Patent GB-755571-A (GB)
Title: Improvements relating to metallisable polyazo dyestuffs and their use
IPC: C09B35/38
Filed: 1954-06-09
Abstract: The invention comprises dyestuffs of formula <FORM:0755571/IV(c)/1> where A is the residue of a hydroxynaphthalene sulphonic acid and containing a hydroxyl group in the o-position to the azo group, X is a substituent which forms a metal complex, Y is a direct link or - NH - CO - Ph -, - NH - CO - NH - Ph -, or <FORM:0755571/IV(c)/2> where Ph is a phenylene radicle, Cy is a triazinyl radicle and 2 a halogen atom, a hydroxyl group or an amine radicle, B is a residue of a diazo compound of the benzene or naphthalene series containing a carboxyl or hydroxyl group in the o-position to the azo group, the naphthalene radicle contains the hydroxyl group in the o-position to the azo group and the aromatic nuclei of A, B, D and Y may be further substituted, D preferably containing a sulphonic acid group.  The dyestuffs may be converted to their copper or cobalt compounds and the aromatic nuclei may contain substituents such as halogen, alkyl, hydroxyl, alkoxy, nitro, acylamino, arylamino, carboxyl, sulphonic acid, sulphonamide, aryl or alkylsulphonyl, alkoyl and aroyl groups. The dyestuffs may be made by coupling the necessary tetrazotized 4, 41-diaminodiphenyl in an alkaline medium with equimolecular amount of a hydroxynaphthalene sulphonic acid and a monoazo dyestuff obtained from an an acetoacetylamino-hydroxy-naphthalene by coupling with an o-carboxy- or preferably an o-hydroxydiazo benzene or -naphthalene in a weakly acid to weakly alkaline medium and optinally in the presence of a tertiary nitrogen base.  The monoazo dyestuff may also be used in the form of its metal complex.  Advantageously the monoazo dyestuff contains a water-solubilizing group.  Components mentioned which yield B are derivatives of 1-amino-7-hydroxynaphthalene and its 3- and 4-sulphonic acids, 1-amino-8-hydroxynaphthalen -3, 6- and -4, 6-disulphonic acids, 2-amino-6-hydroxynaphthalene-8-sulphonic acid and especially 1- or 2-amino-5-hydroxynaphthalene-7-suphonic acid, 2-amino-8-hydroxynaphthalene-6-sulphonic acid and 31 and 41 - aminobenzoyl or -aminophenyl-carbamyl derivatives thereof.  These compounds on treatment with diketene, preferably in an aqueous solution of their alkali metal salts, yield the corresponding acetoacetylaminocompound.  The components may also be treated with cyanuric chloride, an acetoacetylamino compound of the benzene series and, if desired, an amine, to yield the triazinyl derivative. Specified diazo components used in the preparation of the monoazo dyestuffs are 2-aminobenzene-1-carboxylic acid and its 4-chloro- and 5-nitro-, -sulpho- and -sulphonamido-derivatives, 2-aminonaphthalene-3-carboxylic acid, 2-amino-1-hydroxybenzene, 4-methyl-, -chloro-, nitro-, -methylsulphonyl-, -acetyl- and acetyllamino-, 5 nitro-, 4, 6 dichloro- and -dinitro-, 4-methyl- or -chloro-6-nitro-, 6-methyl- or -chloro-4-nitro-, 4-tert. amyl-6-nitro, 4-acetylamino-6-nitro-, 4-nitro-6-acetylamino- and 4-methyl- and -chloro-5-nitro-2-amino-1-hydroxybenzene, 4-methyl-, -chloro-, -nitro- and -benzoylamino-2-amino-1-hydroxybenzene-6-sulphonic acid, 6-methyl-, -chloro-, -nitro- and -benzoyll-amino-2-amino-1-hydroxybenzene-4- sulphonic acid, 3-amino-2-hydroxybenzene-1-carboxylic acid -5- sulphonic acid, 4-hydroxy-3-aminobenzene-1-carboxylic acid, 4 - hydroxy - 3 - aminobenzene - 1 - sulphonic acid, - sulphonamide, and sulphonic acid methyl-, dimethyl-, diethyl- and oxethylamides, 1- amino-2-hydroxynaphthalene-4- and -6-sulphonic acid and 6-nitronaphthalene -1, 2-diazoxide-4-sulphonic acid, 4, 41 - diaminodiphenyl derivatives specified are the 3, 31- dihydroxy-, di-carboxy-, -dimethoxy- and -di-carbomethyoxy compounds.  Specified naphthol sulphonic acids for coupling with the diphenyl are 1-hydroxynaphthalene- 3, 6-, -4, 8- and especially -3, 8- disulphonic acids, 1-hydroxynaphthalene- 3, 6, 8- trisulphonic acid, 2-hydroxynaphthalene -3, 6- and -6, 8- disulphonic acids, 1, 8-dihydroxynaphthalene -3, 6-disulphonic acid, 1- hydroxynaphthalene -4- and -5- sulphonic acid, 2-hydroxynaphthalene -4-, -6-, -7- and -8- sulphonic acid, 2-amino-, -acetylamino- and -(31-sulphonphenyl) 8-hydroxynaphthalene-7-sulphonic acid, 2-amino-acetylamino- and -(31-sulphonphenyl) -8-hydroxynaphthalene-6-sulphonic acid and 1-amino-8-hydroxynaphthalene-3, 6- and -4, 6- disulphonic acid. Before or after metallization, which may be effected in substance or on the fibre, the dyestuffs dye cellulose material in grey-violet to grey-green shades.  Treatment with copper- and cobalt-yielding substances is effected in conventional fashion. Dyestuffs containing both cobalt and copper may be made. Examples are provided illustrating the preparation of dyestuffs from certain of the above specified components and additional diazo component used in the preparation of the monoazo dyestuffs is 1-amino-2-hydroxy-5-chlorobenzene and the triazinyl portion of a dyestuff is derived from the product of the reaction between 1-amino-8-hydroxynaphthalene-3, 6-disulphonic acid, cyanuric chloride, 1-amino-4-acetoacetylaminobenzene and aniline or p-methoxyaniline.