Liquor, alcohol

Akyilmaz and Dinijkaya [55] Wine Beer Liquor Alcohol oxidase in C. tropicalis cells/cells over a Teflon membrane and immobilised with glutaraldehyde yeast cells (Saccharomyces ellipsoideus)/micro-orgamsms Clark type 02 electrode -... 

Tertiary butyl alcohol, trimethyl carbinol, tertiary butanol. 2-methyl-2-propanol, Me3COH. Colourless prisms, m.p. 25°C, b.p. 83°C. Prepared by absorbing isobutene (2-methylpropene) in sulphuric acid, neutralizing and steam distilling the liquor. Converted to isobutene by heating with oxalic acid. Potassium-/-buloxide is a very strong base. 

Spirits are described as so many degrees over proof (OP) or under proof (UP). Sometimes, for alcoholic liquors, spirit strength is given in degrees proof, e.g. proof spirit is 100° proof and 70° proof 30° under proof (i.e. a solution eontaining 70% of proof spirit). 

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). 

Place 25 g. of phenylacetic acid (Section IV,160) in a 500 ml. round-bottomed flask, cool the latter in running water and add 250 ml. of fuming nitric acid, rather slowly at first and then more rapidly. The addition occupies about 15 minutes. Attach a condenser to the flask, reflux the solution for 1 hour, and pour into about 500 ml. of cold water. When cold, filter the crude 2 4-dinitrophenylacetic acid at the pump and wash it with cold water the resulting acid, after drying at 100°, is almost pure (m.p. 181°) and weighs 31 g. Recrystallise it from 300 ml, of 20 per cent, alcohol. Collect the first main crop (25 g.), and allow the mother liquor to stand overnight when a further 2 g. of pure acid is obtained dry at 100°, The yield of pure 2 4-dinitrophenylacetic acid, m.p. 183°, is 27 g. 

To decompose the acetone semicarbazone, warm 58 g. with 50 ml. of concentrated hydrochloric acid until it just dissolves. Cool in ice the semicarbazide hydrochloride separates as a thick crystaUine mass. Filter at the pump through a sintered glass funnel, and wash with a small quantity of alcohol and then with ether dry in the air. The yield of pure semicarbazide hydrochloride, m.p. 173° (decomp.), is 35 g. A further quantity of product may be obtained either by saturating the mother liquor with hydrogen chloride or by treating it with twice its volume of alcohol and then with ether. 

Many other recovery alternatives have been proposed that iaclude ion exchange (qv), pyrolysis, and wet combustion. However, these have not gained general acceptance. A limited number of calcium-based mills are able to utilize their spent pulpiag liquors to produce by-products such as lignosulfates for oil-weU drilling muds, vanillin, yeast, and ethyl alcohol (see PETROLEUM Vanillin). 

If the crystals are allowed to remain in contact with the mother liquor for several hours without filtering, they become somewhat dark in color. This color may be removed by washing with liol absolute alcohol. 

The mother liquor and washings are returned to the flask and again boiled for seventy-two hours under reflux. The liquid is concentrated to 8oo cc. and again chilled to 0°, inoculated and allowed to stand at 0° for twenty-four hours. The second crop of glucoside so obtained is filtered by suction and washed with three loo-cc. portions of cold methyl alcohol. This yield is no-145 g-i nielting at i64-r65°. The mother liquor and washings are combined and concentrated to about 300 cc., chilled to 0°,... 

The alcohol may be distilled from the mother liquor of the recrystallization. The residue from this distillation may be added to the mother liquor of the first crystallization, which is then concentrated to the crystallization point. The crop of crystals thus obtained will usually require double recrystallization. Alcohol recovered from the first mother liquor will contain too much volatile oil of nutmeg to be used for other purposes. 

The heptamethylene glycol was separated by continuous ether extraction from the alkaline reduction solution after the latter had been diluted and distilled to remove the alcohol. The nonamethylene glycol was separated from the alkaline liquor by decantation (as above) and distilled. All the others were crystallized from benzene (without alcohol). Equally successful results have also been obtained with larger runs (e.g., 0.5 mole of ester),... 

Hexafluoro-2-phenyl-2-propanol may be recovered from mother liquors, recovered solvent, and the KBr salt cake by extracting the mixture with aqueous base. Neutralization of the aqueous phase gives the alcohol (13-23 g.) which is purified by distillation. 

The combined crude material is crystallized from 75 cc. of 95 per cent alcohol, and yields 37-39 g. of slightly colored material, m.p. 123-124°. A second crystallization from alcohol gives 34-36 g. of colorless product melting at the same temperature. By the systematic working of the alcoholic mother liquors, an additional 5-6 g. of pure material is obtained, making the total yield 40-41 g. (57-58 per cent of the theoretical amount). 

In a 2-1. three-necked round-bottomed flask, equipped with a mechanical stirrer (Note 1), reflux condenser, and dropping funnel, are placed 30 g. of pure 2-nitrofluorene, m.p. 157° [Org. Syntheses, Coll. Vol. 2, 447 (1943)], and 250 ml. of 95% ethanol. After warming to 50° on a steam bath, 0.1 g. of palladized charcoal catalyst (previously moistened with alcohol) is added (Note 2) and the stirrer is started. About 15 ml. of hydrazine hydrate is added from the dropping funnel during 30 minutes (Note 3). At this point an additional 0.1 g. of catalyst (previously moistened with alcohol) is added and the mixture is heated until the alcohol refluxes gently. After 1 hour the nitrofluorene has dissolved completely and the supernatant liquor is almost colorless. 

