DE2619887A1 - METALIZED AZO DYES - Google Patents

Description

The invention relates to new metallized azo dyes and in particular to new chromium or cobalt-containing azo dyes which are particularly suitable for dyeing textile materials, in particular cellulosic textile materials.

According to the invention, new chromium or cobalt-containing complexes of monoazo dyes are proposed which, in the form of the free acid, have the formula:

can be represented in which A 'and A "each represent identical or different aromatic radicals; B 'and B''each represent identical or different radicals of a coupling component which couples in the ortho or vicinal position to D' or D ''; Z 'and Z ", which are bonded to A' or A" in ortho positions to the azo group, are identical or different and are -O- or -COO-; D 'and D "are the same or different and represent -O-, -NH-, -N-lower alkyl or -N-phenyl; M represents Cr or Co; and at least one of the radicals A ', A ", B' and B" carries one or more phosphonic acid groups.

The dyes of the formula (1) can be symmetrical, i.e. A '= A ", Z' = Z", B '= B "and D' = D". However, the dyes can also be asymmetrical, i.e. one or more of the pairs A 'and A ", Z' and Z", B 'and B ", D' and D" consist of two different groups. It should be noted that the symmetrical dyes necessarily contain an even number of at least 2 phosphonic acid groups.

For reasons of simpler preparation, symmetrical dyes of the formula (1) are often preferred.

The preferred radicals D 'and D "are -NH-, -N-phenyl and very particularly -O-.

The aromatic radicals A 'and A "are radicals of diazotizable aromatic amines and preferably belong to the phenyl or naphthyl series. They can contain phosphonic acid groups which are bonded directly to a carbon atom of the ring or to a carbon atom of a substituent which in turn is linked to a carbon atom of the ring. Examples of such substituents are alkylene radicals or N-hydrocarbyl aminosulfonyl radicals, e.g.

or Hydrocarbonaminocarbonylreste, such as

where the group SO [deep] 2 or CO is bonded to a carbon atom of the ring. The aromatic radical can carry other substituents, such as fluorine, chlorine, bromine, lower alkyl, lower alkoxy, nitro, COOH, SO [deep] 3H and acylamino, and contains an ortho substituent as defined for Z 'or Z " .

The preferred substituents on the naphthyl or phenyl radicals A 'and A ", apart from the radicals Z' or Z", are SO [deep] 3H, PO [deep] 3H [deep] 2, lower alkyl, in particular methyl, lower alkoxy , especially methoxy, NO [deep] 2, Cl, CH [deep] 2PO [deep] 3H [deep] 2, where G is H or OCH [deep] 3, and -CONHCH [deep] 2CH [deep] 2PO [deep] 3H [deep] 2.

Throughout the specification, the term "lower" refers to C [low] 1-4.

It is particularly preferred that each of A 'and A "is a phenyl group which has the substituents indicated above.

A particularly preferred form of A 'and A' 'is 3-phosphono phenyl, where the Z 'or Z "is an -O- in the 6-position.

The residues of coupling components B 'and B' 'can be residues of any known series of coupling components which couple in the ortho or vicinal position to a hydroxy or amino group. However, B 'and B' 'are preferably the radicals of coupling components of the phenol, naphthol, acetoacetarylamide, 5-aminopyrazole, 5-pyrazolone (especially 1-phenyl-5-pyrazolone) or naphthylamine series, all of which may contain substituents , for example those mentioned for A 'and A "and OH, NH [deep] 2, alkylamino and arylamino.

Examples of acylamino radicals which can be bonded to A ', A ", B' and B" are acylamino groups which are derived from lower aliphatic carboxylic acids, such as, for example, formylamino, acetylamino and propionylamino radicals; Carbo-lower alkoxyamino radicals such as carbomethoxyamino, carboethoxyamino and carbopropoxyamino radicals; Acylamino residues derived from aromatic monocarboxylic acids such as benzoylamino and toluylamino residues; Acylamino residues derived from aromatic monosulfonic acids such as benzenesulfonylamino and p-toluenesulfonylamino residues; and acylamino groups derived from heterocyclic compounds such as s-triazinylamino and pyrimidinylamino groups.

