DE3808617A1 - Azo dyes, their preparation and use - Google Patents

Abstract

The azo dyes containing at least one water-solubilising group, of the formula <IMAGE> in which K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series, R1 is a group of the formula -CN, -CON(R2)R3, -COR4, -COOR5 or -SO2R6, the ring A is a substituted or unsubstituted benzene ring, R2 and R3 independently of one another are hydrogen or a substituted or unsubstituted C1-C10-alkyl, C5-C7-cycloalkyl, phenyl or naphthyl radical and R4, R5 and R6 are a substituted or unsubstituted C1-C10-alkyl, C5-C7-cycloalkyl, phenyl or naphthyl radical, give dyeings on fibre materials containing nitrogen groups or hydroxyl groups that have good fastness properties.

Description

The present invention relates to new azo dyes, processes for their manufacture and use of these dyes for dyeing and Printing of fiber materials, especially textile fiber materials.

The present invention relates to azo dyes which contain at least one water-solubilizing group, the formula

where K is the rest of a coupling component of the benzene or naphthalene Series or the heterocyclic series, R₁ is a group of Formula -CN, -CON (R₂) R₃, -COR₄, -COOR₅ or -SO₂R₆ is the benzene ring A is optionally substituted, R₂ and R₃ independently one another is hydrogen or an optionally substituted one C₁-C₁₀-alkyl, C₅-C₇-cycloalkyl, phenyl or naphthyl radical, and R₄, R₅ and R₆ are an optionally substituted C₁-C₁₀ alkyl, C₅-C₇ cycloalkyl, phenyl or naphthyl radical mean.

The remainder K can be the usual substituents for azo dyes included, e.g. B. alkyl groups with 1 to 8, preferably 1 to 4, Carbon atoms, such as B. methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, sec-butyl, tert-butyl, hexyl, octyl, alkoxy groups with 1 to 8 carbon atoms, in particular 1 to 4 carbon atoms,  such as B. methoxy, ethoxy, propoxy, isopropoxy, butoxy, Acylamino groups such as alkanoylamino groups with 2 to 8 carbon atoms and alkoxycarbonylamino groups having 2 to 8 carbon atoms such as B. acetylamino, propionylamino, methoxycarbonylamino, ethoxy carbonylamino, benzoylamino, amino, mono- or dialkylamino with 1 to 8 carbon atoms in the alkyl radical, phenylamino, alkoxycarbonyl with 1 to 8 carbon atoms in the alkoxy radical, nitro, cyano, trifluoromethyl, Halogen, such as fluorine, bromine or, in particular, chlorine, sulfamoyl, on the nitrogen atom once or twice by C₁-C₄-alkyl, C₅-C₇-cycloalkyl or phenyl substituted sulfamoyl, carbamoyl, ureido, Hydroxy, C₁-C₈ alkylsulfonyl, phenylsulfonyl, carboxy, sulfomethyl, Sulfo, sulfato, thiosulfato, fiber-reactive residues and arylazo groups such as B. the phenylazo and naphthylazo group.

The benzene ring A can e.g. B. be substituted with alkyl groups 1 to 8, preferably 1 to 4, carbon atoms, such as. B. methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, Hexyl, octyl, alkoxy groups with 1 to 8 carbon atoms, in particular 1 to 4 carbon atoms, such as. B. methoxy, ethoxy, propoxy, Isopropoxy, butoxy, acylamino groups such as alkanoyl or alkoxy carbonylamino groups with 2 to 8 carbon atoms such as. B. acetylamino, Propionylamino, methoxycarbonylamino, ethoxycarbonylamino, Benzoylamino, amino, mono- or dialkylamino with 1 to 8 carbon atoms in the alkyl radical, phenylamino, alkoxycarbonyl with 1 to 8 Carbon atoms in the alkoxy radical, nitro, cyan, trifluoromethyl, Halogen, such as fluorine, bromine or especially chlorine, sulfamoyl, am Nitrogen atom once or twice by C₁-C₄-alkyl, C₅-C₇-cycloalkyl or phenyl substituted sulfamoyl, carbamoyl, ureido, hydroxy, C₁-C₈ alkylsulfonyl, phenylsulfonyl, carboxy, sulfomethyl, sulfo, Sulfato, thiosulfato, fiber-reactive residues and arylazo groups such as e.g. B. the phenylazo and naphthylazo group.

As C₁-C₁₀ alkyl for R₂, R₃, R₄, R₅ and R₆ in formula (1) z. B. into consideration: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl or decyl, and the corresponding radicals, the z. B. are substituted by hydroxy, alkoxy having 1 to 4 carbon atoms, phenyl, sulfo, sulfato, thiosulfato, cyan or halogen, for. B. β- hydroxyethyl, β- methoxyethyl, β- chloroethyl, benzyl, β- sulfatoethyl, γ- methoxypropyl.

As C₁-C₁₀ alkyl for R₂ and R₃ is also suitable: a group of the formula - (CH₂-CH₂-O) _x -CH₂-CH₂-Y, -C (CH₂) _y -O-CO-Z or -CH₂ -CH₂-O- (CH₂) _y -Y where Y is cyan, halogen, sulfo, sulfato, C₁-C₄ alkoxycarbonyl or phenoxycarbonyl, x is a number from 2 to 8 and Z is C₁-C₄ alkyl or phenyl and y is a Number from 1 to 8 means.

As C₅-C₇-cycloalkyl for R₂, R₃, R₄, R₅ and R₆ in formula (1) e.g. B. into consideration: cyclopentyl, cyclohexyl and cycloheptyl, and the corresponding residues, the z. B. by halogen, such as fluorine, chlorine or Bromine, C₁-C₄-alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, sec-butyl and tert-butyl, C₁-C₄ alkoxy, such as methoxy, Ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy are substituted. The methylcyclohexyl radical is an example called.

As phenyl or naphthyl comes in for R₂, R₃, R₄, R₅ and R₆ Formula (1) is an unsubstituted or by C₁-C₄-alkyl, such as Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, C₁-C₄ alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, Butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as Fluorine, chlorine and bromine, C₂-C₄-alkanoylamino, such as acetylamino and Propionylamino, benzoylamino and sulfo substituted phenyl or Naphthyl.

Preference is given to azo dyes of the formula (1), in which either

• - The diazo component at least one water-solubilizing group contains; or
• - The coupling component at least one water-solubilizing Group contains; or
• - The diazo and the coupling component at least one each contain water-solubilizing group.

In particular, the sulfonic acid, Sulfato and thiosulfato groups into consideration. Preferably contain the azo dyes of the formula (1) 1 to 3 groups of Formulas -SO₃H, -OSO₃H or -SSO₃H, either of the diazo component and / or are bound to the coupling component.

