Patent GB-880036-A (GB)
Title: Improvements relating to chromium-containing azo dyestuffs and their use
Filed: 1959-04-13
Abstract: The invention comprises chromium complexes which contain one atom of metal complexed with one mol of a dye of formula A1-N = N-B1 (I) and one mol of a dye of formula (A2-N = N-B2)-X-(Y-N = N-Z) (II) where A1 and A2 are residues of diazo components of the benzene or naphthalene series containing metallisable groups o-to the azo link, B1 and B2 are residues of azo components coupling adjacent to hydroxy groups, X is a carbonyl- or sulphonyl-amino or sulphonyloxy group and Y-N = N-Z is the residue of a non-metallisable compound.  The dyes are made by chroming a mixture of (I) and (II) dyes or preferably by treating a 1,1-complex, advantageously of formula (I), with the appropriate dye. Preferably X is a sulphonic acid derivative. The carbonyl or sulphonyl radicle may be bound to the metallisable or non-metallisable part of II.  For textile dyes at least one of (I) and (II) contains a water-solubility increasing sulphonyl substituent, e.g. sulphonamide and low alkyl-sulphonyl groups and advantageously not more than one sulphonic acid group.  Indicated as metallisable groups for A1 and A2 are COOH and OH and groups which may be converted into the latter during metallisation e.g., MeO and EtO groups.  The dyes may contain other substituents, e.g. halogen, alkyl, alkoxy, aryloxy, nitro, cyano, acyl, acylamino, alkyl- and aryl-sulphonyl and sulphonic and carboxylic acid amide groups which may be substituted on the N-atom.  Indicated components for B2 are 4-alkyl, 2,4-dialkyl or 2 - acylamino - 4 - alkyl - phenols, naphthols, dihydroxynaphthalenes, 1-aryl-3-alkyl-5 - pyrazolones and 1 - aryl - 5 - pyrazolones - 3 - carboxylic acids and their amides. Disazo dyes (II) may be obtained by reacting together metallisable and non-metallisable monoazo dyes one of which contains a group such as an amino or hydroxy group and the other a group such as a carboxylic acid or sulphonic acide halide group.  Preferably dyes (II) are made by reacting together either a diazo or azo component and a monoazo dye each of which contains appropriate groups to form X and coupling the product with the remaining component to form a disazo dye.  In a preferred form of the latter method an acyloxynaphthalene sulphonyl chloride is condensed with a non-metallisable hydroxy or amino monoazo dye, the acyloxy group is saponified and the naphthol sulphonamide or corresponding ester is coupled in an alkaline medium with an o-carboxy- or -hydroxy-benzene or naphthalene diazonium salt. Acyloxynaphthalene sulphonyl chlorides indicated are the carbo-methoxy- or toluenesulphonyl derivatives of 1-naphthol-3- or -4-sulphonyl chlorides and 2-naphthol-4,5-, 6- or -7-sulphonyl chlorides.  4-amino- and -hydroxyazo benzenes are indicated as non-metallisable monoazo dyes.  The corresponding carbonyl compounds may be obtained by replacing the above sulphonyl chlorides with carbonyl chlorides.  Disazo dyes containing the sulphonyl group bound to the diazo component of the metallisable portion are obtained by condensing a benzoxazolone sulphonyl chloride with 4-amino-azobenzene or a derivative thereof, splitting the oxazolone ring in an alkaline medium and diazotising and coupling the product with a metallisable azo component. Disazo dyes containing the carbonyl or sulphonyl radicle in the non-metallisable portion are made by condensing an azobenzene-4-carboxylic or - sulphonic acid chloride with a phenol or naphthol which contains a primary or secondary amino group and which couples o to a hydroxy group, and coupling the condensation product with an o-carboxy or -hydroxydiazo-benzene or -naphthalene.  Advantageously the disazo dyestuff contains a sulphonamide group X which is substituted at the N- atom.  Such dyes may be made from appropriate secondary amino-monoazo dyes or products containing an -SO2NH- group may be alkylated.  The dyes colour organic materials in orange, brown, olive, blue, grey and violet shades.  Insoluble dyes may be used in lacquers, varnishes, paper, viscose, nylon, cellulose ester and ether and polyester condensates.  Water-soluble dyes are used in particular on wool, casein, leather, furs and superpoly-amide and urethanes. Dyes containing the sulphonyl group X and a sulphonic acid group have good neutral drawing power on wool.  In a preferred class of dyes, (I) is derived from a sulphonated o-hydroxybenzene-azo-o1-hydroxynaphthalen or o1,o1-dihydroxynaphthalene.  Examples are provided of the preparation of the dyes and their use in dyeing wool.  Reference has been directed by the Comptroller to Specifications 637,404, 667,168 and 758,016.