EP1086180A1

EP1086180A1 - Trisazo and polyazo dyes and the mixtures thereof

Info

Publication number: EP1086180A1
Application number: EP99955488A
Authority: EP
Inventors: Manfred Patsch; Gerhard Scholz; Gunther Lamm
Original assignee: BASF SE
Current assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Priority date: 1998-06-05
Filing date: 1999-05-22
Publication date: 2001-03-28
Also published as: WO1999064520A1; DE19825202A1; AR018625A1

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

Tris and polyazo fabrics and their mixtures

description

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

K-NHCH ₂ CH ₂ (CH ₂ ) _n S0 ₂

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 hydroxyl, cyano, carboxyl, hydroxysulfonyl, methoxycarbonyl, ethoxycarbonyl or acetoxy

n 0 or 1

m 1 or 2

k 0 or, if X ^{3 is} NH, 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

-S0 ₂ NH-A-, -S0 ₂ NAlk-A-, -SO ₃ -A-, -NH-A-, -NAlk-A-, -S0 ₂ -A-, -SONH-A-, -CONH -A- or -CO-A-, wherein A is phenylene, which can be substituted by hydroxysulfonyl or carboxyl, or naphthylene, which can be substituted by hydroxysulfonyl or carboxyl, where A is linked to the azo bridge,

Alk -CC 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 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 a possibly substituted derivative of the benzene, naphthalene, pyrazole, pyridine, pyrimidine, indole or N-arylacetoacetamide series

X ^{3 is} hydrogen or amino and

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 is aGbruSDpaallttbbaarree GGrruupDDpee 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} Ci-Cβ-alkylene, the 1 to 3 non-adjacent oxygen atoms, imino and optionally substituted with hydroxy or methoxy -CC Alkylimino groups or a radical

N- _J

can be interrupted and which can be substituted with hydroxy, carboxy, Cχ-C ₄ alkanoyloxy, benzoyloxy, halogen, cyano, carbamoyl, phenyl, carboxyphenyl or amino, phenylene, carboxyphenylene, and

D ^{5 is} also a radical of the formula

-Z ² -NZ ³ D ⁷

wherein D ^{7 is} hydrogen or optionally substituted with hydroxy or methoxy -CC ₄ alkyl or D ⁶ and D ⁷ together represent -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 and their use for dyeing natural or synthetic substrates.

EP-A-0 247 618 teaches trisazo dyes based on l-amino-8-hydroxynaphthalenedisulfonic acids, onto which sulfanilamide and tetraazotated, 4'-diaminobenzenesulfanilide are coupled in succession and the product is coupled onto a heterocyclic coupling component. These dyes are particularly distinguished as paper dyes.

As a rule, other requirements are placed on leather dyes. It is often undesirable for the dye to penetrate deep into the material. Surface dyes are advantageous with a high substantivity of the dye. Furthermore, fastness properties such as wet and sweat fastness are important criteria.

It was therefore an object of the present invention to provide new azo color substances which are distinguished by advantageous application properties.

We have found that this object is achieved by the compounds mentioned above, their mixtures, a process for their preparation and their use for dyeing natural or synthetic substrates. The dyes of the formula I are each given in the form of the free acid. The use of their salts is of course also 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 understood to mean unsubstituted or substituted ammonium cations. Substituted ammonium cations are, for example, monoalkyl, dialkyl, trialkyl, tetraalkyl or benzyltrialkylammonium cations or cations which are derived from nitrogen-containing five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium, piperazinium or N-piperazinium- or N- or their N-monoalkyl- or N, N-di-alkyl-substituted products. Alkyl is generally understood to mean straight-chain or branched C ₁ -C ₂ -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, all of the alkyl and alkylene groups mentioned above and also those appearing in the formulas below can be both straight-chain and branched.

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

If alkyl radicals which are interrupted by oxygen atoms in ether function occur in the formulas mentioned above, preference is given to those alkyl radicals which are interrupted by 1 or 2 oxygen atoms in ether function.

If substituted phenyl radicals occur in the above formulas, they generally 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, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

Residues X ¹ and X ² are, for example, hydroxymethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, cyanomethyl, 2-cyanoethy1, 2- or 3-cyanopropy1, 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-methoxycarbonylpropyl, 2- or 4-methoxycarbonylbutyl, acetoxymethyl, acetoxyethyl, 2- or -acetoxypropyl or 2- or 4-acetoxy-butyl.

