Ammonia silver oxide

D-Lyxose diacetamide. Ammonia-silver oxide.y Ten grams of pentaaoetyl-n-galactononitrile was dissolved in 30 ml. of ethanol, and a solution of silver oxide (from 5 g. of silver nitrate) in 50 ml. of 30 % ammonia added. After two days at room temperature, the precipitated silver cyanide was removed by filtration and the solution evaporated in vacuo at 40° imtil all ammonia was eliminated. The residue was diluted with water and the soluble silver eliminated by treatment with hydrogen sulfide and filtration. The filtrate was treated with decolorizing carbon, filtered and evaporated to dryness. When the residue crystallized, it was suspended in warm ethanol and filtered yield, 2.5 g. (40%). After recrystallization from 60% ethanol, the product had a melting point of 230-231°. 

D-Ardbinoae. Tetraacetyl-D-arabononitrile was prepared by Deu-lofeu and degraded to triacetyl-D-erythrose and D-erythrose diacetamide by ammonia-silver oxide. Hockett and Maynard improved the yield of the nitrile and by hydrolysis of D-erythrose diacetamide with 0.6 N sulfuric acid obtained D-erythrose as a sirup from which methyl D-ery-throside was prepared. 

D-Glucose. WohP obtained pentaacetyl-n-glucononitrile in 40% yield by the action of sodium acetate-acetic anhydride. The nitrile when treated with ammonia-silver oxide gave a 47 % yield of n-arabinose diacetamide. Hydrolysis of the diacetamide derivative with 6 N sulfuric acid produced crystalline n-arabinose in 50-60 % yield. The process was improved by Neuberg and Wohlgemuth, who obtained n-arabinose in an over-all yield of 34.7 % of the n-glucose employed. 

D-Galactose. Wohl and List prepared pentaacetyl-n-galactononitrile from the oxime in 40% yield. Degradation with ammonia-silver oxide gave 40% of n-lyxose diacetamide. Hydrolysis of the diacetamide with... 

Pentapropionyl-D-galactononitrile has been prepared in 52 % yield by Gim6nez from the oxime and pyridine-acetic anhydride. Degradation with ammonia-silver oxide produced D-lyxose diacetamide in 30% yield. 

Numerous conditions have been developed for this transformation, but reproducible yields have usually been obtained by mixing a silver salt with a coreagent, such as silver nitrate associated with wet ammonia, silver oxide with triethylamine or sodium thiosulfate, and silver benzoate with triethylamine. Nonbasic conditions have also been described by Koch and Podlech using silver trifluoroacetate deposited on silica.6 These modifications have been developed for the homologation of Fmoc-protected amino acids. 

Reduction of ammoniacal silver nitrate. Place about 5 ml. of AgNOj solution in a thoroughly clean test-tube, and add 2-3 drops of dil. NaOH solution. Add dil. ammonia solution, drop by drop, until the precipitated silver oxide is almost redissolved, then add 2 - 3 drops of formaldehyde or acetaldehyde. A silver mirror is formed. 

Since the silver salts of the carboxylic acids are usually soluble in dilute nitric acid, they must be prepared by treating an aqueous solution of a neutral salt of the acid (and not the free acid itself) with silver nitrate solution. It is not practicable to attempt to neutralise the acid with sodium or potassium hydroxide solution, because the least excess of alkali would subsequently cause the white silver salt to be contaminated with brown silver oxide. The general method used therefore to obtain a neutral solution j to dissolve the acid in a small excess of ammonia solution, and then to boil the solution until all free... 

It is preferable to use Tollen s ammoniacal silver nitrate reagent, which is prepared as follows Dissolve 3 g. of silver nitrate in 30 ml. of water (solution A) and 3 g. of sodium hydroxide in 30 ml. of water (solution B). When the reagent is requir, mix equal volumes (say, 1 ml.) of solutions A and JB in a clean test-tube, and add dilute ammonia solution drop by drop until the silver oxide is just dissolved. Great care must be taken in the preparation and use of this reagent, which must not be heated. Only a small volume should be prepared just before use, any residue washed down the sink with a large quantity of water, and the test-tubes rinsed with dilute nitric acid. 

Rearrangement of the diazo ketone, with loss of nitrogen, in the presence of suitable reagents and a catalyst (colloidal silver, silver oxide, or silver nitrate in the presence of ammonia solution). An acid is formed In the presence of water, an amide results when ammonia or an amine is used, and an ester is produced in the presence of an alcohol ... 

