Trinitrotoluene Alcohol

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... 

The most important of these explosive isomers is the alpha-trinitrotoluene, known as TNT. In crude, commercial TNT, 4 to 5% of impurities are present, consisting mainly of. a mixture of beta-, or 2,3,4-, and gamma, or 3,4,6-trinitrotoluenes. These impurities may be removed by treating the crude TNT with an aqueous solution of sodium sulfite. Ac-, cording to Davis (Ref 3) the beta- and gamma-isomers react with lead oxide in alcohol to form lead dinitrocresolates, while alpha-TNT remains unaffected under similar conditions Refs 1) M. Copisarow, Chem News 118, 13-14 (1919) CA 13, 791 (1919) 2) M.M. Kos-tevitch, Trinitrobenzene Trinitrotoluene, Paris (1927) 3) Davis (1943) p 147... 

Cyanuric triazide is insoluble in water, sparingly soluble in cold alcohol and readily soluble in hot alcohol, acetone, benzene, chloroform, ether, and molten trinitrotoluene, It is slightly hygroscopic and slightly volatile. It irritates the skin causing dermatitis. Its heat of formation — AHf is 219kcal/mole (H. Muraour [162]). 

Nitrotoluenes, Van No strand, NY(1918) 2)M.Kostevitch, "Tarry Matter of Alpha Trinitrotoluene, Part II, Imprd Art Vol-taire,P aris( 1927), 8 3)Sidgwick( 19 37), 259 et seq 4)Davis(1943), 136-7, 147, 149-51 170-1 5>negering( 1950), 139 seq 6) Dept of the Army TM 9-1910( 1955), 146 Alkalies, Action on Nitric Esters. Organic nitrates in general are readily saponified by alkaline solns. A simple metathetical reaction to yield the alkali nitrate and alcohol does not take place instead, as a result of simultaneous oxidation and reduction, alkali nitrite and a variety of products are formed depending on the conditions of the reaction. The resistance of different nitric esters to alkalies varies considerably. Thus, starch nitrate is decomposed much more slowly than cellulose nitrate and amylopectin nitrate still more alowly... 

The denitration system works satisfactorily only for spent acid from the nitration of glycerine and similar alcohols. In spent acid from trinitrotoluene production the high content of dissolved nitrated hydrocarbons causes an excessive reduction of nitric arid at the top of the denitrating tower. Thus spent acid from the nitration... 

Trinitrohydroxyethylbenzene nitrate or trinitrophenyl-/J-ethyl nitrate, melting at 83°C, is obtained from trinitrotoluene, that undergoes an addition reaction with formaldehyde in an alkaline medium to produce the corresponding alcohol (m.p. 112°C), which is then nitrated (Vender [87]) ... 

Although successfully carried out with model compounds, the cyclopentyl i dene acetal here could not be hydrolyzed selectively in the presence of the other protecting groups. Selective deprotection occurred only upon addition of trinitrotoluene, which us a more electron-deficient aromalic system forms a charge-transfer complex with the electron rich aromalic portion of the PMPh acetal. The charge-transfer complex decreases the electron density of the acetal and thus increases its stability, presumably due to reduced stabilization of cation 38 In this way it proved possible to release the alcohol functions at C-12 and C-13 selectively with acid. 

Tertiary nitro compounds, of course, do not undergo tautomeric transformation, and they might be expected to be resistant to alkalis. Nevertheless aromatic nitro compounds, and polynitro-ones in particular, are very sensitive to alkalis, and undergo transformation when treated with them. For example, sym-trinitrobcnzcnc and also a- trinitrotoluene, when reacted with potassium hydroxide in methyl alcohol solution, form dark addition products (see also p. 202). Under certain conditions the nitro group can break off to form high molecular compounds. 

Dinitrotoluene does not give this reaction. Trinitro compounds (such as sym-trinitrobenzene and a- trinitrotoluene) also give the colour reaction but this is less typical, as the trinitro compounds give a similar colour with alcoholic NaOH alone without primary nitroparaffins. 

Hantzsch and Kissel [81] by treating trinitrotoluene with potassium alcoholate (e.g. methylate) obtained an addition product to which they ascribed the structure given earlier by Angeli [82] for the product obtained from trinitrobenzene and CH3OK (I). 

Copisarow [86] tried to express the changes which trinitrotoluene undergoes under the action of alcoholates or alkali metal hydroxides by the following scheme, in which he postulated the formation of nitro-nitroso derivatives of dibenzyl (III), and stilbene (IV), followed by the formation of an azoxy compound (V), which might be transformed into more complex azoxy compounds ... 

Stefanovich [88], on the basis of Meisenheimer s formulae, ascribes the formulae VII and VIII to the addition products of a- trinitrotoluene with two or three molecules of potassium alcoholate respectively. 

