Patent GB-847635-A (GB)
Title: New azo-dyestuffs containing a triazine nucleus, their manufacture and use
IPC: C09B62/08
Filed: 1957-07-01
Abstract: The invention comprises azo dyes which contain at least two sulphonic acid groups and a residue of formula:  <FORM:0847635/IV (c)/1> where R is a residue of a diazo component which advantageously contains an SO3H group, R1 is an aryl residue, A is the residue of a coupling component which contains an SO3H group and may contain an azo group, n is 1 or 2 and Y is an alkoxy group as above or a phenoxy group which contains a COOH or SO3H group, and of formula: <FORM:0847635/IV (c)/2> which is bound to the dye molecule via a bridge of formula -N-C (n- 1) H(2n- 1) where n is 1 or 2 and Y is a hydroxyl group etherified with an alcohol having 1-7 C atoms, or a phenol which may be substituted in the nucleus.  Dis-azo dyes should have at least 3 sulphonic acid groups.  They may be made by replacing two halogen atoms of a triazine trihalide by reaction with appropriate amino-azo dyes and alcohols or phenols or their alkali metal alcoholates or phenates.  Condensation is preferably effected at low temperatures in an aqueous or organic medium and in the presence of an acid-binding agent.  Alternatively the triazine residue may be incorporated in appropriate diazo or coupling components and the dye subsequently formed in the usual manner. Advantageously the triazine residue is linked to the diazo part of the dye molecule which is preferably of the benzene series and at most bicyclic.  Preferred classes of dyes are those of formula D-N=N-A where D is the residue of a diazo component which may contain an azo link and A is the residue of a coupling component and in which either A or D, which together have at least two sulphonic acid groups, contains bound thereto via an -NH- group, a residue of formula:  <FORM:0847635/IV (c)/3> where Y is the above alkoxy group, a benzeneoxy group or a phenoxy group which may contain a COOH or SO3H group. Particularly preferred classes of dyes are those of formula:  <FORM:0847635/IV (c)/4> where Y is an alkyl group of 1-7 C atoms or a benzene residue containing a COOH or SO3H group, A is as above and R is a residue of the benzene series, advantageously monocyclic and containing an SO3H group, and those of formula: <FORM:0847635/IV (c)/5> where A is a residue of a 5-pyrazolone bound in 4 position to the azo link and containing an SO3H group, or of an oxy- or amino-naphthalene sulphonic acid, especially an N-acylaminonaphthol mono- or di-sulphonic acid and Y is an alkyl group of 1-7 C atoms or a benzene residue.  Representative of alcohols specified as corresponding to Y are methanol, isopropanol, and benzyl, furyl and cyclohexyl alcohols.  Examples of phenols from which Y may be derived are p-cresol chlorophenols, salicylic acid and phenol 2-sulphonic acid.  Indicated as coupling components containing acylatable amino groups are benzene and naphthalene derivatives which couple by virtue of amino or hydroxy groups illustrative of those mentioned being o -methane sulphonic acid derivatives of aniline o -methoxy-and -carboxy -anilines,mtoluidine, 3-acetylamino and -ureido -1- aminobenzene, a - and b -naphthylamines, 1-naphthylamine-7-, 2-amino -8- naphthol-6, 2-methylamino -5-naphthol -7-, 2-(41-aminobenzoylamino- and -amino-phenylamino) -5-naphthol -7-, acetoacetic -acid arylides e.g. 1-acetoacetylamino -3- aminobenzene -4- sulphonic acid, 1-benzoylacetamino3-(41-aminobenzoyl)-amino-benzene, 1-acetoacetylamino -41- aminodiphenylmono- and -di-sulphonic acids, 1-acetoacetylamino -41- aminostilbene -2, 21-disulphonic acid, and 5-pyrazolones e.g. 1-(31- and 41-amino)- and [-41-(411-aminophenyl)]- phenyl -3- methyl -5- pyrazolones and corresponding sulphonic acids and 1-[41-(411-aminophenyl)-phenyl] -5- pyrazolone-3-carboxylic acid and compounds obtainable by nitrobenzoylation and reduction of 1-aminoaryl -5- pyrazolones. Indicated as diazo components, for use with the above coupling components, are aniline, naphthylamine, aminonaphthol, aminophenol, aminopyrene and aminochrysene sulphonic acids which may contain one or two azo links.  