Copper® cyanide

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. 

In the flask were placed 40 ml of ethanol, 10 ml of water, 12 g of finely powdered CuCN and 0.40 mol of 3-bromo-l-butyne (compare VIII-2, Exp. 3). The mixture was warmed to 55°C and a solution of 26 g of KCN in 60 ml of water was added drop-wise or in small portions care was taken that complete dissolution of the copper cyanide did not occur (note 2). The temperature of the mixture was maintained close to 60°C throughout the period of addition. The conversion was terminated... 

Note 2. If the addition is performed at too fast a rate, all of the copper cyanide may dissolve temporarily. The free KCN, present in the solution may cause partial resinification of the allenic nitrile. 

Copper compounds Copper concentrates Copper-constantan Copper-constantan Copper-Count-N Copper cyanide... 

A further improvement in the cuprate-based methodology for producing PGs utilizes a one-pot procedure (203). The CO-chain precursor (67) was first functionalized with zirconocene chloride hydride ia THF. The vinyl zirconium iatermediate was transmetalated direcdy by treatment with two equivalents of / -butyUithium or methyUithium at —30 to —70° C. Sequential addition of copper cyanide and methyUithium eUcited the /V situ generation of the higher order cyanocuprate which was then reacted with the protected enone to give the PG. 

Barrel plating of parts in copper cyanide solutions utilizes various formulations, some weaker, some stronger than the high speed baths. When plating parts that tend to stick together or nest during the barrel rotation, the free cyanide may need to be increased. This may require 35—40 g/L free potassium cyanide or more with an equal copper content. 

For strike on nonferrous metals and a second strike on steel, first strike uses 1.5 g/L AgCN, 75—90 g/L KCN, and 10—15 g/L copper cyanide. 

Cyanide Disinfectants SPA Sodium cyanide Copper cyanide Heat treatment of metal Coal distillation Electroplating Photographic Synthetic fibre Agriculture and horticulture Abattoirs Eood processing... 

Cyanide Copper cyanide Nickel cyanide Potassium cyanide Silver cyanide Sodium cyanide Zinc cyanide... 

COPPER CYANIDE COPPER CYANIDE COPPER SELENATE COPPER SELENITE... 

The TiVC) coordinated organocopper compounds 260 and 261 were obtained from 2-lithiothiophene and copper cyanide and iodide, respectively (990M1571). 

In an alternative syntliesis of panaatistaliti (S7) by Trost et al. [52], fSdieme 9.15) addilioti of tlie Grlgtiatd teagetil 63 [53] lo a mixture of tlie azide 62 and copper cyanide reprodudbly gave tlie desired adduct 64. Because of tlie difliciilties associated witli purification of adduct, tlie overall yield of tlie two steps ftlie next being diliydroxylation of tlie olefin) was 6 296. 

Cyan-kalium, n. potassium cyanide, -kalium-losung, /. potassium cyanide solution, -ko-balt, m. cobalt cyanide, -kohlensaure, / cyanocarbonic acid. -kupfer, n. copper cyanide, -laugerei, -laugung, /. cyaniding. cyanidation. -losung, / cyanide solution, -metall, n. metallic methyl cyanide, -natrium, n. sodium cyanide. -platin, n. platinum cyanide. 

Kupfer-bromid, n. copper bromide, specif, cupric bromide, copper(II) bromide, -bro-mtir, n. cuprous bromide, copper(I) bromide, -chlorid, n. copper chloride, specif, cupric chloride, copper(II) chloride, -chloriir, n. cuprous chloride, copper(I) chloride, -cyamd, Ti. copper cyanide, specif, cupric cyanide, copper(II) cyanide, -cyaniir, n. cuprous cyanide, copper(I) cyanide, -dom, m. slag from liquated copper, -draht, m. copper wire, -drahtnetz, n. copper gauze, -drehspane,... 

The vapor-phase chlorination reaction occurs at approximately 200-300°C. The dichlorobutene mixture is then treated with NaCN or HCN in presence of copper cyanide. The product 1,4-dicyano-2-butene is obtained in high yield because allylic rearrangement to the more thermodynamically stable isomer occurs during the cyanation reaction ... 

