Patent GB-832199-A (GB)
Title: Metal complexes of benzene-azo-pyrazolone compounds and materials dyed therewith
IPC: C09B45/14
Filed: 1956-03-26
Abstract: The invention comprises metal complexes wherein chromium, cobalt, copper, iron, manganese, nickel or vanadium is in complex combination with a monoazo dye of formula Q-N = N-Q1 wherein Q is a benzene nucleus having an alkoxy or hydroxyalkoxy group of 1 or 2 carbon atoms in either the 2- or 4-position or in each of the 2- and 5-positions to the azo group and Q1 is a 5-pyrazolone residue linked in the 4-position and not having a cyanophenyl group at the 1-position, the said monoazo dye being free of COOH and SO3H groups. The metal complexes contain 1 metal atom to 2 molecules of monoazo dye; the alkyl and hydroxyalkyl group are not split off from the alkoxy and hydroxyalkoxy groups in Q during the complex formation, and the "complex combination" is defined as the bonding of the metal atoms to the dye molecules at the azo group and at the oxygen atoms at the 5-positions of the pyrazolyl rings.  The dyes are metallized in neutral or mildly acid aqueous or organic solvent medium, preferably with heating, using the halides, sulphates, acetates, cyanides and preferably thiocyanates of the specified metals.  The monoazo dyes are prepared by coupling suitable diazotized anilines with suitable 5-pyrazolones and specified components include o- and p-anisidine, 2 : 5-dimethoxy- or -diethoxy-di-p-hydroxyethoxy-, 2 : 5 - dimethoxy - or - diethoxy - 4 - chloro-or nitro - and 2 : 5 - dimethoxy - 4 - tert. butylaniline, 4 - N - methylsulphonamido - 2 : 5 - dimethoxyaniline; 5 - pyrazolones substituted by 3 - methyl - or - carbomethoxy - or - trifluoromethyl - or - amino - or - hydroxy - or phenyl -, 1 - phenyl - 3 - amino - or - hydroxy - or - carbomethoxy -, 1 - (21 - benzothiazolyl)-or - (71 - quinolinyl) - 3 - amino -, 1 : 3 - diphenyl - or - dimethyl - and 1 - (p - methyl-or - nitro - or - chloro - or - sulphonamido-phenyl) - 3 - methyl - groups.  The complexes are used to dye or colour cellulose esters, polyacrylonitrile, nylon, polyesters or natural nitrogenous textile materials or other objects in yellow, orange and brown shades.  The dye may be metallized on the fibre.  The metallized or unmetallized dye may be added to a spinning dope of nylon, a polyester, polyacrylonitrilo or a cellulose ester (see Group IV (a)) a fibre spun therefrom and subsequently metallized, if necessary.  In an example the dye 2 : 5-dimethoxyaniline \> 1-phenyl-3-methyl-5-pyrazolone is prepared and metallized by heating with nickel acetate, sodium carbonate and ethylene glycol monomethyl ether.  The preparation of many dyes of the above formula and their nickel and cobalt complexes is specified. Specifications 764,296, 764,297, 764,298, 781,435 and 799,708 are referred to.ALSO:Spinning melts or dopes of nylon, a polyester, polyacrylonitrile, or a cellulose alkyl carboxylic acid ester having 2-4 carbon atoms in the acid radical are coloured by incorporating therein a metal complex of a monoazo dye of formula Q-N=N-Q1, wherein Q is a benzene radical having an alkoxy or hydroxyalkoxy group of 1 or 2 carbon atoms in the 2- or 4-position or in both the 2- and 5-positions to the azo group and Q1 is a 5-pyrazolone residue linked in the 4-position and not having a cyanophenyl group in the 1-position, the said monoazo dye being free of carboxylic and sulphonic acid groups (see Group IV (c)).  Alternatively, the unmetallized dye or the metallizing agent is added to the melt or dope and the product spun therefrom is treated with the dye or the metallizing agent.  In an example, 2% of the nickel complex of the dye 2:5-dimethoxyaniline --> 3-trifluoromethyl - 5 - pyrazolone is dispersed in a cellulose acetate-acetone dope which is then extruded to form a bright yellow yarn.  Specifications 764,296, 764,297, 764,298, 781,435 and 799,708 are referred to.