Patent GB-577673-A (GB)
Title: Manufacture of copper-containing disazo dyestuffs
IPC: C09B33/04
Filed: 1943-04-27
Abstract: Disazo dyes containing copper are obtained by treating with an agent yielding copper, a product obtained by coupling 1 : 3-dihydroxybenzene or an acid derivative thereof (1 mol.) with a diazotized aminosulphonic acid of the benzene or naphthalene series carrying in o-position to the amino group a hydroxy group or a substituent convertible into a hydroxy group under coppering conditions (1 mol.) and a diazotized aryl amine (1 mol.), free from sulphonic acid groups, at least one of the diazo components being substituted by a phenyl nucleus linked by a non-basic bridge, such as -SO2-, -SO2N(C2H5)-, -SO2.N(CH3)-, -O.SO2-, -O-, -CO-, -CO.NH-, or -CO.N(C2H5)-.  The coppering may be effected prior to the coupling with the second diazo component. The products are applicable for dyeing animal fibres such as wool and silk.  A specified acid derivative of 1 : 3-dihydroxybenzene is b -resorcylic acid. Specified first diazo components are 2-aminophenol-4-sulphonic acid and its O-methyl and O-benzyl derivatives, 4- or 6-methyl-2-amino-1-hydroxy-or ethoxy-benzene-6- or 4-sulphonic acid, 4- or 6 - nitro- or chloro - 2 - amino - 1 - hydroxy - or methoxy - benzene-6- or 4-sulphonic acid, 1 : 2-aminonaphthol-4-sulphonic acid and 6-nitro-2 : 1-aminonaphthol-4-sulphonic acid, 3-amino-4 - hydroxy-, methoxy- or chlorodiphenylsul - phone-31-sulphonic acid, 3-amino-4-hydroxy - diphenylsulphone-5-sulphonic acid, 3-amino-4-hydroxy- or methoxy - benzenesulphonethyl - anilide-31- or 41-sulphonic acid, 3-amino-4-hydroxybenzenesulphonethylanilide - 41 - sul - phonic acid, 3-amino-4-hydroxy- or methoxybenzenesulphonic acid-phenylester-31-sulphonic acid and 4- or 6-benzoylamino-2-aminophenol-6-or 4-sulphonic acid.  Specified second diazo components are 2-methyl-, methoxy- or chloro-4-or 5-nitro-aniline, 4- or 6-methyl-, methoxy- or chloro - 3 - aminodiphenylsulphone, 3 - amino - 6 - phenylamino-diphenylsulphone, 4- or 6-methyl-, methoxy- or chloro-3-amino-benzenesulphonethylanilide, 4- or 6-methyl-, methoxy- or chloro-3-aminobenzenesulphonic acid-phenyl or o-, m- or p-cresyl ester, 2-, 3- or 4-aminophenolbenzenesulphonic acid ester or the corresponding 21- or 41-methyl- or chloro-benzenesulphonic acid esters, 3-amino-benzophenone, 3-aminobenzoylethylanilide, 2- or 4 - aminodiphenyl ethers and their alkyl and halogen substitution products.  In examples: (1) the dyestuff, 3-amino-4-hydroxydiphenylsulphone-31-sulphonic acid --> 1 : 3-dihydroxybenzene, is coppered and coupled with diazotised 4-methyl-3-amino-diphenylsulphone; the product gives yellowish brown dyeings, fast to light and washing, on animal fibres; (2) the dyestuff, 2-aminophenol-4-sulphonic acid --> 1 : 3-dihydroxybenzene \sM 4 - chloro - 2 - aminodiphenyl ether, is coppered; the product gives fast dark brown dyeings on silk; (3) the dyestuff, 3-amino-4-hydroxybenzenesulphonethylanilide - 41 - sulphonic acid --> 1 : 3-dihydroxybenzene, is coppered and coupled with diazotised 2-methoxy-4-nitroaniline; the product gives fast dark brown dyeings on wool and silk; (4) the dyestuff, 4 - nitro - 2 - aminophenol - 6 - sulphonic acid --> 1 : 3 - dihydroxybenzene \sM 21-methyl-2-aminodiphenyl ether, is coppered; the product gives fast brown dyeings on wool or silk; (5) the dyestuff, 2-aminoanisol-4-sulphonic acid --> 1 : 3-dihydroxybenzene, is coppered and coupled with diazotised 4-methyl-3-aminodiphenylsulphone; the product gives fast reddish brown dyeings on silk; (6) the dyestuff, 3-amino-4-hydroxydiphenylsulphone-31-sulphonic acid --> 1 : 3-dihydroxybenzene, is coppered and coupled with diazotised 4-aminophenol-p-toluenesulphonic acid ester; the product gives pure yellowish brown dyeings on wool or silk.  A table is also given showing the shades of the dyeings obtainable with the copper compounds of disazo dyes from various combinations of components. 2-Amino-1-ethoxybenzene-4-sulphonic acid is obtained by reduction of the product of sulphonation of 2-nitrophenetol.  4- or 6-Methyl-2-amino-1-ethoxybenzene-6- or 4-sulphonic acid is obtained by reduction with iron and acetic acid of the product of sulphonation of 3-nitro-4- or 2-ethoxytoluene respectively.  