Patent GB-684842-A (GB)
Title: Improvements in or relating to water soluble acylated and sulphonated derivatives of diaminodibenzothiophene
IPC: C07D333/76
Filed: 1949-08-17
Abstract: Water-soluble sulphonated derivatives of diacylated 3 : 7-diaminodibenzothiophene-5 : 5-dioxides, of the general formula <FORM:0684842/IV (b)/1> (wherein R and R1 represent aliphatic, aromatic, araliphatic or alicyclic hydrocarbon or heterocyclic groups or such groups containing alkyl, alkoxy or halogen substituents, each X represents hydrogen, halogen or an alkyl, alkoxy, hydroxy or sulphonic group, and each Y represents hydrogen, or, when R or R1 is aromatic or heterocyclic, may represent a sulphonic group, at least one X or Y representing a sulphonic group), are manufactured by (a) reacting a 3 : 7-diaminodibenzothiophene-5 : 5-dioxide, which may be substituted by one or more halogen atoms or alkyl, alkoxy or hydroxy groups, with at least two equivalents of an acylating agent containing the group HR.CO-(when R and R1 are identical) or successively with a total of at least two equivalents of acylating agents containing the groups HR.CO- and HR1.CO- (when R and R1 are different), and sulphonating the resulting diacyl compound, or (b) when each Y is hydrogen, reacting a 3 : 7-diaminodibenzothiophene-5 : 51-dioxide, which contains at least one sulphonic group and may be further substituted with one or more halogen atoms or alkyl, alkoxy or hydroxy groups, with an acylating agent or agents as defined in (a).  In process (a), both reactions are advantageously carried out in the same solvent (e.g. a nitrohydrocarbon, especially when using chlorosulphonic acid as the sulphonating agent), without isolation of the intermediate product.  The products are useful as brightening agents for cellulosic materials (see Groups III, IV (c) and VIII). In examples: (1) the disodium salt of 3 : 7-diaminodibenzothiophene - 5 : 5 - dioxide - 2 : 8 - disulphonic acid is heated with p-anisoyl chloride in the presence of pyridine; (2) the p-anisoyl chloride in (1) is replaced by p-toluyl chloride; (3) the starting material of (1) is replaced by the 3 : 7-diaminodimethyldibenzothiophene - 5 : 5 - dioxide disulphonic acid obtained by heating o-tolidine sulphate with oleum; and (4) by the dimethoxy - 3 : 7 - diaminodibenzothiophene - 5 : 5-dioxide monosulphonic acid obtained by acetylating dianisidine, heating the product with oleum, diluting the mixture and further heating; (5) 3 : 7-diaminodibenzothiophenedioxide - 2 - sulphonic acid (obtained by heating benzidine sulphate with oleum) is refluxed with anisoyl chloride and pyridine in chlorobenzene; (6) 3 : 7-diaminodibenzothiophene-5 : 5-dioxide is heated with p-anisoyl chloride in nitrobenzene and the reaction mixture is cooled and treated with chlorosulphonic acid (two sulphonic acid groups entering the nuclei of the anisoyl groups); (7) 3 : 7 - diaminodibenzothiophenedioxide is treated with 2 : 4-dimethoxybenzoyl chloride in pyridine, and the product is isolated and treated with chlorosulphonic acid; (8) the dichloro-3 : 7-diaminodibenzothiophenedioxide obtained by warming 3 : 31-dichlorobenzidine sulphate with oleum is refluxed with p-anisoyl chloride in pyridine and the product is treated with chlorosulphonic acid in nitrobenzene.  Further acylating agents specified are acetic anhydride, butyryl chloride, trifluoroacetyl chloride, crotonyl chloride, ethoxyacetyl chloride, benzoyl and phenylacetyl chlorides and their alkyl, halogen and alkoxy substitution products, naphthoyl chlorides, cinnamic chloride, hydrocinnamic chloride, hexahydrobenzoyl chloride, cyclohexylacetyl chloride, furoyl chloride, nicotinic chloride, picolinic chloride, cinchoninic chloride and thiophene - a  - carboxylic acid chloride.  