Patent GB-408989-A (GB)
Title: Manufacture of materials containing ethanol
IPC: C12H1/14
Filed: 1932-07-15
Abstract: Methods of preparing various carbohydrate ethers suitable for addition to alcoholic beverages according to the invention are described.  Thus an ethyl cellulose soluble in water and in aqueous ethanol solution may be prepared by steeping wood-pulp or cotton linters in caustic soda solution, pressing, adding sodium carbonate, ethylating in a rotating autoclave at 100 DEG  C. with an ethyl halide such as ethyl chloride, diluted or not with benzene, separating the ethyl cellulose, dissolving it and reprecipitating it by heating the solution, washing with hot water, and drying. Alternatively, alkali cellulose which has been wholly or partially freed from water, for example by being shredded and dried at reduced pressure, may be ethylated in a similar manner. Another method is to ethylate with ethyl chloride or diethyl sulphate a mixture of cellulose and caustic soda solution; or a mixture of cellulose caustic soda solution, and solid caustic soda; or a mixture of cellulose, caustic soda solution, sodium carbonate, and solid caustic soda methyl celluloses soluble in water and aqueous ethanol solution may be made by methylating an alkaline solution of a cellulose derivative or conversion product soluble in caustic soda with dimethyl sulphate in the manner in which the alkylation is conducted in Examples I to VI of Specification 12854/12, [Class 2 (ii)]; or by methylating with dimethyl sulphate at temperatures from room temperature to 40 or 50 DEG  C., or with methyl chloride at temperatures such as 70 to 80 DEG  C., one of the alkali celluloses prepared as described above in the making of ethyl cellulose.  Ethyl and methyl starches and ethyl and methyl dextrins may be obtained by first preparing an alkali starch or alkali dextrin by the methods employed in making ethyl cellulose soluble in water and in aqueous ethanol, and ethylating or methylating with diethyl sulphate or ethyl chloride or dimethyl sulphate or methyl chloride in the same manner as when making ethyl or methyl celluloses respectively.  When the starch or dextrin ether is soluble in hot water, separation thereof from the reaction mixture may be effected by dissolving the latter in water, dialysing the aqueous solution and evaporating the dialysed solution to dryness or precipitating with alcohol-ether mixture or the like.  Oxyalkyl ethers of carbohydrates of the type n(C6H10O5) soluble in water and aqueous ethanol are obtainable by treating cellulose, starch, or dextrin, for example, with a mixture of caustic soda solution and powdered caustic soda or with powdered caustic soda, and oxyalkylating the mixture with a halohydrin or an alkylene oxide in the cold or at a raised temperature.  Mixed alkyl ethers of cellulose, starch, or dextrin may be prepared either by treating the starting material with a mixed alkyl sulphate in presence of caustic alkali, or by alkylating partially with an alkylating agent such as dialkyl sulphate or alkyl halide and treating the low alkylated alkyl ether obtained with an alkylating agent containing another alkyl group.  Alkyloxyalkyl ethers may be prepared by alkylating oxyalkyl ethers of cellulose, starch, or dextrin, particularly such as are of low degree of alkylation; the oxyalkyl ethers may be prepared by known methods, or by any of the methods described above for the preparation of alkyl ethers.  Oxyalkyl ethers soluble in caustic soda solution can also be alkylated by acting upon their solutions in caustic alkali with dialkyl sulphate as described in Specifications 12854/12, or 3370/14, [Class 2 (iii)]. In any of the above methods, a cellulose hydrate or hydrocellulose or oxycellulose may be used instead of cellulose as starting material.  Ethers of soluble starch, inulin, lichenin, vegetable gums, tragacanth, or agar-agar may be obtained by analogous methods.  Ether of cellulose, starch, dextrin or the like containing nitrogen may be obtained by ethylating or methylating according to any of the above methods, the intermediate products of the examples of Specification 367,920 intended to be xanthated. Ethers containing nitrogen and sulphur suitable for use according to the invention may be obtained by ethylating or methylating as above described, the thiourethanes of cellulose of N-substituted thiourethanes of cellulose described in Specification 231,801 or 231,802, [both in Class 2 (ii)].  The corresponding derivatives of starch and dextrin are obtained by analogous methods. To obtain clear solutions of the carbohydrate ethers in aqueous alcohol, they may be purified by dissolving in water, filtering the solution, and, if the ether is precipitable by heat, precipitating by heat, washing and drying, or by dissolving in aqueous ethanol filtering, and evaporating to dryness or precipitating with an agent such as alcohol-ether mixture.  