Cuprous chlorid

Metallic Derivatives, (a) Cuprous Acetylide. CujCg. Prepare an ammoniacal solution of cuprous chloride by first adding dilute ammonia to 2-3 ml. of dilute copper sulphate solution until the initial precipitate just redissolves and a clear deep-blue solution is obtained now add an aqueous solution of hydroxylamine hydrochloride drop by drop with shaking until the solution becomes first green and then completely colourless, the cupric salt being thus reduced to the cuprous derivative. 

Meanwhile, during the cooling of the cuprous chloride solution, prepare a solution of benzenediazonium chloride by dissolving 20 ml. (20-5 g.) of aniline in a mixture of 50 ml. of concentrated hydrochloric acid and 50 ml. of water, and after cooling to 5°, adding slowly a solution of 17 g. of sodium nitrite in 40 ml. of water. Observe carefully the general conditions for diazotisation given in the preparation of iodobenzene (p. 184). 

The success of the Bart reaction when applied to nuclear- substituted anilines is often much affected by the pH of the reaction-mixture. Furthermore, the yields obtained from some m-substituted anilines, which under the normal conditions are usually low, arc considerably increased by the modifications introduced by Scheller, and by Doak, in which the diazotisation is carried out in ethanolic solution followed by reaction with arsenic trichloride in the presence of a cuprous chloride or bromide catalyst. 

Cuprous chloride. Hydrated copper sulphate (125 g.) and sodium chloride (32-5 g.) are dissolved in water (400 ml.) boiling may be necessary. An allialine solution of sodium sulphite (from 26 5 g. of sodium bisulphite and 17 -5 g. of sodium hydroxide in 200 ml. of water) or the solution of the sodium bisulphite alone is added to the resulting hot solution during about 5 minutes with constant shaking. The solution will be decolourised or nearly so. It is then cooled to room temperature (or in an ice bath), and the supernatant liquid is decanted... 

Cuprous cyanide solution. The most satisfactory method is to dissolve the cuprous cyanide (1 mol) in a solution of technical sodium cyanide (2 5-2-6 mols in 600 ml. of water). If it is desired to avoid the preparation of solid cuprous cyanide, the following procedure may be adopted. Cuprous chloride, prepared from 125 g. of copper sulphate crystals as described under 1 above, is suspended in 200 ml. of water contained in a 1-litre round-bottomed flask, which is fitted with a mechanical stirrer. A solution of 65 g. of technical sodium cyanide (96-98 per cent.) in 100 ml. of water is added and the mixture is stirred. The cuprous chloride passes into solution with considerable evolution of heat. As the cuprous cyanide is usually emplo3 ed in some modification of the diazo reaction, it is usual to cool the resulting solution in ice. 

The only reaction which calls for comment here is the formation of red cuprous acetylide with an ammoniacal solution of cuprous chloride ... 

Dissolve 3 g. of copper sulphate pentahydrate and 1 g. of sodium chloride in 12 ml. of hot water, and add a solution of 1 g. of sodium bisulphite in 10 ml. of 5 per cent, sodium hydroxide solution. Shake, cool under the tap, and wash the precipitated wlute cuprous chloride with water by decantation. Dissolve the cuprous chloride in a few ml. of concentrated ammonia solution and dilute with water to 10 ml. 

Allyl Chloride. Comparatively poor yields are obtained by the zinc chloride - hydrochloric acid method, but the following procedure, which employs cuprous chloride as a catalyst, gives a yield of over 90 per cent. Place 100 ml. of allyl alcohol (Section 111,140), 150 ml. of concentrated hydrochloric acid and 2 g. of freshly prepared cuprous chloride (Section II,50,i one tenth scale) in a 750 ml. round-bottomed flask equipped with a reflux condenser. Cool the flask in ice and add 50 ml. of concen trated sulphuric acid dropwise through the condenser with frequent shaking of the flask. A little hydrogen chloride may be evolved towards the end of the reaction. Allow the turbid liquid to stand for 30 minutes in order to complete the separation of the allyl chloride. Remove the upper layer, wash it with twice its volume of water, and dry over anhydrous calcium chloride. Distil the allyl chloride passes over at 46-47°. 

The procedure is not usually applicable to aminosulphonic acids owing to the interaction between the amino group and the phosphorus pentachloride. If, however, the chlorosulphonic acid is prepared by diazotisation and treatment with a solution of cuprous chloride in hydrochloric acid, the crystalline chlorosulphonamide and chlorosulphonanilide may be obtained in the usual way. With some compounds, the amino group may be protected by acetylation. Sulphonic acids derived from a phenol or naphthol cannot be converted into the sulphonyl chlorides by the phosphorus pentachloride method. 

The following mechanism of the Sandmeyer reaction has been proposed as a result of a kinetic study, and incidentally accounts for the formation of the azu compounds as by-products. The catalyst is the CuCl ion produced in the dissolution of cuprous chloride in the chloride solution ... 

