Nitrates preparation

Despite the fact that solutions of acetyl nitrate prepared from purified nitric acid contained no detectable nitrous acid, the sensitivity of the rates of nitration of very reactive compounds to nitrous acid demonstrated in this work is so great that concentrations of nitrous acid below the detectable level could produce considerable catalytic effects. However, because the concentration of nitrous acid in these solutions is unknown the possibility cannot absolutely be excluded that the special mechanism is nitration by a relatively unreactive electrophile. Whatever the nature of the supervenient reaction, it is clear that there is at least a dichotomy in the mechanism of nitration for very reactive compounds, and that, unless the contributions of the separate mechanisms can be distinguished, quantitative comparisons of reactivity are meaningless. 

When nitration of pyridazine iV-oxides is carried out with acyl nitrates (prepared in situ from acyl chlorides and silver nitrate) the reaction takes place at the /3-position relative to the iV-oxide group. Under these circumstances only mononitro derivatives are formed. For example, nitration of pyridazine 1-oxide with acetyl nitrate yields 3-nitropyridazine 1-oxide (17%) and 5-nitropyridazine 1-oxide (0.8%), whereas with benzoyl nitrate a better yield of 5-nitropyridazine 1-oxide is obtained. 

Furazan compound 278 was obtained as a by-product from cholestan-3-one oxime 277 by prolonged heating in an acetic anhydride-pyridine mixture followed by treating with acetyl nitrate prepared from acetic anhydride and nitric acid (Equation 53) <1997T16161>. 

Solutions of acetyl nitrate, prepared from fuming nitric acid and acetic anhydride, can react with alkenes to yield a mixture of nitro and nitrate ester products, but the /3-nitroacetate is usually the major product. ° Treatment of cyclohexene with this reagent is reported to yield a mixture of 2-nitrocyclohexanol nitrate, 2-nitrocyclohexanol acetate, 2-nitrocyclohexene and 3-nitrocyclohexene. °/3-Nitroacetates readily undergo elimination to the a-nitroalkenes on heating with potassium bicarbonate. /3-Nitroacetates are also reduced to the nitroalkane on treatment with sodium borohydride in DMSO. ... 

Cadmium nitrate, preparation of, 6 135 Cadmium phthalocyanine electronic absorption spectra of, 7 68 preparation of, 7 41 Cadmium selenocyanates, 17 337 Cadmium sulfoxide complexes, 24 167-168... 

C2 domains, 46 460-465 y-carboxyglutamic acid sites, 46 465 70 Calcium nitrate, preparation of, 6 125 Calcium pentaphosphate, 4 37-38 Calcium phthalocyanine, preparation of, 7 ... 

Preparation of Anhydrous Copper Nitrate. Prepare 7-10 ml of liquid nitrogen(IV) oxide (see Fig. 86a). If the oxide has solidified,... 

Alcohols, Nitrated, Preparation from nitro-paraffins by condensation with aldehydes in the presence of an alkaline catalysts is discussed by H.A.Aaronson in PATR 1125 (1941)... 

Nitration of pyridazine A-oxides with acyl nitrates prepared from acyl chlorides and silver nitrate also occurs at the (3-position relative to the /V-oxide group. Thus, pyridazine 1-oxide yields 3-nitropyridazine 1-oxide. 

Ammonium nitrate prepared from ammonia obtained by the dry distillation of coal should not be used as component of any explosive material because of the ammonium thiocyanate and pyridine present in it (the latter as nitrate). When the ammonia liquor from dry distillation of coal was the sole source af ammonia and ammonium nitrate, decomposition of mixtures containing ammonium nitrate with TNT (amatols), was brought about at the melting point TNT reacted with ammonium thiocyanate or with pyridine nitrate and evolved gaseous products. Minute traces of these impurities were sufficient to cause abundant gas evolution to develop during the fusion, pouring, and cooling of amatol. 

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