Patent GB-595181-A (GB)
Title: Manufacture of new azo-dyestuffs
IPC: C09B43/16
Filed: 1943-09-29
Abstract: Azo-stilbene dyestuffs, of the general formula <FORM:0595181/IV/1> wherein three of the symbols x represent residues of aminoazo dyestuffs of the general formula NH2-y-R1-N = N-R2, wherein R1 and R2 represent aromatic nuclei of the benzene series, the NH2-ygroup and the -N = N- linkage being in p-relationship and R2 containing a hydroxy group in o-position to a carboxyl group, and y represents a direct linkage between NH2 and R1 or a grouping of the formula <FORM:0595181/IV/2> (one Z representing the linkage connecting this grouping to the NH2 group, and the other representing hydrogen, whilst the NH- group is attached to R1), and the fourth x represents the residue of any desired aminoazo dyestuff, are manufactured by condensing (1) 2 mols. of a 1 : 3 : 5 - trihalogen - triazine (e.g. cyanine bromide or, preferably, chloride) with 1 mol. of 4 : 41 - diaminostilbene - 2 : 21 - disulphonic acid, and the product with 3 mols. of the same or different aminoazo dyestuffs of the general formula above and 1 mol. of any aminoazo dyestuff, or (2) 1 mol. of a 1 : 3 : 5-trihalogen-triazine with 2 mols. of the same or different aminoazo dyestuffs of the general formula above, a further mol. of a 1 : 3 : 5-trihalogen-triazine with 1 mol. of an aminoazo dyesteuff of the general formula above and 1 mol. of any aminoazo dyestuff, and the products with 1 mol. of 4 : 41-diaminostilbene-2 : 21-disulphonic acid, or (3) 2 mols. of a 1 : 3 : 5-trihalogen-triazine with 2 mols. of the same or different aminoazo dyestuffs of the general formula above and then with 1 mol. of 4 : 41-diaminostilbene-2 : 21-disulphonic acid, and the product with 1 mol. of an aminoazo dyestuff of the general formula above and 1 mol. of any aminoazo dyestuff, or (4) 2 mols. of a 1 : 3 : 5-trihalogen-triazine with 1 mol. of an aminoazo dyestuff of the general formula above and 1 mol. of any aminoazo dyestuff and then with 1 mol. of 4 : 41-diaminostilbene-2 : 21-disulphonic acid, and the product with 2 mols. of the same or different aminoazo-dyestuffs of the general formula above. The products yield mainly yellow dyeings, which may be after-treated with agents yielding metal, especially copper, or also, for example, chromium, cobalt or nickel, particularly on natural or regenerated cellulose fibres, e.g. cotton, ramie, flax or viscose or cuprammonium artificial silk, which may be matted if desired, or mixtures of these materials with animal fibres such as wool or silk, e.g. a mixture of wool and viscose staple fibre, the dyeing of these mixed materials being advantageously conducted in a neutral bath in the presence of sodium or potassium chromate, or, if desired, in conjunction with acid or mordant wool dyestuffs.  In examples: (1) 2 mols. of cyanuric chloride are condensed with 1 mol. of the disodium salt of 4 : 41-diaminostilbene-2 : 21 disulphonic acid and the product is condensed with 4 mols. of the sodium salt of 41-amino-1 : 11-azobenzene-4-hydroxy-3-carboxylic acid; (2) cotton is dyed with the product of (1) from a bath containing sodium carbonate and sodium sulphate, and is after-treated with a solution of copper sulphate and tartaric acid neutralized with caustic soda, yielding a greenish yellow shade. A table gives the properties of further dyestuffs containing as the residues represented by x in the general formula: (a) 4 residues of 4-amino-41-hydroxy-51-methyl-1 : 11 - azobenzene - 31 - carboxylic acid; (b) 4 residues of 4 - amino - 3 - methyl - 6 - methoxy - 41 - hydroxy - 1 : 11-azobenzene-31-carboxylic acid; (c) 3 residues of 4-amino-41-hydroxy-1 : 11-azobenzene-31-carboxylic acid and one of 4-(411-amino) -benzoylamino-2-methyl-5-methoxy-41-hydroxy - 1 : 11 - azobenzene - 31 - carboxylic - 5 - sulphonic acid; (d) 2 residues each of the aminoazo dyestuffs of (c); (e) 3 residues of 4 - amino - 41 - hydroxy - 1 : 11 - azobenzene - 31 - carboxylic acid and one of (5-aminobenzoic acid)-(2-azo-41)-(31-methyl-51-pyrazolone); (f) 3 residues of 4-amino-41-hydroxy-1 : 11-azobenzene-31-carboxylic acid and one of (5-aminobenzoic acid)-(2-azo-11)-(21-hydroxy-31-naphthoic acid); (h) 3 residues of 4-amino-41-hydroxy - 1 : 11-azobenzene-31-carboxylic acid and one of 4-amino-1 : 11-azobenzene-41-sulphonic acid.  