Patent GB-573903-A (GB)
Title: Manufacture of new sulphonamide derivatives
Filed: 1943-01-14
Abstract: A sulphonamide which is free from basic amino groups and contains at least one hydrogen atom of a sulphonamide group is reacted with an aralkylating agent, and a group imparting solubility in water, if not already present, is introduced by treating the product with a sulphonating agent, a salt of an aldehyde bisulphite compound or of an aldehyde-sulphoxylic acid, or with a halogen-carboxylic or halogen-sulphonic acid.  The initial sulphonamide may be aliphatic or aromatic or partially hydrogenated aromatic, e.g. ethane, octane and cetyl sulphonic acid amides, benzene, p-toluene, xylene, cymene, chlor-cymene, naphthalene, isopropyl-, di-isopropyl-, butyl- and dibutyl - naphthalene, tetrahydronaphthalene, diphenyl, anthracene, phenanthrene and acenaphthene sulphonamides, sulphonamides of the products obtained by condensing tetrahydronaphthalene with aluminium chloride, and mixtures obtained by treating aliphatic hydrocarbons with chlorine and sulphur dioxide and reacting the product with ammonia or a primary amine.  Substituent groups in addition to halogen include hydroxyl, acylamino and methoxy.  Such a substituted sulphonamide is N-hydroxy-ethylcymene sulphonamide. Groups giving solubility such as sulphonic acid, neutralized carboxyl or sulphuric acid ester groups may be present in a residue attached either to the sulphur or the nitrogen of the sulphonamide group.  Such sulphonamides are 4-(phenyl-sulphonamino)- and 4-(11-methyl-41-isopropyl - phenyl - sulphonamino) - benzene sulphonic acid-1.  They may be obtained by reaction of an aryl sulphonic acid chloride with an amino-aryl sulphonic acid.  Reaction products of sulphonamides with halogen-carboxylic acids or salts of aldehyde-bisulphite compounds or aldehyde-sulphoxylic acids, prepared, for example, as in Specifications 565,487 and 578,654 are also used.  The aralkylating agent may be a chlormethyl derivative of an aromatic or partially hydrogenated aromatic compound, e.g. benzyl chloride, chlormethyl-toluene, xylene or cumene, 2-chlormethylcymene, 1 - chlormethyl - naphthalene, chlormethyl - tetrahydronaphthalenes, chlormethyl - cyclohexylbenzene, obtainable by treating the addition product of benzene and cyclohexene with formaldehyde and hydrogen chloride, and chlormethyl compounds of more condensed ring systems such as anthracene, octahydroanthracene or octahydrophenanthrene. Such compounds can be obtained by passing hydrogen chloride into a mixture of the hydrocarbon, concentrated formaldehyde solution, and aqueous hydrochloric acid, if required together with zinc chloride, at 60-70 DEG  C.  Chlormethyl derivatives of hydroxyaryl compounds, such as the phenolic addition product of phenol and diterpene, or of ethers, e.g. the condensation product of diterpene with b -naphthol, may also be used.  These may be prepared by a method analogous to that described for the hydrocarbon derivatives.  Aralkylation of the sulphonamide may be effected at 60-70 DEG  C. with the addition of an acid-binding agent such as sodium hydroxide.  The products, if they still contain a hydrogen atom in a sulphonamido group, may be reacted with, e.g. chloracetic or bromethane-sulphonic acid.  An easily sulphonated aromatic nucleus or hydroxy group may be sulphonated with sulphuric acid or an addition product of sulphur trioxide and a tertiary amine to give solubility in water.  The products are used as textile assistants, e.g. wetting, dispersing, washing, softening, levelling or foaming agents, alone or with materials such as inorganic salts.  In examples: (1) the condensation product obtained by reaction of cymene sulphonamide with sodium formaldehyde bisulphite in presence of diamylamine at 160-165 DEG  C. is treated with ar-2-chlormethyl-tetrahydronaphthalene and sodium hydroxide solution at 65-70 DEG  C.; (2) the condensation product of tetrahydronaphthalene sulphonamide and sodium formaldehyde bisulphite is treated as in (1); (3) the condensation product obtainable by heating cymene sulphonamide with sodium formaldehyde sulphoxylate at 120 DEG  C. is treated with chlormethyl-cymene and sodium hydroxide at 65-70 DEG  C.; (4) the reaction product of tetrahydronaphthalene sulphonamide and sodium formaldehyde sulphoxylate is treated with ar-2-chlormethyl-tetrahydronaphthalene; (5) tetrahydronaphthalene is heated with aluminium chloride at 100 DEG  C. to give condensed products such as octahydro-anthracene and -phenanthrene.  The mixture of higher hydrocarbons is treated with chlorsulphonic acid at -5 DEG to -10 DEG  C. and reacted with ammonia to give a mixture of sulphonamides which are heated with sodium formaldehyde sulphoxylate at 115-120 DEG  C.  The product is reacted with ar-2-chlormethyl-tetrahydronaphthalene; (6) sodium tetrahydronaphthalene sulphonaminoacetate, prepared from the sulphonamide and chloracetic acid in alkaline solution, is reacted with ar-2-chlormethyl-tetrahydronaphthalene; (7) N-hydroxyethyl - N - cymylmethyl - cymene - sulphonamide, prepared by reacting cymene sulphonchloride with monoethanolamine and treating the product with 2-chlormethyl-cymene, is treated with chlorsulphonic acid in ether and the sodium salt of the sulphuric ester salted out; (8) a bath for washing woollen yarn contains 1 gram per litre of the product of example (2) or (5).  The Specification as open to inspection under Sect. 91 comprises also the use of sulphonamides containing amino or substituted amino groups, and treatment of the aralkylated products with a salt of thiosulphuric acid to impart solubility.  Condensation products of 2-aminonaphthalene-sulphonic acid-6 or disulphonic acid-6, 8 with N - chloracetyl - cymene or tetrahydronaph - thalene-sulphonamide may be used.  In an additional example, chloracetyl - tetrahydro - naphthalene sulphonamide is condensed with disodium 2-aminonaphthalene disulphonate-6,8 and the product treated with ar-2-chlormethyl-tetrahydronaphthalene.  This subject - matter does not appear in the Specification as accepted.