Acetone sodium bisulphite

Sodium mlphanilate.—Burns with difficulty, leaving a residue of (chiefly) sodium sulphide. Add dil. HCl, and confirm without delay the evolution of HjS by means of a filter-pa per moistened with lead acetate solution. Typical of salts of the sulphonic acids. Acetone sodium bisulphite.—Almost non-inflammable, leaving a colourless residue of sodium sulphite and sulphate. Transfer residue to a test-tube, add dil. HCl, warm, and confirm the SO2 evolved. 

The distillate is fiaetionated, and the portion, boiling between 50° and 60° C., mixed with strong solution of sodiiun bisulphite. The erystalline cake of acetone sodium bisulphite, which separates on standing, is well pressed, to free it from impiuities, decomposed by distillation with dilute sodiiun carbonate, and the aqueous distillate of pure acetone dehydrated over calcium chloride. Acetone is a colourless, mobile liquid of sp. gr.. 792 at 20° C., it boils at 56.5° C., has a peculiar, pleasant, ethereal odour, and is mixible with water, alcohol, and ether in all proportions. 

This ketone, of the formula Cj H O, isomeric with those above described, is found in the oils of thuja, tansy, wormwood, and sage. It is identical with the bodies formerly described under the names tan-acetone and salvone. It is best prepared in a state of purity from oil of wormwood. According to Semmler, 200 c.c. of the oil, 0 c.c. of a saturated solution of sodium bisulphite, 75 c.c. of water, and 300 c.c. of alcohol are well shaken at intervals during a fortnight. The crystals formed, consisting of the compound of thujone with the sodium bisulphite, are separated, washed with alcohol-ether, and pressed. On treatment with caustic soda solution, the thujone, amounting to over 40 per cent, of the oil used, separates, and can be distilled with steam. 

The manner in which chloroacetone reacts with other compounds is also interesting. With gaseous ammonia, for example, aminoacetone is formed, and with nascent hydrogen (from zinc and acetic acid) it is converted into acetone. Damp silver oxide oxidises it to glycollic, formic and acetic acids. On combination with sodium bisulphite, acicular crystals are formed, probably of an additive compound of the formula ... 

The organic phase contained (1) ethanol, (2) propanol, (3) methyl sulphide, (4) acetone, (5) propanol-2. (6) n-butanol, (7) butanone-2 and (8) carbon tetrachloride. Simultaneously, 0.4 ml of sodium bisulphite was added to 1 ml of the aqueous solution under test, and 15 min later the organic compounds were extracted with 3 ml of carbon tetrachloride. The extract was analysed by GC on a column of dinonyl phthalate at 80 C... 

This double spot formation is not observed on silica gel or alumina layers. The sensitivity to oxidation of the adrenaline derivatives is, however, increased by the metal or heavy metal impurities present in such layers. Adrenaline and noradrenaline have therefore been chromatographed on buffered silica gel layers (Sorensen buffer, pH 6.8), prepared with addition of sodium bisulphite and using 10% ethanol as solvent [163]. The sympathomimetics and the secondary products formed by oxidation tend moreover to form complex salts this manifests itself in elongated spots. Silica gel layers which had been prepared with O.IM EDTA have been used with the solvent acetone-formic acid-water (70 + 10 + 20) for the separation of adrenaline, noradrenaline and various substances of similar structure [110] silica gel HR (Krm 88) ought to be especially advisable for this purpose. On the other hand, Halmekoski [74] has made use of this very ability of the adrenaline-type of sympathomimetic to form complexes, in order to accomplish fractionation on buffered layers containing molybdate, tungstate or borax components... 

Acetylcyclohexanone. Method A. Place a mixture of 24-6 g. of cyclohexanone (regenerated from the bisulphite compound) and 61 g. (47 5 ml.) of A.R. acetic anhydride in a 500 ml. three-necked flask, fitted with an efficient sealed stirrer, a gas inlet tube reaching to within 1-2 cm. of the surface of the liquid combined with a thermometer immersed in the liquid (compare Fig. II, 7, 12, 6), and (in the third neck) a gas outlet tube leading to an alkali or water trap (Fig. II, 8, 1). Immerse the flask in a bath of Dry Ice - acetone, stir the mixture vigorously and pass commercial boron trifluoride (via an empty wash bottle and then through 95 per cent, sulphuric acid) as fast as possible (10-20 minutes) until the mixture, kept at 0-10°, is saturated (copious evolution of white fumes when the outlet tube is disconnected from the trap). Replace the Dry Ice-acetone bath by an ice bath and pass the gas in at a slower rate to ensure maximum absorption. Stir for 3 6 hours whilst allowing the ice bath to attain room temperature slowly. Pour the reaction mixture into a solution of 136 g. of hydrated sodium acetate in 250 ml. of water, reflux for 60 minutes (or until the boron fluoride complexes are hydrolysed), cool in ice and extract with three 50 ml. portions of petroleum ether, b.p. 40-60° (1), wash the combined extracts free of acid with sodium bicarbonate solution, dry over anhydrous calcium sulphate, remove the solvent by... 

An alternative procedure, suitable for the preparation of cyanohydrins which readily form bisulphite complexes, is illustrated by the preparation of mandelic acid described in Expt 5.168 (see also the preparation of acetone cyanohydrin). Here the procedure involves the addition of a saturated solution of sodium metabisulphite to a stirred solution of the carbonyl compound and aqueous sodium cyanide, and when applicable is usually to be preferred to the in situ generation of hydrogen cyanide or the use of the highly poisonous liquid hydrogen cyanide as a reagent. 

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