic methyl group of 2,4,6-trinitrotoluene (97) (TNT) to give a ,2,4,6-tetramtrotoluene (99) in 89 % yield. ... 

A solution of dinitrogen tetroxide in sulfuric acid is also a powerful nitrating agent. In this medium dinitrogen tetroxide is ionized to nitronium and nitrosonium ions. Titov reported using a solution of dinitrogen tetroxide in oleum for the nitration of nitrotoluene to dinitrotoluene and then to trinitrotoluene, the two separate steps proceeding in 98 % and 85 % yields respectively. 

Trinitrobenzene is present in crude TNT manufactured by mixed acid nitration and results from methyl group oxidation followed by decarboxylation." In fact, a convenient method for the synthesis of 1,3,5-trinitrobenzene involves oxidation of 2,4,6-trinitrotoluene with a solution of sodium dichromate in sulfuric acid, followed by decarboxylation of the resulting 2,4,6-trinitrobenzoic acid in boiling water." 1,3,5-Trinitrobenzene is prepared from 2,4,6-trinitro-m-xylene by a similar route." 2,4,6-Trinitroanisole can be prepared from the... 

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. 

The most important of these explosive isomers is the alpha-trinitrotoluene, known as TNT. In crude, commercial TNT, 4 to 5% of impurities are present, consisting mainly of. a mixture of beta-, or 2,3,4-, and gamma, or 3,4,6-trinitrotoluenes. These impurities may be removed by treating the crude TNT with an aqueous solution of sodium sulfite. Ac-, cording to Davis (Ref 3) the beta- and gamma-isomers react with lead oxide in alcohol to form lead dinitrocresolates, while alpha-TNT remains unaffected under similar conditions Refs 1) M. Copisarow, Chem News 118, 13-14 (1919) CA 13, 791 (1919) 2) M.M. Kos-tevitch, Trinitrobenzene Trinitrotoluene, Paris (1927) 3) Davis (1943) p 147... 

Nitroguanidine intended for use in a fusible mixture with trinitrotoluene takes the form of fairly large, very regular crystals. For this purpose a colloidal substance is added to the nitroguanidine solution, which is allowed to crystallize slowly. 

Crude TNT contains isomers and nitrated phenolic compounds resulting from side reactions. The usual method of purification is to treat crude TNT with 4% sodium sulfite solution at pH 8-9, which converts the unsymmetrical trinitro compounds to sulfonic acid derivatives. These by-products are then removed by washing with an alkaline solution. Pure TNT is then washed with hot water, flaked and packed. It is important to remove the waste acid and unsymmetrical trinitrotoluenes together with any by-products of nitration as they will degrade the TNT, reduce its shelf life, increase its sensitivity and reduce its compatibility with metals and other materials. Trace amounts of unsymmetrical trinitrotoluenes and by-products will also lower the melting point of TNT. TNT can be further recrystallized from organic solvents or 62% nitric acid. 

Y. Okamoto et al, The Removal of 2,4,6-Trinitrotoluene (TNT) from Aqueous Solutions with Surfactants , ARLCD-TR-77038, US... 

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