Trinitrobenzene manufacture

Trinitrobenzene (TNB) (2) is a more powerful explosive than TNT. However, the direct synthesis of TNB from benzene is not practical and the need for an indirect route for its synthesis makes its manufacture too expensive for use as a practical high explosive. 

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... 

With sodium polysulphide, sym-trinitrobenzene yields tetranitroazoxybenzene along with dinitroaniline. All three nitro groups can be reduced by tin or iron in hydrochloric acid, triaminobenzenc being formed, which is the starting material for the manufacture of phloroglucinol. sym-Trinitrobenzene can react with sodium borohydride to yield trinitrocyclohexane (Severin [66]). 

Preparation from a- trinitrotoluene. In 1893 a patent was granted to the Chemische Fabrik Griesheim [47a] for the manufacture of sym-trinitrobenzene from trinitrotoluene. The method was based on the fact observed by Tiemann [48] Mid by Claus and Becker [49], that trinitrotoluene can be oxidized with nitric acid to trinitrobenzoic acid, the latter being readily decarboxylated to form sym-trinitrobenzene ... 

When using chlorodinitrobenzene in the manufacture of explosives, the products obtained from it (e.g. dinitroanisole, dinitrodiphenylamine) are nearly always subjected to further nitration. Both the 1,2,6- and 1,2,4-isomers then yield the same trinitro derivative, l-chloro-2,4,6-trinitrobenzene. In such cases separation of the isomers and the preparation of highly pure 1,2,4-isomer is not necessary. 

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. 

Even though 1,3,5-trinitrobenzene (TNB) has more shattering power (more hrisance) and is no more dangerous to handle, 2,4,6-trinitrotoluene (TNT) has always been the high explosive in more general use. Can you suggest a reason (connected with manufacture) for the popularity of TNT (Benzene and toluene are both readily available materials for many years benzene was cheaper.)... 

One of the characteristic features of aromatic nitro compounds, particularly those with two or more nitro groups is their ability to react with bases and in many instances the reaction is accompanied by an intense colour. The colour had caught the attention of chemists by the late nineteenth century and initiated a considerable amount of research on the nature of the formed substances. Thus considerable literature appeared on reactions known as Janovsky or Jackson-Meisenheimer or Meisenheimer reactions which are discussed later. They are nucleophilic reactions and are not only of theoretical but also of practical importance. Thus the Janovsky reaction became an important analytical method, and reactions of di- and trinitrobenzene and their homologues with bases, are of great importance in the problem of the safety of manufacture and of the stability of these nitro compounds. 

Trinitrotoluene (TNT) is the most commonly used energetic compound and found in the soils at U.S. Army installations [16,17], Military grades of TNT contain up to 8% DNTs (2,4-dinitrotoluene and 2,6-dinitrotoluene) as manufacturing impurities, and TNT is often degraded to DNT in hydric soils (i.e., wet anaerobic environments) [18,19], Other compounds are also generated when TNT is degraded (e.g., 2-amino-4,6-dinitrotoluene [2-ADNT], 4-amino-2,6-dinitrotoluene [4-ADNT], 1,3,5-trinitrobenzene [TNB], and others). Contamination from TNT, DNTs, and their environmental breakdown products is known to persist in soil for years [20],... 

Trinitro derivatives of chlorobenzene Picryl chloride Physical properties Chemical properties l-Chloro 2,4.5-trinitrobenzene Diagram of the nitration of chlorobenzene Thermochemical and explosive properties of chloronitrobenzenes Nitro derivatives of p-chlorobenzene Mononitro derivative of p-chlorobenzene Dinitro derivative ofp-dichlorobenzene 2,4,6-Trinilroderivativc of L3.5-trichlorobcnzene Manufacture of L3,5-lrichloro-2.4,6-irinitrobenzene Nitro derivatives of fluorobenzene Literature... 

Badische Anilin-und Sodafabrik of Germany. This process was less expensive than the chamber method previously used. As such acid was required for mixed nitric-sulfuric acid to nitrate aromatic hydrocarbons to polysubstitution, trinitrobenzene and trinitrotoluene (TNT) could be inexpensively manufactured. 

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