DE19825202A1 - Tris and polyazo dyes and their mixtures - Google Patents

Abstract

The invention relates to azo dyes having general formula (I), wherein one of radicals X<1> and X<2> represents hydroxy and the other represents amino or C1-C4-alkylamino optionally substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, methoxycarbonyl, ethoxycarbonyl or acetoxy; n equals 0 or 1; m equals 1 or 2; k equals 0 or additionally 1, 2, 3 or 4 when X<3> stands for NH2; D<1>, D<2>, D<3> and D<4> independently represent hydrogen or hydroxysulfonyl; Z<1> represents a direct bond or a binding link of formula SO2NH-A, -SO2Nalk-A, -SO3-A-, NH-A-, Nalk-A-, -SO2-A-, SONH-A-, or CO-A, wherein A represents phenylene which may be substituted by hydroxysulfonyl or carboxyl, or naphthylene which may be substituted by hydroxysulfonyl or carboxyl, whereby A is bonded to the azo bridge; Alk represents C1-C8-alkyl which may be interrupted by 1 to 3 non-adjacent oxygen atoms, 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxy, C1-C4-alkanoyloxy, benzoyloxy, halogen, cyano, carboxy, hydroxysulfonyl, carbamoyl, phenyl or hydroxysulfonylphenyl or C5-C8-cycloalkyl; K represents the radical of an optionally substituted derivative of a benzol, naphthalene, pyrazole, pyridine, pyrimidine, indole or N-arylacetoacetamide series; X<3> represents hydrogen or amino and Y represents a radical -CH2CH2OH, -CH2CH2-ND<5>D<6>, -CH=CH2 or -CH2CH2Q, wherein Q represents a group that may be separated under alkaline reaction conditions. The invention further relates to the mixtures of said dyes, to a method for their production and to their use for dying natural or synthetic substrates.

Description

The present invention relates to azo dyes of the general formula I.

in the
one of the radicals X ¹ and X ² hydroxy and the other amino or C ₁ -C ₄ alkylamino which is optionally substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, methoxycarbonyl, ethoxycarbonyl or acetoxy
n 0 or 1
m 1 or 2
k 0 or, if X ³ denotes NH ₂ , additionally a number 1, 2, 3 or 4
D ¹ , D ² , D ³ and D ^{4 are} independently hydrogen or hydroxy sulfonyl
Z ^{1 is} a direct bond or a bridge member of the formula -SO ₂ NH-A-, -SO ₂ NAlk-A-, -SO ₃ -A-, -NH-A-, -NAlk-A-, -SO ₂ -A -, SONH-A-, CONH-A- or -CO-A-, wherein
A is phenylene, which can be substituted with hydroxysulfonyl or carboxyl, or naphthylene, which can be substituted with hydroxysulfonyl or carboxyl, where A is linked to the azo bridge,
Alk C ₁ -C ₈ alkyl, which can be interrupted by 1 to 3 non-adjacent oxygen atoms, 1 sulfur atom or 1 sulfonyl group and by hydroxy, C ₁ -C ₄ alkanoyloxy, benzoyloxy, halo gene, cyano, carboxy, hydroxysulfonyl, carbamoyl , Phenyl or hydroxysulfonylphenyl may be substituted, or C ₅ -C ₈ cycloalkyl
K is the residue of an optionally substituted derivative of the benzene, naphthalene, pyrazole, pyridine, pyrimidine, indole or N-arylacetoacetamide series
X ^{3 is} hydrogen or amino and
Y represents a radical -CH ₂ CH ₂ OH, -CH ₂ CH ₂ -ND ⁵ D ⁶ , -CH = CH ₂ or -CH ₂ CH ₂ Q, in which Q represents a group which can be split off under alkaline reaction conditions,
D ⁵ and D ⁶ independently of one another are hydrogen or a radical of the formula Z ² -H, in which Z ^{2 is} C ₁ -C ₈ -alkylene which is substituted by 1 to 3 non-adjacent oxygen atoms, imino and optionally substituted by hydroxy or methoxy C ₁ -C ₄ alkylimino groups or a radical

can be interrupted and which can be substituted with hydroxy, carboxy, C ₁ -C ₄ alkanoyloxy, benzoyloxy, halogen, cyano, carbamoyl, phenyl, carboxyphenyl or amino, phenylene, carboxyphenylene, and
D ^{5 is} also a radical of the formula

wherein D ^{7 is} hydrogen or C ₁ -C ₄ alkyl optionally substituted with hydroxy or methoxy, or D ⁶ and D ⁷ together represent C ₁ -C ₄ alkylene and
Z ^{3 is} a radical of the formula

where x 1, 2, 3, 4 or 5 and y = 1 or if x = 1 also mean y = 0
or D ⁵ and D ⁶ together with the nitrogen atom connecting them represent a 5- or 6-membered heterocyclic radical which optionally has nitrogen or oxygen as a further hetero atom and can be substituted,
mean.

It also relates to their mixtures, a process for their preparation position and their use for dyeing natural or synthetic substrates.

EP-A-0 247 618 teaches trisazo dyes based on 1-Amino-8-hydroxynaphthalenedisulfonic acids, one after the other Sulfanilamide and tetraazotated 4,4'-diaminobenzenesulfanilide be coupled and the product to a heterocyclic Coupling component is coupled. Draw these dyes primarily as paper dyes.

Other requirements are usually placed on leather dyes poses. So it is often undesirable that the dye is deep in the material penetrates. Surface dyes are advantageous for nevertheless high substantivity of the dye. Furthermore are real such as wet and sweat fastness are important criteria.

It was therefore an object of the present invention to provide new azo color to provide substances that are characterized by advantageous application distinguish technical properties.

Accordingly, the above compounds have been found, their Mixtures, a process for their preparation and their Use for coloring natural or synthetic sub straten.  

The dyes of the formula I are each in the form of the free acid specified. It goes without saying that their salts are also used encompassed by the present invention.

Suitable cations are derived from metal or ammonium ions. Metal ions are in particular the lithium, sodium or potassium ions. Ammonium ions in the sense of the invention are unsubstituted or substituted ammonium cations. Substituted ammonium cations are e.g. B. monoalkyl, dialkyl, trialkyl, tetraalkyl or benzyltrialkylammonium ions or such cations which are derived from nitrogen-containing five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium, piperazinium or N-alkylpiperazinium cations N-monoalkyl or N, N-di alkyl substituted products. Alkyl is generally to be understood as straight-chain or branched C ₁ -C ₂₀ -alkyl which can be substituted by 1 or 2 hydroxyl groups and / or interrupted by 1 to 4 oxygen atoms in ether function.

In general, everyone, both the above and in the following formulas appearing alkyl and alkylene groups be both straight and branched.

Unless otherwise stated, substituted alkyl radicals have preferably 1, 2 or 3 substituents, in particular 1 or 2 Substituents in any position.

If alkyl radicals occur in the above formulas, which are caused by Oxygen atoms are interrupted in ether function, so are those alkyl radicals preferred, which have 1 or 2 oxygen atoms are interrupted in ether function.

When substituted phenyl radicals in the above formulas occur, they usually have 1 to 3 substituents.

If the phenylene group is substituted, it usually has 1 or 2, preferably a hydroxysulfonyl radical.

