Patent GB-300987-A (GB)
Title: The manufacture of polyazo dyestuffs
IPC: C09B43/16
Filed: 1928-11-21
Abstract: 300,987. I. G. Farbenindustrie Akt.- Ges. Nov. 22, 1927, [Convention date]. Azo dyes.-For the production of trisazo and higher polyazo dyes any initial diazo component is coupled with a 1-naphthylamine derivative containing an O-alkyl or S-alkyl group or a sulphonic or carboxylic acid of such a derivative, capable of coupling in p-position to the NH2 group, and the product is diazotized and coupled /A with a compound of the type Cy - R, in which \X Cy represents a cyanuric ring, A represents a substituted or unsubstituted residue of a 1: 8- aminonaphthol, e.g. a 1: 8-amino.benzoylaminonaphthol or a substitution product thereof or an equivalent in which -NH.CO- is replaced by "NH.CO.NH-, R represents a residue of an aminoazo compound, and X represents either halogen or a residue united to the ring through N, 0, or S. Alternatively the residue A may be united with the cyanuric ring after the coupling with the diazoazo compound, and as a further alternative the aminoazo residue R may be replaced by a residue such as -NH.C6H4. /NH2 NH2-, -NH.C6H3 ,-NH.C6H4.NO2, \SO3H - NH.C6H4.NHAc (in which Ao is -CO.CH3, - CO.COOH, -S03H, or the like) into which after the coupling with the diazoazo compound, and after reducing or saponifying if necessary, the final azo group is introduced by diazotization and coupling in substance or on the fibre. The following examples are specified :-(1) The aminoazo compound 4-amino-1 : 3-dimethylbenzene-5-sulphonic acid # 1-amino-2-ethoxynaphthalene-6-sulphonic acid is diazotized and coupled. preferably in presence of pyridine, with the condensation product from 1 mol. of cyanuric chloride or bromide, 1 mol. of H-acid, 1 mol. of 4-amino-4<1>-oxyazobenzene-3<1>-carboxylic acid, and 1 mol. of aniline; the product dyes cotton from a Glauber's salt-sodium carbonate bath brilliant green shades fast to light; the 4-amino-1: 3- dimethylbenzene-5-sulphonic acid may be replaced by other aminosulphonic acids of the benzene or naphthalene series and by 4'-methyl-2- aminodiphenylsulphone-4-sulphonic acid or dehydrothiotoluidine-o-sulphanie acid; the 1-amino-2- ethoxynaphthalene-6-sulphonic acid may be replaced by other O-alkyl or S-alkyl derivatives of 1-naphthylamine such as 1-amino-2-ethoxynaphthalene-6-carboxylic acid or those referred to in Specifications 298,518 and 320,030; the dyestuff 2 : 8-aminonaphthalene sulphonic acid # 1- amino-2-methoxynaphthalene - 6 - sulphonic acid # the same condensation product dyes cotton a clear yellowish green; the 2 : 8-naphthylaminesulphonic acid may be replaced by the product 2 : 8-naphthylaminesulphonic acid # o-toluidine; the dyestuffs of the type, diazo component # 1-amino-2 : 7-naphthylene-di-#-oxypropionic acid # the compound obtained by boiling with aqueous alkali the condensation product, from 1 mol. cyanuric chloride, 1 mol. of H-acid, and 1 mol. of 4-amino-5<1>-methyl-4<1>-oxyazobenzene-3<1> carboxylic acid, dye cotton clear green; the dyestuffs 4-amino-2-sulphooxanilic acid -> 2- ethoxy- or 2-methylmercapto-1-aminonaphthalene # the condensation product from 1 mol. of cyanuric chloride, 1 mol. of H-acid, 1 mol. of 4-amino-4<1>-oxyazobenzene-3<1>-carboxylic acid, and 1 mol. of ammonia. with saponification to remove the