Aqueous layer

Ethyl bromide soon distils over, and collects as heavy oily drops under the water in the receiving flask, evaporation of the very volatile distillate being thus prevented. If the mixture in the flask A froths badly, moderate the heating of the sand-bath. When no more oily drops of ethyl bromide come over, pour the contents of the receiving flask into a separating-funnel, and carefully run oflF the heavy lower layer of ethyl bromide. Discard the upper aqueous layer, and return the ethyl bromide to the funnel. Add an equal volume of 10% sodium carbonate solution, cork the funnel securely and shake cautiously. Owing to the presence of hydrobromic and sulphurous acids in the crude ethyl bromide, a brisk evolution of carbon dioxide occurs therefore release the... 

Transfer the reaction-mixture to a separating-funnel, run off the aqueous layer, and collect the ethereal layer. Extract the aqueous layer twice with ether (2 x 25 ml.), add the extracts to the main ethereal solution and dry over sodium sulphate. 

Place the distillate in a separating-funnel and extract the benzonitrile twice, using about 30 ml. of ether for each extraction. Return the united ethereal extracts to the funnel and shake with 10% sodium hydroxide solution to eliminate traces of phenol formed by decomposition of the benzenediazonium chloride. Then run off the lower aqueous layer, and shake the ethereal solution with about an equal volume of dilute sulphuric acid to remove traces of foul-smelling phenyl isocyanide (CaHjNC) which are always present. Finally separate the sulphuric acid as completely as possible, and shake the ether with water to ensure absence of acid. Run off the water and dry the benzonitrile solution over granular calcium chloride for about 20 minutes. 

Now transfer the cold distillate to a separating-funnel, and shake vigorously with about 50-60 ml. of ether run oflF the lower aqueous layer and then decantf the ethereal solution through the mouth of the funnel into a 200 ml. conical flask. Replace the aqueous layer in the funnel, and extract similarly twice more with ether, combining the ethereal extracts in the conical flask. Add 3-4 g. of dry powdered potassium carbonate to the ethereal solution, securely cork the flask and shake the contents gently. The ethereal solution of the phenol... 

To 2 ml. of the ester in a test-tube add slightly more than the same volume of a cold saturated aqueous copper acetate solution. The blue colour of the latter turns immediately to a pale green. Now shake the tube vigorously in order to produce an emulsion of the ester in the aqueous layer. Scratch the sides of the tube with a rod, and shake vigorously as before. Crystallisation may be delayed for about 5 minutes, but, when once started, rapidly gives a copious precipitate... 

A 1500 ml. flask is fitted (preferably by means of a three-necked adaptor) with a rubber-sleeved or mercury-sealed stirrer (Fig. 20, p. 39), a reflux water-condenser, and a dropping-funnel cf. Fig. 23(c), p. 45, in which only a two-necked adaptor is shown or Fig. 23(G)). The dried zinc powder (20 g.) is placed in the flask, and a solution of 28 ml. of ethyl bromoacetate and 32 ml. of benzaldehyde in 40 ml. of dry benzene containing 5 ml. of dry ether is placed in the dropping-funnel. Approximately 10 ml. of this solution is run on to the zinc powder, and the mixture allowed to remain unstirred until (usually within a few minutes) a vigorous reaction occurs. (If no reaction occurs, warm the mixture on the water-bath until the reaction starts.) The stirrer is now started, and the rest of the solution allowed to run in drop-wise over a period of about 30 minutes so that the initial reaction is steadily maintained. The flask is then heated on a water-bath for 30 minutes with continuous stirring, and is then cooled in an ice-water bath. The well-stirred product is then hydrolysed by the addition of 120 ml. of 10% sulphuric acid. The mixture is transferred to a separating-funnel, the lower aqueous layer discarded, and the upper benzene layer then... 

Colorations with resorcinol and naphthol. Dissolve about 0-2 g. of resorcinol in I ml. of 30% aqueous NaOH solution, add i ml. of chloroform and warm gently the aqueous layer turns red and shows a slight fluorescence. 

Repeat using using 1- or 2-naphthol in place of resorcinol the aqueous layer becomes deep blue, fading to green. 

In the separations (2) and (3) above, it is often advisable to dissolve the original mixture in a water-insoluble solvent. Select a solvent which will dissolve the entire mixture, and then shake the solution with either (i) dil. NaOH or (ii) dil. HCl. Separate the aqueous layer, and to it add either (i) dil. HCl or (ii) dil. NaOH to liberate the organic acid or the organic base, as the case may be. The non-aqueous layer now contains the neutral component. Reextract this layer with either (i) dil. NaOH or (ii) dil. HCl to ensure removal of traces of the non-neutral component. 

Residual solution. Make just acid with dil. HjSO, and then just alkaline to litmus-paper with Na,COs solution. Extract phenol with ether, distil off latter and identify the residue. Identify the organic acid in the aqueous layer, as in (A) (ii). 

Let >2 grams remain in the aqueous layer after the second extraction, then ... 

Place 35 ml. of water in the separatory funnel and run it into the vigoroiisly stirred reaction mixture at such a rate that rapid refluxing occurs. Follow this by a cold solution of 15-5 ml. of concentrated sulphuric acid in 135 ml. of water. Two practically clear layers will now be present in the flask. Decant as much as possible of the ethereal layer A) into a 500 ml. round-bottomed flask. Transfer the remainder, including the aqueous layer, into a separatory funnel wash the residual solid with two 10 ml. portions of ether and combine these washings with the liquid in the separatory funnel. Separate the ethereal portion and combine it with (A). Distil off the ether through an efficient fraction-... 

Mix 40 g. (51 ml.) of isopropyl alcohol with 460 g. (310 ml.) of constant boiling point hydrobromic acid in a 500 ml. distilling flask, attach a double surface (or long Liebig) condenser and distil slowly (1-2 drops per second) until about half of the liquid has passed over. Separate the lower alkyl bromide layer (70 g.), and redistil the aqueous layer when a further 7 g. of the crude bromide will be obtained (1). Shake the crude bromide in a separatory funnel successively with an equal volume of concentrated hydrochloric acid (2), water, 5 per cent, sodium bicarbonate solution, and water, and dry with anhydrous calcium chloride. Distil from a 100 ml. flask the isopropyl bromide passes over constantly at 59°. The yield is 66 g. 

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