Alkali cyanides

Sodium cyanide is very poisonous and must be handled with great care. The hands should be washed immediately after using it. All the residual solution.s containing alkali cyanides must be emptied into the main drain of the laboratory and washed down with a liberal supply of water they should never be treated with acid. 

Benzoin condensation. Aromatic aldehydes when treated with an alkali cyanide, usually in aqueous solution, undergo condensation to the -hydroxyketone or benzoin. The best known example is the conversion of benzaldehyde to benzoin ... 

Salts of thiols (170) or of sulfinic acids (171) react like the alkoxides, giving 4-alkylthio- or 4-alkylsulfono-substituted butyrates. Alkali cyanides give 4-cyanobutyrates (172), hydroxylamine gives a hydroxamic acid (173), and hydra2ine a hydra2ide (174). 

This Michael-type addition is catalyzed by lanthanum(3+) [16096-89-2] (80). Ethylene glycol [107-21-1] reacts with maleate under similar conditions (81). A wide range of nucleophilic reagents add to the maleate and fumarate frameworks including alcohols, ammonia, amines, sulfinic acids, thioureas, Grignard reagents, Michael reagents, and alkali cyanides (25). 

Germanium [7440-56-4] M 72.6, m 937 , 925-975 , b 2700 , d 5.3. Copper contamination on the surface and in the bulk of single crystals of Ge can be removed by immersion in molten alkali cyanide under N2. The Ge was placed in dry cyanide powder in a graphite holder in a quartz or porcelain boat. The boat was then inserted into a heated furnace which, after a suitable time, was left to cool to room temperature. At 750°, a 1mm thickness requires about Imin, whereas 0.5cm needs about half hour. The boat was removed and the samples were taken out with plastic-coated tweezers, carefully rinsed in hot water and dried in air [Wang J Phys Chem 60 45 7956]. 

This method is particularly applicable to the more reactive benzyl halides which are easily hydrolyzed in the aqueous media usually employed for the metathetical reaction with alkali cyanides. For example, anisyl chloride treated with sodium cyanide in aqueous dioxane gives, as a by-product, 5-10% of anisyl alcohol as determined by infrared analysis. The use of anhydrous acetone not only prevents hydrolysis to the alcohol but also decreases the formation of isonitriles. This method was also applied successfully by the submitters to the preparation of -chlo-rophenylacetonitrile in 74% yield. 

This method is an adaptation of that of Dengel. -Methoxy-phenylacetonitrile can also be prepared by the metathetical reaction of anisyl chloride with alkali cyanides in a variety of aqueous solvent mixtures by the nitration of phenylaceto-nitrile, followed by reduction, diazotization, hydrolysis, and methylation 1 by the reduction of ct-benzoxy- -methoxy-phenylacetonitrile (prepared from anisaldehyde, sodium cyanide, and benzoyl chloride) and by the reaction of acetic anhydride with the oxime of -methoxyphenylpyruvic acid. ... 

Enamine salts react with many nucleophilic reagents. The reaction with the cyanide ion is noteworthy. l-Methyl-2-ethyl-2-cyanopyrrolidine (170) is formed on treatment of alkali cyanide with l-methyl-2-ethyl-.d -pyrrolin-ium perchlorate (242). The reduction of the tertiary nitrile (170) with... 

With alkali cyanides, a reaction via a SN2-mechanism takes place the alkyl halide is attacked by cyanide with the more nucleophilic carbon center rather than the nitrogen center, and the alkylnitrile is formed. In contrast, with silver cyanide the reaction proceeds by a SnI-mechanism, and an isonitrile is formed, since the carbenium intermediate reacts preferentially with the more electronegative center of the cyanide—i.e. the nitrogen (Kornblum s rule, HSAB concept). ... 

Alkalizyanid, n. alkali cyanide, alkaloidartig, a. alkaloid4ike, alkaloidal. alkaloidisch, a. alkaloidal. 

Cyan-, of or combined with cyanogen, cyano-(as Cyanpropionadure, cyanopropionic acid), cyanide of (as Cyanammonium, ammonium cyanide), -alkali, n. alkali cyanide, -alkyl, n. alkyl cyanide. 

Example 2 Finely divided gold is agitated with an oxygen-saturated alkali-cyanide solution of pH = 12 containing 10 moldm of CN . Calculate the concentration of Au(CN)2 ions in solution at 25°C when the reaction is at equilibrium. The standard chemical potentials of the species involved (in kJ) are CN, 165 HjO, —237 Au(CN)f, 244 OH", —157. Assume that fl jo = 1, and take 2-303RT = 5710. 

A simple example of the application of a complexation reaction to a titration procedure is the titration of cyanides with silver nitrate solution. When a solution of silver nitrate is added to a solution containing cyanide ions (e.g. an alkali cyanide) a white precipitate is formed when the two liquids first come into contact with one another, but on stirring it re-dissolves owing to the formation of a stable complex cyanide, the alkali salt of which is soluble ... 

Discussion. The theory of the titration of cyanides with silver nitrate solution has been given in Section 10.44. All silver salts except the sulphide are readily soluble in excess of a solution of an alkali cyanide, hence chloride, bromide, and iodide do not interfere. The only difficulty in obtaining a sharp end point lies in the fact that silver cyanide is often precipitated in a curdy form which does not readily re-dissolve, and, moreover, the end point is not easy to detect with accuracy. 

The reaction between aryl halides and cuprous cyanide is called the Rosenmund-von Braun reactionP Reactivity is in the order I > Br > Cl > F, indicating that the SnAt mechanism does not apply.Other cyanides (e.g., KCN and NaCN), do not react with aryl halides, even activated ones. However, alkali cyanides do convert aryl halides to nitrilesin dipolar aprotic solvents in the presence of Pd(II) salts or copper or nickel complexes. A nickel complex also catalyzes the reaction between aryl triflates and KCN to give aryl nitriles. Aromatic ethers ArOR have been photochemically converted to ArCN. 