Residues X ¹ , X ² , alk, D ⁵ , D ⁶ and D ⁷ are e.g. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

X ¹ and X ² are still z. B. hydroxymethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, cyanomethyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 2- or 4-cyanobutyl, carboxymethyl, 2-carboxyethyl, 2- or 3-carboxypropyl, 2- or 4-carboxybutyl, hydroxysulfonylmethyl, 2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl, 2- or 4-hydroxysulfonylbutyl, methoxycarbonylmethyl, methoxycarbonylethyl, 2- or 3-methoxy carbonylpropyl, 2- or 4-methoxycarbonylbutyl , Acetoxymethyl, acetoxyethyl, 2- or 3-acetoxypropyl or 2- or 4-acetoxy butyl.

Residues A are preferably 1,2-, 1,3- and 1,4-phenylene, 2-hydroxy sulfonyl-1,3-phenylene, 2-hydroxysulfonyl-1,4-phenylene or 2,5-dihydroxysulfonyl-1,4-phenylene.

Halogen stands for fluorine, chlorine or bromine.

Residues Alk, D ⁵ and D ⁶ are still z. B. pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethyl pentyl, octyl, 2-ethylhexyl, isooctyl (The above term iso-octyl is a trivial name and comes from those after oxosynthesis alcohols obtained - see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 1, pages 290 to 293, and Vol. A 10, pages 284 and 285), 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-prop oxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl , 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxa decyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 2-methylthioethyl, 2-ethylthioethyl, 2- or 3-methylthiopropyl, 2- or 3- Ethyl thiopropyl, 2- or 4-methylthiobutyl, 2- or 4-ethylthiobutyl, chloromethyl, 2-chlorine thyl, 2- or 3-chloropropyl, benzyl, 1- or 2-phenylethyl, 3-benzyloxypropyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2- or 3-cyano propyl, carbamoylmethyl, 2 -Carbamoylethyl, 2- or 3-carbamoyl propyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 3-isobutyryloxypropyl, carboxylmethyl, 2-carboxylethyl, 2- or 3-carboxylpropyl, cyclopentyl, cyclo hexyl, cycloheptyl or cyclooctyl.

Residues Alk are still z. B. 2-methylsulfonylethyl, 2-ethylsul fonylethyl, 2- or 3-methylsulfonylpropyl, 2- or 3-ethylsulfo nylpropyl, 2- or 4-methylsulfonylbutyl, 2- or 4-ethylsulfo- nylbutyl, 2-, 3- or 4-hydroxysulfonylbenzyl, 2- (2-, 3- or 4-hydroxysulfonylphenyl) ethyl, 2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl.

Residues D ⁵ and D ⁶ are still z. B. 4-hydroxy-2-methyl-3-azabutyl, 4-hydroxy-3-hydroxymethyl-2-methyl-3-azabutyl, 5-hydroxy-2-methyl-3-azapentyl, 5-hydroxy-3- (2nd -hydroxyethyl) -2-methyl-3-azapentyl, 8-hydroxy-2-methyl-3-aza-6-oxaoctyl, 11-hydroxy-2-methyl-3-aza-6,9-dioxaundecyl, 8-hydroxy- 3- (5-hydroxy-3-oxapentyl) -2-methyl-3-aza-6-oxaoctyl or 11-hydroxy-3- (8-hydroxy-3,6-dioxaoctyl) -2-methyl-3-aza- 6,9-dioxa undecyl, N, N-dimethylaminoethyl, N, N-diethylaminoethyl, N, N-di-propylaminoethyl, N, N-dibutylaminoethyl, 3- (N, N-dimethylamino) propyl, 3- (N, N-diethylamino) propyl, 3- (N, N-dipropylamino) propyl, 3- (N, N-dibutylamino) propyl, aminoethyl, 2- or 3-aminopropyl, 2- or 4-aminobutyl, 2- , 3- or 4-carboxyphenyl methyl or 2- (2-, 3- or 4-carboxyphenyl) ethyl.

If the radicals D ⁵ and D ⁶ together with the nitrogen atom connecting them represent a 5- or 6-membered heterocyclic radical which may have nitrogen or oxygen as a further res heteroatom, then saturated radicals such as pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl , which can be substituted on nitrogen with methyl, ethyl, propyl, isopropyl, n-, iso- and sec-butyl, 2-hydroxyethyl or 2- or 3-hydroxypropyl. Furthermore, unsaturated radicals such as pyrrolyl, pyrazolyl, oxazolyl, isooxazolyl or imidazolyl, which can be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl or N-3- (C ₁ -C ₄ ) alkyli midazolyl, which may still be substituted with methyl, ethyl, propyl or butyl in the 2- and / or 4-position.

Rest D ⁷ are still z. B. hydroxymethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, methoxymethyl, 2-meth oxyethyl, 2- or 3-methoxypropyl or 2- or 4-methoxybutyl.

The rest Q stands for hydroxy or a group which can be split off under alkaline reaction conditions. Such groups are e.g. B. chlorine, bromine, C ₁ -C ₄ alkylsulfonyl, phenylsulfonyl, OSO ₃ H, SSO ₃ H, OP (O) (OH) ₂ , C ₁ -C ₄ alkylsulfonyloxy, phenylsulfonyloxy, C ₁ -C ₄ alk anoyloxy, C ₁ -C ₄ dialkylamino, cyanamino or a radical of the formula

where W ¹ , W ² and W ³ each independently have the meaning of C ₁ -C ₄ -alkyl or benzyl and AnU each have the meaning of one equivalent of an anion. As anions z. B. fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methyl sulfonate, phenyl sulfonate or 2- or 4-methylphenyl sulfonate come into consideration.

K are residues of optionally substituted derivatives HKX ^{3 of} the benzene, naphthalene, pyrazole, pyridine, pyrimidine, indole or N-arylacetoacetamide series.

Such coupling components HKX ³ are preferably compounds of the naphthalene, aniline, pyrazolone, aminopyrazole, 2,6-diaminopyridine, pyridone, hydroxypyrimidine, indole, N-arylacetoacetamide series and correspond, for example, to the compounds of the formulas II am