Residues A are preferably 1,2-, 1,3- and 1,4-phenylene, 2-hydroxysulfonyl-1, 3 -phenylene, 2-hydroxysulfonyl-1, 4 -phenylene or 2, 5 -di (hydroxysu1fony1) -1 , 4-phenylene.

Halogen stands for fluorine, chlorine or bromine.

Residues Alk, D ⁵ and D ⁶ are furthermore, for example, 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 the alcohols obtained after oxo synthesis - cf. 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-propoxypropyl, 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-dioxadecyl, 3, 6, 9-trioxadecyl, 3, 6, 9-trioxaundecyl, 2-methylthioethyl, 2 - Ethylthioethyl, 2- or 3-methylthiopropyl, 2- or 3-ethylthiopropyl, 2- or 4 -Methylthiobutyl, 2- or 4 -ethylthiobutyl, chloromethyl, 2-chloroethyl, 2- or 3-chloropropyl, benzyl, 1- or 2-phenylethyl, 3-benzyloxypropyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, cyanoethyl, 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, cyclohexyl, cycloheptyl or cyclooctyl.

Residues Alk are further e.g. 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2- or 3-methylsulfonylpropyl, 2- or 3-ethylsulfonylpropyl, 2- or 4-methylsulfonylbutyl, 2- or 4-ethylsulfonylbutyl, 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 furthermore, for example, 4-hydroxy-2-methyl-3-azabutyl, 4-hydroxy-3-hydroxymethyl-2-methyl-3-azabutyl, 5-hydroxy-

2-methyl-3-azapentyl, 5-hydroxy-3- (2-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 -dioxaundecyl, N, N-dimethylaminoethyl, N, N-diethylaminoethyl, N, N-dipropylaminoethyl, 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 heteroatom, then saturated radicals such as pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl, the 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.

Residue D ⁷ are furthermore, for example, hydroxymethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, methoxymethyl, 2-methoxyethyl, 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.

Chlorine, bromine, -CC ₄ alkylsulfonyl, phenylsulfony1, 0S0H, SS0 ₃ H,

OP (0) (OH) _2, Cι-C ₄ alkylsulfonyloxy, phenylsulfonyloxy, Cι-C anoyloxy ₄ ~ alk, C ₁ -C ₄ -Dialkyla1rd.no, cyanoamino or a radical of the formula

^A n,

where W ¹ , W ² and W ³ each independently of the other are C ₁ -C ₄ alkyl or benzyl and An® each have the meaning of one equivalent of an anion. Anions that can be used here are, for example, fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methyl sulfonate, phenyl sulfonate or 2- or 4-methylphenyl sulfonate. 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

(na) (iib) (HO

)

[lim) wherein

q 0, 1, 2 or 3,

p 0, 1 or 2,

R ^{1 is} hydrogen or C ₁ -C ₄ alkyl which is substituted by hydroxy, cyano,

Carboxyl, hydroxysulfonyl, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy can be substituted,

R ^{2 is} hydrogen, Cχ-C-alkyl, which can be substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy, benzyl or phenyl, which can be substituted by -CC ₄ -alkyl, Cχ-C-alkoxy, Chlorine or hydroxysulfonyl can be substituted,

R ^{3 is} hydrogen or Cχ-C ₄ alkyl, which can be substituted by hydroxysulfonyl or carboxyl,

R ⁴ Cι-C ₆ alkylureido, phenylureido by chlorine, methyl,

Methoxy, nitro, hydroxysulfonyl or carboxyl can be substituted, -CC 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 in each case be substituted by phenyl, C 1 -C ₄ -alkoxy, hydroxy, phenoxy or C 1 -C ₄ -alkanoyloxy, C5-C ₇ -cycloalkyl , Hydroxysulfonylphenyl, -CC ₄ alkanoyl, carbamoyl, mono- or di- (C ₁ -C ₄ ) alkylcarbamoyl, phenylcarbamoyl or cyclohexylcarbamoyl,

R ⁶ hydroxy, -CC ₄ alkoxy, chlorine, bromine, hydroxysulfonyl,

Cι-C ₄ alkanoylamino, amino, ureido, methylsulfonylamino, ethylsulfonylamino, dimethylaminosulfonylamino, methylamino, ethylamino, dimethylamino or diethylamino

