chloride, treated with an excess of sodium methylate or of strong caustic soda solution, turns dark red and deposits handsome brilliant red crystals of the empirical composition, trinitro-anisol-NaOCH3. The probable constitution of these crystals is indicated below. On treatment with acid the substance yields trinitroanisol.
The red material is sparingly soluble in alcohol and in water, and is easily decomposed by aqueous acids. It is a primary explosive, stable to moderate heating but decomposing at 165° and exploding violently when introduced into a flame. It is not altered by dry air, but water decomposes it slowly to form first trinitroanisol and later picric acid. On boiling with ethyl alcohol, it yields the sodium ethylatc addition product of trinitrophenetol—an interesting reaction analogous to the ester interchange in the aliphatic series.
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.
Since the methoxy group exercises a greater effect in promoting substitution than the chlorine atom does, it is to be expected that dinitroanisol would take on a third nitro group more easily than dinitrochlorobenzene (to form picryl chloride), and with less expense for acid and for heat. The reactions indicated below are probably the best for the large-scale commercial production of trinitroanisol.
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