Preferred forms of the groups -B'-D'- and -B "-D" - are those which are derived from the following coupling components: resorcinol, 1- and 2-naphthols, which are optionally replaced by one or more of the following Groups are substituted: SO [deep] 3H, PO [deep] 3H [deep] 2, NH [deep] 2, NH-acyl, especially when acyl stands for acetyl, benzoyl or small beta-chloropropionyl, NH-alkyl, especially when Alkyl represents lower alkyl and very particularly methyl, and NH-aryl, especially when aryl represents phenyl or sulfophenyl; 3-methyl- or 3-carboxy-5-pyrazolones, which have a 1-phenyl radical, which optionally carries one or more of the following substituents: SO [deep] 3H, PO [deep] 3H [deep] 2, acryloylamino, acylamino, especially acetylamino, Cl, NO [deep] 2, lower alkyl, especially CH [deep] 3 , and lower alkoxy, in particular OCH [deep] 3, or which have a 1-naphthyl radical which is substituted by SO [deep] 3H or PO [deep] 3H [deep] 2; 2-naphthylamines, 2-N-alkylnaphthylamines and 2-N-phenylnaphthylamines, all of which are substituted by SO [deep] 3H and / or PO [deep] 3H [deep] 2; and N- (sulfo- or -phosphonophenyl) acetoacetamides.

Particularly preferred coupling components are the naphthols and pyrazolones listed above.

The invention further relates to a process for the preparation of the new chromium or cobalt-containing azo dyes of the formula (1), which is carried out by adding an azo compound of the formula: wherein A ', B', D 'and Z' have the meanings given above, and a 1: 1 chromium or cobalt complex of an azo compound of the formula: where A ", B", D "and Z" have the meanings given above and at least one of the radicals A ', A ", B' and B" carries one or more phosphonic acid groups, are reacted with one another.

Alternatively, a 1: 1 chromium or cobalt complex of the azo compound of the formula (2) can be reacted with the azo compound of the formula (3).

The above procedure can conveniently be carried out by that the reactants are reacted in water or in a mixture of water and a water-miscible organic liquid such as ethanol, ethylene glycol or small beta-ethoxyethanol. The dye can be isolated in a conventional manner in the acid form or in the form of an ammonium salt or partly in one of these forms and partly as the alkali metal salt, for example the Li, Na or K salt. The salts can be obtained by adding a halide, such as the chloride, of the desired alkali metal, or an ammonium halide or ammonia, to the final reaction mixture prior to isolation. Alternatively, by adding an alkanolamine, such as diethanolamine, to the finished reaction mixture, a highly soluble form of the dye can be obtained, which can be used in the form of the entire liquid for dyeing or printing.

When carrying out the process according to the invention, it is preferred to use 1 molecular proportion of the azo compound and 1 molecular proportion of the 1: 1 chromium or cobalt complex. In some cases, however, advantageous results are obtained when a little more than 1 molecular fraction of the 1: 1 chromium or cobalt complex is used.

The azo compounds of the formulas (2) and (3) can in turn be obtained by adding an amine of the formula: or where A ', A ", Z' and Z" have the meanings given above and -Z'H and -Z''H are in ortho positions to the groups -NH [deep] 2, diazotized and the like obtained diazo compounds with the corresponding coupling components of the formula:

HB '- D'H or HB' '- D''H wherein B ', B ", D' and D" have the meanings given above, coupling, the primary amines and coupling components being selected so that one or both of the resulting azo compounds contain one or more phosphonic acid groups.

The 1: 1 chromium complexes of the azo compounds of the formulas (2) or (3) can in turn be obtained by adding the azo compounds with a salt of trivalent chromium, such as chromium triacetate, in water or in a mixture of water and one with water Miscible organic liquid, such as ethylene glycol, is heated to form the 1: 2 chromium complex, an acid such as hydrochloric acid or sulfuric acid is added and heating is carried out until the 1: 2 chromium complex is converted into the 1: 1 chromium complex is. Alternatively, the azo compound can be heated with a chromium salt such as the sulfate or formate in water containing an acid such as sulfuric acid.

The 1: 1 cobalt complexes of the azo compounds of the formulas (2) or (3) can be obtained by mixing a cobalt (II) amine salt, such as, for example, hexamminocobalt sulfate, with the azo compounds in an aqueous solution. The reaction proceeds at room temperature or with moderate heating. The complex can be isolated as described above.

If the above process is used to prepare symmetrical dyes of formula (1), ie that the azo compounds (2) and (3) are identical, it will of course be understood that it is not necessary to use the 1: 1 chromium or To isolate cobalt complex for the reaction with further azo compound, since the production of such symmetrical dyes can be achieved by mixing 2 mol of the azo compound with a chromium or cobalt salt, such as chromium triacetate or cobalt (II) acetate, in a solvent such as water, heated and then Then isolate or treat the product as described above.

