Patent GB-1111544-A (GB)
Title: Azo dyestuffs containing metal and a reactive sulphonamide residue and processes for their manufacture
IPC: C09B62/535
Filed: 1965-07-21
Abstract: The invention comprises complex metal compounds of azo-dyestuff of the formula <FORM:1111544/C4-C5/1> or <FORM:1111544/C4-C5/2> wherein D represents a diazo component residue which may contain groups imparting solubility in water and one futher azo group, A represents a coupling component residue which may contain groups imparting solubility in water, a1 represents -OH or -COOH, in the o-position to the azo-linkage, a2 represents -OH or -NH2 in the o-position to the azo-linkage, R and R1 represent H, alkyl or aralkyl radicals which may be substituted, X represents -SO2-, -CO- or -CONH-, Y represents H or a substituent, Z represents an inorganic or organic radical capable of being split off under alkaline conditions selected from a halogen atom, an alkanoyl, sulphuric acid ester, phenoxy or a dialkylamino group or a quaternary nitrogen base, n represents 1 or 2 and m represents 1 or 2.  They may be obtained by (i) treating azo-dyestuffs of the above formulae in which a1 may additionally be H or alkoxy (a) with agents yielding metal when a1 represents -OH or -COOH; (b) by coppering under oxidizing conditions when a1 represents H; or (c) by coppering under de-alkylation when a1 represents alkoxy. The complex copper azo-dyestuffs obtained by methods (b) and (c) may be converted into azo-dyestuffs free from metal by treating them with mineral acid and subsequently treating them with an agent yielding a metal other than copper; or (ii) treating azo dyestuffs of the formula: <FORM:1111544/C4-C5/3> with agents yielding metal as in (a), (b) and (c) above, and then reacting the complex metal compounds with compounds of the formula <FORM:1111544/C4-C5/4> or <FORM:1111544/C4-C5/5> wherein X1 represents a carboxylic acid halide, sulphonic acid halide, arylurethane or isocyanate group or firstly with these acylating agents and then with metal yielding agents as above.  Specified substituents for Y are alkyl groups, halogen atoms, sulphonic acid group, COOH, NO2, CN, alkoxy groups, sulphonamide groups, sulphonic acid ester groups or carboxylic acid ester groups.  Specified metal yielding agents are agents yielding Mn, Fe, Al, Co, Cr, Cu and Ni.  Examples are given for the production of the dyes.  They are useful for dyeing or printing materials containing OH groups or nitrogen such as cotton, linen, natural or regenerated cellulose, silk, leather, synthetic polyamides or polyurethanes, regenerated protein fibres, wool or modified polyacrylonitrile fibres.  The metal-free dyestuffs of the above general formulae (1) and (2) are obtained (a) by reacting azo dyestuffs qualified for complex metal formation and containing at least one amino group of the formula <FORM:1111544/C4-C5/6> which can be acylated with compounds of the formulae (6) and (7); or (b) by reacting suitably substituted diazo components and coupling components of which at least one contains a substituent of the formula <FORM:1111544/C4-C5/7> or <FORM:1111544/C4-C5/8>ALSO:Dyestuff intermediates are obtained by reacting a compound of the formula <FORM:1111544/C2/1> wherein X1 represents a carboxylic halide group, a sulphonic acid halide group or the isocyanate group or an arylurethane group, R1 represents a H atom, substituted or unsubstituted alkyl or aralkyl radicals, Y represents a H atom or a substituent, Z represents an inorganic or organic radical which can be split off under alkaline conditions and n represents 1 or 2, with 6-nitro-2-amino-phenol-4-sulphonic acid, 2 - amino - 8 - hydroxynaphthalene - 6 - sulphonic acid, 1 - amino - 8 - hydroxynaphthalene 3,6 - disulphonic acid, or 2 - amino - 5 - hydroxynaphthalene - 7 - sulphonic acid. The products are useful in the preparation of dyes (see Division C4].