Congo

Arylarsonic acids have usually a very low solubility in cold water. They are however amphoteric, since with, for example, sodium hydroxide they form sodium salts as above and with acids such as hydrochloric acid they form salts of the type [CaHjAsCOHljlCl. Both types of salt are usually soluble in water, and to isolate the free acid the aqueous solution has to be brought to the correct pH for most arsonic acids this can be achieved by niaking the solution only just acid to Congo Red, when the free acid will usually rapidly separate. 

Cool the reaction-solution, and pour it into a 250 ml. beaker, washing out the flask with ca. 50 ml. of water into the beaker. Chill the solution in ice-water and add dilute hydrochloric acid with stirring until the solution is just acid when spotted externally on to Congo Red paper. The arsinic acid rapidly separates. Filter at the pump, wash well with water and drain. (Yield of crude dry product, 7-5-8 o g. m.p. 200-203°.)... 

If the original ester is a fat or oil and produces an odour of acrolein when heated, it may be a glyceride. Esters of ethylene glycol and of glycol with simple fatty acids are viscous and of high b.p. They are hydrolysed (method I) and the ethyl alcohol distilled ofl. The residue is diluted (a soap may be formed) and acidified with hydrochloric acid (Congo red paper). The acid is filtered or... 

Benzoates. Dissolve 0-5 g. of the amino acid in 10 ml. of 10 per cent, sodium bicarbonate solution and add 1 g. of benzoyl chloride. Shake the mixture vigorously in a stoppered test-tube remove the stopper from time to time since carbon dioxide is evolved. When the odour of benzoyl chloride has disappeared, acidify with dilute hydrochloric acid to Congo red and filter. Extract the solid with a little cold ether to remove any benzoic acid which may be present. RecrystaUise the benzoyl derivative which remains from hot water or from dilute alcohol. 

With phenylalanine and tyrosine, the sodium salt of the derivative is sparingly soluble in water and separates during the initial reaction. Acidify the suspension to Congo red the salts pass into solution and the mixture separates into two layers. The derivative is in the etheresil lay and crystallises from it within a few minutes. It is filtered off and recrystaUised. 

Dissolve 0 01 g. equivalent of the amino acid in 0 03 g. equivalent of N sodium hydroxide solution and cool to 5° in a bath of ice. Add, with rapid stirring, 0 -01 g. equivalent of 2 4-dichlorophenoxyacetyl chloride dissolved in 5 ml. of dry benzene at such a rate (5-10 minutes) that the temperature of the mixture does not rise above 15° if the reaction mixture gels after the addition of the acid chloride, add water to thin it. Remove the ice bath and stir for 2-3 hours. Extract the resulting mixture with ether, and acidify the aqueous solution to Congo red with dilute hydrochloric acid. Collect the precipitate by filtration and recrystallise it from dilute alcohol. 

Introduce 197 g. of anhydrous brucine or 215 g. of the air-dried dihydrate (4) into a warm solution of 139 g. of dZ-acc.-octyl hj drogen phthalate in 300 ml. of acetone and warm the mixture vmder reflux on a water bath until the solution is clear. Upon cooling, the brucine salt (dA, IB) separates as a crystalline solid. Filter this off on a sintered glass funnel, press it well to remove mother liquor, and wash it in the funnel with 125 ml. of acetone. Set the combined filtrate and washings (W) aside. Cover the crystals with acetone and add, slowly and with stirriug, a slight excess (to Congo red) of dilute hydrochloric acid (1 1 by volume about 60 ml.) if the solution becomes turbid before the introduction of... 

Place 84 g. of iron filings and 340 ml. of water in a 1 - 5 or 2-litre bolt-head flask equipped with a mechanical stirrer. Heat the mixture to boiling, stir mechanically, and add the sodium m-nitrobenzenesulphonate in small portions during 1 hour. After each addition the mixture foams extensively a wet cloth should be applied to the neck of the flask if the mixture tends to froth over the sides. Replace from time to time the water which has evaporated so that the volume is approximately constant. When all the sodium salt has been introduced, boU the mixture for 20 minutes. Place a small drop of the suspension upon filter paper and observe the colour of the spot it should be a pale brown but not deep brown or deep yellow. If it is not appreciably coloured, add anhydrous sodium carbonate cautiously, stirring the mixture, until red litmus paper is turned blue and a test drop upon filter paper is not blackened by sodium sulphide solution. Filter at the pump and wash well with hot water. Concentrate the filtrate to about 200 ml., acidify with concentrated hydrochloric acid to Congo red, and allow to cool. Filter off the metanilic acid and dry upon filter paper. A further small quantity may be obtained by concentrating the mother liquid. The yield is 55 g. 

It is advisable to test the potassium iodide - starch pap>er with acidified sodium nitrite solution the commercial test paper is, particularly if it has been kept for a considerable period, sometimes almost useless. The solution must contain an excess of acid at all times, i.e., it must give a blue colour on Congo rod paper. 

Warm the copper sulphate solution to 50-60°, and add dilute sulphuric acid until it is acid to Congo red. Add the sodium bisulphite solution. 