wherein
q 0, 1, 2 or 3,
p 0, 1 or 2,
R ^{1 is} hydrogen or C ₁ -C ₄ -alkyl, which can be substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy,
R ^{2 is} hydrogen, C ₁ -C ₄ alkyl, which can be substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy, benzyl or phenyl, which can be substituted by C ₁ -C ₄ alkyl, C ₁ - C ₄ alkoxy, chlorine or hydroxysulfonyl can be substituted,
R ^{3 is} hydrogen or C ₁ -C ₄ alkyl, which may be substituted by hydroxysulfonyl or carboxyl,
R ⁴ C ₁ -C ₆ -alkylureido, phenylureido, which can be substituted by chlorine, methyl, methoxy, nitro, hydroxysulfonyl or carboxyl, C ₁ -C ₆ -alkanoylamino, which can be substituted by hydroxysulfonyl or chlorine, cyclohexylcarbonylamino, benzoylamino, which can be substituted by chlorine, methyl, methoxy, nitro, hydroxysulfonyl or carboxyl, or hydroxy,
R ^{5 is} hydrogen, C ₁ -C ₆ -alkyl, in particular C ₁ -C ₄ -alkyl, which can each be substituted by phenyl, C ₁ -C ₄ -alkoxy, hydroxy, phenoxy or C ₁ -C ₄ -alkanoyloxy, C ₅ -C ₇ cycloalkyl, hydroxysulfonylphenyl, C ₁ -C ₄ alkanoyl, carbamoyl, mono- or di- (C ₁ -C ₄ ) alkylcarbamoyl, phenylcarbamoyl or cyclohexyl carbamoyl,
R ^{6 is} hydroxy, C ₁ -C ₄ alkoxy, chlorine, bromine, hydroxysulfonyl, C ₁ -C ₄ alkanoylamino, amino, ureido, methylsulfonylamino, ethylsulfonylamino, dimethylaminosulfonylamino, methylamino, ethylamino, dimethylamino or diethylamino
R ^{7 is} hydrogen, hydroxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, hydroxysulfonyl, chlorine or bromine,
T the rest of a benzene or naphthalene ring,
T ¹ C ₁ -C ₄ alkyl, cyclohexyl, benzyl or phenyl which is mono- to trisubstituted by fluorine, chlorine, bromine, methoxy, nitro, hydroxysulfonyl, carboxyl, acetyl, acetylamino, methylsulfonyl, sulfamoyl or carbamoyl,
R ^{8 is} methyl, carboxyl, C ₁ -C ₄ alkoxycarbonyl or phenyl,
R ^{9 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acetyl, cyano, carboxyl, hydroxysulfonyl, C ₁ -C ₄ alkoxycarbonyl, hydroxy, carbamoyl, mono- or di- (C ₁ -C ₄ ) -alkylcarbamoyl, fluorine, chlorine, bromine or trifluoromethyl,
R ^{10 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, cyano, carboxyl, hydroxysulfonyl, acetylamino, C ₁ -C ₄ alkoxycarbonyl, carbamoyl, mono- or di- (C ₁ -C ₄ ) alkylcarbamoyl, fluorine, chlorine, nitro, sulfamoyl, mono- or di- (C ₁ -C ₄ ) alkylsulfamoyl, C ₁ -C ₄ alkyl sulfonyl, phenylsulfonyl or phenoxy,
R ^{11 is} hydrogen or C ₁ -C ₄ alkyl, which can be substituted by C ₁ -C ₄ alkoxy or cyano,
R ^{12 is} hydrogen, methyl, hydroxysulfonylmethyl, hydroxysulfonyl, cyano or carbamoyl,
R ^{13 is} hydrogen, C ₁ -C ₄ alkyl, which can be substituted by phenyl, hydroxysulfonyl phenyl, hydroxy, amino, C ₁ -C ₄ alkoxyl, carboxyl, hydroxysulfonyl, acetylamino, benzoylamino or cyano, cyclohexyl, phenyl, which optionally substituted by carboxyl, hydroxysulfonyl, benzoylamino, acetylamino, methyl, methoxy, cyano or chlorine, or amino substituted by phenyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkanoyl or benzoyl,
R ^{14 is} hydrogen, C ₁ -C ₄ alkyl, phenyl, hydroxyl, cyano, acetyl, benzoyl, carboxyl, methoxycarbonyl, carbamoyl or hydroxy sulfonylmethyl and
R ^{15 is} hydrogen, chlorine, bromine, acetylamino, amino, nitro, hydroxysulfonyl, sulfamoyl, methylsulfonyl, phenylsulfonyl, carboxyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkanoyl, benzoyl, carbamoyl, cyano or hydroxysulfonylmethyl.

Residues R ¹ , R ² , R ³ , R ⁵ , R ⁷ , T ¹ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹³ , R ¹⁴ are e.g. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

R ⁵ radicals can also be pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

The radicals R ¹ , R ² , R ⁵ and R ¹³ are hydroxy-C ₁ -C ₄ -alkyl such as hydroxymethyl, 1-hydroxyeth-1-yl, 2-hydroxyeth-1-yl, 1-hydroxy prop-1- yl, 2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl, 1-hydroxy prop-2-yl, 2-hydroxyprop-2-yl, 1-hydroxbut-1-yl, 2-hydroxy but-1- yl, 3-hydroxybut-1-yl, 4-hydroxybut-1-yl, 1-hydroxy but-2-yl, 2-hydroxybut-2-yl, 1-hydroxybut-3-yl, 2-hydroxy but-3- yl, 1-hydroxy-2-methyl-prop-3-yl, 2-hydroxy-2-methyl-prop-3-yl, 3-hydroxy-2-methyl-prop-3-yl and 2-hydroxymethyl prop-2- yl.

The radicals R ¹ , R ² , R ¹¹ and R ¹³ are further z. B. cyanomethyl, cyanoethyl, cyanopropyl or cyanobutyl.

The radicals R ¹ , R ² , R ³ and R ¹³ are, for example, carboxylmethyl, carboxylethyl, 2- or 3-carboxylpropyl or 2- or 4-carboxyl butyl.

The radicals R ¹ , R ² and R ³ also represent, for example, hydroxysulfonylmethyl, 2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl or 2- or 4-hydroxysulfonylbutyl.

R ¹ and R ² continue to represent z. B. 2-sulfatoethyl, 2- or 3-sulfatopropyl, 2- or 4-sulfatobutyl, methoxycarbonylmethyl, 2-methoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 4-methoxycarbonylbutyl, ethoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2- or 3-ethoxycarbonylpropyl, 2- or 4-ethoxycarbonyl butyl, acetoxymethyl, 2-acetoxyethyl, 2- or 3-acetoxypropyl or 2- or 4-acetoxybutyl.

The radicals R ² can continue, for. B. 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl, 2-, 3- or 4- Butylphenyl, 2-, 3- or 4-isobutylphenyl, 2-, 3- or 4-sec-butylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3 - or 4-ethoxyphenyl, 2-, 3- or 4-propoxyphenyl, 2-, 3- or 4-iso propoxyphenyl, 2-, 3- or 4-butoxyphenyl, 2-, 3- or 4-iso butoxyphenyl, 2- , 3- or 4-sec-butoxyphenyl, 2-, 3- or 4-tert-butoxyphenyl or 2-, 3- or 4-chlorophenyl.

The radicals R ² , R ⁵ and T ¹ are still z. B. 2-, 3- or 4-hydroxy sulfonylphenyl.

The rest R4 is e.g. B. methylureido, ethylureido, propylureido, Butylureido, pentylureido, hexylureido, formylamino, acetylamino, Propionylamino, butyrylamino, isopropylcarbonylamino, valeryl amino, isobutylcarbonylamino, sec-butylcarbonylamino, tert-butyl carbonylamino or pentylcarbonylamino.

The radicals R ⁵ and R ¹³ can, for. B. Benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1 -yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl, 3-phenylbut-2- yl, 4-phenylbut-2-yl, 1- (phenylmethyl) -eth-1-yl, 1- (phenylmethyl) -1- (methyl) -eth-1-yl and 1- (phenylmethyl) prop-1- yl, preferably benzyl and 2-phenylethyl.

