Potassium cyanide, also

The substance is stable at ordinary temperatures and up to 100°C. Like cupric acetylide it decomposes on being heated in hydrochloric acid (Berthelot [102], Sabaneyev [107]). A solution of potassium cyanide also causes decomposition with the loss of acetylene. Makowka [108] showed that aldehyde-like compounds are formed from cuprous acetylide on reaction with a 30% solution of hydrogen peroxide. 

Silver cyanide is soluble in a solution of potassium cyanide, also forming a double salt, of the formula... 

Treatment of the i r-benzyl isoquinolinium bromide with potassium cyanide gave 73. A similar compound was obtained from the ethiodide. Use of potassium thiocyanate in place of potassium cyanide also gave a similar compound. Treatment of 73 or the other analogs with ethanolic picric acid resulted in the liberation of the cyano or thiocyano group to give 2-benzyl- or 2-ethylisoquinolinium picrate. These compounds fail to react as typical Reissert compounds in the presence of phenyllithium or sodium hydride. 

Acylcyanides are useful synthetic intermediates and are sometimes not easily prepared, often involving the use of heavy-metal cyanides. A new procedure efficiently converts aroyl chlorides to aroyl cyanides with potassium cyanide in acetonitrile or aqueous acetonitrile. Palladium-catalysed carbonylation of aromatic iodides in the presence of potassium cyanide also gives aroyl cyanides via cyanocarbonylation. ... 

Silver chloride is readily soluble in ammonia, the bromide less readily and the iodide only slightly, forming the complex cation [Ag(NH3)2]. These halides also dissolve in potassium cyanide, forming the linear complex anion [AglCN) ] and in sodium thiosulphate forming another complex anion, [Ag(S203)2] ... 

Other sources of hazard arise from the handling of such chemicals as concentrated acids, alkalis, metallic sodium and bromine, and in working with such extremely poisonous substances as sodium and potassium cyanides. The special precautions to be observed will be indicated, where necessary, in the experiments in which the substances are employed, and will also be supplied by the demonstrator. The exercise of obvious precautions and cautious handling will in most cases reduce the danger to almost negligible proportions. Thus, if concentrated sulphuric acid should be accidentally spilled, it should be immediately washed with a liberal quantity of water or of a solution of a mild alkali. 

The Sandmeyer reaction may also be applied to the preparation of nitriles. The solution of the diazonium salt is added to a solution of cuprous cyanide in excess of sodium or potassium cyanide solution (sometimes improved yields are obtained by substituting nickel cyanide for cuprous cyanide), for example CH3 CH, CH3... 

In the first method a secondary acetylenic bromide is warmed in THF with an equivalent amount of copper(I) cyanide. We found that a small amount of anhydrous lithium bromide is necessary to effect solubilization of the copper cyanide. Primary acetylenic bromides, RCECCH Br, under these conditions afford mainly the acetylenic nitriles, RCsCCHjCsN (see Chapter VIII). The aqueous procedure for the allenic nitriles is more attractive, in our opinion, because only a catalytic amount of copper cyanide is required the reaction of the acetylenic bromide with the KClV.CuCN complex is faster than the reaction with KCN. Excellent yields of allenic nitriles can be obtained if the potassium cyanide is added at a moderate rate during the reaction. Excess of KCN has to be avoided, as it causes resinifi-cation of the allenic nitrile. In the case of propargyl bromide 1,1-substitution may also occur, but the propargyl cyanide immediately isomerizes under the influence of the potassium cyanide. 

Nitdles may be prepared by several methods (1). The first nitrile to be prepared was propionitdle, which was obtained in 1834 by distilling barium ethyl sulfate with potassium cyanide. This is a general preparation of nitriles from sulfonate salts and is referred to as the Pelou2e reaction (2). Although not commonly practiced today, dehydration of amides has been widely used to produce nitriles and was the first commercial synthesis of a nitrile. The reaction of alkyl hahdes with sodium cyanide to produce nitriles (eq. 1) also is a general reaction with wide appHcabiUty ... 

