Crushed ice

Naphthyl Acetate. CHgCOOCi H,. Dissolve 1 g. of pure 2-naphtnol in 5 ml. (r8 mols.) of 10% sodium hydroxide solution as before, add 10 g. of crushed ice, and i-i ml. (1-14 g., 1 5 mols.) of acetic anhydride. Shake the mixture vigorously for about 10-15 minutes the 2-naphthyl acetate separates as colourless crystals. Filter at the pump, wash with water, drain, and dry thoroughly. Yield of crude material, 1-4 g. (theoretical). Recrystallise from petroleum (b.p. 60-80 ), from which, on cooling and scratching, the 2-naphthyl acetate separates as colourless crystals, m.p, 71 yield, 10 g. 

A) Diazotisation of Anthranilic Acid, Dissolve 20 g. of anthranilic acid in a solution of 7 5 g. of anhydrous sodium carbonate in 200 ml. of water contained in a 400 ml. beaker, (The mixture may be warmed very gently with stirring to obtain a solution more rapidly, and then cooled.) Add slowly 12 g. of sodium nitrite and cool the stirred solution below 10 , Pour this cold solution slowly on to a vigorously stirred mixture of 40 ml, of concentrated hydrochloric acid and 120 g. of crushed ice in a 600 ml. beaker. 

Dissolve 4 5 ml. of aniline in a mixture of 10 ml. of concentrated hydrochloric acid and 20 ml. of water cool the solution to 5°, and diazotise by the addition of 4 g. of sodium nitrite dissolved in 20 ml, of water, observing the usual precautions given on page 181. Dissolve 7 g. of 2-naphthol in 60 ml. of 10% sodium hydroxide solution contained in a 200 ml. beaker, and cool this solution to 5 by external cooling, aided by the direct addition of about 20-30 g. of crushed ice. Now add the diazotised solution very slowly to the naphthol solution, keeping the latter well stirred meanwhile the mixed solutions immediately develop a deep red colour, and the benzeneazonaphthol should... 

Now remove the flask from the water-bath, and slowly add a solution of 5 ml. (5-2 g.) of dry ethyl benzoate in 15 ml. of anhydrous ether down the condenser in small quantities at a time, mixing the contents of the flask thoroughly between each addition. When the boiling of the ether again subsides, return the flask to the water-bath and reheat for a further 15 minutes. Then cool the mixture in ice-water, and carefully pour off the ethereal solution into a mixture of about 60 ml. of dilute sulphuric acid. and 100 g. of crushed ice contained in a flask of about 500 ml. capacity fitted for stearn-distillation, taking care to leave behind any unchanged magnesium. 

Sodium Hypochi ite. zM- This may be prepared with sufficient accuracy by dissolving 100 g. of NaOH in 200 ml. of water in a large beaker, cooling the solution, and then adding about 500 g. of crushed ice. Now counterpoise the beaker on a rough set of scales, and pass in chlorine from a cylinder until an increase in weight of 72 g. is obtained. Make up the solution to i litre and stir well. The solution must be kept in a cool dark place, but even then slowly decomposes. 

It is often necessary to obtain temperatures below that of the laboratory. Finely-crushed ice is used for maintaining the temperature at 0-5° it is usually best to use a slush of crushed ice with sufficient water to provide contact with the vessel to be cooled and to stir frequently. For temperatures below 0°, the commonest freezing mixture is an intimate mixture of common salt and crushed ice a mixture of one part of common salt and three parts of ice will theoretically produce a temperature of about — 20° but, in practice, the ice salt mixtures give temperatures of — 5° to — 18°. Greater cooling may be obtained by the use of crystalline calcium chloride temperatures of — 40° to — 50° may be reached with five parts of CaCl2,6H20 and 3 5-4 parts of crushed ice. 

Hydrobromic acid. Method 1 (from bromine and sulphur dioxide). A mixture of 600 g. (or 188-6 ml.) of bromine, 250 ml. of water and 760 g. of crushed ice is placed in a 1 6 litre round-bottomed flask and a rapid stream of sulphur dioxide (from a siphon of the liquefied gas) is passed into the flask, care being taken that the outlet of the gas-delivery tube is below the surface of the bromine layer. The rate of flow of the gas is adjusted so that it is completely absorbed. It is advisable to cool the flask in ice and also to shake the contents from time to time. The reduction is complete when the mixture assumes a uniform yellowish-brown or yellow colour, which is unaffected by further introduction of sulphur dioxide excess of the latter gas should be avoided as it will be... 