Also preferred are azo dyes of the formula (1), in which K is the rest an amino or alkoxybenzene, amino or alkoxynaphthalene, Phenols, naphthols, aminonaphthols, 5-pyrazolones, 5-aminopyrazoles, Pyridons, pyrimidins, indoles, acetoacetic amides, naphthimidazoles, Dihydroquinoline, tetrahydroquinoline, 2,3-dihydro-1,4-benzoxazine or pyrazolo [2,3-a] pyrimidine, the said radicals may be further substituted.

The azo dyes of the formula are particularly preferred

wherein X is a group of the formula -SO₃H or -OSO₃H, and A, R₁ and K have the meanings given under formula (1), and the Azo dyes of the formula

wherein X is -SO₃H, m is the number 1 or 2, and A, R₁ and K have the meanings given under formula (1).

The azo dyes of the formulas (2) and (3) contain as water-soluble making group preferably only the group specified for X. The rest K in formulas (2) and (3) corresponds in particular to that preferred radical K of formula (1).

The azo dyes of the formula are very particularly preferred

which contain only a single -SO₃H- or -OSO₃H group, wherein R₇ Is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or sulfo, and R₁ and K have the meanings given under formula (1); and the azo dyes of the formula

which contain only a single -SO₃H- or -OSO₃H group, wherein R₈ Is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or sulfo, and R₁ and K have the meanings given under formula (1).

The very particularly preferred dyes of the formulas (4) and (5) preferably contain the radical K as the radical of an amino or Alkoxybenzene, amino or alkoxynaphthalene, phenol, naphthol, Aminonaphthol, 5-pyrazolone, 5-aminopyrazole, pyridone, pyrimidine, Indoles, acetoacetic acid amides, naphthimidazole, tetrahydroquinolines, 2,3-dihydro-1,4-benzoxazine or pyrazolo [2,3-a] pyridine, where the radicals mentioned may be further substituted z. B. by the above for the radical K indicated substituents. In formulas (2) to (5) the radical K is in particular an N-C₁-C₄-alkylamino or N, N-di- C₁-C₄-alkylamino-benzene radical in the benzene ring by C₁-C₄-alkoxy, especially methoxy, C₁-C₄-alkyl, especially methyl, halogen, especially chlorine, and C₂-C₅-alkanoylamino, especially acetyl  amino, may be substituted, and wherein the N-alkyl radicals are independent from each other by cyano, hydroxy, sulfo, sulfato, thiosulfate or Phenyl may be substituted; a C₁-C₂ alkoxybenzene, the can be substituted by C₁-C₄-alkyl, in particular methyl; a Methoxynaphthalene residue; a phenol radical which is C₁-C₄-alkyl, in particular methyl, may be substituted; an amino naphthalene residue, which can be substituted by sulfo; an amino naphthol residue, which is substituted by sulfo in the naphthalene nucleus, and in which the Amino group by C₁-C₄-alkyl, especially methyl, and / or one fiber-reactive radical can be substituted; a hydroxynaphthalene residue, which can be substituted by sulfo and halogen; a 1-phenyl-3-methyl-5-pyrazolone residue, which in the phenyl residue by C₁-C₄- Alkyl, halogen and sulfo may be substituted; a 1-phenyl-3- methyl-5-aminopyrazole, which in the phenyl radical by C₁-C₄-alkyl, C₁-C₄ alkoxy, halogen and sulfo may be substituted; an indole residue, in the 1-position by C₁-C₁₀-alkyl and in the 2-position C₁-C₆ alkyl or phenyl or sulfophenyl and in 5-, 6- or 7-position can be substituted by sulfo; a 1-chlorophenylamino 2-pentyl-naphthimidazole residue, which in the naphthalene nucleus Hydroxy and sulfo may be substituted; a 1-C₁-C₄-alkyl-4-C₁-C₄- alkyl-3-cyano or -3-carbonamido-6-hydroxypyridone-2-residue; a N-C₁-C₄-alkyl-1,2,3,4-tetrahydroquinoline residue, which is represented by C₁-C₄-alkyl, C₁-C₄ alkoxy, halogen, sulfato or sulfo may be substituted; or a 2,4,6-triaminopyrimidine residue; or a 2,3-dihydro-1,4- benzoxazinrest in the 2- and / or 3-position by C₁-C₄-alkyl or C₂-C₅ alkanoylamino may be substituted on the nitrogen atom by a C₁-C₄-alkyl, which by hydroxy, halogen, sulfamoyl, Carbamoyl, cyano, C₂-C₅-alkanoylamino, C₁-C₄-alkoxycarbonyl, or C₂-C₅ alkanoylamino is substituted and in the benzene nucleus by C₁-C₄ alkyl or C₂-C₅ alkanoylamino may be substituted.

In the very particularly preferred dyes of the formulas (4) and (5), R₁ means in particular the -CON (C₁-C₄-alkyl) ₂, -CON (H) (CH₂) _n -OSO₃H, -COOC₁-C₄-alkyl or - SO₂-C₁-C₄-alkyl radical, where n = 1 to 4.

Important dyes of the formula (4) and (5) are those in which R₁ and X are a group of the formula -CON (H) (CH₂) _n -OSO₃H, in particular a group of the formula -CON (H) CH₂CH₂-OSO₃H, and K is an N-C₁-C₄- alkylamino or N, N-di-C₁-C₄-alkylamino-benzene radical which is in the benzene ring by C₁-C₄-alkoxy, in particular methoxy, C₁-C₄-alkyl, in particular methyl, halogen, in particular chlorine, and C₂-C₅-alkanoylamino, in particular acetylamino, and in which the N-alkyl radicals can be substituted independently of one another by cyano, hydroxy or phenyl; a C₁-C₂ alkoxybenzene radical, which can be substituted by C₁-C₄-alkyl, in particular methyl; a methoxynaphthalene residue; a phenol radical which can be substituted by C₁-C₄-alkyl, in particular methyl; an amino naphthalene residue; an amino naphthol radical, in which the amino group can be substituted by C₁-C₄ alkyl, in particular methyl, and / or a fiber-reactive radical; a hydroxynaphthalene residue which may be substituted by halogen; a 1-phenyl-3-methyl-5-pyrazolone radical which can be substituted in the phenyl radical by C₁-C₄-alkyl and halogen; a 1-phenyl-3-methyl-5-aminopyrazole, which can be substituted in the phenyl radical by C₁-C₄-alkyl, C₁-C₄-alkoxy and halogen; an indole radical which can be substituted in the 1-position by C₁-C₁₀-alkyl and in the 2-position by C₁-C₆-alkyl or phenyl; a 1-chloro phenylamino-2-pentyl-naphthimidazole residue which can be substituted in the naphthalene nucleus by hydroxy; a 1-C₁-C₄-alkyl-4-C₁-C₄-alkyl-3-cyano or -3-carbonamido-6-hydroxypyridon-2-residue; an N-C₁-C₄ alkyl, 1,2,3,4-tetrahydroquinoline residue which can be substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy and halogen; or a 2,4,6-tri aminopyrimidine residue; or a 2,3-dihydro-1,4-benzoxazine residue which can be substituted in the 2- and / or 3-position by C₁-C₄-alkyl or C₂-C₅-alkanoylamino; which is substituted on the nitrogen atom by a C₁-C₄- alkyl, which is substituted by hydroxy, halogen, sulfamoyl, carbamoyl, cyano, C₁-C₄-alkoxycarbonyl or C₂-C₅-alkanoylamino and which is substituted in the benzene nucleus by C₁-C₄-alkyl or C₂- C₅-Alkanoylamino may be substituted.

