Patent GB-536881-A (GB)
Title: Process for the production of water-soluble high molecular ª‡-substituted aralkyl amines and derivatives thereof, and the resulting products
Filed: 1939-11-24
Abstract: 536,881. α-Aralkylamine derivatives; wetting &c. agents ; proofing permeable materials. GEIGY AKT.-GES.. J. R. Nov. 24, 1939, Nos. 30704 and 30705. Convention dates, Nov. 25, 1938 and Dec. 1, 1938. [Classes 2 (iii) and 15 (ii)] [Also in Groups III and VIII] Aralkylamines containing an aliphatic residue having at least eight carbon atoms and having the formula AC (HR)N(R 1 X) in which A is a benzene, naphthalene or partly hydrogenated naphthalene residue, R is alkyl, aralkyl or aryl, R 1  is hydrogen, alkyl, hydroxyalkyl or aralkyl and X is hydrogen, alkyl, hydroxyalkyl or aralkyl are converted into water soluble derivatives by reacting them with acids to form salts, if necessary after partial alkylation or aralkylation, or exhaustively with alkylating or aralkylating agents. When the aralkylamines have an N-acyl group, solubility may also be effected by treating with sulphonating agents if necessary in combination with partial alkylation, aralkylation or acylation. The hydrochlorides, sulphates, oxalates, acetates and lactates of secondary and tertiary derivatives of the aralkylamines are mentioned. As alkylating and aralkylating agents the following are specified : alkylhalides such as methyl and allylchloride, diethylsulphate, sulphonic acid ester, halogen ketones, halogenalkylnitriles, halogenalkylihodanides, and halogenhydroxybenzylhalides. For acylation of the aralkylamines when the sulphonation process is employed carboxylic and sulphonic acids or their esters or halides such as benzoyl-chloride, palm nut fatty acid chloride, propionylchloride, naphthenic acid chloride, toluene, sulphochloride, benzylsulphonic acid chloride and tetrahydronaphthalenesulphochloride may be used. Sulphonic acid groups may be introduced directly or by re-acting with sulphoalkyl or sulphoaralkyl halides. The products are stated to have wetting, washing, softening, foaming, equalizing and dispersing properties and may be used as mothproofing agents, insecticides and disinfectants. They also produce insoluble precipitates with dyestuffs having acid groups and may thus be used for rendering acid dyeings fast. In examples : (1) α-undecylbenzylamine is converted into a tertiary base by means of dimethylsulphate and then into the corresponding quaternary ammonium compound by treating with dimethylsulphate, glycerolchlorhydrin and allylbromide; (2) 4-dimethylamino-α-undecylbenzylamine is treated with. dimethylsulphate to form a quaternary ammonium salt; (3) α- heptadecylbenzylamine is converted into α- heptadecylbenzyldimethylamine by means of dimethyl sulphate and then sulphonated or converted into a quaternary ammonium salt by means of chloracetic acid ethylester , (4) 4- methoxy-α-undecylbenzylamine is treated first with dimethyl sulphate and then with 3:4- dichlorbenzylchloride ; (5) α-methyl-4-laurylbenzylamine is treated first with dimethylsulphate and a quaternary ammonium salt formed with diethylsulphate, allylbromide or chloracetamide ; (6) α-undecylbenzylamine is acylated and the resulting formyl-, acetyl-, butyryl-, benzoyl-, phenoxyacetyl-, phenylacetyl-, and salicylyl-α- undecylbenzylamines sulphonated; (7) N-methyl-undecylbenzylamine is similarly acylated and then sulphonated ; (8) 4-methyl-α-undecylbenzylamine is treated with benzylchloride dimethylsulphate glycerinchlorhydrin benzylsulphochloride, toluene sulphochloride and then sulphonated ; (9) 4-methoxy-α-undecylbenzylamine is treated with benzylchloride and acetyl chloride and then sulphonated; (10) α-methylbenzylamine is treated with palm fatty acid chloride and the lauric acid-N- (α-methylbenzyl) amide sulphonated ; α-substituted benzylamines derived from butyrophenone, amylphenylketone and naphthylmethylketone may also be similarly treated ; (11) 4-dodecyl-α-methylbenzylamine is benzoylated and sulphonated ; (12) 4-phenoxy-α-methylbenzylamine is first treated. with capric acid chloride and then sulphonated ; (13) α-undecylbenzyl amine is treated with toluenesulphochloride and dimethylsulphate and the resulting N-methyl-α-undecylbenzyltoluenesulphamide sulphonated ; (14) α-undecylbenzylamine is treated with tetra-hydronaphthalenesulphochloride and the product sulphonated ; (15) α-benzyl-4-methylbenzylamine is treated with stearic acid chloride and sulphonated ; (16) α-phenylbenzylamine is treated with palm fatty acid chloride and the resulting lauric acid-N-(α-phenylbenzyl) amide sulphonated: (17) α-undecylbenzylamine is ,reacted with benzylchloride-4-sulphonic acid and chlorethane sulphonic acid α-substituted aralkylamines are prepared by reacting the appropriate arylketone with ammonium formate. Thus laurophenone by heating with ammonium formate and saponification of the resulting formyl compound yields α-undecylbenzylamine and stearophenone yields α-heptadecylbenzylamine. The ketones, by hydrogenating in the presence of ammonia also give the α-substituted aralkylamines. 4-Dimethylamino - α - undecylbenzylamine is prepared by reacting 4-chlorlaurophenone with dimethylamine and heating the product with ammonium formate. 4- methoxylaurophenone is produced from palm fatty acid and anisol. α-Methyl-4-laurylbenzylamine is prepared by refluxing laurophenone with amalgamated zinc and hydrochloric acid to give laurylbenzene. The latter is condensed with acetic anhydride, using aluminium chloride in carbondisulphide and the resulting 4-laurylacetophenone treated with ammonium formate. 4-Methyl-α-undecylbenzylamine is prepared by condensing palm fatty acid with toluene to give 4-methyllauroylbenzene and heating the latter with ammonium formate. Samples have been furnished under Sect. 2 (5) of salts prepared by treating α-undecylbenzylamine with hydrochloric, lactic and citric acids and N-dimethyl-α-undecylbenzylamine with hydrochloric acid. The Specification as open to inspection under Sect. 91 comprises also the treatment of the aralkylamines with sulphocarboxylic acid halides of the aliphatic and aromatic series and also with sulphoalkyl and sulphoaralkyl alcohols. Treatment with chloracetone and chloracetophenone is mentioned. This subject-matter does not appear in the Specification as accepted.