1.3.5- Trichloro-2,4,6-trinitrobenzene

Sorm and Drapalova (Ref 8) prepd it by boiling 1,3,5-trichloro-2,4,6-trinitrobenzene (or triaminotrinitrobenzene) with an ale NaOH soln. 

Tris(picrylamino)-l,3,5-trinitrobenzene (113), the product from condensing three equivalents of aniline with 1,3,5-trichloro-2,4,6-trinitrobenzene followed by nitration with mixed acid, is a high-molecular weight explosive which shows good thermal stability (m.p. 234 °C) but is readily detonated. " ... 

All reported syntheses of TATB to date involve the nitration of substrates containing leaving groups which are subsequently replaced by amino groups. The current industrial synthesis of TATB (14) involves the nitration of 1,3,5-trichlorobenzene (33) to 1,3,5-trichloro-2,4,6-trinitrobenzene (34) followed by reaction with ammonia in toluene under pressure. Both nitration and amination steps require forced conditions with elevated temperatures. 

Similar routes have been used for the synthesis of other polynitrophenylenes. 1,3,5-Tris(2,4,6-trinitrophenyl)-2,4,6-trinitrobenzene (160) is synthesized from the reaction of 1,3,5-trichloro-2,4,6-trinitrobenzene with three equivalents of picryl chloride in the presence of activated copper powder in refluxing mesitylene. " 2,2",4,4, 4",6,6, 6"-Octanitro-m-terphenyl (161) has been synthesized from picryl chloride and l,3-dichloro-4,6-dinitrobenzene. ... 

Benzenetrifuroxan (66) is a powerful explosive which was first synthesised by Turek in 1931 by heating 1,3,5-triazido-2,4,6-trinitrobenzene (65) to its melting point (131 °C) the latter prepared from the reaction of 1,3,5-trichloro-2,4,6-trinitrobenzene with sodium azide in aqueous ethanol. 

Nitric acid, Sulfuric acid, Sodium bicarbonate 1,3,5-Trichloro-2,4,6-trinitrobenzene, Dioxane, Ammonia gas... 

As a starting material for the preparation of sym-trinitrotriazidobenzene, 1,3,5-trichlorobenzene is used. It is obtained by the chlorination of aniline and the removal of the amino group. Nitration to the trinitro derivative is described in Vol. I. The final reaction is simple powdered 1,3,5,-trichloro-2,4,6-trinitrobenzene is added to an aqueous alcohol solution of sodium azide. The precipitated product is washed with alcohol and water and dried at a moderate temperature. The product so obtained may be purified by crystallization from chloroform. 

Trichloro-2,4,6-trinitrobenzene is prepared by the nitration of trichlorobenzene with a mixture of nitric acid and sulfuric acid. 1,3,5-Trichloro-2,4,6-trinitrobenzene is then converted to l,3,5-trinitro-2,4,6-triaminobenzene (TATB) by nitrating with ammonia as shown in Reaction 7.4. The yellow-brown crystals of TATB are filtered and washed with water. 

Trichloro-2,4,6-trinitrobenzene (m. p. 187°C) can be prepared by the nitration of 1,3,5-trichlorobenzene with anhydrous nitric acid and oleum (Jackson and Wing [42]). However, according to van Ryn [43] the yield is poor. 

Summary TATB can be made by reacting dry ammonia gas with 1,3,5-trichloro-2,4,6-trinitrobenzene in dioxane solvent. The resulting precipitated product is then filtered-off, washed, and then dried. Commercial Industrial note For related, or similar information, see Serial No. 813,039, May 13th, 1959, by The United States Navy, to Lloyd A. Kaplan, Adelphi, MD, and Francis Taylor, Jr., Baltimore MD. Part or parts of this laboratory process may be protected by international, and/or commercial/industrial processes. Before using this process to legally manufacture the mentioned explosive, with intent to sell, consult any protected commercial or industrial processes related to, similar to, or additional to, the process discussed in this procedure. This process may be used to legally prepare the mentioned explosive for laboratory, educational, or research purposes. 

Going from one of the most sensitive of the aromatic explosives to one of the very least sensitive, we have TATB (Figure 3.18). This is a new, very insensitive, high explosive that is finding broad use in nuclear weapons development. The extreme degree of insensitiveness boosts the safety in handling and in accident situations, which is so crucial in that particular application. It is made by direct nitration of 1,3,5-trichlorobenzene to 1,3,5-trichloro-2,4,6-trinitrobenzene. This, in turn, is then converted to the 1,3,5-triamino- by amine substitution of the three chlorine atoms. 

Triazido-2,4,6-trinitrobenzene can be easy synthesized by the action of alkaline azide on 1,3,5-trichloro-2,4,6-trinitrobenzene. The product is slightly soluble in the reaction mixture from which it precipitates. The sodium azide can be used in the form of an aqueous ethanol solution while l,3,5-trichloro-2,4,6-trinitrobenzene in the form of an acetone solution or alone [153, 154,159, 160]. Purification of TATNB may be done by crystallization from solvents such as chloroform [153,154,159,160], acetic acid, or mixture of acetic acid and acetone 1/1 (the last mixture is recommended for preparation of single crystals for stractural studies) [155]. 

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