Trinitroanisol preparation

A mixture of ammonium nitrate and 2,4,6-trinitroanisole, prepared as an explosive by mixing the hot components, ignited spontaneously and later exploded violently. 

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... 

Other explosives, such as 2,4,6-trinitroanisole (7),33b.226 2,4,6-trinitroaniline (picramide), and tetryl (101), ° are conveniently prepared from the nitration of the corresponding 2,4-dinitro derivatives, which in turn, are prepared from the reaction of 2,4-dinitrochlorobenzene with the appropriate nucleophile. 

Trinitrophenetole (8) can be prepared by heating 2,4,6-trinitroanisole (7) in ethanol containing a catalytic amount of sodium ethoxide. This reaction is so facile that methanol... 

This product was prepared by Blanksma [69] by the nitration of 2,4,6-trinitro-1,3,5-trimethylaminobenzene. The latter was obtained from 3,5-dichloro-(or di-bromo)-2,4,6,-trinitroanisole by the action of an alcoholic solution of methylamine. 

Trinitroanisol may also be prepared by the interaction of methyl iodide and silver picrate, and by the nitration of anisic acid, during which the carboxyl group is lost, but the most convenient method appears to be that of Jackson70 and his collaborators by which a methoxy group is substituted for chlorine in a nucleus already nitrated. A methyl alcohol solution of picryl... 

Preparation of Trinitroanisol. Thirty-five grams of picryl chloride is dissolved in 400 cc. of methyl alcohol with warming under reflux, and the solution is allowed to cool to 30-35°. A solution of 23 grams of sodium hydroxide in 35 cc. of water is added slowly through the condenser, while the liquid is cooled, if need be, to prevent it from boiling. The mixture is allowed to stand for an hour or two. The red precipitate is filtered off, washed with alcohol, and stirred up with water while strong hydrochloric acid is added until all red color has disappeared. The slightly yellowish, almost white, precipitate, washed with water for the removal of sodium chloride, dried, and recrystallized from methyl alcohol, yields pale yellow leaflets of trinitroanisol, m.p. 67-68°. From anhydrous solvents the substance separates in crystals which are practically white. 

Trinitrophenetol or ethyl picrate, m.p. 78°, is prepared by the same methods as trinitroanisol. The explosive properties of the two substances have been studied by Desparmets and Calinaud, and by Desvergnes,72 who has reported the results of the earlier workers together with data of his own and discussions of methods of manufacture and of the explosive properties of mixtures with picric acid, ammonium nitrate, etc. Drop test with a 5-kilogram weight were as follows ... 

When products of the reaction of higher alcoholates with trinitroanisole were hydrolysed, ethers of higher alcohols were formed. According to the authors, this could be a convenient method of preparing higher ethers of picric acid. 

Trinitroanisole was first obtained by Cahours [2a] by the direct nitration of anisole. The reaction proceeds very vigorously, as file presence of a methoxy group greatly facilitates the introduction of nitro groups and some highly coloured by-products are formed [20]. For this reason it is preferable to prepare trinitroanisole via chlo-rodinitrobenzene (p. 547). 

The compound was first obtained by treating picryl chloride (Pisani [12]) or trinitroanisole with ammonia (Salkowski [13]). Later Witt and Witte [14] obtained it by the nitration of o- or p- nitroacetanilide in oleum solution. For the nitration a solution of KN03 in concentrated sulphuric acid was used. Spencer and Wright [15] applied Kym s method [lo] for the preparation of picramide, heating picric acid with urea at 173°C for 36 hr. The yield obtained was about 90% of the theoretical. 

The preparation of this compound resembles that of -+ Trinitroanisol. 

Summary TATB is prepared from the intermediate 3,5-dichloro-2,4,6-trinitroanisole. This intermediate is prepared by treating 3,5-dichloroanisole with nitric and sulfuric acids. The resulting 3,5-dichloro-2,4,6-trinitroanisole is then dissolved in... 

CHAPTER 10 THE PREPERATION OF AMINO NITRO BENZENES toluene, and the mixture treated with ammonia gas. An autoclave is used in the reaction between the 3,5-dichloro-2,4,6-trinitroanisole and ammonia. An autoclave is a special laboratory machine, which is widely available but expensive. Commercial Industrial note For related, or similar information, see Application No. 534,896, June 8, 1990, by The United States of America, to Donald G. Ott, Los Alamos, NM, Theodore M. Benziger, Santa Fe, NM. 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. 

Trinitrophenetol or ethyl picrate, m.p. 78 , is prepared by the same methods as trinitroanisol. The explosive properties of the two substances have been studied by Despannets.and Calinaud,... 

Equilibrium constants and rates of fonnation for the adduct MI-733 have been measured and compared with those of 2,4,6-trinitroanisole. An annular nitrogen in the 4-position to a reactive center results in a relative decrease in stability of the Meisenheimer compound and an increase in its rate of formation when compared to the effect of a p-nitro The 4-methoxypyridone (W-736) has been used to prepare a number of 4-hydrazino- and substituted-4-amino-l-methyl-2-pyridones. ... 

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