The benzyl group has been widely used for the protection of hydroxyl functions in carbohydrate and nucleotide chemistry (C.M. McCloskey, 1957 C.B. Reese, 1965 B.E. Griffin, 1966). A common benzylation procedure involves heating with neat benzyl chloride and strong bases. A milder procedure is the reaction in DMF solution at room temperatiue with the aid of silver oxide (E. Reinefeld, 1971). Benzyl ethers are not affected by hydroxides and are stable towards oxidants (e.g. periodate, lead tetraacetate), LiAIH, amd weak acids. They are, however, readily cleaved in neutral solution at room temperature by palladium-catalyzed bydrogenolysis (S. Tejima, 1963) or by sodium in liquid ammonia or alcohols (E.J. Rcist, 1964). 

To minimize the formation of fuhninating silver, these complexes should not be prepared from strongly basic suspensions of silver oxide. Highly explosive fuhninating silver, beheved to consist of either silver nitride or silver imide, may detonate spontaneously when silver oxide is heated with ammonia or when alkaline solutions of a silver—amine complex are stored. Addition of appropriate amounts of HCl to a solution of fuhninating silver renders it harmless. Stable silver complexes are also formed from many ahphatic and aromatic amines, eg, ethylamine, aniline, and pyridine. 

Oxidation catalysts are either metals that chemisorb oxygen readily, such as platinum or silver, or transition metal oxides that are able to give and take oxygen by reason of their having several possible oxidation states. Ethylene oxide is formed with silver, ammonia is oxidized with platinum, and silver or copper in the form of metal screens catalyze the oxidation of methanol to formaldehyde. Cobalt catalysis is used in the following oxidations butane to acetic acid and to butyl-hydroperoxide, cyclohexane to cyclohexylperoxide, acetaldehyde to acetic acid and toluene to benzoic acid. PdCh-CuCb is used for many liquid-phase oxidations and V9O5 combinations for many vapor-phase oxidations. 

The indolinol character of eseretholemethine is indicated by the fact that the methiodide on treatment with picric acid yields a diquaternary pierate (m.p. 170°) with the loss of the hydroxyl group. More definite proof is afforded by the oxidation of eseretholemethine with ammoniaeal silver nitrate or potassium ferricyanide, when a dehydroeseretholemethine (oxyeseretholemethine of Polonovski), pierate, m.p. 199°, is produced which is assumed to have formula (VI), since on exhaustive methylation it yields trimethylamine and an unsaturated product (deep-red pierate, m.p. 103°), which absorbs two atoms of hydrogen, forming 5-ethoxy-l 8-dimethyl-S-ethyl-2-indolinone (VII), colourless cubes, m.p. 68°. The... 

To identify the specific aldehyde that is actually involved in the light-emitting reaction of living luminous bacteria, Shimomura et al. (1974a) extracted and purified the aldehyde from 40 g each of the bacterial cells of P. phosphoreum, Achromobacter (Vibrio or Photobacterium) fischeri, and an aldehydeless mutant of A. fischeri. The aldehyde fractions were purified, and then oxidized with Tollens reagent (silver oxide dissolved in ammonia) to convert the CHO group into the COOH group. Then the acids obtained were analyzed by mass spectrometry. The results indicated that P. phosphoreum had contained a mixture of aldehydes dodecanal (5%), tetradecanal (63%) and hexadecanal (30%), as shown in Table 2.2. Thus, tetradecanal was clearly predominant in... 

Tri-O-acetyl-a-D-xylopyranosyl bromide106 (138) and N-tosyl-L-serine methyl ester107 (139) were condensed in the presence of Drierite and silver oxide, and then the O-acetyl and methyl ester groups were removed by treatment with sodium hydroxide, and the N-tosyl group by means of sodium in liquid ammonia, to give 140. Synthesis of this compound has also been described by other workers108-110 and the a-D an-omer by Brendel and Davidson.108... 

During preparation of an oxidising agent on a larger scale than described [1], addition of warm sodium hydroxide solution to warm ammoniacal silver nitrate with stirring caused immediate precipitation of black silver nitride which exploded [2], Similar incidents had been reported previously [3], including one where explosion appeared to be initiated by addition of Devarda s alloy (Al—Cu—Zn) [4], The explosive species separates at pH values above 12.9, only produced when alkali is added to ammoniacal silver solutions, or when silver oxide is dissolved with ammonia [5], The Sommer Market reagent mixture used to identify cellulose derivatives led to a severe explosion [6],... 

The clear solution, obtained by centrifuging a solution of the oxide in aqueous ammonia which had been treated with silver nitrate until precipitation started, exploded on two occasions after 10-14 days storage in closed bottles in the dark. This was ascribed to slow precipitation of amorphous silver imide, which is very explosive even when wet [1], When silver oxide is dissolved in ammonia solution, an extremely explosive precipitate (probably Ag3N4) will separate. The explosive behaviour is completely inhibited by presence of colloids or ammonium salts (acetate, carbonate, citrate or oxalate). Substitution of methylamine for ammonia does not give explosive materials [2],... 