Examples of amines of the formula or which can be used to prepare the azo compounds of formulas (2) and (3) are:

Anthranilic acid

4-, 5- and 6-chloroanthranilic acid

4- and 5-nitroanthranilic acid

4- and 5-sulfoanthranilic acid

1-amino-2-naphthol-4-sulfonic acid

6-nitro-1-amino-2-naphthol-4-sulfonic acid

2-aminophenol

2-aminophenol-4-sulfonic acid

2-aminophenol-6-sulfonic acid

4-, 5- and 6-nitro-2-aminophenol

4- and 6-chloro-2-aminophenol

4,6-dinitro-2-aminophenol

4-chloro-2-aminophenol-6-sulfonic acid

4-methoxy-2-aminophenol

4-methyl-2-aminophenol

6-nitro-2-aminophenol-4-sulfonic acid

4-acryloylamino-2-aminophenol

4-small beta-chloropropionylamino-2-aminophenol

4- and 5-acryloylaminoanthranilic acid

4-acetylamino-2-aminophenol

4- and 5-acetylaminoanthranilic acid

1-amino-4-cyano-2-hydroxynaphthalene and

2-aminophenol-4,6-disulfonic acid

Examples of amines A'-NH [deep] 2 and A '' - NH [deep] 2 that contain phosphonic acid groups are:

2-aminophenol-4-phosphonic acid

6-sulfo-2-aminophenol-4-phosphonic acid

6-nitro-2-aminophenol-4-phosphonic acid

6-acetylamino-2-aminophenol-4-phosphonic acid

3-amino-4-hydroxybenzyl-phosphonic acid

3- and 4- (N- [3-Amino-4-hydroxyphenylsulfonyl] amino) phenyl-phosphonic acid

4- (N- [3-Amino-4-hydroxyphenylsulfonyl] amino) benzyl-phosphonic acid

3- (N- [3-Amino-4-hydroxyphenylcarbonyl] amino) phenylphosphonic acid

N- [3-Amino-4-hydroxyphenylcarbonyl] -small beta-aminoethane-phosphonic acid

6-chloro-2-aminophenol-4-phosphonic acid

3-amino-4-carboxyphenyl-phosphonic acid

3- and 4- (N- [3-Amino-4-carboxyphenylsulfonyl) amino] phenyl-phosphonic acid

4- (N- [3-Amino-4-carboxyphenylsulfonyl] amino) benzyl-phosphonic acid

N- [3-Amino-4-hydroxysulfonyl] -small beta-aminoethane-phosphonic acid and

3- and 4- (N- [3-Amino-4-hydroxyphenylcarbonyl] amino) benzyl phosphonic acid

Examples of coupling components of the formula:

H-B'-D'H or H-B '' - D''H

which can be used to prepare the monoazo compounds of formulas (2) and (3) are:

Phenols, e.g.

p-cresol

4-hydroxydiphenyl

2- and 3-acryloylamino-4-methylphenol

2- and 3-small beta-chloropropionylamino-4-methylphenol;

Acetoaceterylamides, e.g.

Acetoacetanilide

Acetoacetanilide-3- and -4-sulfonic acid

4-acryloylaminoacetoacetanilide and

Acetoacet-2- and -4-anisidide;

Naphthols, e.g.