Other important dyes of the formulas (4) and (5) are those where R₇ or R₈ is sulfo and K is the above for the important dyes of the formula (4) or (5) has the meaning given.

Other important dyes of the formulas (4) and (5) are those wherein R₇ or R₈ is hydrogen, C₁-C₄ alkyl, C₁-C₄ alkoxy or halogen and K is the rest of a coupling component, which is at least contains a water-solubilizing group, especially a through 1 to 2 sulfo or sulfato groups of substituted N-C₁-C₄-alkylamino or N, N-di-C₁-C₄-alkylamino-benzene radical in the benzene ring by C₁-C₄-alkoxy, especially methoxy, C₁-C₄-alkyl, in particular Methyl, halogen, especially chlorine, and C₂-C₅ alkanoylamino, in particular acetylamino can be substituted, and wherein the N-alkyl radicals independently of one another by cyano, hydroxy or phenyl can be substituted; an amino naphthalene residue; an amino naphthol residue, wherein the amino group by C₁-C₄ alkyl, in particular Methyl, and / or a fiber-reactive radical may be substituted; a hydroxynaphthalene residue which may be substituted by halogen; a 1-phenyl-3-methyl-5-pyrazolone residue, which in the phenyl residue C₁-C₄ alkyl and halogen may be substituted; a 1-phenyl-3- methyl-5-aminopyrazole, which in the phenyl radical by C₁-C₄-alkyl, C₁-C₄ alkoxy and halogen may be substituted; an indole residue, the in the 1-position by C₁-C₁₀-alkyl and in the 2-position by C₁-C₆-alkyl or may be substituted phenyl; a 1-chlorophenylamino-2-pentyl naphthimidazole residue, which is substituted in the naphthalene nucleus by hydroxy can be; or an N-C₁-C₄-alkyl-1,2,3,4-tetrahydroquinoline residue is substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen can be; and R₁ -CON (C₁-C₄-alkyl) ₂, -CON (H) C₁-C₄-alkyl, -COOC₁-C₄-alkyl or -SO₃-C₁-C₄-alkyl.

A particularly important dye corresponds to the formula (4), in which R₁ -COOCH₃, R₇ is hydrogen and K is N- β- sulfatoethyl-2,2,4,7-tetra methyltetrahydroquinoline or 2-amino-8-hydroxynaphthalene-6-sulfonic acid. Rest is.

Among a fiber-reactive residue in particular as possible substituents the coupling component K, such acyl residues understood that one or more reactive groups can be split off Have substituents in the molecule which, for. B. with cellulose materials in the presence of acid-binding agents and, if appropriate under the influence of heat with the hydroxyl groups of cellulose, or with synthetic or natural polyamide fibers, such as. B. Wool, with the NH₂ groups of these fibers to form covalent Bonds are able to react. Such fiber reactive groups are known from the literature in large numbers, for. B. EP-A-01 42 104.

It is preferably a fiber-reactive residue of aliphatic or heterocyclic series, directly or via a Bridge member is bound to the azo dye.

The fiber-reactive radical is preferably one optionally monoalkylated amino group such as e.g. B. -NH-, -N (CH₃) -, -N (C₂H₅) - or -N (C₃H₇) or via an amino group-containing bridge member to the Azo dye bound.

As a fiber-reactive radical is particularly preferably an acryloyl, mono-, di- or Trihalogenacryloyl- or methacryloyl, mono- or Dihalogenpropionyl-, Phenylsulfonylpropionyl-, Vinylsulfonylpropionyl, β -Chloräthylsulfonylpropionyl-, Methylsulfonylpropionyl-, β -Sulfatoäthylsulfonylrest or a radical of mono- , Di- or trihalopyrimidyl or mono- or dihalotriazinyl series.

The 2,4-difluoro-5-chloropyrimidin-6-yl radical and the α, β- dibromopropionyl radical and the α- bromacryloyl radical are very particularly preferred as the fiber-reactive radical.

The preferred fiber-reactive radicals are especially one Bridge member of the formula

bound to the azo dye, where R is hydrogen or C₁-C₄ alkyl means. The azo dyes can contain up to four fiber-reactive Leftovers included. One or two fiber-reactive are preferred Leftovers.

The invention further relates to a method for producing the Azo dyes of the formula (1), which is characterized in that that you have an amine of the formula

diazotized and on a coupling component of the formula

HK (7)

couples, wherein A, R₁ and K in the formulas (6) and (7) under Formula (1) have the meanings given.

The diazotization of the diazo component of the formula (6) takes place in the Usually by the action of nitrous acid in aqueous mineral acid Solution at low temperature, the coupling on the coupling component of the formula (7) for acidic, neutral to alkaline pH values.

Optionally, a free amino group in the radical K after the Coupling with an acylating or alkylating agent in one Acylamino or alkylamino group can be converted, and also a hydroxy group by acylation or alkylation into an acyloxy or alkoxy group can be converted.  

Furthermore, a free hydroxyl group in the radical K and in particular in the diazo component in the radical R₂ or R₃, preferably in the radical R₂ into a water solubilizing group such as B. by sulfation in a sulfato group.

The azo dyes of the formula (1) which have a fiber-reactive radical contain are prepared by using a diazo component of Formula (6), a coupling component of formula (7), the one contain acylatable amino or hydroxy group, and an acylating agent, that contains a fiber reactive residue, in any Order implemented with each other.

Preferred coupling components are those which are acylatable Contain group, those of the benzene or naphthalene series used.

Preferred embodiments of the method according to the invention are characterized in that either

• - A diazo component of formula (6) used, the at least one contains water solubilizing group; or
• - A coupling component of formula (7) used, the at least contains a water solubilizing group; or
• - A diazo component of formula (6) and a coupling component of formula (7) used, each having at least one water-solubilizing Group included.