R ^{7 is} hydrogen, hydroxyl, -CC ₄ -alkyl, Cx- -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, methylsulfony1, 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,

Ri ° 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 _X -C ₄ ) alkylsulfamoyl, C 1 -C ₄ alkylsulfonyl, phenylsulfony1 or phenoxy,

R ^{11 is} hydrogen or C ₁ -C ₄ -alkyl, which can be substituted by -C-C ₄ -alkoxy or cyano,

R ^{12 is} hydrogen, methyl, hydroxysulfonyimethyl, hydroxysulfonyl, cyano or carbamoyl,

R ¹³ is hydrogen, C ₁ -C ₄ -alkyl which may be substituted by phenyl, hydroxysulfonyl, hydroxy, amino, Cι-C ₄ alkoxyl, carboxyl, hydroxysulfonyl, acetylamino, benzoylamino or cyano, cyclohexyl, phenyl which is optionally substituted by carboxyl , Hydroxysulfonyl, benzoylamino, acetylamino, methyl, methoxy, cyano or chlorine is substituted, or amino which is substituted by phenyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkanoyl or benzoyl,

R ^{14 is} hydrogen, -CC ₄ alkyl, phenyl, hydroxyl, cyano, acetyl, benzoyl, carboxyl, methoxycarbonyl, carbamoyl or hydroxysulfonyimethyl 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 mean.

R ¹ , R ² , R ³ , R ⁵ , R ⁷ , T ¹ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹³ , R ¹⁴ are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. R ⁵ radicals can also pentyl, isopentyl, neopentyl, tert. - be pentyl, hexyl or 2-methylpentyl.

The radicals R ¹ , R ² , R ⁵ and R ¹³ are hydroxy-C 1 -C 6 -alkyl such as hydroxymethyl, 1-hydroxyeth-1-yl, 2-hydroxyeth-1-yl, 1-hydroxyprop-1- yl, 2-hydroxyprop-1-yl, 3-hydroxyprop-l-yl, 1-hydroxyprop-2-yl, 2-hydroxyprop-2-yl, 1-hydroxbut-l-yl, 2-hydroxy-but- l-yl, 3-hydroxybut-l-yl, 4-hydroxybut-l-yl, 1-hydroxybut-2-yl, 2-hydroxybut-2-yl, l-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 -hydroxymethyl - prop-2-yl.

The radicals R ¹ , R ² , R ¹¹ and R ¹³ are furthermore, for example, cyanomethyl, cyanoethyl, cyanopropyl or cyanobutyl.

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

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

R ¹ and R ^{2 also} represent, for example, 2-sulfatoethyl, 2- or

3-sulfatopropyl, 2- or 4-sulfatobutyl, methoxycarbonylimethyl, 2-methoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 4-methoxycarbonylbutyl, ethoxycarbonyimethyl, 2-ethoxycarbonylethyl, 2- or 3-ethoxycarbonylpropyl, 2- or 4 -Ethoxycarbony1-butyl, acetoxymethyl, 2-acetoxyethyl, 2- or 3-acetoxypropyl or 2- or 4-acetoxybutyl.

The radicals R ² can furthermore, for example, 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-isopropoxyphenyl, 2-, 3- or 4-butoxyphenyl, 2-, 3- or 4 -Isobutoxyphenyl, 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 furthermore, for example, 2-, 3- or 4-hydroxysulfonylphenyl. The radical R ⁴ is, for example, methylureido, ethylureido, propylureido, butylureido, pentylureido, hexylureido, formylamino, acetylamino, propionylamino, butyrylamino, isopropylcarbonylamino, valerylamino, isobutylcarbonylamino, sec- butylcarbonylarrd.carbon, pentyl-butyl or carbonyl.