2-naphthol

2-naphthol-6- and -8-sulfonic acid

6-bromo-2-naphthol

1-acryloylamino-4-, -6- and -7-naphthol

2-acryloylamino-6- and -7-naphtol

1-small beta-chloropropionylamino-4-, -6- and -7-naphthol

2-small beta-chloropropionylamino-6- and -7-naphthol

1-naphthol-4-sulfonic acid

5-chloro-1-naphthol

5,5-dichloro-1-naphthol

2-acryloylamino-5-naphthol-7-sulfonic acid

2-small beta-chloropropionylamino-5-naphthol-7-sulfonic acid

2-acryloylamino-8-naphthol-6-sulfonic acid

2-small beta-chloropropionylamino-8-naphthol-6-sulfonic acid

1-acetylamino-4-, -6- and -7-naphthol

1-benzoylamino-7-naphthol

1-carboethoxyamino-7-naphthol

1 carbopropoxyamino-7-naphthol

2-acetylamino-8-naphthol-6-sulfonic acid

2-Benzoylamino-5-naphthol-7-sulfonic acid

4-acetyl-1-naphthol

6-methoxy-2-naphthol

6-acetyl-2-naphthol

1-phenylamino-7-naphthol

5,6,7,8-tetrahydro-2-naphthol

5,6,7,8-tetrahydro-2-naphthol-3-sulfonic acid

2-amino-8-naphthol-3,6-disulfonic acid

2-amino-5-naphthol-1,7-disulfonic acid

1-amino-8-naphthol-3,6-disulfonic acid

1-amino-8-naphthol-2,4-disulfonic acid

1-amino-8-naphthol-4,6-disulfonic acid

2-amino-8-naphthol-6-sulfonic acid

3-amino-8-naphthol-6-sulfonic acid

4-amino-8-naphthol-6-sulfonic acid

2-methylamino-8-naphthol-6-sulfonic acid

3-methylamino-8-naphthol-6-sulfonic acid

1-phenylamino-8-naphthol-3,6-disulfonic acid

1-Benzoylamino-8-naphthol-3,6-disulfonic acid

1-acetylamino-8-naphthol-3,6-disulfonic acid

2- (3-sulfophenylamino) -8-naphthol-6-sulfonic acid

3- (3-sulfophenylamino) -8-naphthol-6-sulfonic acid

2- (3-carboxyphenylamino) -8-naphthol-6-sulfonic acid

3- (3-carboxyphenylamino) -8-naphthol-6-sulfonic acid

3-acetylamino-8-naphthol-6-sulfonic acid

2-Benzoylamino-8-naphthol-6-sulfonic acid

3-Benzoylamino-8-naphthol-6-sulfonic acid

2-benzoylamino-5-naphthol-1,7-disulfonic acid

2-N-acetyl-N-methylamino-5-naphthol-7-sulfonic acid

2-N-acetyl-N-methylamino-8-naphthol-6-sulfonic acid and

1,8-dihydroxynaphthalene-3,6-disulfonic acid;

5-aminopyrazoles, especially 1-aryl-5-aminopyrazoles, e.g.

1-phenyl-3-methyl-5-aminopyrazole and

1- (2'-, -3'- and -4'-sulfophenyl) -3-methyl-5-aminopyrazole;

5-pyrazolones, e.g.

3-methyl-5-pyrazolone and

1,3-dimethyl-5-pyrazolone;

but especially 1-aryl-5-pyrazolones, e.g.

1-phenyl-3-methyl-5-pyrazolone

1- (2'-, -3'- and -4'-methylphenyl) -3-methyl-5-pyrazolone

1- (2'-, -3'- and -4'-methoxyphenyl) -3-methyl-5-pyrazolone

1- (2'-, -3'- and -4'-sulfophenyl) -3-methyl-5-pyrazolone

1- (2'-, -3'- and -4'-chlorophenyl) -3-methyl-5-pyrazolone

1- (2 ', 5'-dichloro-4'-sulfonophenyl) -3-methyl-5-pyrazolone

1- (3'- and -4'-acryloylaminophenyl) -3-methyl-5-pyrazolone

1- (3'- and -4'-small beta-chloropropionylaminophenyl) -3-methyl-5-pyrazolone

1- (3'-Acryloylamino-4'-sulfophenyl) -3-methyl-5-pyrazolone

1- (4'-Acryloylamino-3'-sulfophenyl) -3-methyl-5-pyrazolone

1- (4'-sulfonaphth-1'-yl) -3-methyl-5-pyrazolone and

1- (6'-sulfonaphth-2'-yl) -3-methyl-5-pyrazolone

as well as the 3-carboxy analogs of all 3-methylpyrazolones mentioned above;

Naphthylamine coupling components, e.g.

2-naphthylamine-6-sulfonic acid

2-naphthylamine-7-sulfonic acid

N-phenyl-2-naphthylamine and

2-N-phenylaminonaphthalene-6-sulfonic acid.

Examples of coupling components H-B'-D'-H and H-B '' - D '' - H which contain phosphonic acid groups are:

Acetoacetanilide-3-phosphonic acid

1- (3-phosphonophenyl) -3-methyl-5-pyrazolone

1- (3-phosphonophenyl) -3-carboxy-5-pyrazolone

1- (7-phosphononaphth-2'-yl) -3-methyl-5-pyrazolone

2-naphthylamine-7-phosphonic acid

2-naphthol-7-phosphonic acid

2-phosphono-7-naphthol

3-phosphono-8-naphthol and

2-naphthylamine-5-sulfo-7-phosphonic acid.

