JPS61174266A - Asymmetric 1 : 2-chromium complex dye - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to J + symmetrical form 1:2-ChloJ of general formula (1)
, concerning complex 111 dye*l.

(In the formula, Z is nitrogen or a CH- group, and A and D are benzene-based or naphthalene-based residues having a hydroxyl group or carboxyl group at the 0-position with respect to an azo group or an azomethine group independently of each other.

B is the remainder of the coupling component when Z is nitrogen)
1 (meaning in which case the force, the sampling component has a group
means a residue of 0-hydroxyaldehyde when represents a CH- group, X is oxygen or, when 2 is nitrogen, the formula --NR
- means a group of -, where R is hydrogen or C1-0
4-alkyl group, Y is hydrogen or formula -3O2-Q or -GO-(
0). -Q, where n is O or 1 and Q is c, -C5-alkyl or phenyl, where phenyl is optionally nido.

halogen, c, -C5-alkyl or c, -C5
- optionally substituted by alkoxy, p and q are independently of each other O or l, via τ K
a○ means a cation).

The dyes according to the invention are asymmetrical 1:2-chromium complex dyes. When A and D and p and q are the same, the camping component B in one azo dye may not be the same as the camping component in the other azo dye.

In the chromium complex dyes of the l-formula (1) according to the invention, the residues A and D can further carry one or more substituents. For example, lower alkyl or alkoxy groups, halogens such as chlorine or bromine, nitro, cyano,
It may have substituents such as sulfo, carboxy, phosphono, alkylsulfonylphamide such as sulfamide or N-methylsulfamide, acylamino, phenylazo, sulfophenylazo or methoxyphenylazo. In this specification, the lower alkyl or alkoxy group generally refers to a group having 1 to 6, preferably 1 to 2 carbon atoms. In addition, paacylaminopa contains low molecular weight alkanoylamino, alkylsulfonylamino,
Refers to alkoxysulfonylamino groups as well as aroylamino, aryloxycarbonylamino and arylsulfonylamino groups.

Residues A and D are, for example, residues obtained from the amines described below.

Anthranilic acid, 4- or 5-chloroanthranilic acid, 4- or 5
-sulfoanthranilic acid, 2-amino-3-naphthoic acid, 2-amino-l-hydroxybenzene, 4-chloro- and 4,6-dichloro-2-amino-l-hydroxybenzene, 4- or 5-nitro -2-amino-l-hydroxybenzene, 4-chloro-, 4-methyl- and 4-acetylamino-6-nitro-2-amino-l-hydroxybenzene, 6-acetylamino- and 6-chloro-4- Nitro-2-amino-1-hydroxybenzene, 4-cyano-2-amino-l-hydroxybenzene, 4-sulfonami]-2-amino-1-hydroxybenzene, ■-HiIroxy2-aminebenzene-4- Sulfoanthranilide.

4-Methoxy-2-amino-1-hydroxybenzene.

4-7 Toxicity 5-chloro-2-amino-1-hydroxybenzene, 4-methyl-2-amino-1-hydroxybenzene.

4-chloro- and 4-methyl-5-nitro-2-amino-1-hydroxybenzene, 3.4.6-dolychlor-2-amino-1-hydroxybenzene, 6-acetylamino-4-chloro-2-amino -1-hydroxybenzene, 4.6-sinitro 2-amino-1-hydroxybenzene, 2-amino-1-hydroxybenzene-4- or -5
-sulfonic acid, 4-nitro-2-amino-1-hydroxybenzene-6
-sulfonic acid, 6-nitro-2-amino-1-hydroxybenzene-4
-sulfonic acid, 4-chloro-2-amino-1-hydroxybenzene-6
-sulfonic acid, l-amino-2-hydroxynatuta phosphorus-4-sulfonic acid, l-amino-2-hydroxy-6-nitronaphtha, phosphorus-4-sulfonic acid.

l-amino-2-hydroxy-6-chlornaphthalene-
4-sulfonic acid, 1-amino-2-hydroxynaphthalene-4,6-disulfonic acid, 2-amino-1-hydroxybenzene-4,6-disulfonic acid.

