Cupric

Anhydrous cupric sulphate is white but forms a blue hydrate and a blue aqueous solution. The solution turns yellow when treated with concentrated hydrochloric acid, dark blue with ammonia, and gives a white precipitate and brown solution when treated with potassium iodide. A yellow-brown aqueous solution of ferric chloride becomes paler on acidification with sulphuric or nitric... 

Acetic Acid, CH3COOH, in Aqueous Solution, and crystalline Cupric Acetate, (CH3C00)2Cu,H20. (Semi-micro scale). 

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. 

Potassium cupro-cyanide is the most convenient form in which cuprous cyanide can be used in Sandmeyer s Reaction. It is prepared by adding an excess of potassium cyanide to copper sulphate solution, whereby the cupric cyanide which is formed immediately breaks down to give cuprous cyanide and cyanogen, and the cuprous cyanide then dissolves in the excess of potassium... 

Prepare the cupric hydroxide by dissolving 2 g. of copper sulphate in about too ml. of water, and adding with stirring 16 ml. of N.NaOH solution. Filter off the precipitate and wash thoroughly with water. 

Several variations of the chemical method are in use. In the one described below, a freshly prepared Fehling s solution is standardised by titrating it directly against a standard solution of pure anhydrous glucose when the end-point is reached, I. e., when the cupric salt in the Fehling s solution is completely reduced to cuprous oxide, the supernatant solution becomes completely decolorised. Some difficulty is often experienced at first in determining the end-point of the reaction, but with practice accurate results can be obtained. The titrations should be performed in daylight whenever possible, unless a Special indicator is used (see under Methylene-blue, p. 463). 

Cellulose. This is insoluble in water, hot and cold. It dissolves in a solution of Schweitzer s reagent (precipitated cupric hydroxide is washed free from salts and then dissolved in concentrated ammonia solution), from which it is precipitated by the addition of dilute acids. Cellulose is not hydrolysed by dilute hydrochloric acid. 

The special reducing agent (a solution containing cupro-ammonia ions) is first prepared. Dissolve 63 g. of crystallised copper sulphate in 250 ml. of water in a 1-Utre heaker, add 100 ml. of concentrated ammonium hydroxide solution (sp. gr. 0-88), and cool the solution to 10°. Dissolve 17 8 g. of hydroxylammonium chloride or 21 g. of hydroxylammonium sulphate in 60 ml. of water, cool to 10°, and add 42 -5 ml. of QN sodium hydroxide solution if the resulting solution of tydroxylamine is not clear, filter it at the pump. Without delay add the hydroxylamine solution, with stirring, to the ammoniacal cupric sulphate solution. Reduction occurs at once, a gas is evolved, and the solution assumes a pale blue colour. Protect the reducing agent from the air if it is not used immediately. 

Oxidation of benzoin with concentrated nitric acid or by catalytic amounts of cupric salts in acetic acid solution, which are regenerated continuously by ammonium nitrate, yields the diketone benzil ... 

Method 2. Place 0-2 g. of cupric acetate, 10 g. of ammonium nitrate, 21 2 g. of benzoin and 70 ml. of an 80 per cent, by volume acetic acid -water solution in a 250 ml. flask fitted with a reflux condenser. Heat the mixture with occasional shaking (1). When solution occurs, a vigorous evolution of nitrogen is observed. Reflux for 90 minutes, cool the solution, seed the solution with a crystal of benzil (2), and allow to stand for 1 hour. Filter at the pump and keep the mother liquor (3) wash well with water and dry (preferably in an oven at 60°). The resulting benzil has m.p. 94-95° and the m.p. is unaffected by recrystallisation from alcohol or from carbon tetrachloride (2 ml. per gram). Dilution of the mother liquor with the aqueous washings gives a further 1 Og. of benzil (4). 

Dissolve 15-0 g. of A.R. barium nitrate and 130 g. of A.R. cupric nitrate trihydrate in 450 ml. of water at 80°. Prepare a solution of sodium chromate by dissolving 89 g. of recrystallised sodium dichromate dihydrate in 200 ml. of water and adding 112 5 ml. of cone, ammonia solution (sp. gr. 0-90). Add the warm solution (80°) of nitrates in a thin stream, with stirring, to the sodium chromate solution (at 25°). Collect the orange precipitate by suction Bltration, wash it with two 50 ml. portions of 5fiter, drain well, and dry at 75-80° for 12 hours powder finely. 

Cholestenone. Place a mixture of 1 0 g. of purified cholesterol and 0-2 g. of cupric oxide in a test-tube clamped securely at the top, add a fragment of Dry Ice in order to displace the air by carbon dioxide, and insert a plug of cotton wool in the mouth of the tube. Heat in a metal bath at 300-315° for 15 minutes and allow to cool rotate the test-tube occasionally in order to spread the melt on the sides. Warm with a few ml. of benzene and pour the black suspension directly into the top of a previously prepared chromatographic column (1) rinse the test-tube with a little more benzene and pour the rinsings into the column. With the aid of shght suction (> 3-4 cm. of mercury), draw the solution into the alumina column stir the top 0 -5 cm. or so with a stout copper wire to... 

In a 1 litre round-bottomed flask, equipped with an air condenser, place a mixture of 44 g. of o-chlorobenzoic acid (Section IV,157) (1), 156 g. (153 ml.) of redistilled aniline, 41 g. of anhydrous potassium carbonate and 1 g. of cupric oxide. Reflux the mixture in an oil bath for 2 hours. Allow to cool. Remove the excess of aniline by steam distillation and add 20 g. of decolourising carbon to the brown residual solution. Boil the mixture for 15 minutes, and filter at the pump. Add the filtrate with stirring to a mixture of 30 ml. of concentrated hydrochloric acid and 60 ml. of water, and allow to cool. Filter off the precipitated acid with suction, and dry to constant weight upon filter paper in the air. The yield of iV-phenylanthranilic acid, m.p. 181-182° (capillary tube placed in preheated bath at 170°), is 50 g. This acid is pure enough for most purposes. It may be recrystaUised as follows dissolve 5 g. of the acid in either 25 ml. of alcohol or in 10 ml. of acetic acid, and add 5 ml. of hot water m.p. 182-183°. 

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. 

METHOD 4 [110, 111] - guaiacol and cupric perchlorate (Cu(CI04)2)-ascorbic acid (that s vitamin C, bubba ) are mixed in an appropriate solvent under oxygen atmosphere in a flask to give about 30% catechol. 

Alkoxythiazoles are prepared by heterocyclization (274, 462). The Williamson method using catalytic amounts of KI and cupric oxide is also possible (278. 288, 306). 5-Acetoxy-4-alkenylthiazoles are obtained by treatment of 242 with acetyl chloride and triethylamine or with acetic anhydride and pyridine (450). Similarly, the reaction of diphenylketene with 242 affords 5-acyloxy-4-alkenylthiazoles (243) (Scheme 120) (450). The readiness of these o-acetylations suggests that 4-alkylidene thiazoline-5-one might be in equilibrium with 4-alkenyl-5-hydroxythiazoles (450). 

Cryolite, see Sodium hexafluoroaluminate Cryptohalite, see Ammonium hexafluorosilicate Cupric and cuprous, see under Copper Cuprite, see Copper(I) oxide... 

Barfoed s reagent (test for glucose) dissolve 66 g of cupric acetate and 10 mL of glacial acetic acid in water and dilute to 1 liter. 

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