Patent GB-811740-A (GB)
Title: New metal-containing polyazo colouring matters derived from benzthiazole
IPC: C09B33/12
Filed: 1956-07-13
Abstract: The invention comprises complex copper or nickel derivatives of compounds of formula <FORM:0811740/IV (c)/1> where A and A1 are aromatic radicles, X is a carboxyl, terephthaloyl, fumaryl or 2,4-divalent - 6 - amino- or -substituted amino - 1,3,5 - triazinyl residue and B and B1 may be further substituted.  They are made, in conventional fashion, by treating dyestuffs of the above formula with appropriate metallising agents.  The above azo compounds may be made by coupling two molar proportions of a diazotized amine, or one molar proportion of each of two diazotized amines with one molar proportion of a coupling component obtained by acylating two molar proportions of a 2-amino-4-hydroxybenzthiazole with one mol. proportion of a diacylchloride.  Indicated as substituents for B and B1 are alkyl, alkoxy, sulphonic acid and halogen groups.  A and A1 are indicated as phenyl, naphthyl, pyrenyl, 4-phenylvinylphenyl, 4 - 21 - benzthiazylphenyl, 3- or 4-phenylazophenyl, 3- or 4 - 21 - naphthylazophenyl, 4 - phenylazo - 1 - naphthyl, 2 - phenyl-11,21 - (4,5) - naphthalene - triazolyl and their alkyl, alkoxy, hydroxy, nitro, halogen, sulpho, carboxy and acylamino derivatives.  Specified coupling components are N,N1-di-(4-hydroxy-2-benzthiazolyl) - urea, -terephthalamide and -fumaramide and 2-anilino-4,6-di-(41-hydroxy-21-benzthiazolylamino) - 1,3,5-triazine. Amines specified for use in preparing the azo compounds are 4 - chloroaniline, 5 - amino - 2 - hydroxy - benzoic acid, aniline - 4 - mono- and -2,5 - disulphonic acids, 4 - aminobenzanilide - 21, 51-desulphonic acid, dehydrothio-p-toluidine and its disulphonic acid, 3 - aminopyrene-, 2 - naph - thylamine - 6,8-, 1 - amino - 8 - naphthol - 3,6- and 1 - naphthylamine - 3,6 - disulphonic acids, 4 - aminostilbene - 2,21 - disulphonic acid containing in the 41-position a chloro, nitro, acetamide, benzamido, 7-sulpho- and 6,8-disulphonaphtha - 11,21 - 4,5 - triazolyl - 2,411 - methoxyphenylazo-, 4 - (41-sulpho - 21 - carboxyphenylazo-, 41-nitro-21-hydroxy-51-methylphenylazo- and 41 - nitro - 21 - methoxy - 51 - sulphophenylazo) - 3 - methyl - 5 - hydroxy - 2 - pyrazolyl-, 4 - aminoazobenzene - 3,41- and 21,51-, 5-methoxy - 2 - methyl - 4 - aminoazobenzene - 21,51-, 4 - (411 - aminophenylazo) - benzanilide - 21,51-, 4 - (411 - amino - 311 - methoxy - 611 - methylphenylazo) - benzanilide - 21,51-, 2 - amino- and 2-(311- and 411 - aminobenzamido)-5-hydroxyphenylazo - 6 - naphthalene - 41,7 - disulphonic acids, 2 - amino- and 2-(311- and 411-aminobenzamido) - 5 - hydroxy - 21 - carboxy- and -hydroxy - phenylazo - 6 - naphthalene - 51,71-disulphonic acids, 1-amino-2-methoxy-4-phenylazonaphthalene - 41,6-, 41 - amino - 21,51 - dimethoxyphenylazo-3-naphthalene-1,5- and 4-amino - 3 - methoxy - 1,21-azonaphthalene-41,81-disulphonic acids. Dyestuffs containing at least three solubilizing groups may be applied to cellulose textiles by a direct process.  Dyestuffs containing less than three solubilizing groups are applied by dyeing the cellulose textiles with the azo compounds or their sulphate esters and subsequently metallizing.  The sulphate esters of the azo compounds are made by treating them with a sulphating agent, e.g. chloro-sulphonic acid or sulphur trioxide or a complex thereof with an organic tertiary base or substituted amide in the presence of an organic tertiary base at 25-120 DEG  C. and on treatment with metallizing agents under acidic conditions form the dyestuffs of the invention.  This process may be effected in substance or on the fibre.  Dyestuffs containing less than two solubilizing groups may be used as pigments for viscose and synthetic polymers.  Examples are provided illustrating the preparation of the dyestuffs and their use in dyeing cellulose fibres in a variety of shades, the components being chosen from those specified above with the addition of the following diazo components: 2 - (41 - amino - 51 - methoxyphenyl) - naphtha-11,21,4,5 - triazole - 21,7 - disulphonic acid, 4-amino - 41 - naphthatriazolyl - (211) - stilbene-2,21, 71 and 4 - amino - 41 - [411 - (2111 - carboxyphenylazo) 311 - methyl - 511 - hydroxy - 111-pyrazolyl]-stilbene 2,21,5111-trisulphonic acids, 2 - naphthylamine - 5,7 - disulphonic acid and 4 - amino - 1,21 - azonaphthalene - 41,81 - disulphonic acid and its 2-methyl and 2-methoxy derivatives.  In the Provisional Specification X is a carboxyl or diacyl radicle. Specification 761,776 is referred to.