Patent GB-819840-A (GB)
Title: Tetrakisazo dyestuffs and metal complexes thereof
IPC: C09B35/40
Filed: 1957-08-09
Abstract: The invention comprises tetrakisazo dyestuffs of the formul <FORM:0819840/IV (c)/1> or <FORM:0819840/IV (c)/2> wherein the diphenylamine residue contains at least one sulphonic acid group, A is an aromatic residue, B is the residue of a coupling component, n is 1 or 2 and the benzene nucleus of the resorcinol residue may be dihydrogenized.  The dyes are prepared by diazotization and coupling of the components in any sequence and the final dyes or their components or intermediate products may be treated with metallizing agents to give chromium, cobalt, nickel, iron or preferably copper compounds.  Thus, dyestuffs containing hydroxy, carboxy, carboxymethoxy or methoxy groups ortho to an azo group or a salicyclic acid or 8-hydroxyquinoline residue may be metallized.  The dyestuffs dye leather in brown shades.  In examples: (1) 4 : 41-diaminodiphenylamine - 2 - sulphonic acid or -2 : 31-disulphonic acid is tetrazotized and coupled with salicylic acid (B), the resultant diazoazo compound is coupled with the monoazo dye 1-amino-8-naphthol-3 : 6-disulphonic acid --> resorcinol (C) and the trisazo dye so obtained is coupled with diazotized aniline (A); the procedure of the above example is repeated using 4 : 41 - diaminodiphenylamine - 2 - sulphonic acid and the following reactants, as well as those specified above; component (A): o- or p-anisidine, p-nitroaniline, o-chloroaniline, o- or p-toluidine, o-aminobenzoic acid, 1-aminobenzene-2-, -3- or -4-sulphonic acid, 1-aminobenzene - 2 : 4 - disulphonic acid, 1 - amino - 2 - methylbenzene - 5 - sulphonic acid, 1 - amino-4-methoxybenzene - 4 - sulphonic acid, 1 - amino-4 - nitrobenzene - 2 - sulphonic acid, 1 - amino-2 - methoxybenzene - 5 - sulphonic acid, 5-nitro-2 - aminobenzoic acid, 1 - amino - 2 - methoxy-4 - nitro- or -5 - methyl - benzene, 1 - acetyl - amino - 3 - aminobenzene, 1 - acetylamino - 4 - aminobenzene (the acetylamino group of this component may be saponified after coupling by heating the dyestuff with aqueous caustic soda), 1 - naphthylamine, 1 - aminonaphthalene - 4- or -5 - sulphonic acid, 1 - amino - 2 - methoxynaphthalene-6-sulphonic acid and 2-aminonaphthalene-4 : 8- or 3 : 6- or -6 : 8-disulphonic acid; component (B): 4- or 6-methyl-salicylic acid, p - cresol, acetoacetanilide and 1 - phenyl - 3 - methyl-5-pyrazolone; component (C): 1-amino-8-naphthol-3 : 6- or -4 : 6-disulphonic acid --> resorcinol, 1 - amino - 8 - naphthol - 3 : 6 - disulphonic acid --> dihydroresorcinol and 2-amino - 8 - naphthol - 6 - sulphonic acid, 2-amino - 5 - naphthol - 7 - sulphonic acid, 1-amino - 7 - naphthol - 3 - sulphonic acid or 2 - amino - 3 - naphthol - 6 - sulphonic acid --> resorcinol; (2) 1-aminonaphthalene-4-sulphonic acid --> 1 - amino - 8 - naphthol - 3 : 6 - disulphonic acid --> resorcinol \sM 4:41 - di - aminodiphenylamine - 2 - sulphonic acid --> salicylic acid; (3) salicylic acid \sM 4 : 41-diaminodiphenylamine - 2 - sulphonic acid --> 1 - amino - 8 - naphthol - 3 : 6 - disulphonic acid --> resorcinol \sM o-anisidine; (4) a trisazo dye produced as in (1) from 1-amino-8-naphthol-3:6-disulphonic acid, resorcinol, 4 : 41-diaminodiphenylamine - 2 - sulphonic acid and salicylic acid is coupled with diazotized 1-amino-2-methoxybenzene-5-sulphonic acid, o-anisidine or 2-aminobenzoic acid to form a tetrakisazo dye which is coppered by heating with ammoniacal copper sulphate solution.