The Specification as open to inspection under Sect. 91 comprises also the manufacture of compounds in which the X's in the general formula may additionally represent alkenyl, aryl, aralkyl, aryloxy, acyloxy, nitro, alkylamino, arylamino, carboxy, carbalkoxy, acyl, carbamido, cyano, carbamyl, guanido, mercapto, alkylmercapto, arylmercapto, sulphamyl or aryl- or alkyl-sulphonyl groups, and which may contain in the 3- and 7- positions other carboxylic acylamino groups or also carbamido, thiocarbamido or sulphonylamino groups.  Additional acylating agents specified are adipyl chloride, maleic anhydride, nitro and amino substituted products of benzoyl and phenylacetyl chloride, phthalic anhydride, 2-hydroxy-3-naphthoyl chloride, phenoxyacetyl chloride, methanesulphonyl chloride, benzenesulphonyl chloride and toluene-o -sulphonyl chloride and their substitution products, naphthalenesulphonyl chlorides, acetylsulphanilyl chloride and its substitution products, b -pyridinesulphonyl chloride, phenyl and naphthyl isocyanate and isothiocyanate, p-dimethylaminophenyl isothiocyanate, diethylcarbamyl chloride and phosgene.  This subject-matter does not appear in the Specification as accepted.ALSO:As optical brightening agents for cellulosic materials are employed water-soluble sulphonated derivatives of diacylated 3 : 7-diaminodibenzothiophene-5 : 5-dioxides, of the general formula <FORM:0684842/IV (c)/1> wherein R and R1 represent aliphatic, aromatic, araliphatic or alicyclic hydrocarbon or heterocyclic groups or such groups containing alkyl, alkoxy or halogen substituents, each X represents hydrogen, halogen, or an alkyl, alkoxy, hydroxy or sulphonic group, and each Y represents hydrogen, or, when R or R1 is aromatic or heterocyclic, may represent a sulphonic group, at least one X or Y representing a sulphonic group.  These compounds may be applied, advantageously from minute conjunction with simultaneous or previous soaping), as agents for enhancing the brilliance of discharge effects, or for enhancing the colour effects of dyes and pigments (applied simultaneously, previously or subsequently).  The Specification as open to inspection under Sect. 91 comprises also the use of compounds in which the X's in the general formula may additionally represent alkenyl, aryl, aralkyl, aryloxy, acyloxy, nitro, alkylamino, arylamino, carboxy, carbalkoxy, acyl, carbamido, cyano, carbamyl, guanido, mercapto, alkylmercapto, arylmercapto, sulphamyl or aryl- or alkylsulphonyl groups, and which may contain in the 3- and 7-positions other carboxylic acyl amino groups or also carbamido, thiocarbamido or sulphonylamino groups.  This subject-matter does not appear in the Specification as accepted.ALSO:Soaps or other detergents contain, as optical brightening agents, water-soluble sulphonated derivatives of diacylated 3 : 7-diaminodibenzothiophene-5 : 5-dioxides, of the general formula <FORM:0684842/III/1> wherein R and R1 represent aliphatic, aromatic, araliphatic or alicyclic hydrocarbon or heterocyclic groups or such groups containing alkyl, alkoxy or halogen substituents, each X represents hydrogen, halogen or an alkyl, alkoxy, hydroxy, or sulphonic group, and each Y represents hydrogen, or, when R or R1 is aromatic or heterocyclic, may represent a sulphonic group, at least one X or Y representing a sulphonic group.  The Specification as open to inspection under Sect. 91, comprises also the use of compounds in which each X in the general formula may additionally represent alkenyl, aryl, aralkyl, aryloxy, acyloxy, nitro, alkylamino, arylamino, carboxy, carbalkoxy, acyl, carbamids, cyano, carbamyl, guanido, mercapto, alkylmercapto, arylmercapto, sulphonyl or aryl- or alkyl-sulphonyl groups, and which may contain in the 3- and 7-positions other carboxylic acylamino groups or also carbamido, thiocarbamido or sulphonlyamino groups. This subject-matter does not appear in the Specification as accepted.