An alternative method, which in some cases can be applied to the preparation of the dyes of the formula (1) which contain acylamino substituents, is that a dye of the formula (1) which is an amino or N- (lower alkyl) contains amino substituents, with an acylating agent, such as the anhydride or chloride of a carboxylic acid, is reacted.

The new dyes are soluble in water due to the presence of phosphonic acid groups. In many cases, sulfonic acid groups can also be present to increase their solubility. They can generally be used for dyeing textile materials that can be dyed by dyes which are made soluble by anionic groups, such as natural and synthetic polyamide materials, for example wool, silk, polyhexamethylene adipamide and polycaproamide, but especially natural or regenerated cellulose textile materials, such as e.g. cotton, linen and viscose rayon. In the case of cellulose textile materials, the dyes are preferably fixed on the fiber by a baking treatment at a temperature of 95 to 205 ° C in the presence of a carbodiimide such as cyanamide or dicyandiamide, for example by the method described in DT-OS 2324809.

Textiles which have been colored by the dyes according to the invention have strong hues with good fastness to washing treatments. They often also have good lightfastness, especially in the case of deep shades.

The dyes according to the invention are particularly suitable for application together with disperse dyes from a single dyebath or with a single printing paste. For example, they perform favorably in this regard when compared with most conventional cellulose reactive dyes, which require the presence of alkaline auxiliaries which frequently lead to flocculation of the disperse dye. Such mixed dye baths or printing pastes are often desirable when dyeing textile materials that contain two types of fibers, such as mixtures of cellulose and polyester.

The invention is explained in more detail by the following examples tert, where the parts are expressed by weight:

example 1

A solution of 3.78 parts of 2-aminophenol-4-phosphonic acid in 50 parts of water and 5.0 parts of 10N hydrochloric acid is stirred and the mixture is cooled to 5 ° C. A solution of 1.40 parts of sodium nitrite in 10 parts of water is added and the mixture is stirred at 0-5 ° C. for 45 minutes. The slight excess of nitrous acid is destroyed by adding sulfamic acid. The reaction solution is gradually added at 0-5 ° C. to a stirred solution of 5.62 parts of 3-acetylamino-8-naphthol-6-sulfonic acid in 100 parts of water, a sufficient amount of ammonium hydroxide solution (density 0.880) being added at the same time to keep the pH at 8 throughout the addition. The mixture is stirred at 5-10 ° C. and pH 8 for 2 hours. The product is precipitated by adding 25 parts of ammonium acetate and stirred for 30 minutes. The precipitated product is filtered off, washed with 50 parts of a 15% strength (w / v) ammonium acetate solution and then sucked dry. The filter cake is dissolved in 100 parts of hot water, a solution of 2.76 parts of chromium triacetate in 50 parts of water is added, and the mixture is stirred for 3 hours at the boiling point. The reaction mixture is cooled, 25 parts of ammonium acetate are added, and the mixture is stirred at 20 ° C. to complete the precipitation. The product is filtered off, washed with 15% (w / v) ammonium acetate solution and finally dried at 50.degree. If the dye is applied to cellulose textile materials by the method described in DT-OS 2324809, then it gives deep violet shades with excellent fastness to wet treatments.

The following table relates to further examples of dyes according to the invention, which are obtained according to Example 1 that the 3-acetylamino-8-naphthol-6-sulfonic acid used in this example is replaced by an equimolar amount of a coupling component listed in the second column of the table. The color is given in the third column.