Instead of the hydroxyl-containing amines mentioned above, A and D also come into consideration the corresponding methoxy compounds or the corresponding compounds whose hydroxyl group is tosylated. Examples include anisidide, 4- or 5-chloranidicito, 4- or 5-nidroanidicito, anisidine 4- or -5-sulfonic acid, or tosylated S
1-Hydroxy-2-aminobenzene is considered. In this case, the methoxy or O-tosyl group is converted into an OH group before or during metallization. Compounds having such groups are used in particular when the corresponding l-hydroxy-2-amino compounds are difficult to couple with.

In preferred dyes of formula (1), A and D are residues of 1'-hydroxy-2-aminobenzene substituted or unsubstituted by halogen, nitro, sulfo or lower alkyl- or alkoxy groups. or l-amino-2-hydroxy-4-sulfonaphthalene substituted or unsubstituted in the 6-position by halogen, such as bromine or especially chlorine, nitro or sulfo.

Particularly preferred is l- in which A and D are substituted independently of each other by a nitro group and optionally also by a sulfo group.
Formula (1), which is the residue of hydroxy-2-aminephenol
) is a compound. Among the dyes of formula (1), those in which Z is nitrogen are preferred.

Residue B is preferably derived from the following group of coupling moieties: phenols coupling in the 0-position, substituted or unsubstituted by lower alkyl- or alkoxy groups, dialkylamino or acylamino; Here, acylamino means a CI-C4-furcaloylamino, CI-C4-alkylsulfonylamino, CI-C4-alkoxycarbonylamino, aroylamino or arylsulfonylamino group. Cl-C4-alkyl or alkoxy, chlorine,
Naphthol substituted or unsubstituted by amino, acyla Q mino or sulfo, where acylamino has the above meaning; 5-pyrazolone or 5-7 minopyrazole, preferably chlorine, nitro, C, -C,-alkyl or a phenyl or naphthyl group substituted or unsubstituted by alkoxy or sulfo in the 1-position and a CI -C4-alkyl or carboxy group, especially a methyl group, in the 3-position;
Naphthylamines substituted or unsubstituted by sulfo, sulfonamide or sulfonic groups:
Acetoacetamide, especially acetoacetanilide and benzoylacetanilide, which may optionally be substituted in the anilide ring by chlorine, bromine, nitro, c, -c4-alkyl- or alkoxy or sulfo groups; 6- Hydroxy-3-cyano- or 6-
Hydroxy-3-caroctamoyl-4-argyl-one, which is substituted or unsubstituted at the 1-position (:
1 C a-alkyl, for example methyl, isopropyl, β-hydroxyethyl, β-7minoethyl or γ-isopropoxypropyl, or substituted by phenyl and in the 4-position a CI -C4-alkyl group, especially methyl or hydroxyquinoline.

Examples of such coupling components are shown below.

2-naphthol, l-naphthol, ■-acetylamino-7-naphthol, l-propionylamino-7-naphthol, l-carboxymethoxyamino-7-naphthol, l-carboethoxyamino-7-naphthol, ■-carbopropoxyamino 7 naphthol, 6-acetyl-2-naphthol, 2-naphthol-3-, -4-, -5-, -6-, -7
- or -8-sulfonic acid, l-naphthol-3-, -
4- or -5-sulfonic acid, 1-naphthol-3,6- or -4,8-disulfonic acid, 2-naphthol-6,8-disulfonic acid, 4-methyl-
1-naphthol, 4-methoxy-l-naphthol.

4-7 cetyl l-naphthol, 5,8-dichloro-1-naphthol, 5-chloro-1-naphthol, 2-naphthylamine, 2-naphthylamine-1-sulfonic acid, l-Naphthylamine-4- or -5-sulfonic acid.

2-aminonaphthalene-6-sulfonic acid.

2-amino/naphthalene-5-sulfonic acid, 6-methylsulfonyl-2-aminonaphthalene, l-phenyl-3-methyl-pyrazol-5-one, 1-2enyl-5-pyrazolone-3-carboxylic acid amide, 1-(2'-, 3°- or 4'-methylphenyl)-
3-Methylpyrazol-5-one.

l-(2″-, 3″- or 4″-sulfophenyl)-
3-Methylpyrazol-5-one, 1-(2°-chloro-5′-sulfophenyl)-3-methyl-pyrazol-5-one, 1-(2°- or 4″
-methoxyphenyl)-3-methylpyrazol-5-one, 1-(2'-, 3'- or 4'-chlorophenyl)-3-methylpyrazol-5-one, 1-(2", 3'- or 4゛-nitrophenyl)-3
-Methylpyrazol-5-one, 1-(2°, 5°- or 3°, 4'-dichlorophenyl)-3-methylpyrazol-5-one, 1-(2'5'-dichloro-4 ′-sulfophenyl)-
3-methylpyrazol-5-one, 1-(2'-, 3'- or 4'-sulfophenyl)-
3-Methyl-5-aminopyrazole, 1-phenyl-3-methyl-5-aminopyrazole.

