Patent GB-508801-A (GB)
Title: Manufacture of condensation products of sulphonic acid amides
IPC: C08G12/24
Filed: 1938-01-05
Abstract: 508,801. Sulphonamide derivatives. GROVES, W. W. (I. G. Farbenindustrie Akt.- Ges.) . Jan. 5, 1938, No. 313. [Classes 2 (iii) and 15 (ii)] Condensation products of sulphonic acid amides - are manufactured by causing a sulphonic acid amide of the general formula where R is an aliphatic. aliphatic cycloaliphatic or aliphatic-aromatic radicle containing at least 12 carbon atoms, which may contain substituents and/or may contain an oxygen, sulphur or nitrogen atom as a hetero-atom in an aliphatic carbon chain or as a bridge directly linking an aliphatic portion of the radical to a cycloaliphatic or aromatic nucleus, and R1 is hydrogen or a methyl or ethyl group, or the radicle -CH2CH2NHSO2R, where R is as above, to react at ordinary or raised temperature with formaldehyde or a polymer thereof and an acid, an acid anhydride or an acid salt of a polybasic acid in the presence of a tertiary base or thiourea or alkyl derivative of thiourea capable of reacting in the iso-form ; or by causing a methylol compound, obtained by reaction of formaldehyde or a polymer thereof with a sulphonic acid amide as defined above, to react with an acid, an acid anhydride or an acid salt of a polybasic acid in the presence of a tertiary base or thiourea or an alkyl derivative of thiourea capable of reacting in the isoform, or to react with a salt of a tertiary base or of thiourea or of an alkyl derivative of thiourea capable of reacting in the iso-form ; or by causing an N-halogenmethyl compound of a sulphonic acid amide as defined above to react with a tertiary base or thiourea or an alkyl derivative of thiourea capable of reacting in the iso-form. The reaction may be carried out by gentle heating of the mixture in the absence of a solvent when a liquid or easilyfusible sulphonamide is used, and in other cases it may be effected in the presence of water or an organic solvent, e.g. benzene, toluene, chlorobenzene, methylene chloride, ethylene chloride or carbon tetrachloride. Suitable starting materials are : sulphonamides : dodecylsulphonamide, octadecylsulphonamide, monochloroctadecylsulphonamide (obtainable by the simultaneous action of sulphur dioxide and chlorine on octadecane, the chlorine being caused to act until in addition to that present in the sulphochloride group a further chlorine atom has entered the carbon chain, and treatment of the product with liquid ammonia), dichloroctadecylsulphomethylamide (obtainable by the simultaneous action of sulphur dioxide and chlorine on octadecane until two chlorine atoms have entered the carbon chain, and treatment of the product with liquid methylamine), dodecyloxyethanesulphonamide (obtainable by the action of sodium dodecyl alcoholate on chlorethanesulphonic acid, conversion into the sulphochloride and reaction with liquid ammonia), p-tert. octylphenoxyethanesulphonamide (obtainable similarly from sodium p - (alpha : alpha : #gamma : #gamma - tetramethylbutyl)- phenolate), p -butylphenylbutanesutphonamide (obtainable by condensing butyric acid chloride with benzene to form butyrophenone, reducing this to n-butylbenzene, condensing with succinic anhydride by the Friedel-Crafts reaction, reducing the resulting keto-acid, in the form of its ester, to p-butylphenylbutanol, converting this to the corresponding aralkyl chloride, reacting with sodium bisulphite and converting the resulting sulphonic acid to the sulphochloride and this to the sulphonamide), and p-butylcyclohexylethanesulphonamide (obtainable by reacting butylbenzene with ethylene oxide, reducing the product catalytically to p-butylcyclohexylethyl alcohol and converting this into the corresponding ethanesulphonic acid and then into the sulphonamide) ; tertiary bases : pyridine and its homologues, quinoline, trimethylamine, triethylamine, tributylamine, triethanolamine, methylmorpholine, methylpiperidine, dimethylaniline, tetramethylethylenediamine and hexamethylenetetramine ; thiourea derivatives : methylthiourea, ethylenethiourea and octadecylthiourea (obtainable by reacting octadecylamine with an isothiocyanate) ; acid reacting substances : hydrochloric, hydrobromic, sulphurous, sulphuric, phosphoric, pyrophosphoric, pyrosulphuric, sulphoacetic, sulphophthalic, chlorobenzoic and lactic acids, phosphorus pentoxide, sulphur trioxide, acetic anhydride, succinic anhydride, phthalic anhydride, sodium bisulphate, primary sodium phosphate, secondary sodium pyrophosphate and the acid salts of phthalic and succinic acids. The products have capillary activity and may be used for the treatment of materials such as textiles, fibres, paper, leather or plastic masses. In examples : (1) octadecylsulphonamide (obtainable by the action of liquid ammonia on octadecylsulphochloride) is heated with formaldehyde and pyridine hydrochloride or hydrobromide, in the presence of pyridine as solvent ; (2) a hydrocarbon fraction from the hydrogenation of carbon monoxide containing about 14 carbon atoms in the molecule is heated with sulphur dioxide and chlorine, the product is treated with liquid ammonia, and the resulting sulphonamide is heated with paraformaldehyde and pyridine while passing in sulphur dioxide ; (3) octadecylsulphonamide is heated with paraformaldehyde, phthalic anhydride and pyridine ; (4) tetradecylsulphonamide, obtained as in (2), is heated with paraformaldehyde, diglycollic anhydride and pyridine ; the diglycollic anhydride may be replaced by phthalic anhydride ; (5) octadecylsulphonamide is heated with paraformaldehyde, sodium bisulphite and pyridine ; (6) dodecyl-N-chloromethylsulphonamide (obtained by treating dodecylsulphochloride with liquid ammonia and reacting the product with paraformaldehyde and gaseous hydrogen chloride in methylene chloride) is reacted with pyridine in methylene' chloride ; (7) dodecylmethylchloromethylsulphonamide is reacted with thiourea in alcoholic solution ; (8) tetradecylsulphonamide is reacted with paraformaldehyde and hydrogen chloride or hydrogen bromide in methylene chloride, and the resulting solution is dried and stirred with thiourea ; (9) the thiourea in (8) is replaced by pyridine or by hexamethylenetetramine ; (10) the product obtained by the action of sulphur dioxide and chlorine on hard paraffin with exposure to ultra-violet light is reacted with ethylenediamine, the product is treated with paraformaldehyde and hydrogen chloride in benzene, the resulting solution is dried, the solvent is removed and the chloromethyl coinpound is heated with pyridine ; (11) p-isododecylcyclohexanol is condensed with sodium chlorethanesulphonate, the product is treated with phosphorus pentachloride and then with liquid ammonia, and the resulting sulphonamide is heated with paraformaldehyde, dichloracetic acid and pyridine ; (12) 1-stearylamino-2-nitro- 4-benzenesulphonamide (prepared by acylating 1 - amino - 2 - nitro - 4 - benzenesulphonamide with stearic acid chloride) is reacted with paraformaldehyde and hydrogen chloride in methylene chloride, and the resulting solution is dried and stirred with thiourea ; (13) hard paraffin is reacted with sulphur dioxide and chlorine with exposure to ultraviolet light, the product is reacted with methylamine, and the resulting sulphomethylamide is heated with paraformaldehyde and trimethylamine hydrochloride in benzene. Specification 508,794 is referred to.