He has stated that a maximum of three molecules of an alcoholate can be added to a- trinitrotoluene, the number being equal to the number of nitro groups. 

T. Urbanski and Pawlowski [89] investigated the salts formed on treating trinitrotoluene in acetone-alcohol solution with sodium alcoholate and also with an alcoholic solution of Ba(OH)2. Various addition products were obtained, according to the proportion of the alcoholate or hydroxide, e.g. ... 

There is evidence that the reaction product of trinitrotoluene with potassium alcoholate, which explodes when heated to 130-150°C, may even ignite spontaneously at room temperature. 

When a piece of potassium hydroxide is put into molten trinitrotoluene at 100°C, it becomes coated with a film that prevents it from reacting further. But on addition of a drop of alcohol, which dissolves both trinitrotoluene and potassium hydroxide, the mixture ignites at once. 

The reactivity of the methyl group in trinitrotoluene is also evident in the reaction with formaldehyde, a molecule of the latter being attached to form a trinitro derivative of phenylethyl alcohol (XVII) [162] ... 

Compound II is highly toxic. It results in the formation of methaemoglobin. The presence of trinitrotoluene in the human body leads to an enhancement of the formation of glucuronic acid, which reacts with the alcohols V and VI to form the corresponding esters. 

The residue left after the solvent - alcohol (in the earlier crystallization method) or xylene (from the washing technique) - has been distilled off, is a semi-solid substance consisting of a- trinitrotoluene, its isomers, dim trot oluenes and other nitro compounds, all of them found as impurities in TNT. 

With sodium- or potassium methoxide, trinitroanisole reacts like sym-trinitro-benzene or a- trinitrotoluene, viz. it adds on an alcoholate molecule, forming a red-coloured addition product (I) ... 

Trinitrotoluene (also known as y-TNT) is one of the main impurities in military and commercial grades of TNT. Chick and Thorpe (1971) characterized two polymorphs. Form I (mp 376.2 K) may be obtained by recrystallization from alcohol or solidification of the melt. Form II (mp 347.2 K) is produced in small quantities with difficulty from an undercooled melt. It readily converts to Form I by mechanical perturbation or even spontaneously. Chick and Thorpe also determined latent heats of fusion, entropies of fusion, specific heats, IR spectra. Due to the conversion induced by grinding no X-ray data were presented for either form. No crystal structures have been reported. 

Trinitrotoluene crystallizes in white glistening needles, which are, to all appearances, scarcely different from dinitrotoluene. This substance melts at 82° and is easily soluble in hot alcohol, but very slightly in cold. In ether it is easily soluble. Boiling alkalies react much easier with trinitrotoluene than with dinitrotoluene. From the deep red alkaline solution, acids precipitate dark flocks. (17)... 

The solubilities of the alpha, beta and gamma trinitrotoluenes are very much the same. There are slight variances, it is true, but these are so slight as-to be of no account for instance, all three isomers are very slightly soluble in cold water shghtly soluble in cold alcohol and very soluble in ether, acetone, hot glacial acetic acid, etc. Alpha trinitrotoluene is very soluble in hot alcohol, while beta and gamma isomers are moderately soluble in the same substance. The specific solubihties of alpha trinitrotoluene are ... 

Gamma trinitrotoluene reacts with aniline readily in hot alcoholic solution. Boiling for several hours is necessary to carry the reaction to completion. Orange-colored crystals finally separate which are insoluble in cold alcohol. The first mother liquor from this crystallization reacts with hydrochloric acid giving a gas. Hepp states that this gas is very likely the result of the reaction of a diazo compound. The reactions by both the beta and gamma forms of trinitrotoluene and aniline are the same, but the beta form seems harder to start. The reaction may be represented by the following equation ... 

The reactions of all six isomeric trinitrotoluenes with alcoholic ammonium sulphide are known. Aside from the compounds formed, the color of the solutions are different in each case, and form a very good method of determining which trinitrotoluene is present. 

Sudborough (8) has succeeded in forming addition compounds with alpha and beta naphthylamine and alpha trinitrotoluene. These reactions take place at moderate temperatures in alcoholic solutions. 

Alkalies produce addition, substitution, and condensation products. Alkalies and alkali compounds produce red colorations with alpha trinitrotoluene. Coparisow found that when 5 c.c. of a saturated solution of potassium hydroxide in methyl alcohol, cooled in solid carbon-dioxide-ether mixture, are added to. 166 g. of pure symmetrical trinitrotoluene, dissolved in a mixture of 1 c.c. pryidine and, 5 c.c. methyl alcohol the latter solution being kept cool in solid carbon-dioxide-ether mixture, the color change took place at a temperature as low as —65° C. 

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