1-(2''-chloro-5'-sulfophenyl)-3-methyl-5-aminopyrazole, acetoacetanilide, acetoacetanilide-4-sulfonic acid, acetoaceto-〇-anisidide, acetoaceto-〇-toluiside, acetoaceto-〇 -chloranilide, acetoace)-m-xylidide, tetralol, 4-methylphenol, 3-dialkylaminophenol, especially 3-dimethylamino- and 3-diethylaminophenol, 4-butylphenol, preferably 4-butylphenol. 4-amylphenol, especially 4-t-amylphenol, 2-impropyl-4-methylphenol, 2- or 3-7cetylamino-4-methylphenol, 2-methoxycarbonylamino-4-methyl Phenol, 2-ethoxycarbonylamino-4-methylphenol and 3,4-dimethylphenol, l-methyl-3-
Cyano-4-ethyl-6-hydroxypyridone, l-methyl-3-cyano-4-methyl-6-hydroxypyridone, l-phenyl-3-carhemoyl-4-methyl-6-hydroxypyridone, 1-x ThiAy-4-hydroxy-2-quinolone, 2,4-dihydroxy-quinoline, 3-methylpyrazol-5-one.

Preferably, coupling component B is l- or 2-naphthol substituted or unsubstituted by amino and/or sulfo, l- or 2-naphthylamine substituted or unsubstituted by sulfo, p -Alkyl-(C1-C6)-phenol, 1-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide, in which case the phenyl group in the last two compounds is c, -C4-alkyl , C
, -C4-flukoxy, chlorine, nitro or sulfo.

Coupling component B is especially unsubstituted or amino and/or
or 1- or 2-naphthol substituted by sulfo and especially 2-amino-8-hydroxynaphthalene-6-sulfonic acid.

If Z is a CH- group, B is the residue of an 0-hydroxyaldehyde, in particular 0-hydroxybenzaldehyde optionally substituted by lower alkyl, halogen, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo. or 0-hydroxynaphthaldehyde.

Examples of suitable aldehydes are shown below.

2-Hydroxy-1-naphthaldehyde, ■-Hydroxy-2-naphthaldehyde, 2-hydroxy-benzaldehyde, 3- and 5-methyl-2-hydroxy-benzaldehyde, 3.5-dimethyl-2-hydroxybenzaldehyde, 5 -Butyl-2-hydroxybenzaldehyde
, 5-chloro- or 5-bromo-2-hydroxy-benzaldehyde, 3-chloro-2-hydroxy-benzaldehyde
, 3.5-dichloro-2-hydroxy-benzaldehyde, 5-sulfo-2-hydroxybenzaldehyde, 3-methyl-5-chloro-2-hydroxy-benzaldehyde, 5-(phenylazo)-2-hydroxy-benzaldehyde, 5 -(2′-, 3°- or 4′-sulfophenylazo)-2-hydroxy-benzaldehyde, 5-(6°-sulfonaphthyl-1°-azo)-2-hydroxy-benzaldehyde, 5-(4” -sulfo-4'
-phenylazo)-phenylazo-2-hydroxybenzaldehyde.

KaO means a cation, for example an alkali ion such as lithium, potassium, particularly preferably sodium. Furthermore, KaO may be an ammonium ion or an ammonium salt of an organic amine.

Suitable groups Y in the dyes of formula (1) are, for example:

Hydrogen, acetyl, propionyl, butyryl, imbutyryl, valeryl, invaleryl, piaheroyl, capronyl, methoxycarbonyl, ethoxycarbonylnyl, n-pentoxycarbonyl, methylsulfonyl,
Ethylsulfonyl, butylsulfonyl, phenylsulfonyl, benzoyl or carbonyl. In addition,
The phenyl group in the last three compounds is, for example,
Nitro, halogen such as base or especially chlorine, CI
-, C4-alkyl or -alkoxy.

Preferably R means hydrogen, acetyl, methoxycarbonyl or methylphenylsulfonyl and particularly preferably hydrogen, methoxycarbonyl or acetyl.

