Trinitrotoluene preparation

Reaction of the highly explosive fluorotrinitromethane with the anion of 2,4,6-trinitrotoluene, prepared with potassium hydroxide, gives the highly explosive a,2,4,6-tetranitrotoluene in 89% yield.609 Ketone enol silyl ethers and the equally highly explosive tetranitromethane react to give a-nitro ketones in low to very high yields (Eq. 188).610... 

It occurs in many natural glycosides. It can be prepared by fusing resorcinol with NaOH and is manufactured from trinitrotoluene via trinitrobenzoic acid and triaminobenzene. 

The action of hydroxylamine and sodium acetate in ethanol upon picryl chloride was stated to give 4,6-dinitrobenzofuroxan, and probably some of this compound was formed, although it was later shownthat much of the original work was faulty. A report that hydroxylamine and 2,4,5-trinitrotoluene give 5-methyl-6-nitro-benzofuroxan has been found to be incorrect. Benzofuroxan has not been prepared by V-oxidation of benzofurazan, and it seems unlikely that this could be achieved, since benzofuroxan itself is oxidizable by powerful reagents to o-dinitrobenzene (Section VI, B). A report of the oxidation by nitric acid of anthraceno[l,2-c]furazan to the furoxan is incorrectlv abstracted. 

The Sundberg indole synthesis using aromatic azides as precursors of nitrenes has been used in synthesis of various indoles. Some kinds of aryl azides are readily prepared by SNAr reaction of aromatic nitro compounds with an azide ion. For example, 2,4,6-trinitrotoluene (TNT) can be converted into 2-aryl-4,6-dinitroindole, as shown in Eq. 10.60.83... 

K. Matsumoto, A. Torimaru, S. Ishitobi, T. Sakai, H. Ishikawa, K. Toko, N. Miura, and T. Imato, Preparation and characterization of a polyclonal antibody from rabbit for detection of trinitrotoluene by a surface plasmon resonance biosensor. Talanta 68, 305-311 (2005). 

Trinitrobenzene can be prepared by heating w-dinitro-benzene with nitric acid and sulfuric acid to 1200 1 by heating 2, 4, 6-trinitrotoluene with fuming nitric acid in a sealed tube at 180° for three hours 2 by heating 2, 4, 6-trinitrobenzoic acid or its sodium salt with water, alcohol, dilute sodium carbonate or other suitable solvent.3... 

Trinitrobenzoic acid has been prepared by heating trinitrotoluene with fuming acid in a sealed tube to ioo°, for two weeks,1 the oxidation being only partial. It can also be prepared by heating trinitrotoluene under a reflux condenser, with a mixture of 5 parts of concentrated nitric acid and 10 1 Ber. 8, a 3 (1870). 

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... 

Nitration via diazotisation has been extensively used for the synthesis of isomeric dinitronaphthalenes. Ward and co-workers used nitration via diazotisation to prepare 3,3, 4,4 -tetranitrobiphenyl from 3,3 -dinitrobenzidine, and 3,4,5-trinitrotoluene from 3,5-dinitro-4-toluidine. Ward and Hardy " prepared 1,4,6-trinitronaphthalene from 4,7-dinitro-1-naphthylamine. Korner and Contardi used the nitrate salts of aryldiazonium compounds for the synthesis of polynitro derivatives of benzene " and toluene. " " Accordingly,... 

Romburgh [62] prepared this product by the nitration of N-dimethyl-m-toluidine, British authors [63] obtained it in the following manner during World War I using the product of sulphitation of y-trinitroluene, the main isomer of a-trinitrotoluene (Vol. I) ... 

Trinitrotoluene (TNT)-based aromatic diamines are used for the preparation of substituted polyimides. Interest in substituted polyimides is very understandable due to the known poor tractability of unsubstimted aromatic polyimides [1—4], As is known, the introduction of methoxy substituents to macromolecules of polyimides enhances their solubility in organic solvents [5]. One of the simplest TNT derivatives, 3,5-diaminoanisole, is used for the preparation of methoxy-substituted polyimides [6]. 