Thus, co-deposition of silver and copper can take place only when the silver concentration in the electrolyte falls to a very low level. This clearly indicates that the electrolytic process can, instead, be used for separating copper from silver. When both silver and copper ions are present, the initial deposition will mainly be of silver and the deposition of copper will take place only when the concentration of silver becomes very low. Another example worth considering here is the co-deposition of copper and zinc. Under normal conditions, the co-deposition of copper and zinc from an electrolyte containing copper and zinc sulfates is not feasible because of the large difference in the electrode potentials. If, however, an excess of alkali cyanides is added to the solution, both the metals form complex cyanides the cuprocyanide complex is much more stable than the zinc cyanide complex and thus the concentration of the free copper ions available for deposition is considerably reduced. As a result of this, the deposition potentials for copper and zinc become very close and their co-deposition can take place to form alloys. 

This method has an analogy in the well known acyloin condensation, a reaction which takes place between two molecules of an aromatic aldehyde in a solution containing an alkali cyanide. Thus for example, benzaldehyde gives rise to benzoin, a compound in which the enediolic system, —C(OH)=C(OH)—, exists mainly in the ketonic form —CO—CHOH—. If a hydroxy aldehyde like D-glucose (X) is allowed to... 

N, P, S, or C, is thermodynamically and kinetically favored, yielding pyridine, pyridinium, phosphaben-zene, thiopyrylium, or benzenoid rings. Ring-opening occurs with alkali cyanides ring contraction to... 

Nitriles can also be obtained by the method of Kolbe alkyl iodides (bromides or chlorides) are heated with alkali cyanide (example, benzyl cyanide), or salts of alkylsulphuric acids are subjected to dry distillation with potassium cyanide ... 

Dichloroacetamide has been prepared from ethyl dichloroace-tate with alcoholic ammonia1 or aqueous ammonium hydroxide,2 from ethyl dichloromalonate and alcoholic ammonia,3 by the action of ammonia on pentachloroacetone,4 chloral cyanohydrin,5 and hexachloro-i,3,5-cyclohexanetrione,6 from chloral ammonia and potassium cyanide,7 by the action of hydrogen chloride on dichloroacetonitrile,8 from the reaction of asparagine with the sodium salt of N-chloro- -toluenesulfonamide,9 and by the action of an alkali cyanide and ammonia on chloral hydrate.10... 

Alternatively, it is produced by the reaction of alkali cyanides with a mer-cury(II) salt solution. 

Nickel may he measured quantitatively hy several microanalytical gravimetric methods that include (l)formation of a red precipitate with dimethyl-glyoxime, (2) precipitation as a hlack sulfide with ammonium sulfide, (3) precipitating as a complex cyanide hy treating with alkali cyanide and bromine, and (4) precipitation as a yellow complex hy treating an ammoniacal solution of nickel with dicyandiamide sulfate (Grossman s reagent), followed hy the addition of potassium hydroxide. All of these methods can separate nickel from cobalt in solution. 

White granular powder or cubic crystals refractive index 2.071 darkens on exposure to hght density 5.56 g/cm Moh s hardness 2.5 melts at 455°C vaporizes at 1,547°C vapor pressure 1 and 5 torr at 912 and 1,019°C insoluble in water, alcohol and dilute acids soluble in ammonia solution and concentrated sulfuric acid, alkali cyanide, ammonium carbonate also soluble in potassium bromide and sodium thiosulfate solutions. 

Red monoclinic crystals or brownish-red powder density 5.625 g/cm insoluble in water soluble in nitric acid, ammonia and solutions of alkali cyanides and chromates. 

Grayish-white hexagonal crystals density 3.95 g/cm decomposes at 320°C insoluble in water, alcohol or dilute acids moderately soluble in concentrated ammonia soluble in concentrated boding nitric acid also soluble in alkali cyanide solutions. 

Light yellow hexagonal crystals or powder darkens on exposure to hght density 5.68 g/cm melts at 558°C vaporizes at 1,506°C insoluble in water, most acids and ammonium carbonate solution moderately soluble in concentrated solutions of alkali chloride, bromide, and thiosulfate readily soluble in solutions of alkali cyanides, iodides and in hot concentrated hydriodic acid. 

When heated with alkali cyanide, thiocyanate salt is obtained ... 

Although there have been few new developments in the period since 1993, halogenopyrazines 42 have been convenient precursors for a variety of pyrazine derivatives. For example, the halogenopyrazines 42 are cyanated by palladium-catalyzed cross-coupling with alkali cyanide or by treatment with copper cyanide in refluxing picoline, to yield cyanopyrazines 48. Alkoxypyrazines 49 are produced by treatment with alkoxide-alcohol, and aminopyrazines 50 are prepared by amination with ammonia or appropriate amines. The nucleophilic substitution of chloropyrazine with sodium alkoxide, phenoxide, alkyl- or arylthiolate is efficiently effected under focused microwave irradiation <2002T887>. 

Ethylene cyanohydrin has been prepared by the action of ethylene oxide upon anhydrous hydrocyanic acid 1 but the majority of methods described in the literature have involved the interaction of ethylene chlorohydrin and alkali cyanide. This has been effected in the absence of a solvent by heating to ioo° in a closed vessel,2 by boiling the reagents in 50 per cent aqueous-alcoholic solution,3 by adding a concentrated aqueous solution of potassium or sodium cyanide to a boiling solution of ethylene chlorohydrin in absolute alcohol,4 and in aqueous solution at 45 °.5... 

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