Many baths in which metal is reduced from complex anions (e.g. cyanide baths, stannate baths) give high throwing indices because both polarisation and cathode efficiency variation favour a low value of M. The cathode efficiency for a typical copper cyanide bath (40°C) was ... 

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. 

The copper cyanide bath has excellent macro-throwing power and is chosen whenever irregular-shaped parts are to be plated. The sulphate bath is not inferior when parts with very narrow recesses, i.e. with width of opening less than 6 mm, are to be plated, although its macro-throwing power is... 

Cyanide solutions are used almost exclusively. One typical solution contains copper cyanide 26 g/1, zinc cyanide 11 g/1, sodium cyanide (total) 45 g/1 and sodium cyanide ( free ) 7 g/l This bath is operated at pH 10.3-11.0, 110 A/m and 27-35 C, with 75 Cu-25 Zn alloy anodes. Many other solutions are used including a special rubber-bonding bath and a high-speed bath which is capable of being used at up to 16 A/dm . ... 

The lithium enolate 2a (M = Li ) prepared from the iron propanoyl complex 1 reacts with symmetrical ketones to produce the diastercomers 3 and 4 with moderate selectivity for diastereomer 3. The yields of the aldol adducts are poor deprotonation of the substrate ketone is reported to be the dominant reaction pathway45. However, transmetalation of the lithium enolate 2a by treatment with one equivalent of copper cyanide at —40 C generates the copper enolate 2b (M = Cu ) which reacts with symmetrical ketones at — 78 °C to selectively produce diastereomer 3 in good yield. Diastereomeric ratios in excess of 92 8 are reported with efficient stereoselection requiring the addition of exactly one equivalent of copper cyanide at the transmetalation step45. Small amounts of triphcnylphosphane, a common trace impurity remaining from the preparation of these iron-acyl complexes, appear to suppress formation of the copper enolate. Thus, the starting iron complex must be carefully purified. 

Reaction of the lithium enolate 2 with prochiral aldehydes at low temperature proceeds with little selectivity, producing all four possible diastereomers 3, 4, 5, and 6 in similar amounts50. Transmetalation of the lithium enolate by treatment with three equivalents of diethylaluminum chloride or with one equivalent of copper cyanide generates the corresponding cthylaluminum and copper enolates which react at — 100°C with prochiral aldehydes to produce selectively diastereomers 1 and 2, respectively50. The reactivity of tin enolates of iron- propanoyl complexes has not been described. 

In contrast, transmetalation of the lithium enolate at —40 C by treatment with one equivalent of copper cyanide generated a species 10b (M = Cu ) that reacted with acetaldehyde to selectively provide a 25 75 mixture of diastereomers 11 and 12 (R = CH3) which are separable by chromatography on alumina. Other diastereomers were not observed. Similar transmetalation of 10a (M = Li0) with excess diethylaluminum chloride, followed by reaction with acetaldehyde, produced a mixture of the same two diastereomers, but with a reversed ratio (80 20). Similar results were obtained upon aldol additions to other aldehydes (see the following table)49. 

The regiochcmistry for stoichiometric alkylation with butyl(cyano)copper magnesium bromide is the same as that for the copper cyanide catalyzed reaction. The regiochemistry with dibutyl-copper magnesium bromide is also very similar to that of the copper(I) bromide catalyzed reaction. Lithium cuprates do not exhibit y regioselectivity in this biased system. 

Fig. 10 2-Pyridone carboxylic acids 64 can be selectively decarboxylated to the saturated derivatives 65 via a reagent-free microwave-assisted method. Decarboxylation was also conducted under conventional heating but then copper cyanide was required resulting in mixtures of saturated and unsaturated 2-pyridones...

It was shown in the same article that the decarboxylation could also be performed by conventional heating but then copper cyanide was required and a mixture of saturated and imsaturated 2-pyridones 65 and 66 was obtained in a ratio of 1 10 (Fig. 10). A tentative mechanism was suggested for the reagent-free MAOS method where the carbonyl in the 2-pyridone ring is supposed to assist in the decarboxylation yielding an yUde 67 (Fig. 11). The decarboxylated bicyclic 2-pyridone 68 is thereafter obtained after protonation by the solvent. In agreement with the mechanistic suggestion, it was shown that a selective deuteration occurred when deuterated dimethyl sulfoxide (DMSO-de) was used as solvent. 

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