Particularly preferred dyes according to the invention are of the formula % where Ao and D' are independently of each other unsubstituted or substituted by halogen, nitro, sulfo, lower alkyl or alkoxy. the residue of 2-aminobenzene, or 1-amino- unsubstituted or substituted in the 6-position by nitro or sulfo;
the residue of 2-hydroxy-4-sulfonaphthalene, Bo is unsubstituted or substituted by amino and/or sulfo l- or 2-naphthol, unsubstituted or substituted by sulfo 1- or 2-Naphthylamine, p-alkyl (C+-C6-)-
phenol, l-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide, especially the last two
The phenyl group in two compounds is sometimes c, -c4
-alkyl, optionally substituted by C,-C,-alkoxy, chlorine, nitro or sulfo, Yo means hydrogen, methoxycarbonyl or acetyl and Ka(E) means a cation.

The dyes of formula (1) according to the invention can be produced by methods known per se. For example, it can be manufactured by the following method. That is, a 1:l-chromium complex salt of the acy dye H of the formula (3) is prepared, and this is then mixed with the dye of the following formula (4), or the amine of the formula (5) and the aldehyde HO-B of the formula (6). -CHO(8) to form the l:2-chromium complex salt, or alternatively, the l:l-chromium complex salt of the dye of formula (4) is prepared and this is combined with the dye of formula (3). It causes a reaction. Naoko iron, A, B, D, Z, X, Y, P, t-
3 and q have the meanings defined in formula (1).

The novel metal complex dye obtained by the above method is in its salt form,
It is particularly advantageous to isolate it in the form of alkali salts, for example lithium salts, potassium salts, especially sodium salts, or also as ammonium salts. The dyes are suitable for dyeing various natural or synthetic nitrogen-containing materials, such as polyamides, polyurethanes, wool and especially leather.

For dyeing wool or synthetic polyamides, dyes of the formula (1) with 1 to 2 sulfo groups are particularly suitable. The dyeings obtained are level-dyed and have excellent colorfastness. For example, lightfastness, washfastness,
Excellent water fastness, hot water fastness, perspiration fastness, rubbing fastness, shrinkage fastness, decatizing fastness and carbonization fastness.

For laser dyeing it is preferred to use dyes having 2 to 5 sulfo groups. This dye has vivid colors and excellent covering power. It also has high dyeability and good stability against acids and alkalis. The dyestuffs give dyeings with good diffusion fastness, light fastness, acid and alkali fastness.

It is particularly recommended that the product exhibit good build-up properties for various types of leather, ie leather tanned only with chromium salts and leather retanned with vegetable or synthetic tanning agents. This dye produces shades ranging from olive, brown, blue, or gray to black.

Examples of the present invention are described below. Parts and percentages in the examples are by weight unless otherwise specified.

Example 1 4-nitro-2-amino-1-hydroxybenzene-6
- 60 g of l:1-chromium complex salt containing 48.4 parts of dye from diazotide of sulfonic acid and 2-amino-8-hydroxynaphthalene-6=sulfonic acid and 5.2 parts of chromium.
0 parts of water and added 44.6 parts of a monoazo dye from the diazotide of 4-nitro-2-amino-1-hydroxy-benzene and 2-acetylamino-6-hydroxynaphthalene-8-sulfonic acid. do. The reaction mixture was then heated to 80-85°C and adjusted to pH with sodium hydroxide.
Adjust to 7. This temperature and constant pH are maintained until starting material is no longer detected. After the reaction is complete,
The dye is isolated by evaporation. A dark powder is thus obtained which, when dissolved in water, develops a gray color and dyes the leather in a very light-fast gray color. λwax = 574
nm.

4-nitro-2-amino-1-hydroxybenzene-6
- 60 g of l:l-chromium complex salt containing 48.4 parts of dye from sulfonic acid diasodide 2-amino-8-hydroxynaphthalene-6-sulfonic acid and 5.2 parts of chromium.
0 parts of water and the diazotide of 4-nitro-2-amino-1-hydroxy-benzene-6-sulfonic acid.
52.6 parts of a monoazo dye from -acetylamino-6-hydroxynaphthalene-8-sulfonic acid are added.