The radicals R ⁵ , R ¹¹ and R ¹³ are furthermore, for example, meth oxymethyl, ethoxymethyl, n-propoxymethyl, (1-methylethoxy) methyl, n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1 , 1-dimethylethoxy) methyl, 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (n-propoxy) ethyl, 2- (1-methoxyethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (1-methoxypropoxy) ethyl, 2- (2-methylphenoxy) ethyl, 2- (1,1-dimethylethoxy) ethyl, 2- (methoxy) propyl, 2- (ethoxy) propyl, 2- (n-propoxy) propyl , 2- (1-methylethoxy) propyl, 2- (n-butoxy) propyl, 2- (1-methylpropoxy) propyl, 2- (2-methylpropoxy) propyl, 2- (1,1-dimethylethoxy) propyl, 3 - (Methoxy) propyl, 3- (ethoxy) propyl, 3- (n-propoxy) propyl, 3- (1-methylethoxy) propyl, 3- (n-but oxy) propyl, 3- (1-methylpropoxy) propyl, 3- (2-methylpropoxy) propyl, 3- (1,1-dimethylethoxy) propyl, 2- (methoxy) butyl, 2- (ethoxy) butyl, 2- (n-propoxy) butyl, 2- (1- Methylethoxy) butyl, 2- (n-butoxy) butyl, 2- (1-methylpropoxy) butyl, 2- (2-methylpropoxy) butyl, 2- (1,1-dimethylethoxy) butyl, 3- (methoxy) butyl, 3- (Et hoxy) butyl, 3- (n-propoxy) butyl, 3- (1-methylethoxy) butyl, 3- (n-butoxy) butyl, 3- (1-methylpropoxy) butyl, 3- (2-methyl propoxy) butyl, 3- (1,1-dimethylethoxy) butyl, 4- (methoxy) butyl, 4- (ethoxy) butyl, 4- (n-propoxy) butyl, 4- (1-methylethoxy) butyl, 4- (n-butoxy) butyl, 4- (1-methylpropoxy) butyl, 4- (2-methylpropoxy) butyl or 4- (1,1-dimethylethoxy) butyl.

R ⁵ are also z. B. phenoxymethyl, 2-phenoxyethyl, 2- or 3-phenoxypropyl, 2- or 4-phenoxybutyl, formyloxymethyl, 2- (formyloxy) ethyl, 2- or 3- (formyloxy) propyl, 2- or 4- (formyloxy) butyl , Methylcarbonyloaymethyl, 2- (methylcarbonyloxy) ethyl, 2- or 3- (methylcarbonyloxy) propyl, 2- or 4- (methylcarbonyloxy) butyl, ethylcarbonyloxymethyl, 2- (ethyl carbonyloxy) ethyl, 2- or 3- (ethylcarbonyloxy) propyl , 2- or 4- (ethylcarbonyloxy) butyl, propylcarbonyloxymethyl, 2- (propyl carbonyloxy) ethyl, 2- or 3- (propylcarbonyloxy) propyl, 2- or 4- (propylcarbonyloxy) butyl, cyclopentyl, cyclohexyl or cyclo heptyl.

The radicals R ⁵ and R ¹⁵ and the radicals G ⁴ described below are, for. B. formyl, acetyl, propionyl, butyryl or isobutyryl.

The radicals R ⁵ , R ⁹ and R ¹⁰ are, for example, mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl, mono- or dipropyl carbamoyl or mono- or dibutylcarbamoyl.

Residues R ⁶ , R ⁷ , R ⁹ and R ¹⁰ can e.g. B. methoxy, ethoxy, propoxy, iso propoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy.

The radicals R ⁶ and R ¹³ are, for example, formylamino, methyl carbonylamino, ethylcarbonylamino, propylcarbonylamino or iso propylcarbonylamino.

T ¹ are still z. B. 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-bromophenyl, 2-, 3- or 4-meth oxyphenyl, 2-, 3- or 4 -Nitrophenyl, 2-, 3- or 4-carboxyl phenyl, 2-, 3- or 4-acetylphenyl, 2-, 3- or 4-acetylamino phenyl, 2-, 3- or 4-methylsulfonylphenyl, 2-, 3- or 4-sulfamoylphenyl or 2-, 3- or 4-carbamoylphenyl.

The radicals R ⁸ , R ⁹ , R ¹⁰ and R ¹⁵ are also z. B. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxy carbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxy carbonyl.

The radicals R ¹⁰ are furthermore, for example, mono- or dimethyl sulfamoyl, mono- or diethylsulfamoyl, mono- or dipropylsulfamoyl, mono- or dibutylsulfamoyl, methylsulfonyl, ethyl sulfonyl, propylsulfonyl or butylsulfonyl.

As radicals R ¹³ are also suitable for. B. hydroxysulfonyl phenylmethyl, 2-hydroxysulfonylphenylethyl, 2- or 3-hydroxy sulfonylphenylpropyl, 2- or 4-hydroxysulfonylphenylbutyl, aminomethyl, 2-aminoethyl, 2- or 3-aminopropyl, 2- or 4-aminobutyl, hydroxysulfonylmethyl, 2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl, 2- or 4-hydroxysulfonylbutyl, acetylaminomethyl, 2-acetylaminoethyl, 2- or 3-acetylamino propyl, 2- or 4-acetylaminobutyl, benzoylaminomethyl, 2-benzoylaminoethyl, 2- or 3-benzoylaminopropyl, 2- or 4-benzoylaminobutyl, 2-, 3- or 4-carboxylphenyl, 2-, 3- or 4-hydroxysulfonylphenyl, 2-, 3- or 4-benzoylaminophenyl, 2-, 3- or 4-acetylaminophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-cyanophenyl, 2-, 3- or 4-chlorophenyl, phenylamino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino , sec-butylamino, tert-butylamino or benzoylamino.

In the following, coupling components HKX ³ are listed as examples. In detail, for example, coupling components of the naphthalene series are naphtholsulfonic acids such as
1-naphthol-3-sulfonic acid, 1-naphthol-4-sulfonic acid,
1-naphthol-5-sulfonic acid, 1-naphthol-8-sulfonic acid,
1-naphthol-3,6-disulfonic acid, 1-naphthol-3,8-disulfonic acid,
2-naphthol-5-sulfonic acid, 2-naphthol-6-sulfonic acid,
2-naphthol-7-sulfonic acid, 2-naphthol-8-sulfonic acid,
2-naphthol-3,6-disulfonic acid, 2-naphthol-6,8-disulfonic acid,
2-Naphthol-3,6,8-trisulfonic acid, 1,8-dihydroxy naphthalene-3,6-disulfonic acid, 2,6-dihydroxynaphthalene-8-sulfonic acid or 2,8-dihydroxynaphthalene-6-sulfonic acid.

Furthermore, for example, N-phenyl-1-naphthylamine, N-ethyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene or 2-hydroxy to name naphthalene-3-carboxylic acid.

Naphthalenesulfonic acids are, for example, 2-hydroxysulfonyl methylaminonaphthalene-5-sulfonic acid or 2-hydroxysulfonylmethyl aminonaphthalene-6-sulfonic acid.