Example 9

A solution of 4.68 parts of 6-nitro-2-aminophenol-4-phosphonic acid in 60 parts of water and 5.0 parts of 10N hydrochloric acid is stirred and the mixture is cooled to 5 ° C. A solution of 1.4 parts of sodium nitrite in 10 parts of water is added and the mixture is stirred at 0-5 ° C. for 30 minutes. The slight excess of nitrous acid is removed by adding 10% (w / v) sulfamic acid solution. The resulting diazonium salt is gradually added at 0-5 ° C. to a stirred solution of 7.9 parts of 2- (3-sulfophenylamino) -8-naphthol-6-sulfonic acid in 80 parts of water. sufficient ammonium hydroxide solution (density 0.880) is added to keep the pH at 8 throughout the addition. The mixture is stirred at 5-10 ° C. and pH 8 for 2 hours. The pH is adjusted to 7 by adding 2N hydrochloric acid, and the product is precipitated by adding 48 parts of ammonium chloride and stirred for 2 hours. The precipitated product is filtered off, washed with 50 parts of a 30% strength (w / v) ammonium chloride solution and then sucked dry. The filter cake is dissolved in 75 parts of hot water, a solution of 3.11 parts of cobalt (II) acetate tetrahydrate in 15 parts of water is added, and the mixture is stirred at 95 ° C. for 1 hour. The mixture is cooled, 27 parts of ammonium chloride are added, and the mixture is stirred at 20 ° C. to complete the precipitation. The product is filtered off, washed with 30% (w / v) ammonium chloride solution and finally dried at 50.degree. If the dye is applied to cellulose textile materials by a method described in DT-OS 2324809, then it gives matt violet shades with excellent fastness to wet treatments.

The following table relates to further examples of dyes according to the invention which can be obtained according to Example 9 by replacing the 6-nitro-2-aminophenol-4-phosphonic acid used in this example with an equimolar amount of the diazo component listed in the second column of the table and by replacing the 2- (3-sulfophenylamino) -8-naphthol-6-sulfonic acid used in this example with an equimolar amount of the coupling component listed in the third column of the table. The colors are given in the fourth column.

Example 24

A solution of 4.34 parts of 3-amino-4-carboxyphenylphosphonic acid in 50 parts of water and sufficient ammonium hydroxide solution (density 0.880) so that a pH of 7-8 is obtained is stirred, a solution of 1.38 parts of sodium nitrite in 10 parts of water is added. The reaction mixture is stirred at 0-5 ° C. and then added to a stirred mixture of 40 parts of ice and 7 parts of concentrated hydrochloric acid (density 1.18). The mixture is stirred for 15 min at 0-5 ° C., and the excess nitrous acid is destroyed by adding sulfamic acid. The reaction mixture is added to a stirred solution of 7.9 parts of 2- (3-sulfophenylamino) -8-naphthol-6-sulfonic acid in 100 parts of water and sufficient ammonium hydroxide solution (density 0.880) so that the pH of the reaction mixture is stirred for 15 min of 6.5-7.5 is observed, added. The mixture is stirred overnight at room temperature and at pH 7 and evaporated to dryness in vacuo. The product is dissolved in 100 parts of water, 0.5 part of glacial acetic acid is added, followed by the addition of 2.5 parts of cobalt (II) acetate tetrahydrate in 10 parts of water. The mixture is then stirred at 95 ° C. for 3 hours. The reaction mixture is evaporated to dryness in vacuo at 50 ° C. If the dye is applied to cellulose textile materials in accordance with the method of DT-OS 2324809, then it gives reddish-brown shades with excellent fastness to wet treatments.

The following table relates to further examples of dyes according to the invention, which can be obtained according to Example 24 by adding the 2- (3-sulfophenylamino) -8-naphthol-6-sulfonic acid used in this example by an equimolar amount of the in the second column of The coupling components listed in the table are replaced. The color is given in the third column.

Example 36

9.26 parts of 1- (2-hydroxy-4-nitrophenylazo) -2-phenylaminonaphthalene-6-sulfonic acid are added to 400 parts of ethylene glycol with stirring at 100.degree. 7.5 parts of chromium formate are added and the mixture is heated to 120-130 ° C. The mixture is stirred at 120-130 ° C. for 2 hours, 5 parts of formic acid are added, and the mixture is stirred at 120-130 ° C. for a further hour. 11.0 parts of 10N hydrochloric acid are added and the mixture is stirred for a further 30 min at 120-130 ° C., cooled to 100 ° C. and filtered hot, and the residue is washed with 50% aqueous ethanol and finally dried in vacuo .

2.14 parts of the above 1: 1 chromium complex and 1.2 parts of 1- (4-phosphonophenyl) -4- (2-carboxyphenylazo) -3-methyl-5-pyrazolone are suspended in 100 parts of ethanol and 100 parts of water, whereupon the pH of the mixture is adjusted to 7.5 with ammonium hydroxide solution. 3 parts of ammonium acetate are added, and the mixture is heated to 100 ° C. for 2 hours and stirred. The mixture is filtered to remove traces of insoluble material and the filtrates are poured into acetone to precipitate the product. When the dye is applied to cellulose textile materials in accordance with DT-OS 2324809, it gives a greenish-yellow shade with excellent fastness to wet treatments.

