Potassium acetate acid nitrate

Alternatively, treat a solution of 3 9 g. of the 6is-diazo ketone in 50 ml. of warm dioxan with 15 ml. of 20 per cent, aqueous ammonia and 3 ml. of 10 per cent, aqueous silver nitrate under reflux in a 250 or 500 ml. flask on a water bath. Nitrogen is gently evolved for a few minutes, followed by a violent reaction and the production of a dark brown and opaque mixture. Continue the heating for 30 minutes on the water bath and filter hot the diamide of decane-1 lO dicarboxyhc acid is deposited on cooling. Filter this off and dry the yield is 3 -1 g., m.p. 182-184°, raised to 184-185° after recrystallisation from 25 per cent, aqueous acetic add. Hydrolyse the diamide (1 mol) by refluxing for 2-5 hours with 3N potassium hydroxide (4 mols) acidify and recrystaUise the acid from 20 per cent, acetic acid. The yield of decane-1 10-dicarboxyhc acid, m.p. 127-128°, is almost quantitative. 

Method A. Cool a solution of the nitrate-free dichloride, prepared from or equivalent to 5 0 g. of palladium or platinum, in 50 ml. of water and 5 ml. of concentrated hydrochloric acid in a freezing mixture, and treat it with 50 ml. of formahn (40 per cent, formaldehyde) and 11 g. of the carrier (charcoal or asbestos). Stir the mixture mechanically and add a solution of 50 g. of potassium hydroxide in 50 ml. of water, keeping the temperature below 5°. When the addition is complete, raise the temperature to 60° for 15 minutes. Wash the catalyst thoroughly by decantation with water and finally with dilute acetic acid, collect on a suction filter, and wash with hot water until free from chloride or alkali. Dry at 100° and store in a desiccator. 

Later, a completely different and more convenient synthesis of riboflavin and analogues was developed (34). It consists of the nitrosative cyclization of 6-(A/-D-ribityl-3,4-xyhdino)uracil (18), obtained from the condensation of A/-D-ribityl-3,4-xyhdine (11) and 6-chlorouracil (19), with excess sodium nitrite in acetic acid, or the cyclization of (18) with potassium nitrate in acetic in the presence of sulfuric acid, to give riboflavin-5-oxide (20) in high yield. Reduction with sodium dithionite gives (1). In another synthesis, 5-nitro-6-(A/-D-ribityl-3,4-xyhdino) uracil (21), prepared in situ from the condensation of 6-chloro-5-nitrouracil (22) with A/-D-ribityl-3,4-xyhdine (11), was hydrogenated over palladium on charcoal in acetic acid. The filtrate included 5-amino-6-(A/-D-ribityl-3,4-xyhdino)uracil (23) and was maintained at room temperature to precipitate (1) by autoxidation (35). These two pathways are suitable for the preparation of riboflavin analogues possessing several substituents (Fig. 4). 

To prepare fervenulin 4-oxides 12 or toxoflavine 4-oxides 146, it is convenient to use the reaction of l,3-dimethyl-2,4-dioxopyrimidin-6-yl hydrazone 147 or N-(3-methyl-2,4-dioxopyiimidin-6-yl) iV-methylhydrazone 148 with potassium nitrate in acetic acid [75CPB1885,76CPB338,76JCS(CC)658,82JHC1309,93CPB362]. Diethyl azodicarboxylate can be used instead of potassium nitrate [76JCS(P1 )713]. 

Anilinofervenulin 4-oxides 151 were synthesized by the reaction of 6-hydra-zino-l,3-dimethyluracil with triethyl orthoformate, followed by the treatment of the hydrazide 152 with aniline and further cylization of 153 in the presence of potassium nitrate in acetic acid (82JHC1309). 

Den Hertog and Overhoff - observed that when pyridine in sulfuric acid is added to molten potassium sodium nitrate the 3-nitro derivative is formed at 300°C, whereas at 450°C 2-nitropyridme is the main product. The latter is probably a free-radical process. Schorigin and Toptschiew obtained 7-nitroquinoline by the action of nitrogen peroxide on quinoline at 100°C, possibly through the homolytic addition of NOa. Laville and Waters reported that during the decomposition of pernitrous acid in aqueous acetic acid, quinoline is nitrated in the 6- and 7-positions. They considered that the reaction proceeds as shown in Scheme 3. 