The reaction mixture was then heated to 80-85°C and 5N
Adjust the pH to 7-7.5 with sodium hydroxide. This temperature and constant pH are maintained until the starting material disappears. After the addition reaction is complete, the dye is precipitated by adding potassium chloride, filtered and dried. After drying, a dark powder is obtained which, when dissolved in water, develops a gray color and dyes the leather in a very strong gray color.

Example 3 In 600 parts of water, chromium atom: 1 molecule of dye type,
52 parts of chromium, a diazotide of 6-nitro-1-amino-2-hydroxynaphthalene-4-sulfonic acid, and 2-
48.8 parts of a chromium complex containing 43.9 parts of a monoiso dye from hydroquinaphthalene are suspended.

To this, diazotized product of 6-nitro-4-methyl-2-amino-1-hydroxybenzene and 2-acetylamino-6
- 43.9 parts of monoazo dye from hydroxynaphthalene-8-sulfonic acid are added. This reaction mixture was then mixed with 8
Heat to 0-85°C and adjust pH to 7-7.5 with 5N hydroxide and thorium. This temperature and constant pH are maintained until starting material is no longer detected. After the addition reaction is complete, the dye is precipitated by addition of potassium chloride, filtered and dried. After drying, a dark black powder is obtained which, when dissolved in water, develops a blue color and dyes the leather in a blue color with good fastness properties.

Input wax = 579 nm.

Example 4 4-nitro-2-amino-1-hydroxybenzene-6
- a 1:1-chromium complex salt containing 48.4 parts of a dye from a diazotide of sulfonic acid and 2-amino-6-hydroxynaphthalene-8-sulfonic acid and 5.2 parts of chromium;
4-nitro-2-amino-1
15.4 parts of hydroxybenzene and 30.6 parts of a monoazo dye made from a diazotide of l-aminebenzene-2-sulfonic acid and salicylic acid are added.

The reaction mixture is then heated to 80-85°C and adjusted to 9)+7 with sodium hydroxide. This temperature and −
- Maintain constant pH until starting material is no longer detected. After the reaction is completed, the dye is isolated by evaporation and concentration. A dark powder is thus obtained which dissolves in the wood and develops an olive color and dyes the leather in a very strong olive color.

Example 5 4-nitro-2-amino-1-hydroxybenzene-6
- Monoazo dye from sulfonic acid diazotide and 2-amino-8-hydroxynaphthalene-6-sulfonic acid 4
8.4 parts and a diazotide of 4-nitro-2-amino-1-hydroxybenzene and 2-acetylamino-6-
44.6 parts of monoazo dye from hydroxynaphthalene-8-sulfonic acid are stirred in 400 parts of water and 300 parts by volume of a solution of sodium chromium salicylate (equivalent to 6.25 parts of chromium) are added. Boil the raw material until the starting material disappears. After completion of the chromium chloride reaction, potassium chloride L. is added to precipitate and cure the chromium-containing dye mixture. After drying, a dark powder is obtained which, when dissolved in water, develops a gray color and dyes the leather in a solid gray color.

The operations were carried out analogously to Examples 1-5, but using the aso-dyes or azomethine dyes shown in the following table, which produced leather with the colors mentioned in the last column of the table and with excellent fastness properties. A l:2-chromium complex salt dye is obtained.

Leather dyeing example: 100 parts of suede leather for clothing was placed in a solution of 1000 parts by volume of water and 2 parts of 24% ammonia, concentrated at 50°C for 2 hours, and then mixed with 3 parts of water + ooo' and 2 parts of 24% ammonia. and 1.5 parts of the dye according to Example 1. Dyeing is carried out for 1 hour at a temperature of 60'C. After this water 4
A solution consisting of 0 parts by volume and 4 parts of 85% formic acid is added and dyed for a further 30 minutes. The leather is then thoroughly washed and optionally further treated with 2 parts of dicyandiamide-formaldehyde condensation product for 30 minutes at 50°C.
Process for minutes.

Other suede leathers and glove leathers can also be dyed in a similar manner.

The dyeings thus obtained have excellent dyefastness and good covering power.

Wool Dyeing Example 100 parts of wool are introduced into a dyebath containing 2 parts of the dye according to Example 1, 3 parts of ammonium sulfate and 2 parts of leveling agent in 4000 parts of water at a bath temperature of 50.degree. The bath is heated to temperature for 45 minutes and held at boiling temperature for 45 minutes. After this, the dyed product is removed, washed well with cold water and dried. This results in a dark gray dyed yarn with excellent fastness.