The following table relates to further examples of dyes according to the invention which are obtained according to the procedure of Example 36 by adding the 2.14 parts of the 1: 1 chromium complex of 1- (2-hydroxy-4-nitrophenylazo) -2-phenylaminoaphthalene-6 -sulfonic acid of that example replaced by an equimolar amount of a 1: 1 chromium complex of the second column of the table and by the 1- (4-phosphonophenyl) -4- (2-carboxyphenylazo) -3-methyl-5-pyrazolone by an equimolar Amount of the azo dye listed in the third column of the table replaced. The color is given in the fourth column.

Example 44

A solution of 7.7 parts of cobalt (II) sulfate hexahydrate in 37.5 parts of deaerated water is stirred at room temperature under a nitrogen atmosphere. 44.5 parts of ammonium hydroxide solution (density 0.890) are added, followed by 14.1 parts of 1-amino-7- (2-hydroxy-5-nitro-3-sulfophenylazo) -8-naphthol-3,6-disulfonic acid over 30 minutes can be added. The mixture is stirred overnight at room temperature, isolated by pouring into ethanol and filtering and then washed with ethanol and dried in vacuo at room temperature.

A mixture of 3.7 parts of the 1: 1 cobalt complex of 1-amino-7- (2-hydroxy-5-nitro-3-sulfophenylazo) -8-naphthol-3,6-disulfonic acid prepared above 2.01 parts of 1- (4-phosphonophenyl) -4- (2-carboxyphenylazo) -3-methyl-5-pyrazolone, 100 parts of formamide and 50 parts of water are stirred at pH 8.0, heated to 60 ° C. and 1 st stirred at 60 ° C. The mixture is poured into ethanol, the precipitated product is filtered off, washed with ethanol and dried at 50.degree. If the dye is applied to cellulose textile materials by a method according to DT-OS 2324809, then it gives dull blue shades with excellent fastness to wet treatments.

The following table gives further examples of dyes according to the invention which are obtained according to Example 44 if the 1: 1 cobalt complex of 1-amino-7- (2-hydroxy-5-nitro-3-sulfophenylazo) -8- naphthol-3,6-disulfonic acid of that example by an equimolar amount of the 1: 1 cobalt complex, which is mentioned in the second column of the table, and if the 1- (4-phosphonophenyl) -4- (2-carboxyphenylazo) -3-methyl-5-pyrazolone by an equimolar amount of the azo color listed in the third column of the table Substance replaced. The color is given in the fourth column.

Claims (23)

