Oxynitration

Benzene and some of its derivatives react with solutions of mercuric nitrate in concentrated nitric acid to give nitrophenols. These reactions, known as oxynitrations may proceed by mercuration followed by nitroso-demercuration the resulting nitroso compound becomes a diazonium compound and then a phenol, which is nitrated. ... 

Aqueous solutions of zirconium oxide dinitrate [13826-66-9] (zirconium oxynitrate) and zirconium oxychloride behave very similarly these two compounds have been cocrystallized in soHd solution (202) where ZrO(N03 -5H2 O was the stable hydrate. 

Dissolve 100 g of (+)-tartaric acid in 400 ml of water and add 8.5 g of bismuth oxynitrate. Shake for 1 hour, add 200 ml of a 40% w/v solution of KI and shake well Allow to stand for 24 hours and filter. Store and protect from light. 

Nitric acid in the presence of catalytic amounts of mercury (II) nitrate reacts with some substrates, under certain conditions, to give substimted polynitrophenols. The first example, reported by Boeters and Wolffenstein and known as oxynitration , involved treating benzene with 50-55 % nitric acid in the presence of mercury (II) nitrate. The product is a mixture of unreacted benzene, nitrobenzene, m-dinitrobenzene, 2,4-dinitrophenol and picric acid, from which the latter can be isolated by steam distillation of this crude mixture followed by recrystallization of the residue from hot water. 

The mechanism of oxynitration is generally accepted to involve the formation of phenyl mercuric nitrate which reacts with nitrogen oxides in the nitric acid to form a nitroso compound and then a diazonium salt the latter forms a phenol under the aqueous conditions which is then further nitrated. The use of more concentrated nitric acid favours a process of mercuration-nitration and suppresses the formation of phenols. ... 

Other examples of oxynitration include the formation of (1) 2,4,6-trinitro-m-cresol from toluene, (2) 2,4-dinitronaphth-l-ol from naphthalene, (3) 3-chloro-2,4,6-trinitrophenol from chlorobenzene and (4) 3-hydroxy-2,4,6-trinitrobenzoic acid from benzoic acid. ... 

Bismuth oxynitrate is used in cosmetics, enamel fluxes and ceramic glazes. Medical applications include treatment of diarrhea, and gastric ulcers and opacifier in x-ray diagnosis of ahmentary canal. ... 

Bismuth oxynitrate is prepared by hydrolysis of bismuth nitrate using either water or sodium bicarbonate solution under mild heating (between 30 to 70°C) and stirring. The composition of the product formed can vary depending on the strength of nitric acid and the quantity of water used. 

At 260°C or above, bismuth oxynitrate decomposes to bismuth oxide and... 

The nitrate, (Y(NO)3)3 ) exists as a number of hydrates. The hexahydrate formed by action of HNO3 upon the hydroxide, is dehydrated at 100°C to give the tnhydrate and the anhydrous salt. However, other hydrates are known, as well as double nitrates (especially with the lanthanide elements) and oxynitrates. of the general formula, XY2O3 3 05 -ZH2O. 

Zinc also forms both nitrates and oxynitrates (in various hydrated forms) but the oxynitrate is less stable. It is formed by heating the hexamtrate, or treating the nitrate solution with NH3. 

Silver(II) oxide, 4 12 Silver oxynitrate, Ag70sN03, formation of, by silver(II) oxide, 4 13 Silver subfluoride, Ag2F, 6 18,19 Sodium, calcium metal preparation from a solution in, 6 18, 24... 

Nothing seems to be known of the structures of the oxynitrates, so the writing of the formulas is somewhat arbitrary, e.g., Pb(N03)2.2 PbO = 3Pb0.N205. 

AgjOaNOs Silver oxynitrate, 4 13 AlBr2 Aluminum bromide, 3 30, 33 [A1(C204)s]Kj-3H20 Potassium tri-oxalatoaluminate, 1 36 A1(C6H702)s Aluminum acetylace-tonate, 2 25... 

Zakharov found oxynitration to proceed best at 60% concentration of nitric acid. 

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