The variety of ways in which chloral and trinitrotoluene (TNT) derivatives can be used to prepare novel polyimides and polymeric materials is very promising. The use of chloral and TNT derivatives allows for the synthesis of a large number of monomers which, in turn, can impart a variety of useful properties to their respective polymers. The possibility of preparing, from available raw materials, high-molecular-weight compounds with increased heat and thermal resistance in combination with improved solubility and, consequently, easiness of processing is especially attractive and may provide impetus for further work in this field. 

Around 1902 the Germans and British had experimented with trinitrotoluene [(TNT) (C7H5N306)], first prepared by Wilbrand in 1863. The first detailed study of the preparation of 2,4,6-trinitrotoluene was by Beilstein and Kuhlberh in 1870, when they discovered the isomer 2,4,5-trinitrotoluene. Pure 2,4,6-trinitrotoluene was prepared in 1880 by Hepp and its structure established in 1883 by Claus and Becker. The manufacture of TNT began in Germany in 1891 and in 1899 aluminium was mixed with TNT to produce an explosive composition. In 1902, TNT was adopted for use by the German Army replacing picric acid, and in 1912 the US Army also started to use TNT. By 1914, TNT (1.4) became the standard explosive for all armies during World War I. 

TNT was first prepared in 1863 by Wilbrand and its isomers discovered in 1870 by Beilstein and Kuhlberg. Pure TNT (2,4,6-trinitrotoluene isomer) was prepared by Hepp in 1880 and its structure determined by Claus and Becker in 1883. The development of TNT throughout the 19th and 20th centuries is summarized in Table 2.11. 

Azido, nitramino, nitro and nitroso derivatives are listed under what may be considered as the parent compound. Thus all the mono-, di-, and trinitrotoluenes will be discussed under toluene. For example, nitraminoterrazoles are discussed under aminotetrazole. With this system the various azido, nitro, etc derivatives included above are kept together and are not scattered throughout the Encyclopedia. Since these derivatives of a given parent compound are usually of some related interest from the point of view of properties, preparation and references, we believe tbat this arrangement is the most convenient... 

Amatol is made up in various proportions of ammonium nitrate to trinitrotoluene, such as 50/50, 60/40, and 80/20. The granulated, dried, and sifted ammonium nitrate, warmed to about 90°, is added to melted trinitrotoluene at about 90°, and the warm mixture, if 50/50 or 60/40, is ladled into the shells which have been previously warmed somewhat in order that solidification may not be too rapid, or, if 80/20, is stemmed or extruded into the shells by means of a screw operating within a steel tube. Synthetic ammonium nitrate is preferred for the preparation of amatol. The pyridine which is generally present in gas liquor and tar liquor ammonia remains in the ammonium nitrate which is made from these liquors and causes frothing and the formation of bubbles in the warm amatol—with the consequent probability of cavitation in the charge. Thiocyanates which are often present in ammonia from the same sources likewise cause frothing, and phenols if present tend to promote exudation. 

Pristera, Preparation and Physical Properties of Di- and Trinitrotoluene Isomers , PATR 2525... 

In another approach, a fluorescent conjugated polymer was used as the material for the preparation of a chemosensor to detect 2,4,6-trinitrotoluene (TNT) and its related nitroaromatic compounds. To this end, microparticles, made of three-dimensionally cross-linked poly(l,4-phenylene vinylene) (PPV) via emulsion polymerization, were synthesized [61]. This material was chosen due to its high fluorescence intensity and sensitivity to changes in its microenvironment. The chemosensor was exposed to vapour containing different amounts of TNT and quenching of the polymer luminescence at 560 nm was observed after excitation at 430 nm. The dependence of the fluorescence signal in response to the analyte was described by a modified Stem-Volmer equation that assumes the existence of two different cavity types. The authors proposed the modified Stem-Volmer equation as follows ... 

In the fertilizer industry, it is used to prepare ammonium sulfate, potassium nitrate and urea. It is used to prepare TNT (trinitrotoluene), nitroglycerine and nitrocellulose in the explosives industry. Nitrogen compounds are also used in the manufacture of dyes and medicines. 

---