Illustrative of specified diazo components are aniline -2-, 2-amino -1- methoxybenzene -4-, 3- amino -2- oxybenzoic acid -5-, 2-aminophenol -4-, 5-acetylamino -2- aminobenzene -1-, 1-naphthylamine -6- mon- and -2, 5-di-1-(31-aminobenzoyl) -aminobenzene -3-, 3-aminopyrene -10- mono- and -5, 8-di-, 4-nitro -41-aminostilbene -2, 21- di-, O-acyl derivatives of 1-amino -8- naphthol -3, 6- di- 2-(41-aminobenzoylamino) -5- naphthol -7- and dehydrothiotoluidine mono- or di-sulphonic acids.  Indicated as diazo components containing acylatable amino groups are those derived from monoacyl derivatives of aromatic derivatives e.g. 4, 41-diaminodiphenyl -3-, 4, 41-diaminostilbene -2, 21- di-, 4-(41-aminobenzoylamino) -1- aniline -2- sulphonic acids and 1, 4-diaminobenzene and its 2-carboxylic and -3- sulphonic acids, the acyl residues being saponified after coupling.  Coupling components indicated for use with acylatable diazo components are acetoacetic acid arylides and pyrazolones e.g. 3-methyl -5- pyrazolone, 1-phenyl -3- methyl -5- pyrazolone -41- sulphonic acid, 1-phenyl -5- pyrazolone -3- carboxylic acid, 5-pyrazolone -3- carboxylic acid amide, barbituric acids, oxyquinolines, p-cresol, 2-carboxyphenol, a -naphthol, b -naphthylamine, 2-naphthol-sulphonamides and especially amino-and oxynaphthalene sulphonic acids and their N-alkyl, -aryl or -aryl derivatives, e.g. 1-naphthol -3-mono- and 1, 8- dioxynaphthalene- 3, 6-di-sulphonic acids, illustrative of the acyl groups mentioned being butyryl, chloracetyl, benzoyl, nitro-benzoyl, 3-aminobenzoyl, ethanesulphonyl, p-toluene-sulphonyl, carbomethoxy or residues derived from a cyanuric acid.  Coupling components such as 5, 51- dioxy -2, 21- dinaphthylurea and -dinaphthylamine -7, 71- disulphonic acids and 1-amino -2- naphthol -3, 6- disulphonic acid may be coupled twice with the appropriate diazo components.  Illustrative of amino-azo-compounds to be used as coupling components are those obtainable by coupling, in an acid medium, a simple compound of the benzene or naphthalene series, e.g. a diazotised chloraniline, a naphthylamine, 2-aminobenzoic acid or chloramino-phenol, with 2-amino -5- naphthol -7-mono- or 8-amino- 1-naphthol -3, 6- di-sulphonic acids.  Indicated as diazo-components containing triazine residues are condensation products of 1 mol of cyanuric chloride with 1 mol of methoxyethanol or a phenol sulphonic acid and 1 mol of 4, 41-diaminodiphenyl -3- sulphonic acid, 4, 41- diaminostilbene -2, 21-disulphonic acid, 1, 4- diaminobenzene and its 2-carboxylic acid and 3- sulphonic acid and a compound of formula:  <FORM:0847635/IV (c)/6> Indicated as coupling components containing the triazine residue are e.g. condensation products of 1 mol of cyanuric chloride with 1 mol of methanol or a phenol sulphonic acid and 1 mol of 2-amino -8- naphthol -6- sulphonic acid, 1-aceto-acetylamino -4- aminobenzene -3- carboxylic acid, 1-aceto-acetylamino -41- aminostilbene -2, 21- disulphonic acid, 1-(31-aminophenyl) -5- pyrazolone -3- carboxylic acid or a compound of formula: <FORM:0847635/IV (c)/7> The products may be dried, preferably at low temperatures and under reduced pressure, and, if desired, after the addition of extenders or buffers e.g. mono- and dialkali phosphates.  The dyes dye cellulosic materials especially by a pad-dyeing process with an alkali hydroxide fixing treatment.  Dyes containing metallisable groups may be after-treated with agents yielding metal e.g. chromium but preferably copper.  Examples are provided of the preparation of the dyes and their use in dyeing processes. Specifications 774,925, 775,308, 785,120 785,222, and 797,946 are referred to.