Patent GB-209723-A (GB)
Title: Manufacture of new azo-dyestuffs
IPC: C09B43/16
Filed: 1923-12-22
Abstract: Azo dyes containing one or more cyanuric nuclei are prepared either by coupling suitable components one or both of which contain cyanuric nuclei, or by uniting azo dyes together or with other compounds by means of cyanuric halides.  The products include acid, mordant, and substantive dyes; the latter may be diazotizable on the fibre or may be developed on the fibre with diazo compounds, or may be suitable for after-treatment with metal salts or with formaldehyde.  Soluble metal compounds of the dyes, and products solubilized by the introduction of methyl-o -sulphonic groups into the amino groups, are also included.  The dyes may also be prepared on the fibre by impregnation with the intermediate cyanuric compounds and developing either by diazotizing and coupling or by a diazo compound.  The dyes may also be used in the preparation of lakes, or for dyeing skins, leather, &c.  The intermediate compounds are prepared as described in Specification 221,843 by replacing one or more of the halogen atoms of cyanuric halides by appropriate radicles; these may be the residue (A) of an aminonaphthol or derivative thereof; or another residue (C) which contains groups which render the product suitable as a diazo or coupling component (amino, alkyl or aryl-amino, hydroxy, or an active methylene group); or a residue (J) which though not of the above type contains atoms or groups which affect the tinctorial properties of the dye, for instance, amino, alkylamino, arylamino, acidylamino, hydroxy, alkyloxy, aryloxy, acidyloxy, nitro, carboxy, methyl, sulphonic, &c.  According to examples: (1) A monoazo dye, dyeing wool rose tints, is prepared by coupling diazobenzene in alkaline solution with the condensation product from one molecule of cyanuric chloride and one molecule of 1 : 8-aminonaphthol-3 : 6-disulphonic acid, or by reaction of cyanuric chloride on the monoazo dye from aniline and H-acid coupled alkaline; violet to blue dyes are obtained by using instead of aniline a substitution product thereof containing a positive group, for example, p-toluidine, p-aminoacetanilide, or 2-amino-5-dimethylamino-41-methyldiphenylsulphone; replacement of the chlorine atoms in the condensation product by hydroxyl, amino, diethylamino, or acetylamino groups has little effect on the properties of the dyes; o-oxy- or o-carboxy-diazo compounds give mordant dyes which yield complex metal compounds, for example, the dye from 4-nitro-2-aminophenol, H-acid, and cyanuric chloride, dyes wool green shades with chrome mordants. (2) A monoazo dye, dyeing wool or cotton rose tints from an acid bath, is obtained from aniline coupled alkaline with the condensation product from one molecule each of cyanuric chloride, H-acid, and aniline; chloranilines or aniline carboxylic or sulphonic acids give products of similar tints, while toluidines, aminoacylanilides, anisidines, or naphthylamines give bluish-red to violet dyes; replacement of the remaining chlorine atom of the cyanuric group by amino or hydroxy does not change the shade; o-oxy- or o-carboxydiazo compounds give mordant dyes which yield complex metal compounds; thus the dye from anthranilic acid and the condensation product from cyanuric chloride, H-acid, and aniline, dyes wool rose tints in acid baths, becoming violet on chroming and violet-red on coppering.  (3) A disazo dyes, dyeing cotton blue in alkaline baths, is prepared by coupling tetrazotized benzidine in alkaline solution with two molecules of the condensation product from one molecule each of cyanuric chloride, H-acid, and aniline; instead of benzidine other p-diamines of the diphenyl series may be used, and mixed disazo dyes may also be prepared, for example, the product from benzidine, one molecule of H-acid, and one molecule of the condensation product dedescribed above, dyes blue shades.  (4) A monoazo dye, giving red shades when dyed on wool or printed on cotton with chrome mordants, is prepared by coupling 1-aminobenzene-2-sulphonic acid in alkaline solution with the condensation product from one molecule each of cyanuric chloride, H-acid, and p-aminosalicylic acid; similar mordant dyes of tints ranging to violet are prepared by using as diazo component aniline, toluidines, xylidines, anisidines, phenetidines, or their halogen, carboxylic, sulphonic, or acidylamino derivatives, or naphthylamines or their sulphonic acids, aminoazobenzene or its homologues or substitution products, or an aminosalicylic or aminocyanuric compound; in place of the p-aminosalicylic acid used in preparing the condensation product there may be employed a sulpho-, chloro-, or nitro-aminosalicylic acid, an aminocresotinic acid, or a corresponding naphthalene derivative; the last chlorine atom of the cyanuric residue of the dyestuffs may be readily replaced by an hydroxyl or amino group by treatment with caustic soda or ammonia, or may less readily be replaced by the residue of a primary amine such as aniline.  (5) A monoazo dye, dyeing cotton violet-red shades in acid or alkaline baths, is obtained from o-toluidine coupled alkaline with the condensation product from one molecule of cyanuric chloride, one molecule of H-acid, and two molecules of aniline; less bluish-red dyes are obtained by using negatively-substituted anilines as diazo components, while xylidines, anisidines, or naphthylamines give violets.  In the coupling component another primary or secondary amine may replace one or both of the aniline residues; if this contains the residues of salicylic, benzoic or phthalic acid, or if the diazo component is an o-oxy or o-carboxy compound, mordant dyes are obtained; thus the dye from 1-aminobenzene-2-sulpho-5-carboxylic acid and the condensation product from cyanuric chloride, H-acid, and two molecules of p-aminosalicylic acid, gives rose prints on chrome-mordanted cotton.  (6) Diazotized 1-amino-2-oxybenzene-5-sulphamide is coupled in alkaline solution with the condensation product from cyanuric chloride, 2 : 5 : 7-aminonaphthol sulphonic acid, and two molecules of aniline; the product dyes cotton bordeaux tints and may be after-treated with or dyed in the presence of copper salts; the copper compound of the dye may also be prepared in substance.  Trisazo and polyazo dyes may also be prepared from aminoazobenzene or its sulphonic acid or other derivatives and condensation products containing the residue of 2 : 5 : 7-acid; thus a blue trisazo dye is prepared from metanilic acid, a -naphthylamine, 1-naphthylamine-6-sulphonic acid, and the condensation product from cyanuric chloride, 2 : 5 : 7-acid, aniline, and sulphanilic acid.  (7) A primary disazo dye, dyeing cotton rose tints in alkaline or acid baths, is obtained by coupling two molecules of aniline in alkaline solution with the condensation product from cyanuric, chloride and two molecules of H-acid; the condensation products obtained by using in place of H-acid two molecules of 2 : 5 : 7-, 2 : 8 : 6-, or 1 : 8 : 4-aminonaphthol sulphonic acid give with diazobenzene orange, red, and violet-red dyes respectively; mixed condensation products derived from these aminonaphthols also give red dyes.  Monoazo dyes of this type can be developed on the fibre with diazo compounds; thus, the monoazo dye from o-anisidine coupled alkaline with the condensation product from cyanuric chloride, two molecules of 2 : 5 : 7-acid, and one molecule of ammonia, dyes cotton bluish-red, becoming scarlet on development with diazotized p-nitraniline.  (8) The last chlorine atom of the condensation products containing two aminonaphthol sulphonic acid residues may p  be replaced by the hydroxyl or amino group or by the residue of a primary or secondary amine or an alcohol, phenol, or naphthol.  If the coupling component contains a carboxylic group or a salicylic residue or if o-oxy- or o-carboxydiazo compounds or diazo compounds containing o-oxyazo, or o-o1-dioxyazo groups are employed, mordant dyes are produced.  For instance, a red dye which gives violet prints on chromemordanted cotton is produced by coupling anthranilic acid with the condensation product from cyanuric chloride, two molecules of H-acid, and one molecule of aminosalycylic acid a disazo dye giving red prints on a chrome mordant is prepared from two molecules of 1-aminobenzene-2-sulphonic acid and one molecule of the condensation product made by the reaction of one molecule of p-phenylenediamine on two molecules of the condensation product from one molecule each of cyanuric chloride, H-acid, and p-aminosalicyclic acid; two molecules of 2-aminophenol-4-sulphonic acid are coupled in alkaline solution with the condensation product from one molecule of cyanuric chloride, two molecules of 2 : 5 : 7-acid, and one molecule of ammonia; the copper compound of this dye dyes cotton ruby tints; a tetrakisazo dye, whose copper compound dyes cotton greenish-blue, is prepared by coupling in alkaline solution two molecules of the diazo compound of the monoazo dye 5-nitro-2-aminophenol -->2 : 5 : 7-acid (alkaline coupling) with the condensation product from cyanuric chloride, two molecules of H-acid, and one molecule of aniline.  (9) A condensation product is prepared by first condensing one molecule each of cyanuric chloride and 2 : 5 : 7-acid, two molecules of this product are then condensed with one molecule of m-phenylenediamine and finally the two chlorine atoms are replaced by aniline residues; cotton impregnated with this product and developed with diazotized p-nitraniline is dyed orange-scarlet; condensation products from unsulphonated aminonaphthols are particularly suitable for the production of dyes on the fibre.  (10) A trisazo dye, dyeing cotton rose, is obtained by coupling three molecules of aniline in alkaline solution with the condensation product from cyanuric chloride and three molecules of H-acid, and a trisazo dye, dying cotton bluish-red, is made similarly from three molecules of o-anisidine and the co