This product can be recrystallized by dissolving 10 g. in 20 ml. of hot ethyl alcohol (95%), adding 14 ml. of water, and allowing the solution to cool slowly so that no oiling out takes place. Colorless needles, m.p. 183-185°, [o ] —211 to —217° (in ale.) (Note 6), are obtained (first crop, 7.5-8.5 g., 83-90% recovery further quantities can be recovered from the mother liquor) (Note 7). 

Papaverine, C20H21O4N. This alkaloid, first obtained by Merck, occurs in the mixture precipitated by ammonia from the mother liquors of opium extract from which morphine and codeine have been separated in Gregory s process, and methods for its isolation from this mixture have been published by Hesse and others. The alkaloid may be purified by conversion into the acid oxalate, B. H2C2O4, m.p. 196° or 201-5-202°, which is nearly insoluble in alcohol. 

Laudanosine, C21H27O4N. This alkaloid occurs in the liquor from which thebaine is precipitated, and can be isolated by Hesse s method. The crude alkaloid is purified by extraction with small quantities of ether, in which laudanosine is soluble, and finally by precipitation with potassium iodide. The free base crystallises from hot benzene in needles, m.p. 89°, [ ] f 103-23° (EtOH), is soluble in alcohol, chloroform, hot benzene or... 

Laudanine, C20H25O4N, was isolated by Hesse. The crude alkaloid is purified by recrj stallisation from dilute alcohol for the removal of small quantities of cryptopine, or it may be dissolved in acetic acid and the solution poured into dilute caustic soda, when this impurity is precipitated and laudanine may be recovered from the filtrate by addition of ammonium chloride. It still contains its isomeride laudanidine, which may be separated by repeated crystallisation of the hydrochlorides, laudanidine accumulating in the aqueous mother liquors. The base crystallises from dilute alcohol, or from a mixture of alcohol and chloroform in rhombic prisms, m.p. 166°, [a]o 0°. It dissolves in solutions of alkali hydroxides, fornung metallic derivatives, which are precipitated by excess of alkali, but is nearly insoluble in solution of ammonia. The salts crystallise well ... 

Thebaine, CjgHgiOgN. This base, which occurs in opium to the extent of 0-1 to 1 per cent., was first obtained by Pelletier and Thiboumery, who regarded it as isomeric with morphine, and named it paramorphine. It was examined by Kane, who first called it thebaine, and by Anderson, who described a method of isolation and provided the formula given above. It remains in the mother liquor after the removal of morphine and eodeine hydrochlorides in Gregory s process, and in Hesse s method of isolating it from this source is obtained as the acid tartrate. This is crystallised from hot water, and the alkaloid regenerated from it is reerystallised from dilute alcohol, from which it separates in leaflets, or from dry alcohol in prisms, m.p. 193°, — 218-6° (EtOH) or — 229-5°... 

The process of isolation finally adopted by the former authors consists in precipitating as reineckates the water-soluble bases contained in a methyl alcoholic extract of the curare. The mixed reineckates are further purified, by solution in acetone and precipitation with water as often as may be necessary. The product so cleaned represents the bulk of the biological activity of the crude drug the mother liquors may contain curine (p. 374), which indicates a menisperm as one of the components of such curares. The mixed reineckates are then fractionated chromato-graphically over alumina and the components isolated as chlorides by the use of silver sulphate and barium chloride in succession. This process has been modified in detail by Schmid and Karrer, who have also found that with their curare, the more soluble reineckate fraction includes less potent quaternary alkaloids. 

Cmchonine, C19H22ON2. This alkaloid is usually present in cinchona and cuprea barks. One of the best sources is Cinchona micrantha bark. It occurs in the crude quinine sulphate mother liquors. The mixed alkaloids recovered from these may be extracted with ether to remove quinidine and cinchonidine and the insoluble residue boiled with successive small quantities of alcohol, from which cinchonine crystallises on cooling. The crude alkaloid is neutralised with dilute sulphuric acid and the sulphate recrystallised from boiling water. Cinchonine so prepared contains quinidine, from which it may be freed by crystallisation from boiling alcohol until it ceases to exhibit fluorescence in dilute sulphuric acid. It will then still contain 10 to 15 per cent, of dihydrocinchonine, which may be removed by reprecipitation as the cuprichloride, B. 2HC1. CuClj, or by the simpler mercuric acetate process of Thron and Dirscherl. ... 

Hoshino and Kobayashi (1933) have also described the resolution of di-eserethole by crystallising the mixed d-hydrogen tartrates from alcohol, when d-eserethole d-hydrogen tartrate [m.p. 173-4°, [a]D ° + 113° (HgO) ] separated first. The base recovered from the mother liquors yielded with 1-tartaric acid, l-ha.se i-hydrogen tartrate (m.p. 173-4°, [ajj, — 113°). The active picrates had m.p. 133-6° and the di-picrate m.p. 132°. 

Preparation. The mother liquors from strychnine manufacture are concentrated and the alkaloids precipitated as neutral oxalates. The precipitate is dried and extracted with dry alcohol in which the strychnine salt is the more soluble. The less soluble salt dissolved in water is decolorised with charcoal, the alkaloid regenerated with ammonia and purified by crystallisation as the sulphate. According to Saunders, pure brucine may be obtained by slow crystallisation from a solution of the pure hydrochloride in alcoholic ammonia. A method of separation depending on the greater solubility in water of strychnine hydriodide was employed by Shenstone, whilst others have made use of the sparing solubility of strychnine chromate for the removal of small quantities of this alkaloid from brucine. For a large scale process see Schwyzer. ... 

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