The radicals R ⁵ and R ¹³ can, for example, benzyl, 1-phenylethyl, 2-phenyl-ethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-l-yl, 1-phenylbut-l -yl, 2-phenylbut-l-yl, 3-phenylbut-l-yl, 4-phenylbut-l-yl, l-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2 -yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl, 1- (phenyimethyl) -eth-l-yl, 1- (phenyimethyl) -1- (methyl) -eth-l-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, methoxymethyl, ethoxymethyl, n-propoxymethyl, (1-methylethoxy) methyl, n-Bu oxymethyl, (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-methylpropoxy) ethyl, 2- (l, l-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-dimethylethyloxy) propyl, 3- (methoxy) propyl, 3- (ethoxy) propyl, 3 - (n-propoxy) propyl, 3- (1-methylethoxy) ropyl, 3- (n-butoxy) 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- (l-methylethoxy) butyl, 2- (n-butoxy) butyl, 2 - (1-methylpropoxy) b utyl, 2 - (2-methylpropoxy) butyl, 2- (1,1-dimethylethoxy) butyl, 3- (methoxy) butyl, 3- (ethoxy) butyl, 3 - (n-propoxy) butyl, 3- ( 1-methylethoxy) butyl,

3 - (n-butoxy) butyl, 3 - (1-methylpropoxy) butyl, 3 - (2-methylpropoxy) 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-methylprooxy) butyl or 4- (1, 1-dimethylethoxy) butyl.

R ⁵ radicals are also, for example, phenoxymethyl, 2-phenoxyethyl, 2- or 3-phenoxypropyl, 2- or 4-phenoxybuty1, formyloxymethyl, 2- (formyloxy) ethyl, 2- or 3- (formyloxy) propyl, 2- or

4 - (formyloxy) butyl, methylcarbonyloxymethyl, 2 - (methylcarbony1-oxy) ethyl, 2- or 3 - (methylcarbonyloxy) propyl, 2- or

4- (methylcarbonyloxy) butyl, ethylcarbonyloxymethyl, 2- (ethylcarbonyloxy) ethyl, 2- or 3- (ethylcarbonyloxy) propyl, 2- or 4- (ethylcarbonyloxy) butyl, propylcarbonyloxymethyl, 2- (propylcarbonyloxy) ethyl, 2 - or 3- (propylcarbonyloxy) propyl, 2- or 4- (propylcarbonyloxy) butyl, cyclopentyl, cyclohexyl or cycloheptyl.

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

The radicals R ⁵ , R ⁹ and Ri ° are, for example, mono- or dimethyl-carbamoyl, mono- or diethylcarbamoyl, mono- or dipropyl-carbamoyl or mono- or dibutylcarbamoyl.

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy.

The radicals R ⁶ and R ¹³ are, for example, formylamino, methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino or isopropylcarbonylamino.

T ¹ radicals are furthermore, for example, 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-bromophenyl, 2-, 3- or 4-methoxyphenyl, 2- , 3- or 4 -nitrophenyl, 2-, 3- or 4-carboxyl-phenyl, 2-, 3- or 4-acetylphenyl, 2-, 3- or -acetylamino-phenyl, 2-, 3- or 4-methylsulfonylphenyl , 2-, 3- or -sulfamoylphenyl or 2-, 3- or 4-carbamoylphenyl.

The radicals R ⁸ , R ⁹ , R ¹⁰ and R ¹⁵ are furthermore, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl.

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

Other suitable R ¹³ radicals are, for example, hydroxysulfonylphenylmethyl, 2-hydroxysulfonylphenylethyl, 2- or 3-hydroxysulfonylphenylpropyl, 2- or 4-hydroxysulfonylphenylbutyl, aminomethyl, 2-aminoethyl, 2- or 3-aminopropyl, 2- or 4-aminobutyl , HydroxysulfonyImethyl, 2-Hydroxysulfonylethyl, 2- or 3-Hydroxysulfonylpropyl, 2- or 4-Hydroxysulfonylbutyl, Acetylaminomethyl, 2-Acetylaminoethyl, 2- or 3-Acetylamino-propyl, 2- or 4-Acetylaminobutyl, 2-Benzoylaminomethyl - 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-methylpheny1, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-cyanopheny1, 2-, 3- or 4 -chloro phenyl, phenylamino, methylamine, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, tert-butylamino or benzoylamino.

HKX ³ coupling components are listed below as examples. Specifically, for example, coupling components of the naphthalene series include 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, l-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 To call 2, 8-dihydroxynaphthalene-6-sulfonic acid.

Furthermore, for example, N-phenyl-1-naphthylamine, N-ethyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1-naphthol, -naphthol, 1, 5 -dihydroxynaphthalene, 1, 6 -dihydroxynaphthalene, 1.7 - Dihydroxynaphthalene, 2, 7 -Dihydroxynaphthalin or 2-Hydroxynaphthalin-3-carboxylic acid to name.