Another preferred embodiment of the invention The process is characterized in that a diazo component of formula (6) used, which in a water-solubilizing Group contains convertible group, such as. B. the hydroxy group.

A particularly preferred embodiment of the invention The process is characterized in that an amine of the formula

wherein X is a group of the formula -SO₃H or -OSO₃H, and A and R₁ have the meanings given under formula (2), diazotized and couples to a coupling component of formula (7). In particular only the amine of formula (8) contains a water-solubilizing Group.

Another particularly preferred embodiment of the invention The method is characterized in that one of the amine Formula (6) diazotized and on a coupling component of the formula

HK- (X) _m (9)

couples, wherein K has the meaning given under formula (1), X is -SO₃H and m is the number 1 or 2. In particular, only the coupling component of formula (9) contains a water-solubilizing group.

Two very particularly preferred embodiments of the invention Procedures are characterized in that

• - an amine of the formula wherein R₇ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or sulfo, and R₁ has the meaning given under formula (1), diazotized and coupled to a coupling component of formula (7), the azo dye formed only contains a single -SO₃H or -OSO₃H group; or
• - an amine of the formula wherein R₈ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or sulfo, and R₁ has the meaning given under formula (1), diazotized and coupled to a coupling component of formula (7), the azo dye formed only contains a single -SO₃H- or -OSO₃H- group.

In the particularly and very particularly preferred embodiments of the inventive method for producing the dyes Formulas (2) and (3) with the amines of formulas (6), (8), (10) and (11) coupling components of the formula (7) are preferably used, wherein K is the residue of an amino or alkoxybenzene, amino or Alkoxynaphthalene, phenol, naphthol, aminonaphthol, 5-pyrazolones, 5-aminopyrazole, pyridone, pyrimidine, indole, Acetoacetic acid amides, naphthimidazole, tetrahydroquinoline, 2,3-dihydro Is 1,4-benzoxazine or pyrazolo [2,3-a] pyrimidine, the said radicals may be further substituted, for. B. by the above substituents indicated for the radical K; in particular is the Radical K is an N-C₁-C₄-alkylamino or N, N-di-C₁-C₄-alkylamino-benzene radical, the in the benzene ring by C₁-C₄ alkoxy, especially methoxy, C₁-C₄ alkyl, especially methyl, halogen, especially chlorine, and C₂-C₅ alkanoylamino, especially acetylamino, may be substituted can, and in which the N-alkyl radicals independently of one another by cyano, Hydroxy, sulfo, sulfato, thiosulfato or phenyl may be substituted can; a C₁-C₂ alkoxybenzene radical by C₁-C₄ alkyl, in particular Methyl, may be substituted; a methoxynaphthalene residue; a phenol radical which is substituted by C₁-C₄-alkyl, in particular methyl can be; an amino naphthalene residue which is substituted by sulfo can be; an amino naphthol residue that is in the naphthalene nucleus, is substituted by sulfo, and wherein the amino group is substituted by  C₁-C₄ alkyl, especially methyl, and / or a fiber-reactive radical can be substituted; a hydroxynaphthalene residue, which by sulfo and halogen may be substituted; a 1-phenyl-3-methyl-5-pyrazole onrest, in the phenyl radical by C₁-C-alkyl, halogen and sulfo can be substituted; a 1-phenyl-3-methyl-5-aminopyrazole residue, in the phenyl radical by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen and sulfo can be substituted; an indole residue, in the 1-position C₁-C₁₀-alkyl and in the 2-position by C₁-C₆-alkyl or phenyl or Sulfophenyl and substituted in the 5-, 6- or 7-position by sulfo can be; a 1-chlorophenylamino-2-pentyl-naphthimidazole residue, the can be substituted in the naphthalene nucleus by hydroxy and sulfo; a 1-C₁-C₄-alkyl-4-C₁-C₄-alkyl-3-cyano or -3-carbonamido-6- hydroxypyridone-2 residue; an N-C₁-C₄-alkyl-1,2,3,4-tetrahydroquinoline residue, the by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, sulfato or Sulfo may be substituted; or a 2,4,6-triaminopyrimidine residue; or a 2,3-dihydro-1,4-benzoxazine residue in the 2- and / or 3-position be substituted by C₁-C₄-alkyl or C₂-C₅-alkanoylamino can on the nitrogen atom by C₁-C₄-alkyl, by hydroxy, Halogen, sulfamoyl, carbamoyl, cyano, C₂-C₅-alkanoylamino- C₁-C₄- Alkoxycarbonyl or C₂-C₅-alkanoylamino can be substituted and the in the benzene nucleus by C₁-C₄-alkyl or C₂-C₅-alkanoylamino can be substituted.

In the very particularly preferred amines of the formulas (10) and (11), R₁ means in particular the -CON (C₁-C₄-alkyl) ₂, -CON (H) (CH₂) _n -OSO₃H, -COOC₁-C₄-alkyl or - SO₂-C₁-C₄-alkyl radical, where n = 1 to 4.

Important amines of the formula (10) or (11) are those in which R₁ and X are a group of the formula -CON (H) (CH₂) _n -OSO₃H, in particular a group of the formula -CON (H) CH₂CH₂-OSO₃H, the amines are diazotized and coupled to a coupling component of the formula (7), in which K is an N-C₁-C₄-alkylamino or N, N-di-C₁-C₄-alkylamino-benzene radical which is in the benzene ring by C₁-C₄- Alkoxy, especially methoxy, C₁-C₄-alkyl, especially methyl, halogen, especially chlorine, and C₂-C₅-alkanoylamino, especially acetylamino, and where the N-alkyl radicals can be substituted independently of one another by cyano, hydroxy or phenyl; a C₁-C₂ alkoxybenzene radical, which can be substituted by C₁-C₄-alkyl, in particular methyl; a methoxynaphthalene residue; a phenol radical which can be substituted by C₁-C₄-alkyl, in particular methyl; an amino naphthalene residue; an amino naphthol radical, in which the amino group can be substituted by C₁-C₄ alkyl, in particular methyl, and / or a fiber-reactive radical; a hydroxynaphthalene residue which may be substituted by halogen; a 1-phenyl-3-methyl-5-pyrazolone radical which can be substituted in the phenyl radical by C₁-C₄-alkyl and halogen; a 1-phenyl-3-methyl-5-aminopyrazole, which can be substituted in the phenyl radical by C₁-C₄-alkyl, C₁-C₄-alkoxy and halogen; an indole radical which can be substituted in the 1-position by C₁-C₁₀-alkyl and in the 2-position by C₁-C₆-alkyl or phenyl; a 1-chlorophenylamino-2-pentyl-naphthimidazole residue which may be substituted by hydroxy in the naphthalene nucleus; a 1-C₁-C₄-alkyl-4-C₁-C₄-alkyl-3-cyano or -3-carbonamido-6-hydroxypyridon-2-residue; an N-C₁-C₄-alkyl-1,2,3,4-tetrahydroquinoline residue which can be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy and halogen; or a 2,4,6-triaminopyrimidine residue; or a 2,3-dihydro-1,4-benzoxazine residue which can be substituted in the 2- and / or 3-position by C₁-C₄-alkyl or C₂-C₅-alkanoylamino, which on the nitrogen atom is substituted by C₁-C₄-alkyl, which can be substituted by hydroxy, halogen, sulfamoyl, carbamoyl, cyano, C₂-C₅-alkanoylamino, C₁-C₄-alkoxycarbonyl, or C₂-C₅-alkanoylamino and which is substituted in the benzene nucleus by C₁-C₄-alkyl or C₂-C₅-alkanoylamino can be is.

