Sodium and ammonia

No reaction takes place below 500°C when sodium cyanide and sodium hydroxide are heated in the absence of water and oxygen. Above 500°C, sodium carbonate, sodium cyanamide [19981-17-0] sodium oxide, and hydrogen are produced. In the presence of small amounts of water at 500°C decomposition occurs with the formation of ammonia and sodium formate, and the latter is converted into sodium carbonate and hydrogen by the caustic soda. In the presence of excess oxygen, sodium carbonate, nitrogen, and water are produced (53). 

Isothiazole itself is best prepared by the reaction between propynal, ammonia and sodium thiosulfate (see Section 4.17.9.3). A wide range of substituted mononuclear isothiazoles can be obtained by oxidative cyclization of y-iminothiols and related compounds (see Section 4.17.9.1.1). Substituents at the 3-position need to be in place before cyclization, but 4-substituents are readily introduced by electrophilic reagents (see Section 4.17.6.3), and 5-substituents via lithiation (see Section 4.17.6.4). 

The ethereal solution of crude quinidine and cinchonidine, obtained as described under cinchonine, is shaken with dilute hydrochloric acid, the excess acid neutralised with ammonia and sodium potassium tartrate added. The base is recovered from the precipitated tartrate by dissolving the latter in dilute acid and pouring the filtered solution in a thin stream, slowly and with constant stirring, into excess of ammonia solution. The crude alkaloid is converted into the neutral sulphate, and this recrystallised... 

Ammonia and sodium hydroxide are commonly used to dissolve precipitates containing a cation that forms a stable complex with NH3 or OH- (Table 16.2). The reactions with zinc hydroxide are typical ... 

Many other cyclic and noncyclic organic carriers with remarkable ion selectivities have been used successfiilly as active hosts of various liquid membrane electrodes. These include the 14-crown-4-ether for lithium (30) 16-crown-5 derivatives for sodium bis-benzo-18-crown-6 ether for cesium the ionophore ETH 1001 [(R,R)-AA -bisd l-ethoxycarbonyl)undecyl-A,yVl-4,5-tctramcthyl-3,6-dioxaoctancdiamide] for calcium the natural macrocyclics nonactin and monensin for ammonia and sodium (31), respectively the ionophore ETH 1117 for magnesium calixarene derivatives for sodium (32) and macrocyclic thioethers for mercury and silver (33). 

The reaction of naphthols with ammonia and sodium bisulfite is called the Bucherer reaction. Primary amines can be used instead of ammonia, in which case N-substituted naphthylamines are obtained. In addition, primary naphthylamines can be converted to secondary, by a transamination reaction ... 

It is logical to consider the nncleophile, Nu-, as a source of the electron to be transferred onto the snbstrate molecnle, RX. However, in most cases, the nucleophile is such a poor electron donor that electron transfer from Nn- to RX is extremely slow, if it is possible at all. These reactions reqnire an external stimulation in which a catalytic amount of electrons is injected. Such kinds of assistance to the reactions from photochemical and electrochemical initiations or from solvated electrons in the reaction mediums have been pointed out earlier. Alkali metals in liquid ammonia and sodium amalgam in organic solvents can serve as the solvated electron sources. Light initiation is also used widely. However, photochemical initiation complicates the reaction performance. 

Monogermane is a colorless gas density 3.43 g/L at 0°C liquefies at -90°C solidifies at -165°C insoluble in cold and hot waters soluble in liquid ammonia and sodium oxychloride slightly soluble in hot hydrochloric acid. 

Hydrazine sulfate may be synthesized from aqueous ammonia and sodium hypochlorite solution in a two-step process. In the first stage, aqueous solution of ammonia is boiled with a normal solution of sodium hypochlorite in the presence of 10% gelatin solution to yield hydrazine. In the second stage, the hydrazine solution is ice-cooled followed by slow addition of concentrated sulfuric acid (Adams, R., and B.K. Brown. 1964. In Organic Synthesis, Collective Volume I, ed. H. Gilman and A. H. Blatt, 2nd ed. pp 309-310, New York John Wiley Sons). The reaction steps are as follows ... 

Elemental composition Na 58.93%, N 35.90%, H 5.17%. The compound may he decomposed cautiously with water (reaction is violent) under cooling to yield sodium hydroxide and ammonia. (Or it may he decomposed with anhyrous alcohol to form ammonia and sodium alcoholate. The alcoholate then may he treated with water to form sodium hydroxide). Ammonia liberated is dissolved in water and the solution is measured using an ammonia-selective electrode. Alternatively, ammonia is collected over horic acid solution containing a small quantity of methyl red indicator. The solution is titrated with a standard solution of sulfuric acid. Sodium hydroxide is measured hy titration with a standard solution of hydrochloric or sulfuric acid. 

