2.4.6- trinitrotoluene synthesis

A.T. Nielsen et al, Reduction and Ammonoly-sis Products Derived from Isomeric Trinitrotoluenes. Synthesis and Chemical Stability of the Aminodinitrotoluenes , NWC-TP-5933, NavalWeapCenter, China Lake (1977)... 

The only known example of this type of cyclization is the synthesis of dibenz[, /]azepines 457 from appropriate salicylaldehyde 454 and 2,4, 6-trinitrotoluene (455) via the corresponding intermediate 456 (Scheme 72) (62M766). 

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... 

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... 

Chemists at the Naval Air Warfare Center (NAWC), Weapons Division, China Lake, have reported many examples of polynitroarylamine synthesis via Bamberger rearrangements of arylnitramines. " " The nitration of 4-amino-2,5-dinitrotoluene (36) with a mixture of nitric acid and acetic anhydride in glacial acetic acid at room temperature yields the nitramine (37) which on treatment with neat sulfuric acid, provides 4-amino-2,3,5-trinitrotoluene (38) as the sole product. " Nitration of 3,4-dinitroaniline (39) with a solution of nitric acid in acetic anhydride yields A,3,4-trinitroaniline (40) acid-catalyzed rearrangement of the latter in neat sulfuric acid furnishes a 74 % yield of isomeric 2,3,4- (41) and 2,4,5- (42) trinitroanilines in a 4 6 ratio.Accordingly, a mixture of products can be expected when an unsymmetrical arylnitramine has two unsubstituted ortho positions available. 

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,... 

The displacement of alkoxy groups from polynitroarylenes has been used for the indirect synthesis of some highly nitrated polynitroarylenes. Holleman synthesized 2,3,4,6-tetranitrotoluene (57) by treating 3-methoxy-2,4,6-trinitrotoluene (132) with ammonia in methanol, followed by oxidation of the resulting product (56) with peroxymonosulfuric acid. 

DNB is often made first. Both 1,3-DNB and 1,3,5-TNB are formed as by-products when another explosive, trinitrotoluene (TNT), is made. 1,3-DNB is also used to make certain dyes, as an intermediate in the synthesis of organic chemicals, and in the plastics manufacturing industry. 1,3,5-TNB is used in making rubber. Other names for 1,3-DNB include m-dinitrobenzene,... 

Problem 11.52 Available organic starting materials for synthesizing the pairs of compounds below are PhH, PhMe, and PhNO,. Select the compound in each pair whose synthesis is more expensive and explain your choice, (a) p-C,H4(N02)2 and m-C,H4(N02)2, (b) m-nitrotoluene and p-nitrotoluene, (c) 2,4.6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene, (d) ffi-C H4Cl2 and p-C H4Clj. ... 

Another raw material potentially useful for the synthesis of condensation monomers is 2,4,6-trinitrotoluene (TNT) a well-known military explosive [20, 21]. Presently in a number of countries a large amount of ammunition liable to liquidation has been accumulated. Its major explosive component is TNT, and thus its utilisation has become a basic challenge [20, 21]. 

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. 

The principal methods of synthesis of the aminodinitrotoluenes are as follows 1) Am-monolysis of trinitrotoluenes with excess etha-nolic ammonia at reflux or 25° 2) ammonolysis of hydroxy, alkoxy or halodinitrotoluenes ... 

It has been demonstrated that 2,4,6-trinitrotoluene (TNT) can serve as a useful precursor for the synthesis of indoles, as well as other benzo-fused heterocyclic systems. Thus e.g. the... 

The other major use of nitric acid is in organic nitration. Nitration using mixtures of sulfuric and nitric acid is the first step in the synthesis of amino-and nitro-compounds such as aniline and trinitrotoluene (TNT). Many important dyes and pharmaceuticals are ultimately derived from these reactions. However, their quantities are quite small. Polyurethane polymers are also ultimately derived from nitrated toluene and benzene and this use accounts for 5—10% of nitric acid end uses. 

Although many other explosives and explosives-related compounds exist, only the data for 2,4,6-trinitrotoluene (TNT) and its breakdown products, the cyclic nit-ramines (RDX and HMX), tetryl, trinitrobenzene, and nitroglycerin will be reviewed in this chapter. Two dinitrotoluene isomers are also included, as they are still used as explosives in addition to being side-products of TNT synthesis. 

While no new synthetic methods for this group have appeared improvements in the synthesis of phloroglucinol and that of some of its derivatives have attracted attention. The classic route by way of trinitrotoluene, trinitrobenzoic acid, triaminobenzoic acid and its hydrolysis and decarboxylation has been challenged by methods based on the use of acyclic precursors. 

Building onto the concept of molecularly wired sensors for signal amplification, Swager reported in 1998 the synthesis of a series of porous PPE derivatives in which pentiptycene modules are incorporated into the PPE main chain. The incorporation of the pentypticene moieties makes 29 and 30a (Chart 5) efficient solid-state emitters unaffected by aggregation i.e., their emission spectra in solution and in the solid state are almost identical. The authors found that thin films of these highly fluorescent PPEs are excellent sensors for the detection of trinitrotoluene and dinitrotoluene. Both aromatics suppress the fluorescence of 29 or 30a effectively but reversibly. The headspace, i.e., the atmospheric volume above land mines, contains measurable quantities of dinitrotoluene. As a consequence, polymers 29 and 30 coated on top of a fiber optic sensor will allow their simple detection by these very sensitive molecular wire-type materials. This elegant concept should be extendable and applicable to any other analyte, (a) which has the ability to quench fluorescence and (b) for which a receptor can be attached to PPEs. 

G. A. Olah in Chapter 7 reviews some of the most useful methods in preparing nitro compounds (i.e., electrophilic nitrations with superacid systems, nitronium salts, and related Friedel-Crafts type complexes). Polynitro compounds were traditionally and still are the most widely used explosives [e.g., nitroglycerol, trinitrotoluene (TNT), and Af-nitramines (RDX and HMX)]. Methods of preparing nitro compounds thus remain a key part of the synthesis of energetic materials. 

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