Nitric acid reaction with alcohols

Method 1. Place 20 g. of crude benzoin (preceding Section) and 100 ml. of concentrated nitric acid in a 250 ml. round-bottomed flask. Heat on a boiling water bath (in the fume cupboard) with occasional shaking until the evolution of oxides of nitrogen has ceased (about 1 -5 hours). Pour the reaction mixture into 300-400 ml. of cold water contained in a beaker, stir well until the oil crystallises completely as a yellow solid. Filter the crude benzil at the pump, and wash it thoroughly with water to remove the nitric acid. RecrystaUise from alcohol or methylated spirit (about 2-5 ml. per gram). The yield of pure benzil, m.p. 94-96°, is 19 g. 

Reaction with alcoholic silver nitrate. To carry out the test, treat 2 ml. of a 2 per cent, solution of silver nitrate in alcohol with 1 or 2 drops (or 0 05 g.) of the compound. If no appreciable precipitate appears at the laboratory temperature, heat on a boiling water bath for several minutes. Some organic acids give insoluble silver salts, hence it is advisable to add 1 drop of dilute (5 per cent.) nitric acid at the conclusion of the test most silver salts of organic acids are soluble in nitric acid. 

The final product of the action of nitric acid on hexamine or hexamine dinitrate is RDX see Vol 3, p C614. At low temps, however a number of other compounds are produced (Ref 2). Dilution of the hexamine dinitrate-nitric acid reaction mixture at low temperatures with ethyl ether and subsequent treatment of the gum so obtained with methyl and ethyl alcohols and water severally leads to l-alkoxy-3 5-dinitro-l 3 5-triazacyclohexane (IV), l 3-di-nitro-l 3 5-triaza-n-pentane 5-nitrate (V), and methylenedi-1 -(3 5-dinitro-1 3 5-triaza-cyclo-hexane) (VI). Dilution of the reaction mixture with methyl and ethyl alcohol produces mainly 3 5-dinitro-1 3 5-triazacyclohexane nitrate (II). 

Figure 93. Fulminate Manufacture. (Courtesy Atlas Powder Company.) At left, flasks in which mercury is dissolved in nitric acid. At right, balloons in which the reaction with alcohol occurs.

The use of nitrogen dioxide for the selective oxidation of polysaccharides to polyuronic acids was introduced by Kenyon and his coworkers13,63 in 1941. By this means extensive oxidation of the primary alcohol groups in cellulose was obtained, through the mechanism of preferential nitration followed by decomposition of the nitric acid ester with carboxyl forma-tion.68(0< > Apparently some undissociated nitration products also were formed, since infrared absorption studies54 indicated the presence of nitrate radicals in the polyuronic acid. Side reactions produced carboxyl,... 

Chitosan is insoluble in water, concentrated acids, alkalis, alcohol, and acetone, but dissolves readily in dilute acids. Water-soluble salts of chitosan include the nitrate and the perchlorate. As described on p. 377, formation of chitosan sulfate and the color reaction of chitosan with iodine have been widely used as qualitative tests for the detection of chitin. Nitration of chitosan with a mixture of acetic and nitric acids or with absolute nitric acid enabled both the free ester and its nitrate salt to be isolated. The perchlorate salt of this ester was also prepared, but it was unstable. Chitosan can be W-acetylated to give products similar to chitin except for their greatly reduced chain-length W-formyl-, iV-propionyl-, JV-butyryl-, and iV-benzoyl-chitosan were also prepared. ... 

MERCURIC THIOCYANATE (592-85-8) Hg(SCN)i Moderately unstable solid. Possible violent reaction with strong oxidizers strong acids organic peroxides, peroxides and hydroperoxides potassium chlorate potassium iodate, silver nitrate, sodium chlorate, nitric acid. Incompatible with ammonia, chlorates, hydrozoic acid, methyl isocyanoacetate, nitrates, nitrites, perchlorates, sodium peroxyborate, trinitrobenzoic acid, urea nitrate. When heated, this material swells to many times its original bulk. Attacks aluminum in the presence of moisture. Decomposes above 329°F/165°C, releasing toxic mercury and cyanide fumes, and sulfur and nitrogen oxides. On small fires, use dry chemical powder (such as Purple-K-Powder), alcohol-resistant foam, or COj extinguishers. MERCURIC (Spanish) (7439-97-6) see mercury. 

SODIUM RHODANIDE (540-72-7) NaSCN Exposure to light causes slow decomposition, forming cyanide, sulfur oxides, and nitrous vapors. Violent reaction, possibly explosion, with strong oxidizers, organic peroxides, nitric acid. Incompatible with acids, bases, chlorates, anunonia, amines, amides, alcohols, glycols, caprolactam, nitrates, peroxides and hydroperoxides, potassium chlorate, potassium iodate, silver nitrate, sodium chlorate. Contact with sulfuric acid forms toxic carbonyl sulfide gas. Forms explosive mixture with sodium nitrate. Thermal decomposition releases oxides of sulfur and nitrogen. 

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