TATB synthesis

Z.L. Estes, Trichloronitrosobenzene—A Raw Material for TATB Synthesis , MHSMP-77-25, Mason Hanger. . Amarillo (1977)... 

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. 

The synthesis of TATB (14) from the reaction of 2,3,4,5,6-pentanitroaniline (31) with ammonia has been reported. " In one route, 2,3,4,5,6-pentanitroaniline (31) is synthesized from the nitration of 3,5-dinitroaniline (30) " the latter is obtained from the selective reduction of TNB ° or via a Schmidt reaction with 3,5-dinitrobenzoic acid. Another route to 2,3,4,5,6-pentanitroaniline (31) involves the selective reduction of TNT (1) with hydrogen sulfide in ammonia followed by nitration of the resulting 4-amino-2,6-dinitrotoluene (46), during which the methyl group is lost by oxidation-decarboxylation. 

TNT has been used as a starting material for the synthesis of 2,3,4,5,6-pentani-troaniline (see Section 4.8.4), and hence, for the synthesis of hexanitrobenzene via oxidation with peroxydisulfuric acid, and l,3,5-triamino-2,4,6-trinitrobenzene (TATB) via nucleophilic displacement with ammonia. " " ... 

Agrawal and co-workers have reported the synthesis of A,A -bis(l,2,4-triazol-3-yl)-4,4 -diamino-2,2, 3,3, 5,5, 6,6 -octanitroazobenzene (17) (BTDAONAB) via nitration-oxidative coupling of 4-chloro-3,5-dinitroaniline (152) followed by nucleophilic displacement of the chloro groups with 3-amino-1,2,4-triazole. BTDAONAB has the unique distinction of being the most thermally stable explosive reported so far (DTA exotherm 550 °C) as compared to well known thermally stable explosives such as TATB ( 360 °C), TACOT ( 410 °C), NONA ( 440 50 °C), and PYX ( 460 °C). 

A. R Mitchell, P.F. Pagoria and R.D. Schmidt, A New Synthesis of TATB using Inexpensive Starting Materials and Mild Reaction Conditions , 27th International Annual Conference of ICT, Karlsruhe, Germany, 25-28 June, 1996, 29/1-29/11. 

Amino-1,2,4-triazole is a useful starting material for the synthesis of many 1,2,4-triazole-based explosives. Jackson and Coburn synthesized a number of picryl- and picrylamino-substituted 1,2,4-triazoles. PATO (99) is synthesized from the reaction of 3-amino-1,2,4-triazole (98) with picryl chloride (67). ° PATO has also been synthesized from the reaction of 3-amino-l,2,4-triazole with A,2,4,6-tetranitromethylaniline (tetryl). PATO has a low sensitivity to impact and is thermally stable up to 310 °C. PATO (VOD 7469 m/s) exhibits lower performance to TATB (VOD 8000 m/s) which is the common benchmark standard for thermal stability and insensitivity in explosives. 

Navy. 1983. Synthesis and properties of trisubstituted trinitrobenzenes TATB analogs. Silver Spring, MD Naval Surface Weapons Center. Document no. AD A131619. 

Several methods have been reported in the literature for the synthesis of TATB [24]. Considering the ease of synthesis, purity and yield of the resulting TATB, its synthesis from symmetrical trichlorobenzene (sym.-TCB) is regarded as a method of choice for scaling-up and now almost all countries follow this method for its... 

The high stability of TATB favors its use in military and civilian applications where insensitive high explosives are required. In addition to its applications as a HE, TATB is also used to produce the important intermediate benzenehexamine which has been used in the preparation of ferromagnetic organic salts and in the synthesis of new heteropolycyclic molecule such as 1,4,5,8,9,12-hexaazatriphenyl-ene (HAT) that serves as a strong electron acceptor ligand for low-valence transition metals. 

Experience with explosives such as DATB, TATB, PYX, etc. suggests that the synthesis of explosives with coarse particles may prove to be a real bottleneck and... 

Schmidt, R.D., Mitchell, A.R., and Pagoria, P.F. (1998) New synthesis of TATB process development studies. Proc. 29th ICT Inti. Ann. Conf. of ICT, Karlsruhe, Germany, June 30-July 3, pp. 49/1-49/11. 

Agrawal et al. reported the synthesis of BTDAONAB (Fig. 1.3c) which does not melt below 550 °C and is considered to be a better and thermally more stable explosive than TATB. According to the authors, this material has a very low impact (21J), no friction sensitivity (> 360 N) and is thermally stable up to 550 °C. These reported properties makes BTDAONAB superior to all of the nitro-aromatic compounds which have been discussed. BTDAONAB has a VoD of 8300 m/s while TATB is about 8000 m/s [Agrawal et al., Ind. J. Eng. Mater Sci., 2004,11,516-520 Agrawal et al., Central Europ.. Energ. Mat. 2012, 9(3), 273-290.]... 

The synthesis and properties of several high-nitrogen materials with 3-amino-6-nitroamino-tetrazine (ANAT) as the anion are reported (Scheme 23). These salts (99, 100, 103a,b) provide a new and easy approach to highly energetic salts. All these salts are relatively dense (> 1.55 g/cm ) and exhibit good thermal stability T > 148 C). The calculated detonation velocities and detonation pressures are comparable to those of explosives such as Tetryl, PETN, TATB, and RDX. A combination of theoretical and empirical calculations shows that all these salts have high molar enthalpies of formation (Table 9) [99]. 

Its calculated energy content is 85% that of HMX and 15% more than that of TATB. It is thermally stable, insensitive to shock, spark and friction and has impact insensitivity level approaching that of TATB. These combined properties make it a realistic high performance IHE material attractive for applications that require moderate performance and insensitivity. The synthesis of LLM-105 through the oxidation of 2,6-diamino-3,5-dinitropyrazine with trifluoroaceticperacid at room temperature was first reported in 1995 at the Lawrence Livermore Laboratories. Some of its properties are presented in Table 2.26. 

---