Tetranitrotoluenes

Some substrates show limited solubility in sulfuric acid solutions and this can affect the rate of oxidation. However, the main factor for slow amine oxidation is due to the high concentration of protonated amine under these highly acidic conditions. Under these conditions only weakly basic amines have a high enough concentration of unprotonated form to permit oxidation to occur. As a result, sulfuric acid solutions of peroxydisulfuric acid are only useful for the oxidation of very weakly basic amines. Peroxydisulfuric acid oxidizes trinitrotoluidines to tetranitrotoluenes (Table4.1, Entry 3) but leaves the more basic dinitrotoluidines unaffected. The opposite is true of peroxyacids like peroxytrifluoroacetic acid and so the reagents are very much complementary. 

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. 

With coned nitric acid it forms 2,3,4,6-tetranitrotoluene... 

Ref 2 terms this compd an expl. The compd s deep red expl K salt, Potassium-o ,2,4,6-Tetra-nitrotoluene is formed using a tetrahydrofuran-methanol soln of K hydroxide and a, 2,4,6-tetranitrotoluene, and precipitating the salt with eth. The salt is reported to be v sensitive to impact and heat... 

One, two, or three nitro groups can be introduced by direct nitration of toluene. Tetranitrotoluene can be obtained only by indirect methods. 

The trinitro-m-toluidine thus obtained is oxidized in sulphuric acid solution with potassium persulphate. The yield of this stage of the reaction is about 85% of theory. The tetranitrotoluene thus prepared may then be recrystallized from nitric acid of a sp. gr. of 1.40. 

Tetranitrotoluene is much more stable than tetranitrobenzene. It is considerably, more resistant to hydrolytic action of water. At room temperature the presence of trinitrocresol cannot be detected earlier than 24 hr at 80°C only 57% of the product is converted within this period. 

Holleman reported the following explosive properties of tetranitrotoluene ... 

TeNT = tetranitrotoluene TeNTMB = 3,5, 5 -tetranitro-4,4 -tetra-methyldiaminobiphenyl (USA) TePhUR = tetraphenylurea (USA) Territ = plastic explosive consisting of nitroglycerine, APC, DNT TNI) SN and nitrocellulose (Sweden) test cap 309... 

Thereafter, add and dissolve 14 grams of 2-amino-3,4,5,6-tetranitrotoluene (prepared in step 2) while stirring the acid mixture. Then slowly add 7 milliliters of 98% sulfuric acid, drop wise, over a period of 40 minutes while stirring the reaction mixture. After the addition of the 98% sulfuric acid, stir the reaction mixture overnight at room temperature. Afterwards, extract the reaction mixture with six 150-milliliter portions of chloroform. The chloroform will be the upper layer. After the extraction process, combine all three portions of chloroform (if not already done so), and then remove the chloroform by distillation at 65 Celsius until dry solid remains (the distillation may need to be temporarily stopped in order to filter-off precipitated product). After the chloroform has been removed, remove the heat source and allow the contents in the distillation flask to cool to room temperature. Then collect the dry product from the distillation flask, and then vacuum dry or air-dry any product that may have been filtered-off during the distillation process. Then combine all the dry product, wash with 400 milliliters of water, and then vacuum dry or air-dry. The result will be 13 grams of pentanitrotoluene, as yellow crystals with a melting point of 224 Celsius. 

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... 

Preparation and constitution of unsymmetrical trinitrotoluenes Other by-prodacts in the nitration of toluene Tetranitrotoluene Literature... 

Ice-cooled aq.-methanolic KOH added quickly at 0° to a Dry Ice-acetone cooled, well-stirred soln. of 2,4,6-trinitrotoluene and fluorotrinitromethane in tetrahydro-furan-methanol, whereupon the temp, rises to ca. 5°, then begins to fall, and the product isolated when the temp, has again reached 0° -> a,2,4,6-tetranitrotoluene. Y 89%. M. E. Sitzmann, L. A. Kaplan, and I. Angres, J. Org. Chem. 42, 563... 

Figure 4. Reduction of TNT to 4-amino-2,6-dinitrotoluene (4Am-DNT). 4-Nitroso-2,6-dinitrotoluene (4NO-DNT) could not be detected in the reduction of TNT. 4-Hydroxylamino-2,6-dinitrotoluene (40HA-DNT) is the first detectable intermediate in the reduction course of TNT by P. chrysosporium. 4,4 -Azoxy-2,2 4,4 -tetranitrotoluene is the spontaneous condensation product of 40HA-DNT and 4NO-DNT. It is assumed that the latter is generated from 40HA-DNT by an oxidative force such as manganese dioxide in the culture fluid.

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