1. Dyes, which are the chromium or cobalt-containing complexes of monoazo dyes, which are in the form of the free acid by the formula: are represented in which A 'and A "each represent identical or different aromatic radicals; B 'and B''each represent identical or different radicals of a coupling component which couples in the ortho or vicinal position to D' or D ''; Z 'and Z ", which are bonded to A' or A" in ortho positions to the azo group, are identical or different and are -O- or -COO-; D 'and D "are the same or different and represent -O-, -NH-, -N-lower alkyl or -N-phenyl; M represents Cr or Co; and at least one of the radicals A ', A ", B' and B" carries one or more phosphonic acid groups. 2. Dyes according to claim 1, characterized in that they are symmetrical. 3. Dyestuffs according to Claim 1 and 2, characterized in that D 'and D "are -NH-, -N-phenyl or -O-. 4. Dyestuffs according to Claim 3, characterized in that D 'and D "are -O-. 5. Dyestuffs according to one of claims 1 to 4, characterized in that A 'and A "represent radicals of the phenyl or naphthyl series. 6. Dyestuffs according to Claim 5, characterized in that A 'and A "are phenyl or naphthyl radicals which contain one or more of the following substituents: SO [deep] 3H, PO [deep] 3H [deep] 2, lower alkyl , Nieralkoxy, NO [deep] 2, Cl, CH [deep] 2PO [deep] 3H [deep] 2, where G is H or OCH [deep] 3, and CONHCH [deep] 2CH [deep] 2PO [deep] 3H [deep] 2. 7. Dyestuffs according to claim 6, characterized in that the lower alkyl substituent consists of CH [deep] 3 and that the lower alkoxy substituent consists of OCH [deep] 3. 8. Dyestuffs according to one of Claims 5 to 7, characterized in that A 'and A "are radicals of the phenyl series. 9. Dyestuffs according to Claim 8, characterized in that A 'and A "are 3-phosphonophenyl radicals which, as Z' or Z", have an -O- in the 6-position. 10. Dyes according to one of claims 1 to 9, characterized in that the groups -B'-D'- and -B "- D" - residues of coupling components of the phenol, naphthol, naphthylamine, acetoacetarylamide, Are 5-aminopyrazole or 5-pyrazolone series. 11. Dyestuffs according to claim 10, characterized in that the groups -B'-D'- and -B "-D" - are radicals of the 1-phenyl-5-pyrazolone series. 12. Dyestuffs according to one of claims 1 to 11, characterized in that the groups -B'-D'- and -B "- D" - are residues of coupling components selected from resorcinol, 1- and 2- Naphthols, possibly by an or several of the following groups are substituted: SO [deep] 3H, PO [deep] 3H [deep] 2, NH [deep] 2, acylamino, alkylamino and aryl and sulfoarylamino, 3-methyl- or 3-carboxy-5-pyrazolones which have a 1-phenyl radical which is optionally substituted by one or more of the following atoms or groups: SO [deep] 3H, PO [deep] 3H [deep] 2, acryloylamino, acylamino, Cl, NO [deep] 2 , Lower alkyl and lower alkoxy, or which have a 1-naphthyl radical which is substituted by SO [deep] 3H or PO [deep] 3H [deep] 2, 2-naphthylamines, 2-N-alkylnaphthylamines and 2-N-phenylnaphthylamines, the are all substituted by SO [deep] 3H and / or PO [deep] 3H [deep] 2, and N- (sulfo- or -phosphonophenyl) acetoacetamia. 13. Dyestuffs according to claim 12, characterized in that the groups -B'-D'- and -B "- D" - are radicals of coupling components which are selected from resorcinol, 1- and 2-naphthols, which if necessary are substituted by SO [deep] 3H, PO [deep] 3H [deep] 2, NH [deep] 2, acetylamino, benzoylamino, small beta-chloropropionylamino, methylamino, phenylamino and sulfophenylamino, 3-methyl- or 3-carboxy- 5-pyrazolones which have a 1-phenyl radical which is optionally substituted by one or more of the following atoms or groups: SO [deep] 3H, PO [deep] 3H [deep] 2, acrylamino, acetylamino, Cl, NO [ deep] 2, CH [deep] 3 and OCH [deep] 3 or which have a 1-naphthyl radical which is substituted by SO [deep] 3H and / or PO [deep] 3H [deep] 2, 2-naphthylamines or 2 -N-Phenylnaphthylamines, both of which are substituted by SO [deep] 3H and / or PO [deep] 3H [deep] 2, and N- (sulfo- or -phosphonophenyl) acetoacetamides. 14. Dyes according to one of claims 1 to 13, characterized in that they are at least partially in the form of an ammonium salt. 15. Dyestuffs according to one of claims 1 to 13, characterized in that they are at least partially in the form of an alkanolamine salt. 16. Dyes according to claim 15, characterized in that the alkanolamine consists of diethanolamine. 17. Process for the preparation of the dyes of the formula (1), characterized in that the 1: 1 chromium or cobalt complex of an azo compound of the formula: or an azo compound of the formula: wherein A ', A ", B', B", D ', D ", Z' and Z" have the meanings given in claim 1 and at least one of the radicals A ', A ", B' and B ″ carries one or more phosphonic acid groups, reacts with the other of the above-mentioned azo compounds. 18. The method according to claim 17 for the preparation of the dyes according to claim 2, characterized in that 2 moles of azo compound according to claim 17 are reacted with 1 mole of a chromium or cobalt salt. 19. A process for the preparation of the dyes according to claim 1 which contain an acylamino substituent, characterized in that a dye according to claim 1 which has an amino substituent is treated with an acylating agent. 20. The method according to any one of claims 17 to 19, characterized in that the dye is at least partially isolated in the form of an ammonium salt. 21. The method according to any one of claims 17 to 19, characterized in that the dye is at least partially converted into an alkanolamine salt. 22. The method according to claim 21, characterized in that the dye is at least partially converted into the diethanolamine salt. 23. Use of the dyes according to claim 1 for dyeing cellulose textile materials, the dye being applied to the textile material together with a carbodiimide and the textile material being heated to fix the dye on the material.