To a mixture of 10 g. of the compound and 3-5 ml. of 33 per cent, sodium hydroxide solution in a test-tube, add 2-5 ml. of 50 per cent, chloroacetic acid solution. If necessary, add a little water to dissolve the sodium salt of the phenol. Stopper the test-tube loosely and heat on agently-boiling water bath for an hour. After cooling, dilute with 10 ml. of water, acidify to Congo red with dilute hydrochloric acid, and extract with 30 ml. of ether. Wash the ethereal extract with 10 ml, of water, and extract the aryloxyacetic acid b shaking with 25 ml. of 5 per cent, sodium carbonate solution. Acidify the sodium carbonate extract (to Congo red) with dilute hydrochloric acid, collect the aryloxyacetic acid which separates, and recrystallise it from hot water. 

Coumarin. In a 250 ml. round-bottomed flask, provided with a small reflux condenser and a calcium chloride drying tube at the top, place 2 1 g, of salicylaldehyde, 2 0 ml. of anhydrous triethylamine and 5 0 ml. of acetic anhydride, and reflux the mixture gently for 12 hours. Steam distil the mixture from the reaction flask and discard the distillate. Render the residue in the flask basic to litmus with solid sodium bicarbonate, cool, filter the precipitated crude coumarin at the pump and wash it with a little cold water. Acidify the filtrate to Congo red with... 

Phthalide. In a 1 litre bolt-head flask stir 90 g. of a high quality zinc powder to a thick paste with a solution of 0 5 g. of crystallised copper sulphate in 20 ml. of water (this serves to activate the zinc), and then add 165 ml. of 20 per cent, sodium hydroxide solution. Cool the flask in an ice bath to 5°, stir the contents mechanically, and add 73-5 g. of phthalimide in small portions at such a rate that the temperature does not rise above 8° (about 30 minutes are required for the addition). Continue the stirring for half an hour, dilute with 200 ml. of water, warm on a water bath imtil the evolution of ammonia ceases (about 3 hours), and concentrate to a volume of about 200 ml. by distillation vmder reduced pressure (tig. 11,37, 1). Filter, and render the flltrate acid to Congo red paper with concentrated hydrochloric acid (about 75 ml. are required). Much of the phthalide separates as an oil, but, in order to complete the lactonisation of the hydroxymethylbenzoic acid, boil for an hour transfer while hot to a beaker. The oil solidifles on cooling to a hard red-brown cake. Leave overnight in an ice chest or refrigerator, and than filter at the pump. The crude phthalide contains much sodium chloride. RecrystaUise it in 10 g. portions from 750 ml. of water use the mother liquor from the first crop for the recrystaUisation of the subsequent portion. Filter each portion while hot, cool in ice below 5°, filter and wash with small quantities of ice-cold water. Dry in the air upon filter paper. The yield of phthalide (transparent plates), m.p. 72-73°, is 47 g. 

Add dilute sulphuric acid, with stirring, to the cold alkahne solution until the solution is acid to htmus or Congo red paper and the acid, if a solid, commences to separate as a faint permanent precipitate. Now add dilute sodium carbonate solution until the solution is alkahne (litmus paper) and any precipitate has completely redissolved. Extract the clear solution twice with ether evaporate or distil the ether from the ethereal solution on a water bath CAUTION no flames may be near) and identify the residual phenol as under 1. Remove the dissolved ether from the aqueous solution by boiling, acidify with dilute sulphuric acid and identify the organic acid present (see Sections 111,85 and IV, 175). 

Dimethyl sulphate may be purified (a) by allowing it to stand over anhydrous potassium carbonate until it is neutral to Congo red paper, or (6) by washing, just before use, with an equal volume of ice water, followed by one-third of its volume of cold, saturated sodium bicarbonate solution. 

Reflux a mixture of 15 g. of homoanisamide, 30 g. of potassium hydroxide and 300 ml. of ethanol on a water bath for 5 hours. Dilute with 750 ml. of water, evaporate to 75 ml. and acidify to Congo red. Collect the acid and recrystallise it from ethyl alcohol. The yield of p-methoxy-phenylacetic acid, m.p. 86-87°, is 13 g. 

Cool the flask in ice, acidify with 10 ml. of cold 1 1-hydro-chloric acid and distil under reduced pressure (water pump) until most of the alcohol is removed. Add water to the residue, extract several times with ether, wash the combined ethereal extracts with N ammonia solution until a test portion gives no precipitate upon acidification. Extract the combined alkahne solutions once with a fresh portion of ether, and add the aqueous solution to an excess of dilute hydrochloric acid the final mixture should still be acidic to Congo red. Collect the crystalhne half-ester by filtration at the pump, wash it with water and dry at 100°. The yield is 14-5 g., m.p. 122-125°. Recrystallise by dissolving in about 40 ml. of warm benzene and adding an equal volume of petroleum ether (b.p. 40- 60°) 13 -5 g. of the colourless half-ester, m.p. 125-126°, are obtained. 

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