Cyanides. Salts of the complex ion, [Au(CN)2] , can be formed directiy from gold, ie, gold dissolves ia dilute solutions of potassium cyanide ia the presence of air. Additionally, a gold anode dissolves ia a solution of potassium cyanide. The potassium salt can be isolated by evaporation of the solution and purified by recrystallization from water (177). Boiling of the complex cyanide ia hydrochloric acid results ia formation of AuCN [506-65-01]. Halogens add oxidatively to [Au(CN)2] to yield salts of [Au(CN)2X2] which are converted to the tetracyanoaurates usiag excess cyanide (178). These last can also be prepared directiy from the tetrahaloaurates. 

Synthesis from Aldehydes and Ketones. Treatment of aldehydes and ketones with potassium cyanide and ammonium carbonate gives hydantoias ia a oae-pot procedure (Bucherer-Bergs reactioa) that proceeds through a complex mechanism (69). Some derivatives, like oximes, semicarbazones, thiosemicarbazones, and others, are also suitable startiag materials. The Bucherer-Bergs and Read hydantoia syntheses give epimeric products when appHed to cycloalkanones, which is of importance ia the stereoselective syathesis of amino acids (69,70). 

Many reactions can be carried out between potassium cyanide and organic compounds with the alkalinity of the KCN acting as a catalyst these reactions are analogous to reactions of sodium cyanide. The reactions of potassium cyanide with sulfur and sulfur compounds are also analogous to those of sodium cyanide. Potassium cyanide is reduced to potassium metal and carbon by heating it out of contact with air in the presence of powdered magnesium. Magnesium is converted to the nitride ... 

Potassium cyanide is primarily used for fine silver plating but is also used for dyes and specialty products (see Electroplating). Electrolytic refining of platinum is carried out in fused potassium cyanide baths, in which a separation from silver is effected. Potassium cyanide is also a component of the electrolyte for the analytical separation of gold, silver, and copper from platinum. It is used with sodium cyanide for nitriding steel and also in mixtures for metal coloring by chemical or electrolytic processes. 

Ammonium cyanide may be prepared in solution by passing hydrogen cyanide into aqueous ammonia at low temperatures. It may also be prepared from barium cyanide and ammonium sulfate, or calcium cyanide with ammonium carbonate. It may be prepared in the dry state by gentiy heating a mixture of potassium cyanide or ferrocyanide and ammonium chloride, and condensing the vapor in a cooled receiver. Ammonium cyanide is soluble in water or alcohol. The vapor above soHd NH CN contains free NH and HCN, a very toxic mixture. 

Cyclic a-cyanoketones, when treated with hydroxylamine, yielded 3-amino-4,5,6,7-tetrahydro-2,1-benzisoxazole. This compound could also be obtained by sodium or potassium cyanide interaction with chlorocyclohexanone oxime (Scheme 187) (67AHC(8)277, 66Bail25>. 

Potassium cyanide [15]-50-8 M 65.1, m 634 , d 1.52. A saturated solution in H20-ethanol (1 3) at 60° was filtered and cooled to room temperature. Absolute EtOH was added, with stirring, until crystallisation ceased. The solution was again allowed to cool to room temperature (during 2-3h) then the crystals were filtered off, washed with absolute EtOH, and dried, first at 70-80° for 2-3h, then at 105° for 2h [Brown, Adisesh and Taylor J Phys Chem 66 2426 7962]. Also purified by vacuum melting and zone refining. HIGHLY POISONOUS. 

In a German patent issued in 1929, Bergs described a synthesis of some 5-substituted hydantoins by treatment of aldehydes or ketones (1) with potassium cyanide, ammonium carbonate, and carbon dioxide under several atmospheres of pressure at 80°C. In 1934, Bucherer et al. isolated a hydantoin derivative as a by-product in their preparation of cyanohydrin from cyclohexanone. They subsequently discovered that hydantoins could also be formed from the reaction of cyanohydrins (e.g. 3) and ammonium carbonate at room temperature or 60-70°C either in water or in benzene. The use of carbon dioxide under pressure was not necessary for the reaction to take place. Bucherer and Lieb later found that the reaction proceeded in 50% aqueous ethanol in excellent yields for ketones and good yields for aldehydes. ... 

