Patent GB-791438-A (GB)
Title: Metal complexes of azo-dyestuff mixtures
Filed: 1955-06-24
Abstract: The invention comprises dyestuffs obtainable by treating with metal-yielding agents: (a) two different water-soluble diazo compounds obtainable by the process claimed in Specification 723,632, but of formula <FORM:0791438/IV (b)/1> where I may be substituted and both OH groups are oto azo, R1 is a benzene or naphthalene residue, R11OH is a naphthol, pyrazolene or acetoacetic acid alkyl-or aryl-amide residue and X is at least one of the following groups: sulphonic acid, carboxyl, alkylsulphonyl, sulphonamide and sulphonic acid lower alkyl- and hydroxyalkyl-amide or (b) a compound of formula (A) and one or two compounds of formula R2-N=N-R3-OH, where R2 is a benzene residue free of SO3H groups and containing a metallizable substituent o to -N=N-and R3OH is a phenol, naphthol, pyrazolone or acetoacetic acid alkyl- or aryl-amide residue free of SO3H groups and with OH adjacent to -N=N-, or (c) a compound of formula (A) and one of formula R2-N=N-R4-NH2 where R2 is as above and R4NH2 is a 2-naphthylamine residue free of SO3H groups.  At least 1 mol. of the compound of formula (A) is present, for every 2 mols. of the mixture of azo components.  The dyestuffs consist of a mixture of symmetrical and asymmetrical dyestuffs.  Ammonium and cobalt complexes are preferred. They are 1:2 complexes.  Metallization is effected in the usual way.  The term "lower" refers to compounds containing not more than 4 carbon atoms.  The asymmetrical components of the mixtures are of formula <FORM:0791438/IV (b)/2> are R1, R11 and I are as above and Z is the residue of a disazo compound differing from y but of the same general formula (A) or the residue of monoazo compounds (b) or (c).  Specified or indicated amines for the production of compounds of formula (b) are 2-aminophenol and its 4-halogen, nitro and alkylsulphonyl derivatives, 2-aminophenol-4- and -5-sulphonamides and -4- or -6-halogen- or -6-alkylderivatives thereof, the corresponding 2-amino-1-methoxybenzenes, anthranillic acid, 2-amino-5 - alkylsulphonylbenzene - 1 - carboxylic acid, 2 - amino - 1 - carboxy- or -carboxymethoxy - benzene-4- and -5-sulphonamides and the sulphonamides may be N-substituted by alkyl, hydroxyalkyl, methoxyalkyl, cycloalkyl, aralkyl and/or aryl residues which may be substituted.  Indicated as azo components are 4-alkyl-, 2-acylamino- and 2,4-dialkyl-phenols, 2-naphthol and its -6- or -7- lower alkyl, alkoxy, methylsulphonyl and halogen derivatives and -4-, -5-, -6- and -7-sulphonamides which may be N-substituted, 1,5-, 2,6- and 2,7-dihydroxynaphthalenes, 1-acylamino-6- or -7-naphthols, 1-aryl-3 - alkyl - 5 - pyrazolones, 1 - aryl - 5 - pyrazolone - 3 - carboxylic acids and their amides and acetoacetylamino-alkanes, -benzenes and -naphthalenes.  Indicated as monoazo compounds of formula (c) are those obtainable by coupling the above listed diazo components with 2-naphthylamine and its alkylsulphonyl and sulphonamido derivaties. The dyestuffs dye wool, silk, leather and synthetic nitrogenous fibres.  In examples and a Table which illustrate the preparation of the dyestuffs and their use in dyeing the above indicated materials in green, blue, brown, black and grey shades, the disazo compounds used are derived from the following diazo components 3-amino-4-hydroxy1,11-azobenzene and its -2- and -41-carboxylic acids, -31-sulphonamide and -sulpho-methyland -sulpho - 211 - hydroxyethyl - amides, 3-amino - 2 - hydroxy - 5 - methyl - 1,11 - azobenzene - 31 - sulphonamide, 3 - amino - 4 - hydroxy - 31 - methylsulphonyl - 1,11 - azobenzene and 1 -(31 - amino - 41 - hydroxy) - phenyl -azo-naphthalene-4- and -6-sulphonic acids and the coupling components are 1-carbo-(21-methoxy-and -ethoxy) - ethoxyamino - 7 - naphthol and 2-naphthol and its -4-sulphonic acid and additional components to those indicated above used in the preparation of compounds corresponding to (b) and (c) are 2-amino-5-nitrophenol and 1 - carbo - (21 - propoxy) - ethoxyamino - 7 -naphthol.  Specifications 637,404 and 753,141 are referred to.