As aminonaphtholsulfonic acids such. B. 1-Acetylamino-8-hydroxy naphthalene-3,6-disulfonic acid, 1-benzoylamino-8-hydroxynaphtha lin-3,6-disulfonic acid, 1-acetylamino-8-hydroxynaphtha lin-4,6-disulfonic acid, 1-benzoylamino-8-hydroxynaphthalene-4,6- disulfonic acid, 1-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-methylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl amino-8-hydroxynaphthalene-6-sulfonic acid, 2-hydroxysulfonylmethyl amino-8-hydroxynaphthalene-6-sulfonic acid, 2-hydroxysulfonylmethyl amino-7-hydroxysulfonylmethyl-8-hydroxynaphthalene-6-sulfonic acid, 2-hydroxysulfonylmethylamino-8-hydroxynaphthalene-3,6-disulfone acid, 2-hydroxysulfonylmethylamino-7-hydroxysulfonyl methyl-8-hydroxynaphthalene-3,6-disulfonic acid, 2- (3'- or 4'-hydroxysulfonylphenylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid or 2-acetyl to name amino-8-hydroxynaphthalene-6-sulfonic acid.

Furthermore aminonaphthalenes such as 1-naphthylamine, 1-naphthyl amine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid, 1-naphthyl amine-8-sulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 2-naphthyl amine-5,7-disulfonic acid, 2-naphthylamine-6,8-disulfonic acid,  1-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaph thalin-4-sulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfone acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid, 2-amino-5-hydroxy naphthalene-7-sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfone acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 3-amino-7-hydroxy sulfonylmethyl-8-hydroxynaphthalene-3,6-disulfonic acid, 2-amino-7-hydroxysulfonylmethyl-8-hyrdroxynaphthalene-6-sulfonic acid to call.

Examples of benzene coupling components are resorcinol, 2- and 4-methylresorcinol, 3-hydroxyphenyliminodiacetic acid, 2,4-di to name hydroxybenzoic acid.

Examples of pyrazolone coupling components which may be mentioned are 3-methyl-, 3-carboxy- or 3- (C ₁ -C ₄ -alkoxycarbonyl) pyrazol-5-ones which are hydrogen in the 1-position, optionally by methyl, ethyl, fluorine, Chlorine, bromine, trifluoromethyl, methoxy, ethoxy, cyano, phenoxy, phenylsulfonyl, methylsulfonyl, hydroxysulfonyl, acetylamino, nitro, hydroxyl, carboxyl, carbamoyl or sulfamoyl or phenyl substituted by hydroxysulfonyl or 1- or 2-naphthyl. For example, 1-phenyl-, 1- (2'-chlorophenyl) -, 1- (2'-methoxyplzenyl) -, 1- (2'-methylphenyl) -, 1- (1 ', 5'-dichlorophenyl) -, 1- (2 ', 6'-dichlorophenyl) -, 1- (2'-methyl-6'-chlorophenyl) -, 1- (2'-methoxy-S'-methylphenyl) -, 1- (2'-methoxy - 5'-hydroxysulfonylphenyl) -, 1- (2 ', 5'-dichloro-4'-hydroxysulfonylphenyl) -, 1- (2', 5'-dihydroxysulfonylphenyl) -, 1- (2'-carboxyphenyl) - , 1- (3'-hydroxysulfonylphenyl) -, 1- (4'-hydroxysulfonylphenyl) - or 1- (3'-sulfamoylphenyl) -3-carboxylpyrazol-5-one, 1- (3'- or 4'-hydroxysulfonylphenyl ) -, 1- (2'-chloro-4'- or -5'-hydroxysulfonylphenyl) -, 1- (2'-methyl-4'-hydroxysulfonylphenyl) -, 1- (2 ', 5'-dichlorophenyl) -, 1- (4 ', 8'-dihydroxysulfonyl-1-naphthyl) -, 1- (4'-sulfamoylphenyl) -3-, 1- (6'-hydroxysulfonyl-1-naphthyl) -3-methylpyrazole- 5-one, 1-phenylpyrazole-5-one-3-carboxylic acid ethyl ester, pyrazol-5-one-3-carboxylic acid ethyl ester or pyrazol-5-one-3-carboxylic acid.

Other coupling components from the pyrazole series are for example 1-methyl, 1-ethyl, 1-propyl, 1-butyl, 1-cyclo hexyl-, 1-benzyl- or 1-phenyl-5-aminopyrazole, 1- (4'-chlorine phenyl) -, 1- (4'-methylphenyl) -5-aminopyrazole or 1-phenyl-3-methyl-5-aminopyrazole.  

N-arylacetoacetamides are primarily acetoessiganilide or its in the phenyl nucleus by chlorine, methyl, ethyl, methoxy, ethoxy, Acetylamino, hydroxylsulfonyl, carboxyl, carbamoyl or sulfamoyl mono- or polysubstituted derivatives.

Coupling components derived from pyridine are, for example the derivatives described in DE-A-22 60 827.

As pyrimidine coupling components such. B. the compounds listed in DE-A-22 02 820, DE-A-23 08 663 or DE-A-31 19 349 are suitable. Barbituric acid and its N-substitution products should also be mentioned. C ₁ -C ₄ -Alkyl or phenyl are particularly suitable as N-substituents.

Examples of indole coupling components are 2-methyl indole, 2-phenylindole, 2-phenylindole-5-sulfonic acid, 1-methyl-2-phenylindole, 1- (2'-hydroxyethyl) -, 1- (2'-carboxy ethyl) -, 1- (2'-carbamoylethyl) -2-methylindole or -2-phenylindole to call.

Examples of pyridone coupling components are 1-ethyl-2-hydroxy-4-methyl-5-carbonaoylpyrid-6-one, 1- (2'-hydroxy ethyl) 2-hydroxy-4-methyl-5-carbamoylpyrid-6-one, 1-phenyl-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one, 1-ethyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one, 1-ethyl-2-hydroxy-4-methyl-5-hydroxysulfonylmethylpyrid-6-one, 1-methyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one, 1-methyl-2-hydroxy-5-acetylpyrid-6-one, 1,4-dimethyl-2-hydr oxy-5-cyanopyrid-6-one, 1,4-dimethyl-5-carbamoylpyrid-6-one, 2,6-dihydroxy-4-ethyl-5-cyanopyridine, 2-hydroxy-4-ethyl-5-carba moylpyrid-6-one, 1-ethyl-2-hydroxy-4-methyl-5-hydroxysulfonyl methylpyrid-6-one, 1-methyl-2-hydroxy-4-methyl-5-methylsulfonylpy rid-6-one or 1-carboxymethyl-2-hydroxy-4-ethyl-5-phenylsulfonyl to call pyrid-6-one.

Coupling components HK-NH ₂ carrying amino groups are capable of oligomerization owing to their amino group. In particular, oligomerization-bearing coupling components of the benzene series, such as o-, m- and p-phenylenediamine, 3-aminophenol, 4-methyl-3-aminophenol, 5-amino-2-methylphenol, 4-ethyl-3-aminophenol, 2 , 4-diaminotoluene, 2,4-diaminobenzenesulphonic acid, o- or m-toluidine, o- or m-anisidine, cresidine, 2,5-dimethylaniline, 2,5-dimethoxyaniline, m-aminoacetanilide, 3-amino-4- methoxyacetanilide, 3-amino-4-methylacetanilide, m-amino phenylurea, N-methylaniline, N-methyl-m-toluidine, N-ethyl aniline, N-ethyl-m-toluidine, N- (2-hydroxyethyl) aniline or N - (2-Hydroxyethyl) -m-toluidine suitable.