Quinoxalin-2-one is a very weak base (pK — 1.37) and so the different orientation of substitution in acetic and sulfuric acids may mean that in acetic acid the principal species undergoing nitration is the neutral molecule, and in sulfuric acid, the mono-cation. Treatment of quinoxaline-2,3-dione, or its iViV -dimethyl derivative in sulfuric acid, with 1 equivalent of potassium nitrate, results in nitration at position 6 with 2 equivalents of potassium nitrate, 6,7-dinitro compounds are formed. When quinoxaline is boiled with aqueous nitric acid, 6-... 

Reagents. In view of the sensitivity of the method, the reagents employed for preparing the ground solutions must be very pure, and the water used should be re-distilled in an all-glass, or better, an all-silica apparatus the traces of organic material sometimes encountered in demineralised water (Section 3.17) make such water unsuitable for this technique unless it is distilled. The common supporting electrolytes include potassium chloride, sodium acetate-acetic acid buffer solutions, ammonia-ammonium chloride buffer solutions, hydrochloric acid and potassium nitrate. 

Using Potassium Nitrate-Sulfuric Acid-Acetic Acid... 

Evaporation by heating a filtrate from precipitation of potassium cobaltinitrite caused it to turn purple and explode violently [1]. This was attributed to interaction of nitrite, nitrate, acetic acid and residual cobalt with formation of fulminic or methylnitrolic acids or their cobalt salts, all of which are explosive [2], Mixtures containing nitrates, nitrites and organic materials are potentially dangerous, especially in presence of acidic materials and heavy metals. A later publication confirms the suggestion of formation of nitro- or nitrito-cobaltate(III) [3],... 

Nitration of 206 with a mixture of potassium nitrate and sulfuric acid yielded a mixture of dinitro derivative 240 and oxidation product 46. Heating 206 with sodium borohydride led to hydrolysis to 208 rather than to any reduction product. On the other hand, reduction with zinc in cold acetic acid provided dihydro derivative 241, whereas catalytic hydrogenation over palladium on carbon provided tetrahydro derivative 242 (Scheme 59) [90JCS(P 1) 1463]. 

Lead tetraacetate is added in small quantities, with stirring, to an ice-cold suspension of 11 g. of ethyl 3-(D-arabino-tetrahydroxybutyl)-5-methyl 4-furoate in 100 ml. of benzene plus 40 ml. of glacial acetic acid. Addition is stopped when there is a positive reaction with potassium iodide-starch paper. The mixture is stirred for a further ten minutes, filtered, and the benzene solution washed twice with water. The benzene layer is then dried with anhydrous sodium sulfate, filtered, and the filtrate evaporated to dryness. The residue (6 g.) is mixed with a solution of 7.5 g. of sodium hydroxide plus 20 g. of silver nitrate in 40 ml. of water, and heated for 40 minutes on a steam bath. The aqueous solution is filtered, acidified to Congo Red while being cooled with ice, and the crystals formed are removed by filtration, washed with ice-cold water, and dried over phosphorus pentoxide in the vacuum desiccator yield, 2.2 g. After recrystallization from water, the product has m. p. 234r-235°. 

Polarography has also been applied to the determination of potassium in seawater [535]. The sample (1 ml) is heated to 70 °C and treated with 0.1 M sodium tetraphenylborate (1 ml). The precipitated potassium tetraphenylborate is filtered off, washed with 1% acetic acid, and dissolved in 5 ml acetone. This solution is treated with 3 ml 0.1 M thallium nitrate and 1.25 ml 2M sodium hydroxide, and the precipitate of thallium tetraphenylborate is filtered off. The filtrate is made up to 25 ml, and after de-aeration with nitrogen, unconsumed thallium is determined polarographically. There is no interference from 60 mg sodium, 0.2 mg calcium or magnesium, 20 pg barium, or 2.5 pg strontium. Standard eviations at concentrations of 375, 750, and 1125 pg potassium per ml were 26.4, 26.9, and 30.5, respectively. Results agreed with those obtained by flame photometry. 

Soliman and Belal investigated argentimetric (67,68) and mercurimetric (69) methods. Hydralazine precipitates silver from ammoniacal silver nitrate solution. The silver is dissolved with hot nitric acid and titrated with ammonium thiocyanate solution. Alternatively, mercury is precipitated from alkaline potassium mercuric iodide solution. The precipitated mercury is dissolved by adding excess standard iodine solution. The excess iodine is back-titrated with sodium thiosulfate solution after acidifying with acetic acid. 