Naphthalenesulfonic acids are, for example, 2-hydroxysulfonyl-methylaminonaphthalene-5 -sulfonic acid or 2-hydroxysulfony1-methyl-aminonaphthalene-6-sulfonic acid.

As aminonaphtholsulfonic acids e.g. 1-acetylamino-8-hydroxy-naphthalene-3, 6-disulfonic acid, 1-benzoylamino -8-hydroxynaphthalene-3, 6-disulfonic acid, 1-acetylamino -8-hydroxynaphthalene-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-hydroxysulfonyImethyl- 8-hydroxynaphthalene-6 -sulfonic acid, 2-hydroxysulfonylmethylamino-8-hydroxynaphthalene-3, 6-disulfino acid, 2-hydroxymethylsulfonyl - 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 To name 2-acetylamino-8-hydroxynaphthalene-6 sulfonic acid.

Aminonaphthalenes such as 1-naphthylamine, 1-naphthylamine-6 -sulfonic acid, 1-naphthylamine-7 -sulfonic acid, 1-naphthylamine-8 -sulfonic acid, 2-naphthylamine-3, 6-disulfonic acid, 2-naphthylamine- 5, 7-disulfonic acid, 2-naphthylamine-6, 8-disulfonic acid, 1-amino-5-ydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid, 1-amino-8-hydroxynaphthalene-2, - disulfonic 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-sulfonic 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-Hydroxynaphthalin- 6 - sulfonic acid to name.

Resorcinol, 2- and 4-methylresorcinol, 3-hydroxyphenyliminodiacetic acid, 2,4-di-hydroxybenzoic acid are examples of benzene coupling components.

Examples of pyrazolone coupling components which can be mentioned are 3-methyl-, 3-carboxy- or 3- (C _! -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' -methoxyphenyl) -, 1- (2 '-methylphenyl) -, 1- (1', 5'-dichlorophenyl) -, 1- (2 ', 6'-dichlorophenyl) -, 1- (2'-methyl-6'-chlorophenyl) -, 1- (2 '-methoxy-5' -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, l- (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- methylpyrazol-5-one, 1-phenylpyrazol-5-one-3-carboxylic acid ethyl ester, pyrazol-5-one-3-carboxylic acid ethyl ester or pyrazol-5 -one-3-carboxylic acid.

hexyl, 1-benzyl υαer -rι_eπyj.-_) - cLuι.u.ιujy-rcizu.-., j. ^■ phenyl) -, 1- (4 '-methylphenyl) -5-aminopyrazole or 1 - phenyl - 3-methyl - 5 - aminopyrazole. N-arylacetoacetamides are especially acetoacetanilide or its phenyl nucleus which is substituted by chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino, hydroxylsulfonyl, carboxyl, carbamoyl or sulfamoyl.

Coupling components derived from pyridine are, for example, the derivatives described in DE-A-2 260 827.

Examples of suitable pyrimidine coupling components are the compounds listed in DE-A-2 202 820, DE-A-2 308 663 or DE-A-3 119 349. 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 '-carboxyethyl) - To name 1- (2 '-carbamoylethyl) -2-methylindole or -2-phenylindole.

Examples of pyridone coupling components are

1-ethyl -2-hydroxy- 4 -methyl- 5 -carbamoylpyrid- 6 -one, 1- (2 '-hydroxyethy1) 2 -hydroxy- 4 -methy1 - 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-methyl-5-cyanopyrid-6-one, 1-methyl -2-hydroxy-5-acetylpyride - 6 -on, 1, 4 -dimethyl -2 -hydroxy- 5 -cyanopyrid- 6 -on, 1, 4 -dimethyl - 5 -carbamoylpyrid- 6 -on, 2, 6 -dihydroxy- 4 -ethyl - 5-cyanopyridine , 2-hydroxy-4-ethyl-5-carbamoylpyrid-6-one, 1-ethyl-2-hydroxy-4-methyl-5-hydroxysulfonyl-methylpyrid-6-one, 1-methyl -2-hydroxy-4-methyl 5-methylsulfonylpyrid-6-one or 1-carboxymethyl-2-hydroxy-4-ethyl-5-phenylsulfonyl-pyrid-6-one to name.