Additional aminoazo dyestuffs NH2-y-R1-N = N-R2 specified are: 41-amino - 21- and -31 - methyl-, 41 - amino - 51 - methoxy-21-methyl- and 41-amino-21- and -31-methoxy - 1 : 11 - azobenzene - 4 - hydroxy - 3 - carboxylic acid, 41-amino-21-methoxy-1 : 11-azobenzene - 4 - hydroxy - 3 - carboxylic - 5 - sulphonic acid, 41 - (311- and 411 - amino) - benzoylamino-, 41 - (411 - amino) - benzoylamino - 21 - methyl - 51 - methoxy-, 41 - (411 - amino) - benzoylamino - 31 - methoxy-, 41 - (411 - amino) - benzoylamino - 21 - methyl- and 41 - (311 - amino) - benzoylamino - 21 : 51-dimethyl-1 : 11-azobenzene-4-hydroxy-5-carboxylic acid, 41 - (311- and 411 - amino) - benzoylamino-, 41-(411-amino) - benzoylamino - 31-methoxy-, 41-(311-amino)-benzoylamino-31-methyl- and 41-(311-amino) -benzoylamino-21-acetylamino-51-methoxy - 1 : 11-azobenzene-4-hydroxy - 3 - sulpho - 5 - carboxylic acid, and 41 - (411 - amino) - benzoylamino - 21 - methyl - 51 - methoxy - 1 : 11 - azobenzene - 2 - hydroxy - 3 - carboxy-5-sulphonic acid.  The aminoazo dyestuffs corresponding to the fourth residue x may be additionally the various aminoazobenzene- and aminoazotoluene-sulphonic acids, also products containing naphthalene nuclei, heterocyclic nuclei or aliphatic residues, e.g. 1-amino-4-hydroxybenzene - 3 - carboxylic acid --> a -naphthylamine, 2 - aminonaphthalene - 4 : 8 - disulphonic acid --> m-toluidine, or the reduced reaction product of diazotized 1-amino-4-nitrobenzene-2-carboxylic acid with the anilide or o-anisidide of 2 : 3-hydroxynaphthoic acid or with a compound containing a reactive methylene group, such as 1-phenyl-3-methyl-5-pyrazolone, barbituric acid or the anilide or o-anisidide of acetoacetoacetic acid.  Samples have been furnished under Sect. 2 (5) of dyestuffs prepared as follows: (I) 2 mols. of cyanuric chloride are condensed with 2 mols. of the disodium salt of 4-amino-41-hydroxy-1 : 11-azobenzene - 31 - carboxylic acid - 51 - sulphonic acid, then with a further 2 mols. of the same compound, and the product is condensed with 1 mol. of the disodium salt of 4 : 41-diaminostilbene-2 : 21-disulphonic acid; (II) 2 mols. of cyanuric chloride are condensed with 2 mols. of the aminoazo compound of I, then with 1 mol. of the stilbene compound, and the product is condensed with a further 2 mols. of the aminoazo compound; (III) 1 mol. of the disodium salt of 4 : 41-diaminostilbene-2 : 21-disulphonic acid is condensed with 2 mols. of cyanuric chloride and the product is condensed with 2 mols. of the aminoazo compound of (I) and then with a further 2 mols. of the same compound.  The Specification as open to inspection under Sect. 91 comprises also an alternative process in which there is used, instead of at least one of the aminoazo dyestuffs corresponding to the residues x in the general formula of the products, a suitable diazo component, and the product is diazotized and coupled with the appropriate coupling component; e.g. the amine may be of the general formula NH2-y-R1-v (wherein v represents an amino group, or a group converted thereto after the condensation, in p-position to the NH2-ygroup) and the coupling component an o-hydroxycarboxylic acid of the benzene series. This subject-matter does not appear in the Specification as accepted.