Nitromethane-sulfuric acid solutions

FLUOROSULFONIC ACID (7789-21-1) Reacts violently with moisture (including moisture in air), generating hydrogen fluoride and sulfuric acid. Solution is a strong acid. Aqueous solution is incompatible with sulfuric acid, alkalis, ammonia, aliphatic amines, alka-nolamines, alkylene oxides, amides, epichlorohydrin, organic anhydrides, isocyanates, vinyl acetate. Increases the explosive sensitivity of nitromethane. Attacks metals, especially in the presence of moisture, liberating flammable hydrogen gas. 

It should be mentioned that medium effects do not usually change the characteristic shape of an absorption spectrum to such an extent that it can not be recognized. Thus the characteristic Bactrian camel shape of the absorption band of solutions of trityl chloride in sulfuric acid and in nitromethane leaves no doubt that essentially the same ion is present in both solvents. 

Thianthrene 5-oxide is converted, in concentrated sulfuric acid, into a solution of T (62JA4798) sulfuric or perchloric acid in nitromethane can also be used (63TL993). One view is that this transformation involves homolysis of the O-protonated sulfoxide, with hydroxyl radical as byproduct, though the involvement of a dication has also been suggested (63JOC2828). 

The benzobisazole family of rigid-rod polymers is soluble in acidic solvents such as PPA, methanesulfonic acid, chlorosulfonic acid, 100% sulfuric acid and Lewis acid salts such as antimony trichloride and bismuth trichloride. More recently, PBZT has been reported [22] to form liquid crystalline solutions in nitromethane containing aluminum trichloride or gallium trichloride. Since the glass transition temperature of these materials is above their decomposition temperature, they must be processed from solution. 

When [this nitrile, 4,6-benzylidene-2,3,5-triacetyl-D-gluconic nitrile, was treated with sodium methoxide in methanol solution in the presence of nitromethane, there was obtained readily from the reaction mixture crystalline 4,6-benzylidene-l-nitro-l-desoxy-D-mannitol. Hydrolysis of the benzylidene acetal with dilute sulfuric acid then gave the crystalline 1 -nitro-1 -desoxy-D-mannitol. 

For use as solvent in a kinetic study (Olah ), Eastman spectroscopic grade nitromethane was washed three times with a solution containing 25 g. of NaHCOa and 25 g. of NaHSOs per liter, then with water, 5% sulfuric acid, water, aqueous NaHCOs, dried overnight with Drierite, then passed through a 2-ft. column of A in. type 4A Linde molecular sieves, and distilled at 58°/160 mm. from a small amount of sieve powder to yield solvent neutral to bromphenol blue in ethanol and dry to Karl Fischer reagent ( D 1.3790). 

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