Now run in a solution of 52 g. (53-5 ml.) of pure diethyl carbonate (1) in 70 ml. of anhydrous ether, with rapid stirring, over a period of about one hour. A vigorous reaction sets in and the ether refluxes continually. When the diethyl carbonate has been added, heat the flask on a water bath with stirring for another hour. Pour the reaction mixture, with frequent shaking, into a 2 litre round-bottomed flask containing 500 g. of crushed ice and a solution of 100 g. of ammonium chloride in 200 ml. of water. Transfer to a separatory funnel, remove the ether layer, and extract the aqueous solution with two 176 ml. portions of ether. Dry... 

Place 0 -5 g. of 3 4 5 triiodobenzoyl chloride in a small test-tube, add 0 -25 ml. of the alcohol - ether and heat the mixture gently over a micro burner until the evolution of hydrogen chloride ceases (3-5 minutes). Pour the molten mass into 10 ml. of 20 per cent, alcohol to which crushed ice has been added. Some derivatives solidify instantly those which separate as oils change to solids in a few minutes without further manipulation. Recrystallise from rectified spirit (use 50 per cent, alcohol for esters of methyl and butyl carbitol ). 

This acid mixture may be prepared (compare Section 11,49, 1) by placing 120 g. (37-5 ml.) of bromine and 130 g. of crushed ice in a 500 ml. flask, cooling the latter in ice, and passing sulphur dioxide (from a siphon of the liquefied gas) into the bromine layer at such a rate that the gas is completely absorb. The flask is shaken occasionally, and the flow of gas is stopped inunediately the red colour due to free bromine has disappeared the mixture will then have a yellow colour. The resulting acid mixture is equivalent to 260 g. of 48 per cent, hydrobromio acid to which 75 g. of concentrated sulphuric acid have been added it need not be dis. tilled for the preparation of n-butyl bromide. 

To obtain pure acetaldehyde, the product must be redistilled. Clean and dry the 200-250 ml. flask first used, immerse it in cold or ice water pour in the crude acetaldehyde rapidly, attach the fractionating column, etc. Immerse the receiver in crushed ice. Heat the flask gently in a water bath and adjust the temperature so that the aldehyde distils slowly and at a uniform temperature. The temperature recorded at the top of the column may depend partly upon the temperature of the laboratory, if this is above 21°. Pure acetaldehyde boils at 21°. 

Equip a 1-litre three-necked flask with a mechanical stirrer, a separatory funnel and a thermometer. Place a solution of 47 g. of sodium cyanide (or 62 g. of potassium cyanide) in 200 ml. of water in the flask, and introduce 58 g. (73-5 ml.) of pure acetone. Add slowly from the separatory fumiel, with constant stirring, 334 g. (275 ml.) of 30 per cent, sulphuric acid by weight. Do not allow the temperature to rise above 15-20° add crushed ice, if necessary, to the mixture by momentarily removing the thermometer. After all the acid has been added continue the stirring for 15 minutes. Extract the reaction mixture with three 50 ml. portions of ether, dry the ethereal extracts with anhydrous sodium or magnesium sulphate, remove most of the ether on a water bath and distil the residue rapidly under diminished pressure. The acetone cyanohydrin passes over at 80-82°/15 mm. The yield is 62 g. 

Place 125 ml. of concentrated ammonia solution (sp. gr. 0-88) in a 600 ml. beaker and surround the latter with crushed ice. Stir the ammonia solution mechanically, and introduce the n-caproyl chloride slowly by means of a suitably supported separatory funnel with bent stem. The rate of addition must be adjusted so that no white fumes are lost. The amide separates immediately. Allow to stand in the ice water for 15 minutes after all the acid chloride has been introduced. Filter oflF the amide at the pump use the flltrate to assist the transfer of any amide remaining in the beaker to the Alter (2). Spread the amide on sheets of Alter or drying paper to dry in the air. The crude n-capro-amide (30 g.) has m.p. 98-99° and is sufficiently pure for conversion into the nitrile (Section 111,112) (3). Recrystallise a small quantity of the amide by dissolving it in the minimum volume of hot water and allowing the solution to cool dry on filter paper in the air. Pure n-caproamide has m.p. 100°. 

