Triaminotrinitrobenzene is readily formed by the nitration of 1,3,5-trichlorobenzene to 1,3,5-trichloro-2,4,6-trinitrobenzene followed by amination to triaminotrinitrobenzene. The purity of the triaminotrinitrobenzene is significantly improved if, during the amination step, sufficient water is present that the byproduct ammonium chloride formed during the amination is rendered at least semideliquescent.
A process for producing 1,3,5-trifluoro-2,4,6-trinitrobenzene by: (1) forming a mixture of fuming sulfuric acid and potassium nitrate wherein the fuming sulfuric acid is composed of at least 25 percent by weight sulfur trioxide, and wherein the molar ratio of fuming sulfuric acid to potassium nitrate is from about 2:1 to about 3:1; (2) adding 1,3,5-trifluorobenzene to the mixture until the molar ratio of potassium nitrate to 1,3,5-trifluorobenzene is from 6:1 to 10:1, the temperature of the mixture being maintained in the range of from about 30.degree. C. to about 50.degree. C. during the addition; (3) then raising the temperature of the mixture into the range of from about 140.degree. C. to about 160.degree. C. where it is maintained until the optimum yield of 1,3,5-trifluoro-2,4,6-trinitrobenzene has been obtained; and (4) isolating the product, 1,3,5-trifluoro-2,4,6-trinitrobenzene from the reaction mixture.
The present invention relates to a process to aminate electrophilic aromatic compounds by vicarious nucleophilic substitution of hydrogen using quaternary hydrazinium salts. The use of trialkylhydrazinium halide, e.g., trimethylhydrazinium iodide, as well as hydroxylamine, alkoxylamines, and 4-amino-1,2,4-triazole to produce aminated aromatic structures, such as 1,3-diamino-2,4,6-trinitrobenzene (DATB), 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and 3,5-diamino-2,4,6-trinitrotoluene (DATNT), is described. DATB and TATB are useful insensitive high explosives. TATB is also used for the preparation of benzenehexamine, a starting material for the synthesis of novel materials (optical imaging devices, liquid crystals, ferromagnetic compounds).
A process for the manufacture of 1,3,5-triaminotrinitrobenzene having a large crystal size by aminating 1,3,5-trichlorotrinitrobenzene with an agent at atmospheric pressure at a temperature of at least about 160.degree. C. with an antioxidant added to the reaction mixture.
A method of forming a fine-grained species of the insensitive high explosive sym-triaminotrinitrobenzene (TATB) without grinding. In accordance with the method, 1,3,5-trichloro-2,4,6-trinitrobenzene (TCTNB) is aminated by reaction with gaseous ammonia in an emulsion of toluene in water. The ratio of water to toluene in the emulsion is selected so that toluene is the dispersed phase in the emulsion. The size of the dispersed TCTNB-containing toluene droplets determines the particle size of the resulting TATB. The emulsion is preferably formed with an emulsifier such as ammonium oleate, which may be generated in situ from oleic acid, and stabilized with a protective colloid such as polyvinyl alcohol.
Preparation of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) from 3,5-dichloroanisole. Nitration of 3,5-dichloroanisole under relatively mild conditions gave 3,5-dichloro-2,4,6-trinitroanisole in high yield and purity. Ammonolysis of this latter compound gave the desired TATB. Another route to TATB was through the treatment of the 3,5-dichloro-2,4,6-trinitroanisole with thionyl chloride and dimethylformamide to yield 1,3,5-trichloro-2,4,6-trinitrobenzene. Ammonolysis of this product produced TATB.