The bromide, [Co(NH3)5OH]Br,.H20, is prepared from the corresponding aquo-salt in the same manner as the chloride, and separates from alcohol and water as a violet powder. The iodide, [Co(NHs)5OH]I2, is obtained from the chloride by dissolving it in aqueous ammonia and adding solid potassium iodide. The dithionate, [Co(NH3)5OH]S206. H,0, obtained from the chloride by treating it with ammonia and sodium dithionate, crystallises in short red prisms or leaflets. 

It is possible to oxidize all the CH2OH groups to carboxylic groups, if the conditions of reaction are sufficiently severe, when the content of COOH may reach 25%. The product obtained in this way is a polyanhydroglucuronic add, known as carboxycellulose or celluronic acid. When half the CH2OH groups present in the cellulose are oxidized, a product with a 13% COOH content is obtained, soluble in dilute solutions of caustic soda, ammonia and sodium carbonate. Celluronic acid can form esters with nitric acid. The properties of these esters will be discussed later. 

Although the entire discussion of electrochemistry thus far has been in terms of aqueous solutions, the same principles apply equaly well to nonaqueous solvents. As a result of differences in solvation energies, electrode potentials may vary considerably from those found in aqueous solution. In addition the oxidation and reduction potentials characteristic of the solvent vary with the chemical behavior of the solvent. as a result of these two effects, it is often possible to carry out reactions in a nonaqueous solvent that would be impossible in water. For example, both sodium and beryllium are too reactive to be electroplated from aqueous solution, but beryllium can be electroplated from liquid ammonia and sodium from solutions in pyridine. 0 Unfortunately, the thermodynamic data necessary to construct complete tables of standard potential values are lacking for most solvents other than water. Jolly 1 has compiled such a table for liquid ammonia. The hydrogen electrode is used as the reference point to establish the scale as in water ... 

Phenolphthalein Paper.—Used in acidimetry and alkalimetry. Turned red by alkalis, reacting with ammonia and sodium carbonate, but not with bicarbonate. Used chiefly in analytical work. 

All normal precautions should be observed during the handling of these large quantities of ammonia and sodium. A well-ventilated hood, a gas mask, and a bucket of sand were available to the submitters. The only hazard in this reaction may arise if too much ammonia escapes and the sodium does not react properly as a consequence. The addition of 0.5-1.0 1. of ammonia to the reaction mixture after the sodium has been added is a useful precaution. 

Sodium amide may be prepared readily from sodium and ammonia in either of two ways by the reaction between liquid ammonia and sodium dissolved in it or by the reaction... 

The ammonia and sodium are combined in the presence of a catalytic amount of Fe(N03)3 9H20 at the boiling temperature of NH3 to obtain a solution of NaNH2 in liquid NH3. The ether, ethylene diamine and allene are then added in that order. After a reaction period of about 4.5 hours, quenching and work up, 54.4 grams of distilled product (63.5% acetylene) was obtained. 

Hydrochloric add, ammonia and sodium hydroxide solutions are caustic and M harmful to skin. Avoid contact with the skin and eyes wear chemically resis- tant rubber gloves and chemical safety goggles. Some of the metal salts are M toxic. Handle carefully and wash your hands on completion of the experiment or before eating. H... 

Method 1 Preparation of ammonium perchlorate from household ammonia and sodium... 

An important amination reaction involves hydroxy-substituted naphthalenes (Fig. 13.53). In a process known as the Bucherer reaction, naphthols are heated under pressure with a mixture of ammonia and sodium bisulfite. As... 

Phenolphthalein Paper. This paper is turned red by alkalis, induding ammonia and sodium carbonate solutions, but not bicarbonates. It can be used to advantage for differentiating among the alkalis. The paper is prepared by soaking filter paper in a hot solution of 1 gram of phenolphthalein in 1 liter of water. 

Write the equation for the formation of hydrazine from ammonia and sodium hypdchlorite. 

Mercaptopyrazine in aqueous hydrochloric or acetic acids was chlorinated to give the sulfonyl chloride which with excess liquid ammonia gave 2-sulfamoyl-pyrazine (1006, 1153). Direct sulfonation of the pyrazine ring has never been reported (819) but 2-sulfopyrazine (17) has been prepared from 2-chloropyrazine and aqueous sodium sulfite at 150° (819), and from 2-fluoropyrazine and aqueous sodium sulfite at reflux for 2 hours (882, 884). 2-Amino-3-mercaptopyrazine in aqueous sodium hydroxide with concentrated ammonia and sodium hypochlorite has been shown to give 2-amino-3-sulfamoylpyrazine (1101). 

Preparation of nitrates of ammonia and sodium Preparation of sodium carbonate Preparation of hydrogen cyanide... 

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