The acid, if monobasic, can usually be distilled directly from the reaction mixture. If this procedure is not possible, the reaction mixture is poured into excess of crushed ice, and the acid is isolated by ether extraction or by other suitable means. The acid is then characterised (Section 111,85). The addition of hydrochloric acid (as sodium chloride say 5 per cent, of the weight of sulphuric acid) increases the rate of the reaction. 

Pour the reaction mixture cautiously into 400 g. of crushed ice and acidify it in the cold by the addition of a solution prepared by adding 55 ml. of concentrated sulphuric acid to 150 ml. of water and then coohng to 0°. Separate the ether layer and extract the aqueous layer twice with 50 ml. portions of ether. Dry the combined ethereal solutions over 50 g. of anhydrous potassium carbonate and distil the filtered solution thror h a Widmer column (Figs. II, 17, 1 and II, 24, 4). Collect separately the fraction boihng up to 103°, and the dimethylethynyl carbinol at 103-107° Discard the high boiling point material. Dry the fraction of low boihng point with anhydrous potassium carbonate and redistil. The total 3 ield is 75 g. 

The decomposition of the phosphorus oxybromide may also be conducted in a 1-litre three-necked flask charged with 400 g. of finely crushed ice and fitted with a reflux condenser and mechanical stirrer. 

Preparation of the sulphones. Dissolve the 2 4-dinitrophenyl-sulphide in the minimum volume of warm glacial acetic acid and add 3 per cent, potassium permanganate solution with shaking as fast as decolourisation occurs. Use a 50 per cent, excess of potassium permanganate if the sulphide tends to precipitate, add more acetic acid. Just decolourise the solution with sulphur dioxide (or with sodium bisulphite or alcohol) and add 2-3 volumes of crushed ice. Filter off the sulphone, dry, and recrystaUise from alcohol. 

The apparatus required is similar to that described for Diphenylmelhane (Section IV,4). Place a mixture of 200 g. (230 ml.) of dry benzene and 40 g. (26 ml.) of dry chloroform (1) in the flask, and add 35 g. of anhydrous aluminium chloride in portions of about 6 g. at intervals of 5 minutes with constant shaking. The reaction sets in upon the addition of the aluminium chloride and the liquid boils with the evolution of hydrogen chloride. Complete the reaction by refluxing for 30 minutes on a water bath. When cold, pour the contents of the flask very cautiously on to 250 g. of crushed ice and 10 ml. of concentrated hydrochloric acid. Separate the upper benzene layer, dry it with anhydrous calcium chloride or magnesium sulphate, and remove the benzene in a 100 ml. Claisen flask (see Fig. II, 13, 4) at atmospheric pressure. Distil the remaining oil under reduced pressure use the apparatus shown in Fig. 11,19, 1, and collect the fraction b.p. 190-215°/10 mm. separately. This is crude triphenylmethane and solidifies on cooling. Recrystallise it from about four times its weight of ethyl alcohol (2) the triphenylmethane separates in needles and melts at 92°. The yield is 30 g. 

Place a mixture of 1 0 g. of the hydrocarbon, 10 ml. of dry methylene chloride or ethylene dichloride or syw.-tetrachloroethane, 2 5 g. of powdered anhydrous aluminium chloride and 1-2 g. of pure phthalic anhydride in a 50 ml. round-bottomed flask fitted with a short reflux condenser. Heat on a water bath for 30 minutes (or until no more hydrogen chloride fumes are evolved), and then cool in ice. Add 10 ml. of concentrated hydrochloric acid cautiously and shake the flask gently for 5 min utes. Filter oflf the solid at the pump and wash it with 10-15 ml. of cold water. Boil the resulting crude aroylbenzoic acid with 10 ml. of 2 -5N sodium carbonate solution and 0 2 g. of decolourising carbon for 5 minutes, and filter the hot solution. Cool, add about 10 g. of crushed ice and acidify... 

Add 1 g. of the compound to 4 ml. of concentrated sulphuric acid and cautiously introduce, drop by drop, 4 ml. of fuming nitric acid. Warm the mixture on a water bath for 10 minutes, then pour it on to 25 g. of crushed ice (or 25 ml. of ice water). Collect the precipitate by filtration at the pump, and recrystallise it from dilute alcohol. 

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