To prepare the dyes, a diazo component of the general formula III

in which D ¹ , D ² , Y and n have the meaning given above, diazo animals and on a coupling component of the formula IV

in which X ¹ , X ² and m have the meaning given above, acid coupling (coupling step A). In a second coupling step (coupling B), a diazo component of the formula V

in which D ³ , D ⁴ and Z ^{1 have} the abovementioned meaning, tetraazo tiert and coupled to the reaction product of clutch A. The product of the general formula VI obtained in this way

is now coupled to a clutch component HKX ³ (clutch step C). The order of the coupling steps can be varied depending on the desired target connection. If X ^{1 is} amino or optionally substituted alkylamino, one will choose the above synthetic route, while if X ^{1 is} hydroxy, coupling step B is carried out before coupling step A.

Such syntheses and the synthesis conditions to be selected for them are generally known to the person skilled in the art.

Common diazo components III are such. B. 2-Sulfatoethylsulfonylani lin, 2-sulfatoethylsulfonyl-4-sulfoaniline, 4-sulfatoethylsulfo nyl-2-sulfoaniline, 3-sulfatoethylsulfonylaniline, 3-sulfato ethyl-4,6-disulfoaniline, 4-sulfatoethylsulfonyl-2-sulfoaniline, 4-hydroxyethylsulfonylaniline and 4-sulfatoethylsulfonyl-2-meth oxyaniline.

As coupling components IV are z. B. 1-Amino-5- hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphtha lin-4-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-amino-8-hydroxynaphthalene-4,6-disvulfonic acid, 2-amino-5-hydroxy naphthalene-7-sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfone acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 1-hydroxysulfonyl methylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-methyl amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methylamino-8-hydroxy naphthalene-6-sulfonic acid, 2-hydroxysulfonylmethylamino-8-hydroxy called naphthalene-6-sulfonic acid.

Aromatic diamines V, which are suitable as starting materials for VI, are, for example, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodi phenyl sulfone, 2,2'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone-4,5-disulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diamino diphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid and N- (4-aminophenyl) -4-aminobenzenesulfonamide or benzenediamines, the first protected an amino group or in the form of a nitro wear group.

Dyes of the general formula I in which X ^{3 represents} amino are preferred.

If the coupling step C is carried out with compounds of the general formula VI in which Y is a vinyl radical or a radical —CH ₂ CH ₂ Q (Y ¹ ), with the approximately equimolar amount of a coupling component HK-NH ₂ at a pH from 5 to 14, preferably 6-12, dyestuffs with particularly advantageous properties are obtained. Under these reaction conditions, the free amino groups presumably react with the vinyl sulfones that form to give the likewise preferred dyes with a number of repeat units. Depending on the desired end group, the radical -SO ₂ - (CH ₂ ) _n -CH = CH _{2 can} then optionally with amines of formula VII

or with diamines of formula VIII

be implemented. Usually dye mixtures are obtained, which are characterized by their good surface coloring.

Examples of amines VII are methylamine, ethylamine and n-propyl amine, isopropylamine, butylamine, isobutylamine, sec-butylamine, 1,2-dimethylpropylamine, mono-2-ethylrlexylamine, dimethylamine, Diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, Diisobutylamine, di-sec-butylamine, N-methylbutylamine, N-ethyl butylamine, 2-methoxyethylamine, di-2-methoxyethylamine, 3-methoxy propylamine, 3-ethoxypropylamine, cyclohexylamine, N-monomethyl cyclohexylamine, N-ethylcyclohexylamine, benzylamine, 2-phenylethyl amine, 2-diethylaminoethylamine, dimethylaminopropylamine, diethyl aminopropylamine, ethanolamine, diethanolamine, monoisopropanolamine, Diisopropanolamine, methylethanolamine, 2,2'-aminoethoxyethanol, 3-aminopropanol, 2-aminobutanol-1, N-methylpiperazine, N-methyl piperazinpropylamine, di (carboxymethyl) amine, N-methylanino acetic acid acid, 4-aminobenzoic acid, 2-methylimidazole and imidazole mention.

Examples of diamines VIII are ethylenediamine, 1,2-propylene diamine, 1,3-diaminopropane, 3-amino-1-methylaminopropane, Neo pentanediamine, hexamethylene diamine, 4,9-dioxadodecane-1,12-diamine, Diethylene triamine, 3 (2-aminoethyl) aminopropylamine, dipropylene triamine, N, N'-bis (3-aminopropyl) ethylenediamine, aminoethylethanol amine, n-propylethanolamine, butylethanolamine and piperazine called.

The reaction of the trisazo dyes which carry a vinyl sulfone end group with the diamines VIII leads to the preferred doubling products of the general formula IX

in which n, D ¹ , D ² , D ³ , D ⁴ , D ⁶ , D ⁷ , Z ¹ , Z ² and K have the abovementioned meaning.

It is also possible to use the coupling product from Diazo to double component III and coupling component IV. However is usually used for the sake of solubility of the doubling in preferred last synthesis step.

Correspondingly, the dye oligomers can also be doubled, so that a mixture obtained by oligomerization, which was subsequently treated with diamines VIII, can also contain duplication products. These dyes, which are obtained by reaction of the reaction product of the approximately equimolar coupling of VI with HK-NH ₂ at pH 6 to 14 and subsequent reaction with diamine VIII, are also preferred.

In general, dyes of the general formula I are preferred in which Y represents a radical -CH ₂ CH ₂ -ND ⁵ D ⁶ . Azo dyes are particularly preferred in which D ⁵ and D ⁶ independently of one another are hydrogen or a radical Z ² -H and Z ^{2 is} phenylene, or D ⁵ and D ⁶ together are piperazinyl, N-methylpiperazinyl or imidazolyl.

Azo dyes in which D ^{1 is} hydrogen are also preferred.

Dyes of the formula I in which Y is CH ₂ CH ₂ -OH are likewise preferred.

Furthermore, azo dyes are preferred in which Z ^{1 is} a bridge member of the formula -SO ₂ NH-A- or -NH-A-.

Azo dyes of the general formula X are also preferred

in which n, k, D ¹ , D ² , D ³ , D ⁴ , Z ¹ , K, Y and X ^{3 have} the meaning given above.

Azo dyes of the formula I and X in which k represents the number 0 are also preferred. They themselves have good application properties and, if X ^{3 is} amino and Y is vinyl or a radical —CH ₂ CH ₂ Q, are also intermediates for the preferred oligomeric dyes with k for 1, 2, 3 and 4.

The dyes according to the invention are advantageously suitable Way of dyeing natural or synthetic substrates, for example of cotton, wool, polyamide and in particular Leather. They are also used as paper dyes for bulk dyeing and Recording liquids such as inks, especially for ink jet, suitable.

You get dyeings on leather in green, black and blue to navy blue shades with good wet and sweat fastness.

They are particularly suitable for coloring leather surfaces because they also have a high substantivity.  

The new dyes can be used alone or in a mixture with each other or in a mixture with other dyes turn.

The following examples are intended to explain the invention in more detail.