Other important amines of the formulas (10) and (11) are those in which R₇ or R₈ is sulfo, these are diazotized and on a coupling component of the formula (9) coupled, wherein K is the rest of a those specified above for the important amines of the formula (10) or (11) Coupling components is.  

Other important dyes of the formulas (4) and (5) are prepared by using an amine of formula (10) or (11) wherein R₁ -CON (C₁-C₄-alkyl) ₂, -CON (H) C₁-C₄-alkyl, -COOC₁-C₄-alkyl or -SO₂-C₁-C₄-alkyl and R₇ or R₈ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, diazotized and coupled to a coupling component of the formula (7), wherein K is the rest of a coupling component, the at least one contains water-solubilizing group, in particular one by 1 to 2 sulfo or sulfato groups of substituted N-C₁-C₄-alkylamino or N, N-di-C₁-C₄-alkylamino-benzene, which in the benzene ring C₁-C₄ alkoxy, especially methoxy, C₁-C₄ alkyl, especially Methyl, halogen, especially chlorine, and C₂-C₅ alkanoylamino, in particular acetylamino can be substituted, and wherein the N-alkyl radicals independently of one another by cyano, hydroxy or phenyl can be substituted; an amino naphthalene residue; an amino naphthol residue, wherein the amino group by C₁-C₄ alkyl, in particular Methyl, and / or a fiber-reactive radical may be substituted; a hydroxynaphthalene residue which may be substituted by halogen; a 1-phenyl-3-methyl-5-pyrazolone residue, which in the phenyl residue C₁-C₄ alkyl and halogen may be substituted; a 1-phenyl-3- methyl-5-aminopyrazole, which in the phenyl radical by C₁-C₄-alkyl, C₁-C₄ alkoxy and halogen may be substituted; an indole residue, the in the 1-position by C₁-C₁₀-alkyl and in the 2-position by C₁-C₆-alkyl or may be substituted phenyl; a 1-chlorophenylamino-2-pentyl naphthimidazole residue, which is substituted in the naphthalene nucleus by hydroxy can be; or an N-C₁-C₄-alkyl-1,2,3,4-tetrahydroquinoline residue is substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen can be.

A particularly important dye of formula (4) is prepared by diazotizing an amine of formula (10) in which R₁ is -COOCH₃ and R₇ is hydrogen and is based on N- β -sulfatoethyl-2,2,4,7-tetramethyl- tetrahydroquinoline or 2-amino-8-hydroxynaphthalene-6-sulfonic acid couples.

From the large number of possible coupling components, the following are mentioned as an example.