4- or 6-Chloro-2-amino-1-methoxybenzene-6- or 4-sulphonic acid is obtained by similar reduction of the product of reaction of 2 : 5 : 3- or 3 : 4 : 5-dichloronitrobenzenesulphonic acid respectively with sodium methylate.  4-Nitro-2-amino-1-methoxybenzene-6-sulphonic acid is obtained by partial reduction of the product of reaction of 2 : 4-dinitro-chlorobenzene - 6 - sulphonic acid with sodium methylate. 6-Nitro-2-amino-1-methoxybenzene-4-sulphonic acid is obtained by partial reduction of the corresponding 2 : 6-dinitro compound.  3 - Amino - 4 - methoxy - diphenylsulphone - 31 - sulphonic acid is obtained by reduction with iron and acetic acid of the product of reaction of 4-chloro-3-nitro-diphenylsulphone-31-sulphonic acid with sodium methylate (cf. Specification 324,090) [Class 2 (iii)]. 3-Amino-4-hydroxy-diphenylsulphone-5-sulphonic acid is obtained by sulphonation of 3-amino-4-hydroxy-diphenylsulphone. 3-Amino-4-hydroxy-diphenylsulphone is made by reduction with sodium sulphide of the product of reaction of 4-chloro-3-nitro-diphenylsulphone with sodium hydroxide. 3-Amino-4-hydroxy- or methoxy-benzenesulphonethylanilide - 31 - or 41 - sulphonic acid is obtained by reduction of the nitro group in the product of reaction with sodium hydroxide or sodium methylate of the condensation product from 3-nitro-4-chlorobenzenesulphonyl chloride and N-ethyl-aniline-3- or 4-sulphonic acid.  3-Amino-4-hydroxy- or methoxy-benzenesulphonic acid - phenylester - 31 - sulphonic acid is obtained by reduction of the product of sulphonation of the condensation product from 3-nitro-4-hydroxy- or methoxy-benzenesulphonyl chloride and phenol. 4-Benzoylamino-2-aminophenol-6-sulphonic acid is obtained by reduction with sodium sulphide of the product of nitration of benzoylated 4-aminophenol-2-sulphonic acid. 6-Benzoylamino-2-aminophenol-4-sulphonic acid is obtained by reduction with sodium sulphide of benzoylated 6-amino-2-nitrophenol-4-sulphonic acid.  4- or 6-Methyl-3-aminodiphenylsulphone is obtained by reduction with iron and acetic acid of the product of reaction of benzene in presence of aluminium chloride with 4- or 6-methyl-3-nitrobenzenesulphonyl chloride respectively (cf. Specification 324,090) [Class 2 (iii)]. 4- or 6-Methoxy-3-aminodiphenylsulphone is obtained by reduction with iron and acetic acid of the product of reaction of 4- or 6-chloro-3-nitro-diphenylsulphone respectively with sodium methylate (cf. Specification 324,090) [Class 2 (iii)].  4- or 6-Methyl- or chloro-3-aminobenzenesulphonethylanilide is obtained by reduction of the product of reaction of 4- or 6-methyl- or chloro-3-nitrobenzenesulphonyl chloride respectively with N-ethyl-aniline (cf. Specification 312,582) [Class 2 (iii)].  4- or 6-Methoxy-3-aminobenzenesulphonethylanilide is obtained by reduction of the product of reaction of 4- or 6-chloro-3-nitrobenzene sulphonethylanilide respectively with sodium methylate.  4- or 6-Methyl-, methoxy or chloro-3-aminobenzenesulphonic acid phenyl or o-, m- or p-cresyl ester is obtained by reduction of the product of reaction of the corresponding 3-nitrobenzenesulphonyl chloride with phenol or o-, m- or p-cresol respectively.  2-, 3- or 4-Aminophenol-21- or 41-methyl- or chloro-benzenesulphonic acid ester is obtained by reduction of the product of condensation of 2-, 3- or 4-aminophenol with 2- or 4-methyl- or chloro-benzenesulphonyl chloride respectively.  41-Amyl-2-amino-diphenyl ether is obtained by reduction with iron and hydrochloric acid of the product of reaction of 2-nitrochlorobenzene with p-amylphenol. 3-Amino-6-phenylamino-diphenylsulphone is obtained by reduction with iron and hydrochloric acid of the product of reaction of 6-chloro-3-nitro-diphenylsulphone with aniline. 21 : 41-Dichloro-2-amino-diphenyl ether is obtained by reduction with iron and hydrochloric acid of the product of reaction of 2-nitrochlorobenzene with 2 : 4-dichlorophenol. 3-Aminobenzoylethylanilide is obtained by reduction of the product of reaction of 3-nitrobenzoyl chloride with N-ethyl-aniline.  The Specification as open to inspection under Sect. 91 refers also to 4-nitro-1 : 2-aminonaphthol-6-sulphonic acid as a first diazo component.  This subject-matter does not appear in the Specification as accepted.