Manufacture of coupling components Example A

16.0 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid were dissolved in 100 ml of water at pH 7.0-7.5 and adjusted to pH 1.0 with 10% by weight hydrochloric acid. To this suspension was added a dia zonium solution, which was prepared from 14.1 g p-sulfatoethylsulfonylaniline and 3.5 g sodium nitrite. After 6 hours at 10-15 ° C, no diazonium salt was detectable. 10 g of N-methylpiperazine were added and the pH was adjusted to 10.5 with 10% strength by weight sodium hydroxide solution. After stirring for 10 hours at 25-30 ° C, the pH with conc. Hydrochloric acid set to 1.0 and suction filtered. After drying, 21 g of a red coupling component of the formula were isolated

Analogously to Example A, the amines described in Table 1 can be used in an equivalent amount instead of N-methylpiperazine coupling components are obtained.

Table 1

Example B

The procedure was as in Example A, but 2.2 g of piperazine were added instead of N-methylpiperazine. After the reaction had ended, the product was precipitated by adding isopropanol, filtered off with suction and dried. 37 g of a coupling component of the formula were isolated

λ _max (in water): 552 nm and 318 nm

By mass spectrum (ESI) was with a mol peak at 1112 above structure confirmed.

example 1

79.8 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid were dissolved in 300 ml of water at pH 7.0-7.5 and acidified with 150 g of 10% strength by weight hydrochloric acid. A diazonium solution which had been prepared from 50.3 g of p-hydroxyethylsulfonyl aniline and 17.3 g of sodium nitrite was added to this suspension at 0-5 ° C. After adding the diazonium solution, the pH was adjusted to 1.0 with solid sodium bicarbonate and the reaction solution was stirred for 6 hours at room temperature. After this time, no diazonium ion was detectable. A solution was added which was prepared by tetrazotizing 65.8 g of 4,4'-diaminodiphenylsulfamide and 34.6 g of sodium nitrite, cooled to 10-12 ° C. and adjusted by adding sodium hydroxide solution (10% by weight). %) the pH to 10.5. After 2 hours, 27.0 g of metaphenylenediamine were added and the pH was kept at 10.5% by weight by adding further sodium hydroxide solution. Then the pH was lowered to 1.0 by adding concentrated hydrochloric acid and the precipitate was filtered off with suction. After drying, 273 g of a black dye of the formula were obtained

λ _max (in water): 608 nm, 472 nm, 399 nm

In the mass spectrum (ESI) you can see a peak with the molar mass 924, which corresponds to the above structure.

Example 2

24.5 g of the compound described in Example A were suspended in 300 ml of water and a tetrazonium solution of 11.2 g of 4,4'-diaminodiphenylamine-3-sulfonic acid was added. The pH was raised to 9.5-10.0 by adding 10% strength by weight sodium hydroxide solution and this pH was maintained at 25 ° C. over a period of 3 hours. Then 4.3 g of metaphenylenediamine were added and the mixture was stirred at 25 ° C. for a further 6 hours. By adding conc. Hydrochloric acid, the pH was lowered to 1.0 and the precipitated dyes were suctioned off and dried. 25.7 g of a dye of the formula were obtained

l _max (in water): 610 nm, 488 nm, 322 nm

Examples 3-8

The procedure was as in Example 2, but instead of the one in Bei Game 2 described the compound in Examples A-1-A-6 described connections.

Example 9

The procedure was as in Example 2, but the product from Example B was used and at the same time twice the amount of tetrazotized 4,4'-diaminodiphenylamine-3-sulfonic saxare. 34 g of the dye of the formula were isolated

Example 10

28 g of m-sulfatoethylsulfonylaniline were dissolved in 50 ml of water and concentrated. Hydrochloric acid adjusted to pH 0.2. At 0-5 ° C, 6.9 g of sodium nitrite were added. After 2 hours, residues of nitrite were destroyed with amidosulfonic acid. This solution was added to a solution of 32 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid in 60 ml of water of pH 1.0 and stirred at 10-12 ° C. for 6 hours. Then 20 g of N-methylpiperazine were added, the pH was raised to 10.5 by adding 10% strength by weight sodium hydroxide solution and the mixture was stirred at 25-30 ° C. for a further 3 hours. The pH was adjusted to 1.0 by adding hydrochloric acid, then the precipitate was filtered off with suction and dried. 50 g of the compound of the formula were isolated

λ _max (in water): 534 nm, 310 nm

The procedure was then continued as described in Example 2 and, after drying, 23 g of a dye of the formula are isolated

λ _max (in water): 598 nm, 482 nm, 310 nm

Example 11

To a suspension of 79.8 g of 1-hydroxy-8-amino-naphthalene-3,6-disulfonic acid in 300 ml of water at pH 1.0 was added a diazonium solution consisting of 70.3 g of p-sulfatoethylsulfonylaniline in 1000 ml of water and 17.3 g of sodium nitrite was produced. The mixture was stirred at 5-10 ° C. and pH 0.9-1.0 for 6 hours. A solution was then added, which was prepared by tetrazotizing 65.8 g of 4,4'-diamino diphenylsulfamide and 34.5 g of sodium nitrite. The pH was adjusted to 5.0 by adding sodium acetate and the mixture was stirred at 25 ° C. for a further 6 hours. Then 27 g of metaphenylendiamine were added, the pH was raised to 7.0 and the mixture was stirred at 25 ° C. for a further 4 hours. The homogeneous solution was then spray dried (inlet temperature 170 ° C.). 232 g of a black powder were isolated, the 56.9% salts, 4.8% water and 38.3% of a dye of the formula

contained and colored leather in deep black tones.
λ _max (in water): 606 nm, 458 nm, 398 nm, 312 nm

Example 12

The procedure was as described in Example 11. After the addition of metaphenylenediamine, the pH was raised to 10.5-11.0 with 10% strength by weight sodium hydroxide solution and the mixture was stirred at 25-30 ° C. for 5 hours. Then the pH was lowered to 7.5 and the precipitated dye was suctioned off. After drying, 208 g of a black powder were isolated which contained 16.3% salts and 1.4% water and dyed leather in deep black tones. The colored part is a mixture in which the molecular masses 1921, 2828 and 4563 could be detected by mass spectrometry (ESI).
λ _max (in water): 596 nm, 454 nm, 400 nm, 310 nm

Example 13

The procedure was as described in Example 11. When the reaction with metaphenylenediamine had ended, 42.5 g of imidazole were added and the pH was raised to 10.0. After 8 hours at 25-30 ° C, the pH was adjusted to 6.5-7.0 and the suspension spray dried (inlet temperature 150 ° C). 562 g of a black powder were isolated, which contained 59.2% of salts, 2.2% of water and 38.6% of dye. Molpeaks at 974, 1881, 1920, 2536 and 2787 were detected in the mass spectrogram (ESI method).
λ _max (in water): 614 nm, 468 nm, 320 nm

Example 14

The procedure was as in Example 11. When the reaction with metaphenylenediamine had ended, 78.8 g of N-methylpiperazine were added, the pH was raised to 11.0 with 10% strength by weight sodium hydroxide solution and the mixture was stirred at 25-30 ° C. for 3 hours . The pH was then lowered to 7.5 and the suspension spray dried. 650 g of a black powder were isolated, which contained 46.1% salts, 5.4% water and 48.5% dye and dyed the leather in deep black tones.
λ _max (in water): 614 nm, 466 nm, 320 nm

Example 15

The procedure was as in Example 11. After the reaction with Me taphenylenediamine, 11.3 g of piperazine were added and the pH was raised to 10.0 with 10% strength by weight sodium hydroxide solution. After 8 hours at 25-30 ° C the pH was adjusted to 3-4 with hydrochloric acid and the precipitate was suction filtered. After drying, 246 g of a black powder were isolated, which colored leather in deep black tones.
λ _max (in water): 614 nm, 468 nm, 320 nm

Example 16

The procedure was as in Example 11, but metaphenylene diamine was replaced by 51 g of N-phenyl-3-carboxypyrazolone. Spray drying isolated 600 g of a dark green powder which had 51.3% salts, 4.2% water and 44.5% dye of the formula

λ _max (in water): 604 nm, 478 nm, 310 nm
the leather dyes in dark green tones.