Coupling components HK-NH ₂ carrying amino groups are capable of oligomerization owing to their amino group. Coupling components of the benzene series bearing amino groups, such as o-, m- and p-phenylenediamine, 3-aminophenol, 4-methyl-3-aminophenol, 5-amino-2-methylphenol, are particularly suitable for oligomerization.

4-ethyl-3-aminophenol, 2, 4-diaminotoluene, 2, 4-diaminobenzenesulfonic 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-aminophenylurea, N-methylaniline , N-methyl-m-toluidine, N-ethyl aniline, N-ethyl-m-toluidine, N- (2-hydroxyethyl) aniline or N- (2-hydroxyethyl) - - toluidine.

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 and apply 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 meaning given above, tetraazotated and coupled to the reaction product of clutch A. The product of the general formula VI obtained in this way

D ³

S0 ₂ (CH ₂ ) _n Y

is now coupled to a HKX ³ coupling component (coupling step C). The order of the coupling steps can be varied depending on the desired target connection. If χ ^{i is} amino or optionally substituted alkylamino, then the Select the above synthesis route while, if χ ^{i 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 e.g. 2-sulfatoethylsulfonylaniline, 2-sulfatoethylsulfonyl-4-sulfoaniline, 4-sulfatoethylsulfonyl-2-sulfoaniline, 3-sulfatoethylsulfonylaniline, 3-sulfatoethyl-4, 6-disulfoaniline, 4 - sulfatoethylsulfonyl -2-4 -sulfoaniline Hydroxyethylsulfonylaniline and 4-sulfatoethylsulfonyl -2-meth-oxyaniline.

As coupling components IV are e.g. l-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic 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-sulfonic 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-hydroxynaphthalene -6-sulfonic acid, 2 -HydroxysulfonyImethylamino- 8 -hydroxy- naphthalin-6 -sulfonic acid called.

Aromatic diamines V which are suitable as starting materials for VI are, for example, 3, 3'-diaminodiphenyl sulfone, 4, 4 'diaminodiphenyl 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, which initially protect an amino group or carry them in the form of a nitro 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 ^x ), with the approximately equimolar amount of a coupling component HK-NH ₂ at a pH of 5 to 14, preferably 6-12, dyes 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 repetitive units. Depending on the desired end group, the residue -S0 ₂ - (CH ₂ ) n-CH = CH _{2 can} then optionally with amines of the formula VII

HN-Z "H I (VII)

D ⁶

or with diamines of formula VIII

HN-Z ² "NH II (VIII),

D ⁶ D ⁷

in which Z ² , D ⁶ and D ^{7 have} the meaning given above, are implemented. As a rule, dye mixtures are obtained which are distinguished by their good surface coloring.

Examples of amines VII are methylamine, ethylamine, n-propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, 1,2-dimethylpropylamine, mono-2-ethylhexylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, Dibutylamine, diisobutylamine, di-sec-butylamine, N-methylbutylamine, N-ethylbutylamine, 2-methoxyethylamine, di-2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, cyclohexylamine, N-monomethylcyclohexylamine, N- Ethylcyclohexylamine, benzylamine, 2-phenylethylamine, 2-diethylaminoethylamine, dimethylaminopropylamine, diethyl - aminopropylamine, ethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, methylethanolamine, 2, 2'-aminoethoxyethanol, 3-aminopropanol, 2-1-aminobutanol , N-methylpiperazinpropylamine, di (carboxymethyl) min, N-methylaminoacetic acid, 4-aminobenzoic acid, 2-methylimidazole and imidazole.

Examples of diamines VIII are ethylenediamine, 1, 2-propylene-diamine, 1, 3-diaminopropane, 3-amino-1-methylaminopropane, neopentanediamine, hexamethylenediamine, 4, 9-dioxadodecane-1, 12-diamine, diethylene triamine, 3 (2-Aminoethyl) aminopropylamine, dipropylenetriamine, N, N'-bis (3 -aminopropyl) ethylenediamine, aminoethylethanolamine, n-propylethanolamine, butylethanolamine and piperazine.

The reaction of the trisazo dyes which carry a vinyl sulfone end group with the diamines VIII leads to the preferred duplication products of the general formula IX D ³

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 double the coupling product of diazo component III and coupling component IV. However, preference is usually given to the solubility of the doubling in the last synthesis step.