Aniline, dimethylaniline, diethylaniline, 3-methyldimethylaniline, 3-methyldibutylaniline, 3-methyldiethylaniline, 3-acetylamino- or 3-methoxycarbonylamino- or 3-ureido-dimethylaniline, 3-methyl-6-methoxy-diethylaniline, 3- Methyl-N-ethyl-N-butyl-aniline, 2,5-dimethoxy-diethylaniline, N-ethyl-N-benzylaniline, N-ethyl-N- ( b -cyanethyl) - aniline, N-ethyl-N- ( β -hydroxyethyl) aniline, N-ethyl-N- ( β -acetoxyethyl) aniline, N, N-dibutylaniline, 3-acetylamino-N, N-diethylaniline, N-methyl-N- ( β- cyanoethyl) aniline, 3-methyl-N, N-di- ( β- cyanoethyl) aniline, 3-chloro-N, N-dimethylaniline, 3-methyl-N-ethyl-N-benzylaniline, N, N-di-n-propylaniline, 3-acetylamino-N, N-di- ( β -hydroxyethyl) aniline, 3-methyl-N, N-di- ( b -acetoxyethyl) aniline, 3-methyl-N-ethyl-N- (3'- sulfobenzyl) aniline, N-ethyl-N- ( β- chloroethyl) aniline, 2-methoxy-5-acetylamino-N-benzylaniline, 2-methoxy-5-acetylamino-N- ( β- acetoxyethyl) -N-benzylaniline , 3-methyl-N-ethyl-N- ( β- cyanoethyl) aniline, 2-methyl-5-acetylamino-N, N-dimethylaniline, 2-chloro-5 -acetylamino-N, N-dimethylaniline, 2-chloro-5-acetylamino-N- ( γ- phenoxy- β- hydroxy-n-propyl) -aniline, 3-ureidoaniline, N-ethyl-N- ( β -hydroxyethyl) -aniline, N-ethyl-N- (3'-sulfobenzyl) -aniline, 3-methyl-N-ethyl-N- ( β- sulfoethyl) -aniline, 3-benzoylamino-N, N- diethylaniline, 3- (p -Tolylsulfamoyl) -N, N-diethylaniline, 3- (p-chloro benzoylamino) -N, N-diethylaniline, 3-methoxy-N, N-diethylaniline, 3-methyl-N, N-di- ( β- hydroxyethyl) -aniline, 3-methyl-6-methoxy-N, N-di- ( β- hydroxyethyl) -aniline, 3-acetylaminoaniline, 3-methyl-N-ethyl-N-phenethylaniline, N, N-di- ( β - cyanoethyl) aniline, 3-acetylamino-N, N-di- ( β- cyanoethyl) aniline, 3-methyl-N-ethyl-N- ( β -hydroxyethyl) aniline, 3-methyl-N-ethyl-N - ( β- cyanoethyl) aniline, N- ( β- cyanoethyl) aniline, N-methyl-N-benzylaniline, phenol, 3-methylphenol, 3,4-dimethylphenol, 2-phenylphenol, 1-hydroxy-4-methoxybenzene , 1-hydroxy-4-tert-butyl-benzene, 1-hydroxy-7-amino-3-sulfonaphthalene, 1-hydroxy-7-methylamino- or -7-phenylamino-3-sulfonaphthalene, 2-aminonaphthalene, 2- Amino -6-sulfonaphthalene, 2-amino-5-acetylaminomethylnaphthalene, β- naphthol, 2-amino-5-methylaminosulfonylnaphthalene, 1-hydroxy-8-amino-3,6- or -3,5-disulfonaphthalene, 1-hydroxy-8 -benzoylamino- 3,6- or -3,5-disulfonaphthalene, 1-hydroxy-8-ureido-3,6- or -3,5-disulfonaphthalene, 1-hydroxy-8-acetylamino-3,6- or -3 , 5-disulfonaphthalene, 1- (3'-chlorophenyl) -3-methylpyrazolon-5, 1- (2'-chloro-6'-methylphenyl) -3-methylpyrazolon-5, 1-phenyl-3-methylpyrazolon-5, 1- (2 ′, 3′- or 4′-sulfophenyl) -3-methylpyrazolon-5, 1- (2′-chloro-4′- or 5′-sulfophenyl) -3-methylpyrazolon-5, 1- (3rd '- or 4'- α, β- dibromopropionylamino) benzoylamino-8-hydroxy-3,6- or 4,6-disulfonaphthalene, 2- α, β- dibromopropionylamino-8-hydroxy-6-sulfonaphthalene, 3- α, β- dibromopropionyl-N-methylamino-8-hydroxy-6-sulfonaphthalene, 1- [3 ′ - (2 ″, 5 ″ -difluoro-5 ″ -chloropyrimidylamino) -benzoylamino] - 8-hydroxy-4,6- disulfonaphthalene, 1- (2′-methyl-4′-sulfophenyl) - 3-methylpyrazolon-5, 1- [4 ′, 8′-disulfonaphthyl- (2)] - 3-methylpyrazolon-5, 1- [5 ′, 7′-Disu lfonaphthyl- (2) -3-methylpyrazolon-5, 1- (2'-chloro-5'-sulfophenyl) -3-methyl-5-aminopyrazole, 1- (2'-chloro-4'-sulfophenyl) -3- methyl-5-aminopyrazole, 1- (3'- or 4'-sulfophenyl) -3-methyl-5-aminopyrazole, 2-methylindole, 2-phenylindole, 1-methyl-2-phenylindole, 1-octyl-2-methylindole , N-methyl-N, N-diphenylamine, acetoacetic anilide, 1- (4'-methylphenyl) -3-methylpyrazolon-5, 1-ethyl-2-methylindole, 1-phenyl-3-methyl-5-aminopyrazole, 1- Hydroxynaphthalene, 1-hydroxy-4-sulfonaphthalene, 1- (2'-chlorophenylamino) -9-hydroxy-2-methyl-1H-naphtho (1,2-d) imidazole-7-sulfonic acid, 1- (2'-chlorophenylamino ) -9-hydroxy-2-pentyl-1H-naphtho (1,2-d) imidazole-- 7-sulfonic acid, 2,6-dihydroxy-3-cyano-4-methylpyridine, 1-methyl-3-cyano-4 -ethyl-6-hydroxypyridone- (2), 1-amino-3-cyano-4-methyl-6-hydroxypyridone- (2), 1-phenyl-3-carbonamido-4-methyl-6-hydroxypyridone- (2) , 1-phenyl-3-carbonamido-4-methyl-6-hydroxypyridon- (2), 1- (4′-aminophenyl) -3-methyl-5-pyrazolone, 1- (2 ′, 3′- or 4 ′ -Sulfophenyl) -3-methyl-5-pyrazolone, 1- (2'-chloro-4'- ode r -5'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (2-methyl-6'-chlorophenyl) - 3-methyl-5-pyrazolone, 1- (2'-, 3'- or 4 ' -Chlor- or methyl- or sulfophenyl) -3-carboxy-5-pyrazolone, 1- [5′-sulfonaphthyl (2 ′)] - 3-methyl-5-pyrazolone, 1- [4 ″ -amino-2 ′, 2 ″ -disulfostilben- (4 ′)] - 3-methyl-5-pyrazolone, 1-ethyl-3-cyano-4-methyl-6-hydroxypyridone- (2), 1-ethyl-3-sulfomethyl-4-methyl -6-hydroxypyridone- (2), tetrahydroquinoline, N- β- sulfatoethyl, 2,2,4,7-tetramethyltetrahydroquinoline, N- b -sulfoethyl-2,2,4,7-tetramethyltetrahydroquinoline.

The coupling components of the formula (7) are known per se or can be prepared in analogy to known compounds.

The amines of the formula (6), the coupling components of the formula (7) can be converted into amino groups, such as. B. the acetylamino and the nitro group. For example, an acetylamino group by saponification and a nitro group by reduction in an amino group can be transferred, advantageously subsequently to the preparation of the dyes of formula (1).

Furthermore, the water-solubilizing group can follow Diazotization and coupling into which azo dyes are introduced, e.g. B. by sulfating a hydroxy group in the dye Formula 1).

Compounds of formula (6) which are free from water-solubilizing Groups are, are known or can be analogous to known ones Connections are made. Compounds of formula (6) which contain at least one water-solubilizing group, are new and represent a further subject of the invention. Preferred Compounds of formula (6) as the water-solubilizing group 1 contain up to 3 groups of the formula -SO₃H, -OSO₃H or -SSO₃H.

The compounds of the formulas (8), (10) and (11) which contain at least one water-solubilizing group are particularly preferred. Compounds of the formula (8) in which R₁ is a -CON (H) (CH₂) _n -OSO₃H radical are very particularly preferred.

Compounds of the formulas (10) are also very particularly preferred. and (11), wherein R₇ or R₈ is sulfo.

The compounds of formula (6) which are at least one water solubilizing Group contain are made by using a Compound of formula (6) which is free from water solubilizing Is groups, and the one in a water-solubilizing group  convertible group contains such. B. the hydroxy group to one water-solubilizing group, or by ring A or sulfonated a radical R₁, e.g. B. with concentrated sulfuric acid at a temperature between 60 and 90 ° C, in particular at 75 ° C.

The following may be mentioned as examples of compounds of the formula (6):

3-amino-4-chlorobenzo [b] thiophene-2-carboxylic acid methyl ester, 3-amino-6-chlorobenzo [b] thiophene-2-carboxylic acid methyl ester, 3-amino-4-methoxybenzo [b] thiophene-2-carboxylic acid methyl ester, 3- Amino-4-nitrobenzo [b] thiophene-2-carboxylic acid methyl ester, 3-amino-6-nitrobenzo [b] thiophene-2-carboxylic acid methyl ester, 2-amino-6-trifluoromethylbenzo [b] thiophene-3-carboxylic acid methyl ester, 3-amino 4-nitro-6-trifluoromethylbenzo [b] thiophene-2-carboxylic acid methyl ester, 3-amino-4-nitro-6-methylbenzo [b] thiophene-2-carboxylic acid methyl ester, 2-aminobenzo [b] thiophene-3-carboxylic acid methyl ester, 3- Aminobenzo [b] thiophene-3-carboxylic acid methyl ester.