Example 17-20

In Example 11, metaphenylenediamine was replaced by the following coupling components:

Example 21

100 g of leather tanned in the usual way with a fold 2.2 mm thick were in 50 g of water at a temperature of 40 ° C with 2 g sodium acetate and 0.5 g sodium bicarbonate Walking for 180 minutes and then after adding 100 g of water water at a temperature of 30 ° C overnight in a drum neutralized. The leather was then walked in by 10 minutes Washed 200 g of water. The retanning was then carried out in 30 g Water at a temperature of 30 ° C with 13 g commercially available synthetic tanning agents. The leather was 65 minutes tumbled in the retanning liquid. The coloring then became like this made that 2 g of dye from Example 23 were added and drummed at 25 ° C for 120 minutes. Then 150 g Water added and drummed for another 10 minutes. After adding 1 g conc. Formic acid was drummed for 30 minutes and the liquor drained. The leather was washed by using a Temperature of 40 ° C mixed with 200 g of water and 10 minutes walked. The fleet was then drained again. The fat was in 100 g of water at a temperature of 55 ° C by addition of 5 g of a commercially available fat licker by 40 minutes Walken performed. After acidification with 1 g of formic acid you walked for another 40 minutes. Then the leather was cold rinsed, stretched out, dried, put in sawdust, stollen and vacuum dried. A deep black color is obtained, the is particularly intense on the hair side of the leather.

Claims (12)

1. Azo dyes of the general formula I
in the
one of the radicals X ¹ and X ² hydroxy and the other amino or C ₁ -C ₄ alkylamino which is optionally substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, methoxycarbonyl, ethoxycarbonyl or acetoxy
n 0 or 1
m 1 or 2
k 0 or, if X ³ denotes NH ₂ , additionally a number 1, 2, 3 or 4
D ¹ , D ² , D ³ and D ⁴ independently of one another are hydrogen or hydroxysulfonyl
Z ^{1 is} a direct bond or a bridge member of the formula -SO ₂ NH-A-, -SO ₂ NAlk-A-, -SO ₃ -A-, -NH-A-, -NAlk-A-, -SO ₂ -A -, SONH-A-, CONH-A- or -CO-A-, wherein
A phenylene, which can be substituted with hydroxysulfonyl or carboxyl, or naphthylene, which can be substituted with hydroxysulfonyl or carboxyl, where A is linked to the azo bridge,
Alk C ₁ -C ₈ alkyl, which can be interrupted by 1 to 3 non-adjacent oxygen atoms, 1 sulfur atom or 1 sulfonyl group and by hydroxy, C ₁ -C ₄ alkanoyloxy, benzoyloxy, halogen, cyano, carboxy, hydroxysulfonyl, carbamoyl , Phenyl or hydroxysulfonylphenyl may be substituted, or C ₅ -C ₈ cycloalkyl
K is the residue of an optionally substituted derivative of the benzene, naphthalene, pyrazole, pyridine, pyrimidine, indole or N-arylacetoacetamide series
X ^{3 is} hydrogen or amino and
Y represents a radical -CH ₂ CH ₂ OH, -CH ₂ CH ₂ -ND ⁵ D ⁶ , -CH = CH ₂ or -CH ₂ CH ₂ Q, in which Q represents a group which can be split off under alkaline reaction conditions,
D ⁵ and D ⁶ independently of one another are hydrogen or a radical of the formula Z ² -H, where Z ^{2 is} C ₁ -C ₈ -alkylene, the C not substituted by 1 to 3 oxygen atoms, imino and optionally substituted by hydroxy or methoxy ₁ -C ₄ alkylimino groups or a radical
can be interrupted and which can be substituted with hydroxy, carboxy, C ₁ -C ₄ alkanoyloxy, benzoyloxy, halogen, cyano, carbamoyl, phenyl, carboxyphenyl or amino, phenylene, carboxyphenylene, and
D ^{5 is} also a radical of the formula
in which D ^{7 is} hydrogen or C ₁ -C ₄ -alkyl which is optionally substituted by hydroxy or methoxy or D ⁶ and D ⁷ together represent C ₁ -C ₄ -alkylene,
Z ^{3 is} a radical of the formula
where x 1, 2, 3, 4 or 5 and y = 1 or if x = 1 also mean y = 0
or D ⁵ and D ⁶ together with the nitrogen atom connecting them represent a 5- or 6-membered heterocyclic radical which optionally has nitrogen or oxygen as a further hetero atom, and can be substituted,
mean. 2. Azo dyes according to claim 1, wherein D ^{1 is} hydrogen. 3. azo dyes according to claim 1 or 2, wherein Z ^{1 is} a bridge member of the formula -SO ₂ NH-A-, or -NH-A- and A has the meaning given in claim 1. 4. Azo dyes according to claims 1 to 3 of the general formula X
in which n, k, D ¹ , D ² , D ³ , D ⁴ , Z ¹ , K, Y and X ^{3 have} the meaning given in claim 1. 5. azo dyes according to claims 1 to 4, wherein k is the number 0 means. 6. azo dyes according to claims 1 to 5, wherein Y represents a radical CH ₂ CH ₂ -ND ⁵ D ⁶ . 7. Azo dyes according to claims 1 to 4, wherein X ^{3 is} amino. 8. Azo dyes according to claims 1 to 6 of the general formula IX
in which n, D ¹ , D ² , D ³ , D ⁴ , D ⁶ , D ⁷ , Z ¹ , Z ² and K have the meaning mentioned in claim 1. 9. A process for the preparation of azo dyes according to claims 1 to 4 and 7 by using a diazonium salt of the general formula VI
in the
An ^⊖ the equivalent of an anion and
Y ^{1 represents} a radical -CH = CH ₂ or -CH ₂ CH ₂ Q and
m, n, Q, D ¹ , D ² , D ³ , D ⁴ , Z ¹ , X ¹ and X ^{2 have} the meaning given in claim 1, with the approximately equimolar amount of a coupling component HK-NH ₂ ,
wherein K represents the residue of an optionally substituted derivative of the benzene, naphthalene, pyrazole, pyridine, pyrimidine, indole or N-arylacetoacetamide series,
at a pH of 5 to 14 and then, if necessary, with an amine of the formula VII or VIII
in which Z ² , D ⁶ and D ^{7 have} the meaning given in Claim 2. 10. The method according to claim 9, characterized in that the reaction product obtained is then with a diamine of formula VIII
in which Z ² , D ⁶ and D ^{7 have} the meaning given in Claim 1. 11. Dye mixtures obtainable according to the method of An sayings 9 and 10. 12. Use of the dyes and their mixtures according to the Claims 1 to 10 for dyeing natural or synthetic substrates.