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

In general, dyes of the general formula I in which Y represents a radical —CH ₂ CH ^" ₂ -ND ⁵ D ⁶ are preferred. Azo dyes are particularly preferred in which D ⁵ and D ⁶ independently of one another represent hydrogen or a radical Z ² -H are 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 -S0 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 for dyeing natural or synthetic substrates, for example cotton, wool, polyamide and in particular leather. They are also suitable as paper dyes for bulk coloring and recording liquids such as inks, especially for the inkjet.

Leather, dyeings in green, black and blue to navy blue shades with good wet and sweat fastness properties are obtained.

They are particularly suitable for coloring leather surfaces because they also have a high substantivity. The new dyes can be used either alone or in a mixture with one another or in a mixture with other dyes.

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

Manufacture of coupling components

Example A

16.0 g of l-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. A diazonium solution, which was prepared from 14.1 g of p-sulfatoethylsulfonylaniline and 3.5 g of sodium nitrite, was added to this suspension. 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 was adjusted to 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, further coupling components can be obtained with the amines described in Table 1 in an equivalent amount instead of N-methylpiperazine.

Table 1

Example B

The procedure was as in Example A, but instead put _five thylpiperazin 2.2 g of piperazine to N-Me. 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

5

0 λ _ma x (in water): 552 nm and 318 nm

The above structure was confirmed by the mass spectrum (ESI) with a mol peak at 1112 _c .

example 1

79.8 g of l-hydroxy-8-aminonaphthalene-3, 6-disulfonic acid were dissolved in _Q 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-hydroxyethylsulfonylaniline and 17.3 g of sodium nitrite was added to this suspension at 0-5 ° C. After addition of the diazonium solution the pH with solid Natriumbi- _"5 carbonate was set to 1.0, and the reaction solution stirred for 6 hours at room temperature. After this time, no diazonium ion was detectable. A solution was admitted that tion of 65.8 g of 4,4'-diaminodiphenylsulfamide and 34.6 g of sodium nitrite was cooled to 10-12 ° C. and the pH was adjusted to 10 by adding sodium hydroxide solution (10% by weight). 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

λmax (in water): 608 nm, 472 nm, 399 nm

A mass with a molecular weight of 924 can be seen in the mass spectrum (ESI), which corresponds to the structure above.

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 increased 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 dye which had precipitated was filtered off with suction and dried. 25.7 g of a dye of the formula were obtained

λ _m ax (in water): 610 nm, 488 nm, 322 nm

Examples 3-8

The procedure was as in Example 2, but instead of the compound described in Example 2, the compounds described in Examples A-1 to A-6 were used.

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 acid. 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 l-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 now as described in Example 2 and, after drying, 23 g of a dye of the formula were isolated

/ ~

R = SO, CH, CH-N N-CH, ^{2 2} \ / ³

λm _a x (in water): 598 nm, 482 nm, 310 nm

Example 11

A diazonium solution consisting of 70.3 g of p-sulfatoethylsulfonylaniline in 1000 ml of water was added to a suspension of 79.8 g of l-hydroxy-8-amino-naphthalene-3,6-disulfonic acid in 300 ml of water at pH 1.0 and 17.3 g of sodium nitrite was prepared. 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'-diaminodiphenylsulfamide 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 metaphenylenediamine 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,

λmax (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 weights 1921, 2828 and 4563 could be detected by mass spectrometry (ESI). λ x dn water): 596 nm, 454 nm, 400 nm, 310 nm

Example 13

The procedure was as described in Example 11. After finished

42.5 g of imidazole were added to the reaction with metaphenylenediamine 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 was 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. Mass peaks at 974, 1881, 1920, 2536 and 2787 were detected in the mass spectrogram (ESI method), λmax (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, the 46.1% salts, 5.4% water and 48.5% dye contained and colored the leather in deep black tones, λm _a x (in water): 614 nm, 466 nm, 320 nm

Example 15

The procedure was as in Example 11. When the reaction with metaphenylenediamine had ended, 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 was isolated, which colored leather in deep black tones, λmax (in water): 614 nm, 468 nm, 320 nm

Example 16

The procedure was as in Example 11, but metaphenylenediamine 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

λmax (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 component:

Example 21

100 g of a leather tanned in the usual way with a fold thickness of 2.2 mm were in 50 g of water at a temperature of