oxalyl group, give on cotton from a sodium sulphate-sodium carbonate baths yellowish green dyeings adapted for diazotization on the fibre and development with #-naphthol to green shades fast to washing and to light. (2) The aminoazo compound 4-aminoacetanilide-3-sulphonic acid # the sulphuric ester of 1-amino- 2 - #- oxyethoxynaphthalene is diazotized and coupled with the condensation product from 1 mol. of cyanuric chloride, 1 mol. of N-ethyl-H- acid. 1 mol. of 4-amino-4<1>-oxyazobenzene-2 : 3<1>- dicarboxylic acid, and 1 mol. of 4-methylthiophenol; the product dyes cotton a pure green, fast to the dyestuffs, 2 : 5-dichloraniline-4- sulphonic acid # 1-amino-2-ethoxynaphthalene- 6-sulphonic acid --> the condensation product from 1 mol. of cyanuric chloride, 1 mol. of N-4<1>- aminobenzoyl-H- (or K-) acid, 1 mol. of 4-amino- 4<1>-oxyazobenzene-3<1>-carboxylic acid, and 1 mol. of 4-aminobenzoic acid, 5-aminosalicylic acid, or aniline-4-sulphonic acid, are clear yellowishgreen; bluer products are obtained if the N-(4'- aminobenzoyl)-H- (or K-) acid is replaced by 8- oxy-3 : 6-disulpho-1-naphthyl-4<1>-aminophenylurea alternatively dyestuffs of this type may be prepared by diazotizing the aminoazo compound, e.g. aniline-2 : 5-disulphonic acid # 1-amino-2- ethoxynaphthalene-6-sulphonic acid, coupling with the 1 : 8-aminonaphthol derivative, e.g. N- (4<1>-aminobenzoyl)-H-acid, condensing with 1 mol. of cyanuric chloride, and further condensing with 1 mol. of, for example, 4-amino-4'-oxyazobenzene-3<1>-carboxylic acid and with 1 mol. of, for example, ammonia. (3) The aminoazo compound 4-amino-1 : 3-dimethylbenzene-5-sulphonic acid # 1 - amino - 2 - ethoxynaphthalene-6-sulphonic acid is diazotized and coupled with the condensation product from 1 mol. of cyanuric chloride, 2 mols. of H-acid, and 1 mol. of 4- amino-4<1>-oxyazobenzene-3<1>-carboxylic acid; the product dyes cotton from a Glauber's salt-sodium carbonate bath very clear green shades; the dyestuff 4-ethoxyaniline-2-sulphonic acid # 1- amino-2-ethoxynaphthalene-6-sulphonic acid # the condensation product from 1 mol. of cyanuric chloride, 1 mol. of H-acid, and 2 mols. of 4- amino-4<1>-oxyazobenzene-3<1>-carboxylic acid gives a pure yellowish green dyeing. (4) The aminoazo compound 4-chloraniline-2-sulphonic acid # 1- amino-2-methoxynaphthalene-6-sulphonic acid is diazotized and coupled, preferably in presence of pyridine or much ammonia, at 0‹ C., with the condensation product from 1 mol. of cyanuric chloride, 1 mol. of H-acid, 1 mol. of 2-nitro-4- aminotoluene, and 1 mol. of dimethylamine and the nitro group is reduced; the product is also obtainable by coupling the diazotized aminoazo. compound with the condensation product from 1 mol. of cyanurio chloride, 1 mol. of H-acid, 1 mol. of 2 : 4-diaminotoluene, and 1 mol. of dimethylamine; similar dyestuffs are obtained when in the condensation product used the 2- nitro-4-amino- or 2 : 4-diaminotoluene is replaced by 3-aminoformanilide, 3-aminoacetanilide, 3- aminophent-loxaminie acid, or 3-aminophenylsulphaminic acid, and the acidyl group is removed: the aminodisazo dyestuffs so obtained are finally diazotized and coupled with 1-(2<1>-carboxyphenyl)-3-methyl-5-pyrazolone to obtain products which dye cotton pure yellowish green; bluer green shades, fast to light, are obtained when the final