The dyes of the formula (1), which have at least one water-solubilizing Group included, are either in the form of their free Acid or preferably as its salts.

The salts include, for example, the alkali metal, alkaline earth metal or Ammonium salts or the salts of an organic amine. Examples include the sodium, lithium, potassium or ammonium salts or called the salt of triethanolamine.

The azo dyes of the formula (1) according to the invention are suitable for Dyeing and printing, especially of nitrogenous or hydroxy group-containing fiber materials, such as. B. textile fiber materials made of cellulose, silk and especially wool and synthetic Polyamides. Level dyeings in yellow, brown, orange, red, blue, gray, green and black tones with good General fastness properties, in particular good friction, wet, wet friction and Lightfastness. Furthermore, the dyes of the invention are very  easy to combine with other acid dyes. The above Textile material can be processed in many different ways are present, such as. B. as fiber, yarn, woven or knitted fabric.

In the following examples, parts represent parts by weight. The Temperatures are degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.

Example 1

0.01 mol of 3-amino-2-methoxycarbonylbenzo [b] thiophene are in 15 parts of 60% acetic acid and 2.5 parts of 98% sulfuric acid submitted at 0 to 3 ° C with stirring. Become this solution 0.097 mol of 40% nitrosylsulfuric acid added dropwise so that the Temperature does not exceed 4 ° C. After the addition is complete stirred for 90 minutes at 0 to 5 ° C. This diazonium salt Solution becomes a well-stirred solution within 10 minutes of 0.01 mol of 2-amino-8-hydroxynaphthalene-6-sulfonic acid (sodium salt) in 30 parts of dimethylformamide and 0.1 part of hydrochloric acid (33%) 0 to 5 ° C metered. Then stir for another 60 minutes at approx. 5 ° C and then adjusts the pH of the solution by adding aqueous sodium hydroxide solution (50%) within approx. 180 minutes to 1.5. Then you stir for another 120 minutes, put the pH by adding saturated sodium carbonate solution to 7, heated to 40 ° C and filtered off the precipitated crystals. The Dye of formula (101) obtained dyes synthetic polyamide material in real red tones.  

Example 2

0.01 mol of 3-amino-2-methoxycarbonylbenzo [b] thiophene are placed in 15 parts of acetic acid (60% strength) and 2.5 parts of sulfuric acid (98% strength) at 0 to 5 ° with stirring. 0.0097 mol of nitrosylsulfuric acid (40%) are added dropwise to this solution in such a way that the temperature does not exceed 4 °. After the addition is complete, stirring is continued at 0 to 5 ° for 90 minutes. This diazonium salt solution is metered in over 10 minutes to a well-stirred solution of 0.01 mol of N- β- sulfoethyl-2,2,4,7-tetramethyltetrahydroquinoline in 15 parts of H₂SO₄ (15%) at 0 to 5 °. The mixture is then stirred for a further 60 minutes at 5 ° and the pH of the solution is then adjusted to approximately 1.5 within 20 minutes by adding sodium hydroxide solution (50%). The mixture is then stirred for a further 30 minutes, 15 ml of a saturated sodium carbonate solution are added, the mixture is warmed to 40 ° and the crystals which have precipitated are filtered off. The dye of formula (102) obtained dyes synthetic polyamide material in true red tones.

Example 3

To a well-stirred solution of 10 g sulfuric acid (100%) 2.07 g of 3-amino-2-methoxycarbonylbenzo [b] thiophene are so entered that the internal temperature is below 40 ° C. Subsequently if the mixture is stirred for 10 hours at an internal temperature of 75 ° C., drops are added to 50 ml Ice water and provides for complete crystallization in the Fridge. Then the product is suctioned off and made of ethanol recrystallized. 1.6 g of a white powder are obtained. The Product corresponds to the formula

Example 4

At 10 ° C 2.07 parts of 2-amino-3-carbomethoxybenzo [b] thiophene in a solution consisting of 25 parts glacial acetic acid and 12 parts concentrated hydrochloric acid (33%) entered. Then it is set to 0 ° C cooled and at max. 2 ° C with 0.73 parts NaNO₂ in 4 parts water diazotized. After 15 minutes of stirring, 1 part of sulfamic acid added, stirred briefly and then 2.73 parts of 2-methyl indole 5-sulfonic acid Ca salt (84%) entered at once. Man Stir for 30 minutes at 0 ° -2 ° C and then gives 12 parts of sodium acetate in 3 portions within 15 minutes. Subsequently becomes a solution consisting of 4 parts of sodium acetate, 3 parts of soda and 20 parts of water within 60 minutes at max. 5 ° C added dropwise. The precipitated dye is filtered at 20 ° C and in Vacuum drying cabinet dried at 60 ° C. 3.2 parts of one are obtained Powder that stains polyamide material orange.

If one proceeds as in Examples 1, 2 and 4, however as amine an aminobenzo [b] thiophene as in column 2 of the following Table used and used as a coupling component used as indicated in column 3 of the table below, so dyes are obtained, which polyamide materials in the column 4 Stain the color shown in the table below.  

table

Dyeing Instructions I

Dye 10 parts of Helancatrikot in 500 parts of an aqueous Broth containing 2 g / ammonium acetate and to pH 5 with acetic acid is provided. The proportion of the dye according to Example 1 is 0.7%, based on the fiber weight. The dyeing time for one Temperature of 98 ° is 30 to 90 minutes. The colored Helanca piece is then removed and washed as usual and dried.  

You get a red colored Helanca piece, which is a pure shade and has good overall fastness properties.

Staining instructions II

Dye 10 parts of Helancatrikot in 500 parts of an aqueous Fleet containing 1 g / l monosodium phosphate and with disodium phosphate is adjusted to pH 6. The proportion of the dye according to Example 2 is 1%, based on the fiber weight. The dyeing time at a temperature of 98 ° is 30 to 90 minutes. The colored one Helancastück is then taken out and as usual washed and dried.

You get a red colored Helanca piece, which is a pure shade and has good overall fastness properties.

Staining instructions III

10 parts of wool are dyed in 100 parts of an aqueous liquor. Based on the fiber weight, the proportions of dye are 0.8% according to Example 1, calcium on Glauber's salt. 5% and 80% acetic acid 2%. The dyeing time at a temperature of 98 ° is 60 minutes. The red colored, washed and dried as usual Wollstück has very good general fastness properties.