In summary, the Bucherer-Bergs reaction converts aldehydes or ketones to the corresponding hydantoins. It is often carried out by treating the carbonyl compounds with potassium cyanide and ammonium carbonate in 50% aqueous ethanol. The resulting hydantoins, often of pharmacological importance, may also serve as the intermediates for amino acid synthesis. 

Complexes 79 show several types of chemical reactions (87CCR229). Nucleophilic addition may proceed at the C2 and S atoms. In excess potassium cyanide, 79 (R = R = R" = R = H) forms mainly the allyl sulfide complex 82 (R = H, Nu = CN) (84JA2901). The reaction of sodium methylate, phenyl-, and 2-thienyllithium with 79 (R = R = r" = R = H) follows the same route. The fragment consisting of three coplanar carbon atoms is described as the allyl system over which the Tr-electron density is delocalized. The sulfur atom may participate in delocalization to some extent. Complex 82 (R = H, Nu = CN) may be proto-nated by hydrochloric acid to yield the product where the 2-cyanothiophene has been converted into 2,3-dihydro-2-cyanothiophene. The initial thiophene complex 79 (R = R = r" = R = H) reacts reversibly with tri-n-butylphosphine followed by the formation of 82 [R = H, Nu = P(n-Bu)3]. Less basic phosphines, such as methyldiphenylphosphine, add with much greater difficulty. The reaction of 79 (r2 = r3 = r4 = r5 = h) with the hydride anion [BH4, HFe(CO)4, HW(CO)J] followed by the formation of 82 (R = Nu, H) has also been studied in detail. When the hydride anion originates from HFe(CO)4, the process is complicated by the formation of side products 83 and 84. The 2-methylthiophene complex 79... 

Modern solutions fall mainly into three types (a) the plain cyanide bath which contains typically 20-25 g/1 of copper cyanide, 25-30 g/1 total sodium cyanide (6.2 g/1 free sodium cyanide), and is operated at 21-38 C and 110-160 A/m (b) the Rochelle copper bath to which is added 35-50g/1 of Rochelle salt and which is used at 66 C at up to 645 A/m and (c) the high-efficiency cyanide baths which may contain up to 125 g/1 of copper cyanide, 6-11 g/1 of free sodium or potassium cyanide, 15-30 g/1 of sodium or potassium hydroxide, and are operated at up to 6-9A/dm and 65-90 C. Most bright cyanide copper baths are of the high-efficiency type and, in addition, contain one or more of the many patented brightening and levelling agents available. Periodic reverse (p.r.) current is also sometimes used to produce smoother deposits. 

Traces of many metals interfere in the determination of calcium and magnesium using solochrome black indicator, e.g. Co, Ni, Cu, Zn, Hg, and Mn. Their interference can be overcome by the addition of a little hydroxylammonium chloride (which reduces some of the metals to their lower oxidation states), or also of sodium cyanide or potassium cyanide which form very stable cyanide complexes ( masking ). Iron may be rendered harmless by the addition of a little sodium sulphide. 

The product can also be prepared from benzaldehyde, di-methylamine, and potassium cyanide in cold acetic acid and aqueous ethanol.5... 

Alternatively, unreactive heterocyclic N-oxides might also be readily converted into their a-cyano heterocycles on reaction with the strongly electrophilic Cl3SiCN, Cl2Si(CN)2, or ClSi(CN)3, which should be formed in situ on addition of SiCl4 to a solution or suspension of sodium or potassium cyanide in acetonitrile or DMF (cf the analogous formation of ClSi(N3)3 708 in Scheme 5.70). 

Nitrogen trichloride detonates in the presence of nitrogen monoxide, dioxide or trioxide and also in contact with ammonia and potassium cyanide. 

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