In a 1 5 or 2-Utre rovmd-bottomed flask, prepare cuprous chloride from 105 g. of crystallised copper sulphate as detailed in Section 11,50,1. Either wash the precipitate once by decantation or filter it at the pump and wash it with water containing a httle sulphurous acid dissolve it in 170 ml. of concentrated hydrochloric acid. Stopper the flask loosely (to prevent oxidation) and cool it in an ice - salt mixture whilst the diazo-tisation is being carried out. 

Pour the cold diazonium chloride solution slowly and with shaking into the cold cuprous chloride solution (2). The mixture becomes very... 

The diazonium salt solution decomposes on standing and hence must be mixed with the Cuprous chloride solution without delay. Mechanical stirring is an advantage. 

Chlorobenzene. Prepare a solution of phenyldiazonium chloride from 31 g. (30 -5 ml.) of aniUne, 85 ml. of concentrated hydrochloric acid, 85 ml, of water, and a solution of 24 g. of sodium nitrite in 50 ml. of water (for experimental details, see Section IV,60). Prepare cuprous chloride from 105 g. of crystallised copper sulphate (Section 11,50,1), and dissolve it in 170 ml. of concentrated hydrochloric acid. Add the cold phenyl diazonium chloride solution with shaking or stirring to the cold cuprous chloride solution allow the mixture to warm up to room temperature. Follow the experimental details given above for p-chlorotoluene. Wash the chlorobenzene separated from the steam distillate with 40 ml. of 10 per cent, sodium hydroxide solution (to remove phenol), then with water, dry with anhydrous calcium chloride or magnesium sulphate, and distil. Collect the chlorobenzene (a colourless liquid) at 131-133° (mainly 133°), The yield is 29 g. 

By passing a mixture of carbon monoxide and hydrogen chloride into the aromatic hydrocarbon in the presence of a mixture of cuprous chloride and aluminium chloride which acts as a catalyst (Gattermann - Koch reaction). The mixture of gases probably reacts as the equivalent of the unisolated acid chloride of formic acid (formyl chloride) ... 

METHOD 2 Without a doubt, this is the current world favorite for making P2Ps. This method is known as the Wacker oxidation and involves mixing safrole (or any other allylbenzene), palladium chloride, cuprous chloride and dimethylformamide in an oxygen atmosphere to get MD-P2P very quickly and in a totally clean manner [11, 12]. There s also a very nice review in ref. 13. 

The above reagents (ok the safrole and H2O aren t reagent) are weighed or measured accordingly. The flask is securely clamped into place on the magnetic stirrer. Add the DMF and H2O. Start stirring, and then slowly add the palladium chloride and cuprous chloride. If you add the powders first then the liquids you ll have problems with the stir bar finding a place to spin. 

After 24 hours, the stirring is stopped. Now it s time to fitter out the Cuprous Chloride, which is one of the two slight nuisances regarding this procedure. Note forget about Palladium Chloride recovery. It s too complex for the simplicity of this procedure and purchased from a photo supplier it shouldn t cost more than 6.50 per gram. We ll call this next process Phase Two. 

Palladium Chloride 26.5 grams (50% less big saving in ) Cuprous Chloride 300 grams (could have cut this to 200 g)... 

The next example was a post on the Hive by a bee named TaRa (Could be an alias of TDK. Strike ain t sure.). It is essentially the same old song except this girl proved that CuCl2 (cupric chloride) can indeed be used in place of CuCl (cuprous chloride). It also gives you more examples of technique. The more of this one has the more confident they will be in their understanding of the method. 

Cuprous chloride, CuCl—0.5N 50 g per liter, using 1 5 HCl in place of water. 

Cuprous chloride, acid (for gas analysis, absorption of CO) cover the bottom of a 2-liter bottle with a layer of copper oxide % inch deep, and place a bundle of copper wire an inch thick in the bottle so that it extends from the top to the bottom. Fill the bottle with HCl (sp. gr. 1.10). The bottle is shaken occasionally, and when the solution is colorless or nearly so, it is poured into half-liter bottles containing copper wire. The large bottle may be filled with hydrochloric acid, and by adding the oxide or wire when either is exhausted, a constant supply of the reagent is available. 

Cuprous chloride, ammoniacal this solution is used for the same purpose and is made in the same manner as the acid cuprous chloride above, except that the acid solution is treated with ammonia until a faint odor of ammonia is perceptible. Copper wire should be kept with the solution as in the acid reagent. 

In the presence of a pyridine-cuprous chloride catalyst, the following polymerization occurs ... 

The metallic palladium is reoxidized to PdCl2 by the CUCI2 and the resultant cuprous chloride is then reoxidized by oxygen or ait as shown. 

Using cuprous chloride as catalyst, hydrogen chloride adds to acetylene, giving 2-chloro-1,3-butadiene [126-99-8], chloroprene, C H Cl, the monomer for neoprene mbber. 

Heating with cuprous chloride in aqueous hydrochloric acid isomerizes 2-butene-l,4-diol to 3-butene-l,2-diol (98)] Various hydrogen-transfer catalysts isomerize it to 4-hydroxybutyraldehyde [25714-71-0] (99), acetals of which are found as impurities in commercial butanediol and... 

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