25 40 ° C with 2 g of sodium acetate and 0.5 g of sodium bicarbonate by walking for 180 minutes and then neutralized after adding 100 g of water at a temperature of 30 ° C overnight in a drum. The leather was then washed by drumming in 200 g of water for 10 minutes. The retanning was then carried out in 30

30 g of water at a temperature of 30 ° C with 13 g of commercially available synthetic tanning agents. The leather was drummed in the retanning liquid for 65 minutes. The dyeing was then carried out by adding 2 g of dye from Example 23 and tumbling at 25 ° C. for 120 minutes. Then 150 g

35 water added and drummed for a further 10 minutes. After adding 1 g of conc. Formic acid was drummed for 30 minutes and the liquor was drained. The leather was washed by adding 200 g of water at a temperature of 40 ° C. and rolling for 10 minutes. The fleet was then drained again. The fat

40 was carried out in 100 g of water at a temperature of 55 ° C. by adding 5 g of a commercially available fat licker by walking for 40 minutes. After acidification with 1 g of formic acid, the mixture was drummed for a further 40 minutes. The leather was then rinsed cold, stretched out, dried, laid in sawdust, and chugged

45 and vacuum dried. A deep black color is obtained, which is particularly intense on the hair side of the leather.

Claims

claims

1. Azo dyes of the general formula I

in the

one of the radicals χ ⁱ and X ² hydroxy and the other amino or optionally substituted with hydroxy, cyano, carboxyl, hydroxysulfonyl, methoxycarbonyl, ethoxycarbonyl or acetoxy -CC ₄ alkylamino

n 0 or 1

m 1 or 2

k 0 or, if X ^{3 is} NH, additionally a number 1, 2, 3 or 4

D ⁱ , D ² , D ³ and D ⁴ independently of one another are hydrogen or hydroxysulfonyl

Z ^{i is} a direct bond or a bridge member of the formula -S0 ₂ NH-A-, -S0 ₂ NAlk-A-, -S0 ₃ -A-, -NH-A-, -NAlk-A-, -S0 ₂ -A -, -SONH-A-, -CONH-A- or -CO-A-, wherein A phenylene, which can be substituted by hydroxysulfonyl or carboxyl, or naphthylene, which can be substituted by hydroxysulfonyl or carboxyl, where A is linked to the azo bridge,

K is the residue of an optionally substituted derivative of the benzene, naphthalene, pyrazole, pyridine, pyridine, indole or N-arylacetoacetamide series

X ^{3 is} hydrogen or amino and

Y is a radical -CH ₂ CH ₂ OH, -CH ₂ CH ₂ -ND ⁵ D ⁵ , -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} Ci-Cβ-alkylene, the 1 to 3 non-adjacent oxygen atoms, imino and optionally substituted by hydroxy or methoxy -CC 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 optionally substituted by hydroxy or methoxy, C ₁ -C ₄ alkyl or D ⁶ and D ⁷ together represent Cι-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

mean.

2. Azo dyes according to claim 1, wherein O ^{1 is} hydrogen.

3. Azo dyes according to claim 1 or 2, wherein Z is a bridge member of the formula -S0 ₂ NH-A-, or -NH-A- and A is the in

Claim 1 has the meaning given.

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.

6. azo dyes according to claims 1 to 5, wherein Y is 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

D3

in the

n, D ⁱ , D ² , D ³ , D ⁴ , D ⁶ , D ⁷ , Z ¹ , Z ² and K have the meaning given 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 D ³

in the

An ^Θ the equivalent of an anion and

γ ^{i represents} a radical -CH = CH ₂ or -CH ₂ CH ₂ Q and

, n, Q, D ⁱ , 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 optionally with an amine of formula VII or VIII

HN-Z ² "H HN-Z" NH

1 (VII) or 1 1 (VII I), D ⁶ D ⁶ D ⁷

in which Z ² , D ⁶ and D ^{7 have} the meaning given in Claim 1.

10. The method according to claim 9, characterized in that the reaction product obtained is then with a diamine of formula VIII

HN-Z ^{2 ~} NH

II (VIII) D ⁶ D ⁷

in which Z ² , D ⁶ and D ^{7 have} the meaning given in Claim 1.

11. dye mixtures obtainable according to the processes of claims 9 and 10.

12. Use of the dyes and their mixtures according to claims 1 to 10 for dyeing natural or synthetic substrates.