Solutions of cellulose derivatives of low viscosity for use according to the invention may be obtained by hydrolysing the derivatives with acids or in other known manner. Instead of cellulose, cellulose hydrate, hydrocellulose, oxycellulose acid cellulose or the like may be used.  Examples of the preparation of various carbohydrate ether derivatives are given.  Specifications 6035/13, 149,320, 163,018, 177,810, 203,346, 203,347, 231,807, 231,809, [all in Class 2 (ii)], 367,920, and 374,964 also are referred to.ALSO:Alcoholic beverages of reduced or no inebriating effect contain in solution at least one ether of a carbohydrate of the type n(C6H10O5).  Ethers of cellulose, starch, soluble starch, dextrin, insulin, a vegetable gum, tragacanth, lichenin, hemicelluloses, amyloid, glycogen, and agar-agar are specified. Alkyl-ethers, especially the ethyl, methyl, and propyl derivatives, mixed ethers, oxyalkyl ethers such as glycol or glyceryl ethers, ether-esters such as esterified alkyl and oxyalkyl derivatives, ethers of oxyacids such as glycollic acid, ethers containing alkyl and aralkyl groups, and ethers containing nitrogen or sulphur or the like may be used.  The ethers may be incorporated with the beverage at any stage of its preparation, or into the finished beverage, in which they are either soluble or at least partially soluble.  Thus the ethers may be added to at least one of the ingredients used in the preparation of the beverage, or into the parent material of the beverage, for example, beer, or sparkling wines, before or during fermentation, or to the mineral water of any kind such as soda water intended for admixture with the otherwise finished beverage. Beverages specifically mentioned are brandy, whisky, gin, absinth, kirschwasser, wodka, starka, benedictine, cherry brandy, kümmel, cura<\>ccacao, chartreuse, vermouth, port, sherry, madeira, marsala, malago, Tokay, champagne, aper<\>uitifs, bitters, cider, perry, beer, cocktails, cobblers, and medicinal wines such as quinine, condurango, iron, and pepsin tonics.  The beverages may contain sweetening substances, flavourings, aromatic essences or oils, colouring matters, and fruit juices or syrups.  Examples of ingredients of this kind specified are orange juice, sugar, lemon oil, anise oil, fennel oil, rose oil, Caraway oil, orange peel oil, mace oil, clove oil, angelic oil, peppermint oil, cajaput oil, calamus, coriander oil, melissa oil, hyssop oil, vanilla tincture, cura<\>ccao tincture, and cognac essence.  The proportion of carbohydrate ether in the finished beverage is usually 10 to 25 per cent by weight, but may be more than 25 per cent or less than 10 per cent in certain cases.  Examples are given.  Methods of preparing various carbohydrate ethers suitable for addition to alcoholic beverages according to the invention are also described. Thus an ethyl cellulose soluble in water and in aqueous ethanol solution may be prepared by steeping wood-pulp or cotton linters in caustic soda solution, pressing, adding sodium carbonate, ethylating in a rotating autoclave at 110 DEG  C. with an ethyl halide such as ethyl chloride, diluted or not with benzene, separating the ethyl cellulose, dissolving it and reprecipitating it by heating the solution, washing with hot water, and drying. Alternatively, alkali cellulose which has been wholly or partially freed from water, for example, by being shredded and dried at reduced pressure, may be ethylated in a similar manner.  Another method is to ethylate with ethyl chloride or diethyl sulphate a mixture of cellulose and caustic soda solution; or a mixture of cellulose, caustic soda solution, and solid caustic soda; or a mixture of cellulose, caustic soda solution, sodium carbonate, and solid caustic soda.  Methyl celluloses soluble in water and aqueous ethanol solution may be made by methylating an alkaline solution of a cellulose derivative or convection product soluble in caustic soda with dimethyl sulphite in the manner in which the alkylation is conducted in Examples I to VI of Specification 12854/12, [Class 2 (ii)]; or by methylating with dimethyl sulphate at temperatures from room temperature to 40 or 50 DEG  C., or with methyl chloride at temperatures such as 70 to 80 DEG  C., one of the alkali celluloses prepared as described above in the making of ethyl cellulose.  Ethyl and methyl starches and ethyl and methyl dextrins may be obtained by first preparing an alkali starch or alkali dextrin by the methods employed in making ethyl cellulose soluble in water and in aqueous ethanol, and ethylating or methylating with diethyl sulphate or ethyl chloride or dimethyl sulphate or methyl chloride in the same manner as when making ethyl or methyl celluloses respectively.  When the starch or dextrin ether is soluble in hot water, separation thereof from the reaction mixture may be effected by dissolving the latter in water, dialysing the aqueous soluton, and evaporating the dialysed solution to dryness or precipitating with alcohol-ether mixture or the like.  Oxyalkyl ethers of carbohydrates of the type n(C6H10O5) soluble in wa