Patent GB-382942-A (GB)
Title: Manufacture of sulphuric acid esters of alcohols
IPC: C07B45/02
Filed: 1931-07-17
Abstract: Ethereal sulphates are obtained by treating alcohols containing more than 10 carbon atoms with aminosulphonic acid or with derivatives thereof, for example, such as contain an alkyl, aryl, or acyl group, linked to the nitrogen atom, or a salt of the N-substituted or un-substituted acid with an inorganic or organic base.  Alcohols which may be treated include those with aliphatic residues such as dodecyl alcohol or hexadecyl alcohol, alcohols containing both aliphatic and aromatic or hydroaromatic groups, such as phenyl (or cyclohexyl groups, and alcohols containing substituents such as halogens.  The same method of preparing ethereal sulphates may also be applied to alcohols whose carbon chain is interrupted by other atoms, for example, alcohols containing the groupings -CONH-, -CO-O-, -NH-, or -O-, the number of carbon atoms in this case being immaterial.  Ethers, esters, amines, or amides containing hydroxyl groups, for example, monocarboxylic acid esters of glycerine and polyglycerines, alkylglycerine ethers, fatty acid hydroxyalkyl-amides and the like may be treated in this way.  The alcohols may be treated with the free aminosulphonic acid, if desired, in the presence of a solvent, the ammonium salt of the sulphate being formed.  Instead of the aminosulphonic acid there may be used organic sulphamic acids or the salts thereof, for example, alkali salts, ammonium salts, or the salts of organic bases, the compound produced being the salts of the sulphuric acid esters, and the bases from which the sulphamic acids are derived.  The aminosulphonic acid is preferably used either partially or wholly in the form of its salt with an organic base. The organic base may be present in small or large quantities, and in the latter case may be used as a solvent. The invention also includes the production of the sulphuric acid esters of lower and higher primary, secondary, and tertiary alcohols by heating them with salts of aminodisulphonic acid, if desired, in the presence of a solvent such as pyridine.  According to examples, (1) stearyl alcohol is treated at 110-120 DEG  C. for 20 hours with aminosulphonic acid, the ammonium salt of the acid octadecyl sulphuric acid ester being obtained; (2) an alcohol mixture obtained by the oxidation of paraffin is heated with aminosulphonic acid, a water-soluble product being obtained; (3) stearyl alcohol is treated with 4-methylphenylsulphamic acid; (4) stearyl alcohol is heated with the benzamide-n-sulphonate of benzamide, the benzamide salt of stearyl sulphate being obtained. Since the latter is hydrolysed in presence of water, the clear salt is dissolved in hot water, and sodium hydroxide added until the solution is weakly alkaline.  The whole is cooled to 40 DEG  C., the benzamide which separates filtered off, and the filtrate corporated; (5) stearyl alcohol is heated with ammonium paratoluidinesulphamate, the paratoluidine salt of stearyl being produced; (6) stearyl alcohol is treated with aminosulphonic acid and pyridine.  Instead of pyridine, ethylolamine, dipropylolamine, triethylolamine, or diethylaniline, or the like, may be used; (7) lauroylhydroxylethylamide, pyridine, and aminosulphonic acid are heated for 3 hours at 80-100 DEG  C., and the pyridine is then removed by distillation.  The sulphuric ester of lauroylhydroxylethylamide is obtained.  In an analogous manner the sulphonic ester of glycolmonocetyl ether may be produced; (8) coco nut fatty acid hydroxyethylamide is heated with aminosulphonic acid and 1:2-dichlorethane, carbon tetrachloride, trichlor ethylene, benzene, or other solvent.  When the reaction is complete, water and then the theoretical quantity of sodium hydroxide to convert the product into its sodium salt are added.  The solvent and the ammonia formed are distilled off, the sulphuric ester remaining in the form of a white paste; (9) butanol and pyridine are heated for 8 hours to boiling in a reflux apparatus with an ammonium salt of iminodisulphonic acid each molecular proportion of which contains 0,4 molecular proportions of NH<3>.  The pyridine is removed under reduced pressure, and the ammonium salt of butyl sulphate remains. Instead of the ammonium salt of iminodisulphonic acid, those of the alkalis or of organic bases may be employed; (10) a mixture of primary, secondary, and tertiary alcohols obtained by oxidizing paraffin is heated with an ammonium iminodisulphonate and pyridine as in (9) above, the ammonium salts of the corresponding sul-phuric esters being obtained; (11) cetyl alcohol is treated with an ammonium aminodisulphonate and pyridine, the ammonium salt of cetyl sulphate being produced.  Instead of cetyl alcohol, a cetyl alcohol substituted with chlorine or a phenoxy group may be employed; (12) lauroylhydroxylethylamide is treated with aminodisulphonic acid, and the ammonium salt of the sulphuric ester thus obtained converted to the sodium salt by the addition of caustic soda.  This product can be used as a softening agent for fabrics, artificial silk, and the like; (13) phenyl-n-butanol, an ammonium iminodisulphonate and pyridine are heated together, the product being the ammonium salt of phenyl-n-butylsulphate; and (14) butoxy-ethylalcohol is heated with aminodisulphonic acid, the ammonium salt of butoxyethyl sulphate being obtained.  The aqueous solution of the product possesses a good wetting-out action.