Silver oxide and ammonia or hydrazine slowly form explosive silver nitride and, in presence of alcohol, silver fulminate may also be produced. 

See Gold(III) chloride Ammonia Mercury Ammonia Potassium triamidothallate ammoniate Silver azide Ammonia Silver chloride Ammonia Silver nitrate Ammonia Silver(I) oxide Ammonia See N-METAL DERIVATIVES... 

The presence of three hydroxyl groups per glucose unit was shown by the preparation of a triacetate and a tribenzoate. Six or seven methyla-tions (using dimethyl sulfate and concentrated alkali) of dextran did not raise the methoxyl content above 41% (theoretical maximum 45.6%). Also, Purdie methylations (using methyl iodide and silver oxide) and methylation with thallium ethoxide and methyl iodide were ineffective in raising the methoxyl content of methylated dextran above 43.5%. The maximum theoretical methoxyl content was eventually attained by modified Muskat methylations. 6 Partially methylated dextran suspended in anisole solution was treated with sodium in liquid ammonia, and the sodium salt of methylated dextran thus formed was allowed to react with methyl iodide. The methoxyl content of the partially methylated dextran was raised by three such methylations from 42% to 45.5% and by five such methylations from 30% to 45.4%. 

Fulminating silver is the most violently explosive compound among the nitrogen derivatives of the noble metals. Formed from action of ammonia on silver oxide, or on addition of potassium hydroxide to an ammoniacal solution of a silver salt, it is a black powder which explodes violently in the liquid in which it is formed if the slightest stirring is used. It probably contains amminesilver hydroxides, [Ag(NH3),]OH. 

Silver solutions used in photography can become explosive under a variety of conditions. Ammoniacal silver nitrate solutions, on storage, heating or evaporation eventually deposit silver nitride ( fulminating silver ). Silver nitrate and ethanol may give silver fulminate, and in contact with azides or hydrazine, silver azide. These are all dangerously sensitive explosives and detonators [1], Addition of ammonia solution to silver containing solutions does not directly produce explosive precipitates, but these are formed at pH values above 12.9, produced by addition of alkali, or by dissolution of silver oxide in ammonia [2]. 

Nonporous silver membrane tube (99.99 wt.% Ag), (in double pipe configurationX thickness 100/im. Feed enters the reactor at shell side, oxygen at tube side. Oxidation of ammonia. Silver catalyst in membrane form (see previous column). Oxidation of ethanol to acetaldehyde. Silver catalyst in membrane form (see previous column). r- 250-380°C. The yield of nitrogen was 40%, the yield of nitrogen monoxide was 25%. r- 250-380°C. The yield of acetaldehyde was 83%. The yield with bulk powdered silver catalyst was 56%. Gryaznov, Vedernikov and Guryanova (1986)... 

Ammonia with dissolved silver oxide was employed as the only degradation reagent until Maquenne showed that ammonia alone could be employed with the same success this method has been developed further by Hockett. ... 

The Wohl degradation can be considered to consist of two steps (a) the elimination of the acetyl and nitrile groups by the action of ammonia or ammoniacal silver oxide, and (b) the formation of the diacetamide compound. The formation of the latter was explained by Wohl on the basis of the intermediate formation of oIde%do-D-arabinose... 

The diacetamide compounds were regularly obtained in all degradations employing ammonia with or without silver oxide until Hockett and Chandler applied the method to hexaacetyl-D-gluco-D-flruZo-heptono-nitrile (XLIX) and obtained a monoacetamide derivative that was identified as iV-acetyl-D-glucofuranosylamine (L). The furanose structure of L was established by lead tetraacetate oxidation. They... 

Preparation of o-arabinose diphenylhydraxone from pentaacetyl-xi-glucononitrile, To a cold solution of 100 g. of pentaacetyl-n-glucononitrile in 280 ml. of 96% ethanol, 34 g. of silver oxide (from about 50 g. of silver nitrate) dissolved in 500 ml. of 30% ammonia was added. After forty-eight hours the separated crystalline silver cyanide was removed by filtration and the filtrate concentrated in vacuo to about one-third of the original volume and filtered. Water was added to 500 ml., and the dissolved... 

D-Fucose (Rhodeose). Voto6ek obtained tetraacetyl-D-fucononitrile in 25% yield by treating D-fucose oxime with sodium acetate-acetic anhydride. The nitrile, degraded with ammonia and silver oxide, yielded 5-desoxy-D-lyxose diacetamide in 40% yield. The diacetamide compound was hydrolyzed with 5% hydrochloric acid and the 5-desoxy-D-lyxose was obtained in solution and characterized as the p-bromo-phenylosazone. Hydrolysis of the diacetamide compound with 6 N sulfuric acid was realized by Voto6ek and Valentin and the 5-desoxy-D-lyxose was isolated as a sirup. 

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