Claims (1)

[Claims] 1. Formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, Z is nitrogen or a CH- group, and A and D each independently represent an azo group or an azomethine group. a benzene or naphthalene residue having a hydroxyl or carboxyl group in the o-position, B means the residue of a coupling component when Z is nitrogen, in which case the coupling component is an azo group; or, when Z means a CH- group, means the residue of an o-hydroxyaldehyde; Furthermore, the formula -NR
- means a group of -, where R means hydrogen or a C_1-C_4-alkyl group, Y is hydrogen or a group of the formula -SO_2-Q or -CO-(O)
_n-Q, where n is 0 or 1 and Q is C_1-C_5-alkyl or phenyl, where phenyl is optionally nitro, halogen, C_1-C_5-alkyl or C_1-C_5- optionally substituted by alkoxy, p and q are independently of each other 0 or 1, and Ka
^■ means cation) asymmetric 1:2-chromium complex dye. 2. 1-hydroxy-2, in which A and D are independently of each other unsubstituted or optionally substituted by halogen, nitro, sulfo, lower alkyl or alkoxy
- the residue of aminobenzene or 1-, unsubstituted or substituted in the 6-position by nitro or sulfo;
A dye according to claim 1, meaning the residue of amino-2-hydroxy-4-sulfonaphthalene. 3. A dye according to claim 1 or 2, in which A and D independently of one another signify 1-hydroxy-2-aminophenol substituted by a nitro group and optionally by a sulfo group. 4. The dye according to any one of claims 1 to 3, wherein Z means nitrogen. 5, 1- or 2- where Z is nitrogen and B is unsubstituted or substituted by amino and/or sulfo
naphthol, 1- or 2-naphthylamine, unsubstituted or substituted by sulfo, p-alkyl (
C_1-C_6-)-phenol, 1-phenyl-3-
methyl-5-pyrazolone or acetoacetanilide, with the exception that the phenyl group in the last two compounds is optionally C_1-C_4-alkyl, C_1-C_
A dye according to any one of claims 1 to 4, optionally substituted by 4-alkoxy, chlorine, nitro or sulfo. 6. Claim 1 in which Z denotes a -CH- group and B denotes the residue of o-hydroxybenzaldehyde optionally substituted by phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo. The dye according to any one of items 3 to 3. 7. A dye according to any one of claims 1 to 4, in which B stands for 1- or 2-naphthol, which is unsubstituted or substituted by amino and/or sulfo. 8, B is 2-amino-8-hydroxynaphthalene-6-
A dye according to claim 7, meaning a sulfonic acid. 9. The dye according to any one of claims 1 to 8, wherein Y means hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl. 10. The dye according to claim 9, wherein Y is hydrogen or acetyl. 11. Formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, A' and D' are independently unsubstituted or substituted with halogen, nitro, sulfo, lower alkyl or alkoxy. the residue of 1-hydroxy-2-aminobenzene, or 1-amino-2- unsubstituted or substituted in the 6-position by nitro or sulfo;
the residue of hydroxy-4-sulfonaphthalene, B' is 1- or 2-naphthol, unsubstituted or substituted by amino and/or sulfo, 1- or 2-naphthol, unsubstituted or substituted by sulfo; -Naphthylamine, p-alkyl (C_1-C_6-
)-phenol, 1-phenyl-3-methyl-5-pyrazolone or acetoacetanilide, where the phenyl group in the last two compounds is optionally C_1
dyes optionally substituted by -C_4-alkyl, C_1-C_4-alkoxy, chlorine, nitro or sulfo, Y' is hydrogen, methoxycarbonyl or acetyl and Ka^■ means a cation). 12. In the method for producing the dye of formula (1), a 1:1-chromium complex salt of formula (3) is produced, and then the following formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) Dye or formula (5) amine ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (5) and aldehyde HO-B- of formula (6) CHO(6) to form a 1:2-chromium complex; alternatively, a 1:1-chromium complex of the dye of formula (4) is prepared and this is reacted with a dye of formula (3). A method characterized by reacting (
Note that here, A, B, D, Z, X, Y, p and q have the meanings defined in formula (1)). 13. A dye mixture containing at least one dye of formula (1) according to claim 1. 14. The use of the dyestuffs of formula (1) for the dyeing of wool, polyamide and especially leather or fur.