The same reaction can be applied, not only to the aromatic parent substances, the hydrocarbons, but also to all their derivatives, such as phenols, amines, aldehydes, acids, and so on. The nitration does not, however, always proceed with the same ease, and therefore the most favourable experimental conditions must be determined for each substance. If a substance is very easily nitrated it may be done with nitric acid sufficiently diluted with water, or else the substance to be nitrated is dissolved in a resistant solvent and is then treated with nitric acid. Glacial acetic acid is frequently used as the solvent. Substances which are less easily nitrated are dissolved in concentrated or fuming nitric acid. If the nitration proceeds with difficulty the elimination of water is facilitated by the addition of concentrated sulphuric acid to ordinary or fuming nitric acid. When nitration is carried out in sulphuric acid solution, potassium or sodium nitrate is sometimes used instead of nitric acid. The methods of nitration described may be still further modified in two ways 1, the temperature or, 2, the amount of nitric acid used, may be varied. Thus nitration can be carried out at the temperature of a freezing mixture, at that of ice, at that of cold water, at a gentle heat, or, finally, at the boiling point. Moreover, we can either employ an excess of nitric acid or the theoretical amount. Small scale preliminary experiments will indicate which of these numerous modifications may be expected to yield the best results. Since nitro-compounds are usually insoluble or sparingly soluble in water they can be precipitated from the nitration mixture by dilution with water. 

For purification the crude product is boiled with glacial acetic acid (preferably in the extraction apparatus shown in Fig. 27). Fine red needles melting point 289°. Sublimation in a vacuum from a sausage flask is also to be recommended the sausage should be fixed low down and the bulb completely immersed in a nitrate bath (equal parts of potassium and sodium nitrates). Much poorer yields of alizarin are obtained by using an open round-bottomed flask at 189°-190°. 

B—A (nitrous acid) and D (acetic acid) are weak acids, and E (ammonia) is a weak base. Weak acids and bases are weak electrolytes. C (ethanol) is a nonelectrolyte. Potassium nitrate (B) is a water-soluble ionic compound. 

Materials Required Glyceryl trinitrate tablets 20 glacial acetic acid (90% v/v) 5 ml phenoldisulphonic acid solution (heat 3 g of phenol with 20 ml of sulphuric acid on a water-bath for 6 hours, and transfer the resulting liquid to a stoppered vessel) 2 ml strong ammonia solution 20 ml potassium nitrate (previously dried at 105 °C) 1 g ... 

Dissolve 133.5 mg of potassium nitrate, in sufficient DW to produce 100 ml to 10 ml add sufficient glacial acetic acid to produce 100 ml. Taking 2 ml of this solution, just repeat the assay beginning the procedure at add 2 ml of phenoldisulphonic acid solution. . 

Buffer solution - dissolve 6.0 g ferric nitrate, Fe(N03)3.9FH20, and 0.15 g silver nitrate, AgNOj, in water and make up to 100 ml add this to a solution of 5.0 g potassium acetate in 500 ml glacial acetic acid in a 2-1 beaker and stir to mix. Add 400 ml 2-methylpropan-2-ol (tertiary butyl alcohol, (CH3)3C0H this solidifies s25.5°C, therefore it may need warming to melt before use), and stir to mix. Store in a brown glass bottle. 

Treatment of 6-benzyIidenehydrazinouradls 86 with potassium nitrate and sulfuric acid in acetic acid affords fervenulin-4-oxides 87 <99M819>. 

Glacial acetic acid. Ammonium picramic acid Phenol, Sulfuric acid. Nitric acid. Water Aspirin, Sulfuric acid. Potassium nitrate. Alcohol Phenol, Sodium hydroxide. Sodium nitrite. Nitric acid Chlorobenzene, Potassium nitrate. Sulfuric acid. Acetone, Methanol... 

Potassium nitrate, Sulfuric acid, 1,3,5-Trifluorobenzene, Methylene chloride, Hexane, Tert-butylamine, Trifluoroacetic acid, 1,2-Dichloroethane, 3-Amino-1,2,4-traizole, Glacial acetic acid, Sodium nitrite, Urea, Ethyl acetate, Dimethylformamide, Diethyl ether, Sodium sulfate, Methanol Ethanolamine, Diethyl ether, Ethyl chlorocarbonate, Sodium hydroxide, Magnesium sulfate, Nitric acid, Anhydrous ammonia... 

---