Patent GB-511144-A (GB)
Title: Manufacture of thiuronium salts
IPC: C07C335/30
Filed: 1938-02-10
Abstract: 511,144. Thiuronium salts. GROVES, W. W. (I.G. Farbenindustrie Akt.-Ges.). Feb. 10, 1938, No. 4190. [Classes 2 (iii) and 15 (ii)] Thiuronium salts are obtained by causing a carboxylic acid amide, carboxylic acid nitrile or urethane, carrying at least one hydrocarbon radicle having more than 10 carbon atoms, which radicle may be substituted or be interrupted by one or more hetero-atoms or heteroatom groups, to react with formaldehyde or a polymer thereof, thiourea. or a substitution product or derivative thereof, and an acid in presence of a solvent or diluent.' Alternatively, instead of formaldehyde and the amide, nitrile, or urethane, a methylol derivative of one of these compounds may be used ; also a salt of thiourea may be used instead of thiourea and an acid. The products' are fat-like masses, either soluble in water or capable of being emulsified or dispersed in water, and are applicable for treating textiles. Specified amides, nitriles or urethanes are lauric acid methylamide, iso-octylphenoxyacetic acid amide, the amide of the hydroxystearic acid from hardened castor oil, N-octodecylurethane, and others referred to in the following examples :-(1) lauric acid amide, paraformaldehyde and thiourea hydrochloride are heated'together at 80-90‹C. in glacial acetic acid and the latter is distilled off; the white solid product yields a foaming aqueous solution;' (2) stearic. acid methylolamide and thiourea hydrochloride are heated together at 60‹C. in methyl alcohol and the product is separated by cooling and filtering; the same product is obtainable by stirring stearic acid methylolamide into an. aqueous solution at 40-50‹C., containing thiourea and hydrochloric acid, heating to 55-58‹C., cooling and filtering; (3) hydrogen chloride is passed into a mixture of stearic acid methylolamide and thiourea in methanol at 60‹C. and the methanol is distilled off; (4) a mixture of O- octodecylurethane, paraformaldehyde, and thiourea hydrochloride is heated at 80-90‹C., cooled and filtered; (5) stearic acid nitrile, paraformaldehyde and thiourea hydrochloride are heated together at 70‹C. in glacial acetic acid and the mixture is cooled and filtered, the thiourea may be replaced by its N-benzyl-N<1>- ethyl derivative ; (6) stearic acid methylolamide thiourea and conc. sulphuric acid are heated together at 60‹C. in methanol and the product is crystallized out on cooling; the sulphuric acid may be replaced by phosphoric or dichloracetic acid; (7) the methylolamide of p-isotetradecylphenoxyacetic acid is heated with thiourea and hydrochloric acid in methanol at 60-65‹C. and the mixture is cooled andfiltered ; the product yields a foaming aqueous solution ; (8) the amide of p-n-dodecylbenzoic acid (c.f. Specification 497,353), paraformaldehyde and thiourea hydrochloride are heated together at 65-70‹C. in glacial acetic acid and the latter is distilled off ; (9) lauric acid amide, paraformaldehyde, N:N<1>-triethylthiourea and hydrochloric acid are heated together at 65- 70‹C. in glacial acetic acid and the latter is distilled-off; (10) adipic acid di-(n-dodecylamide), paraformaldehyde and thiourea hydrochloride are heated together in. boiling alcohol and the latter is distilled off , (11) N-n-dodecylacetamide, paraformaldehyde, thiourea and hydrochloric acid are heated together at 65-70‹C. in glacial acetic acid and the product filtered cff; (12) the N-n-dodecylcarbamic acid ester of hydroxystearic' acid amide, paraformaldehyde, thiourea and hydrochloric acid are neated together at 70‹C, in, glacial acetic acid and the - latter is distilled off; the product yields a foaming aqueous solution ; (13) dichlorostearic acid amide, paraformaldehyde, thiourea and hydrochloric acid are heated together in boiling methanol and the latter is distilled off. The Provisional Specification refers to the use as initial materials of compounds capable of reacting with formaldehyde and carrying at least one hydrocarbon radicle having more than 3 carbon atoms and specifies, in addition to the above amides, nitriles and urethanes, various hydroxy, mercapto and amino compounds, amidines, hydrazides and sulphonic acid amides and hydrazides, and includes examples of the use of iso-octylphenol, p-dodecylphenol, heptylurethane and heptylic acid nitrile. p-Iso-tetradecylphenoxyacetic acid is obtained by condensing p-isotetradecylphenol with chloracetic acid. N-n-dodecylcarbamic acid ester of hydroxystearic acid amide is obtained by condensing hydrogenated ricinoleic acid amide with lauryl isocyanate.