Claims (16)

1. Azo dyes which contain at least one water-solubilizing group of the formula wherein K is the rest of a coupling component of the benzene or naphthalene series or the heterocyclic series, R₁ is a group of the formula -CN, -CON (R₂) R₃, -COR₄, -COOR₅ or -SO₂R₆, the ring A is optionally substituted , R₂ and R₃ independently of one another are hydrogen or an optionally substituted C₁-C₁₀ alkyl, C₅-C₇ cycloalkyl, phenyl or naphthyl radical, and R₄, R₅ and R₆ are an optionally substituted C₁-C₁₀ alkyl, C₅- C₇-Cycloalkyl, phenyl or naphthyl radical mean. 2. Azo dyes according to claim 1, characterized in that the Diazo component at least one water-solubilizing group contains. 3. Azo dyes according to claim 1, characterized in that the Coupling component at least one water-solubilizing group contains. 4. Azo dyes according to claim 1, characterized in that the Diazo and the coupling component each have at least one water-solubilizing Group included. 5. Azo dyes according to any one of claims 1 to 4, characterized characterized in that as water-solubilizing groups 1 to 3 groups of the formulas -SO₃H, -OSO₃H or -SSO₃H are included.   6. Azo dyes according to any one of claims 1 to 5, wherein K is the Residue of an amino or alkoxybenzene, amino or alkoxynaphthalene, Phenols, naphthols, aminonaphthols, 5-pyrazolones, 5-aminopyrazoles, Pyridons, pyrimidins, indoles, acetoacetic amides, naphthimidazoles, Tetrahydroquinoline, 2,3-dihydro-1,4-benzoxazines or pyrazolo- Is [2,3-a] pyrimidine, the said radicals being further substituted could be. 7. Azo dyes according to one of claims 1, 2, 5 and 6 of the formula wherein X is a group of the formula -SO₃H or -OSO₃H, and A, R₁ and K have the meanings given in claim 1. 8. Azo dyes according to one of claims 1, 3, 5 and 6 of the formula wherein X is -SO₃H, m is the number 1 or 2, and A, R₁ and K have the meanings given in claim 1. 9. Azo dyes according to one of claims 1 to 3 and 5 to 8 of the formula which contain only a single -SO₃H- or -OSO₃H group, in which R₇ is hydrogen, C₁-C₄-alkyl, C₁-C Alk-alkoxy, halogen or sulfo, and R₁ and K have the in claims 1 to 3 and 5 to 8 have the meanings given. 10. Azo dyes according to one of claims 1 to 3 and 5 to 8 of the formula which contain only a single -SO₃H- or -OSO₃H group, in which R₈ is hydrogen, C₁-C₄-alkyl, C₁-C Alk-alkoxy, halogen or sulfo, and R₁ and K have the in claims 1 to 3 and 5 to 8 have the meanings given. 11. Azo dyes according to any one of claims 7 to 10, wherein K is a N-C₁-C₄-alkylamino or N, N-di-C₁-C₄-alkylamino-benzene, which in Benzene ring by C₁-C₄-alkoxy, especially methoxy, C₁-C₄-alkyl, especially methyl, halogen, especially chlorine, and C₂-C₅-alkanoylamino, in particular acetylamino can be substituted, and wherein the N-alkyl radicals independently of one another by cyano, hydroxy or may be substituted with phenyl; a C₁-C₂ alkoxybenzene radical, which can be substituted by C₁-C₄-alkyl, especially methyl; a methoxynaphthalene residue; a phenol radical which is C₁-C₄-alkyl, in particular methyl, may be substituted; an amino naphthalene residue; an amino naphthol radical in which the amino group is C₁-C₁-alkyl, in particular methyl, and / or a fiber-reactive radical can be substituted; a hydroxynaphthalene residue, which is replaced by halogen can be substituted; a 1-phenyl-3-methyl-5-pyrazolone residue, the can be substituted in the phenyl radical by C₁-C₄-alkyl and halogen; a 1-phenyl-3-methyl-5-aminopyrazole residue, which in the phenyl residue C₁-C₄ alkyl, C₁-C₄ alkoxy and halogen may be substituted; a Indole residue in the 1-position by C₁-C₁₀ alkyl and in the 2-position can be substituted by C₁-C₆ alkyl or phenyl; a 1-chloro  phenylamino-2-pentyl-naphthimidazole residue, which in the naphthalene nucleus by Hydroxy may be substituted; a 1-C₁-C₄-alkyl-4-C₁-C₄-alkyl-3-cyano or -3-carbonamido-6-hydroxypyridone-2 residue; an N-C₁-C₄- Alkyl-1,2,3,4-tetrahydroquinoline residue, which is represented by C₁-C₄-alkyl, C₁-C₄ alkoxy and halogen may be substituted; or a 2,4,6-triamino pyrimidine residue; or a 2,3-dihydro-1,4-benzoxazine residue, which in 2- and / or 3-position by C₁-C₄-alkyl or C₂-C₅-alkanoylamino may be substituted on the nitrogen atom by C₁-C₄ alkyl, by hydroxy, halogen, sulfamoyl, carbamoyl, cyano, C₂-C₅-alkanoylamino, C₁-C₄-alkoxycarbonyl or C₂-C₅-alkanoylamino can be substituted and in the benzene nucleus by C₁-C₄ alkyl or C₂-C₅ alkanoylamino may be substituted. 12. Azo dye according to claim 9, wherein R₁ -COOCH₃, R₇ is hydrogen and K is the N- β- sulfatoethyl-2,2,4,7-tetramethyltetrahydroquinoline residue. 13. Azo dye according to claim 10, wherein R₁ -COOCH₃, R₈ is hydrogen and K is a 2-amino-8-hydroxynaphthalene-6-sulfonic acid residue. 14. A process for the preparation of azo dyes according to claim 1, characterized in that an amine of the formula diazotized and coupled to a coupling component of the formula HK (7), wherein A, R₁ and K in the formulas (6) and (7) have the meanings given in claim 1. 15. Use of the azo dyes according to claims 1 to 13, or the azo dyes obtained according to claim 14 for dyeing and Printing. 16. Compounds containing a water-soluble group of the formula wherein R₁ is a group of the formula -CON (R₂) R₃, -COOR₄ or -SO₂R₅, the ring A represents an optionally substituted benzene ring, R₂ and R₃ independently of one another are hydrogen or an optionally substituted C₁-C₁₀ alkyl, C₅-C₇- Cycloalkyl, phenyl or naphthyl radical, and R₄ and R₅ represent an optionally substituted C₁-C₁₀ alkyl, C₅-C₇ cycloalkyl, phenyl or naphthyl radical.