component is replaced by acetoacetyl-2-anisidine; if the aminodisazo dyestuffs are diazotized on the fibre and coupled with 1- phenyl-3-methyl-5-pyrazolone the dyeings are clear yellowish green, fast to washing and light; the dyestuff 4-chloraniline-2-sulphonic acid # 1-amino-2-methoxynaphthalene-6-sulphonic acid # the condensation product from 1 mol. of cyanuric chloride, 1 mol. of H-acid, 1 mol. of 4-aminotoluene-2-azo-1<1>-(2<11>-carboxy)-phenyl - 3'- methyl-5<1>-pyrazolone, and 1 mol. of dimethylamine is similar, and other similar green dyestuffs are those of the type, diazo component, e.g. 4-chloraniline-2-sulphonic acid, # 1-amino- 2-methoxynaphthalene-6-sulphonic acid or an equivalent compound such as described in Specification 298,518 # the condensation produet from 1 mol. of cyanuric chloride, 1 mol. of a 1 : 8-aminonaphtholsulphonic acid, 1 mol. of 1 : 3-phenylenediamine-4-sulphonic acid or 1: 4- phenylenediamine-3-sulphonic acid, and 1 mol. of dimethylamine or equivalent compounds containing reactive hydrogen attached to N, O, or S # (in substance or on the fibre) methylbetol or its homologues or substitution products, pyrazolones, derivatives of #-ketoaldehydes, 1 : 3-dioxyquinolines, or sulphazones; the dyestuffs of the type 4-chloraniline-2-sulphonic acid # 1-amino-2-methoxynaphthalene-6-sulphonic acid # the saponified condensation product from 1 mol. of cyanuric chloride, 1 mol. of H- acid, and 2 mols. of 3 aminoformanilide # (in substance or on the fibre) methylketol, pyrazolones, or derivatives of #-ketoaldehydes are clear yellowish green. Specification 209,723 also is referred to. The Specification as open to inspection under Sect. 9 (3) (a) comprises also the following subject-matter. (a) 4-Aminotoluene-3-sulphonic acid, 4-benzoylaminoaniline, and 3-chloro-2- toluidine are specified as first components in example (1). (b) The condensation product from 1 mol. of cyanuric chloride, 1 mol. of H-acid, 1 mol. of 4-amino-4<1>-oxyazobenzene-3<1>-carboxylic acid and 1 mol. of aniline is specified as an alternative one for use in example 1. (c) Compounds having a heterocyclic ring in the 1 : 2-position of the naphthalene nucleus, such as 3<1>-aminophenyl- 1 : 3-naphthimidazol-8-oxy-3 : 6-disulphonic acid and other substituted 1 : 8-aminonaphtholsulphonic acids, such as that represented by the formula are specified as replacing the N-(4<1>-aminobenzoyl)-H (or K)-acid in example 2. (d) As an additional example the aminoazo compound 4- aminotoluene-3-sulphonic acid # 1-amino-2- ethoxynaphthalene-6-sulphonic acid is diazotized and coupled with the condensation product from 1 mol. of cyanuric chloride, 1 mol. of H-acid, 1 mol. of 4-amino-4<1>-oxyazobenzene-3<1>-carboxylic acid, and 1 mol. of ammonia.; the product dyes cotton from a Glauber's salt-sodium carbonate bath pure green shades; similar products are obtained by diazotizing 2 mols. of the aminoazo compound aniline-2-sulpho-5-carboxylic acid # 1-amino-2-ethoxynaphthalene-6-sulphonic acid and coupling with 1 mol. of the condensation product of the formula or the isomeric product derived from the 1:8:5- instead of the 1 : 8 : 6-aminonaphtholsulphonic acid. This subject-matter does not appear in the Specification as accepted. 1 - Amino - 2 :7-naphthylene-di-#-oxypropionic acid is obtained by causing the disodium salt of 2 : 7-