DE19740473A1 - Oligomeric azo dyes for dyeing e.g. cotton, wool, polyamide and especially leather - Google Patents

Abstract

Oligomeric azo dyes (I) have alternating tetrazo components and coupling components in >= 4 units consisting of an optionally substituted benzene tetrazo component and coupling component derived from an amino-1-naphthol-mono- or di-sulfonic acid, optionally partly replaced by a benzene derivative. (I) contain >= 4 units of formula (II). D = a tetrazo component of formula (III); and K = a divalent residue of a coupling component of formula (IV), up to 80 mole-% of which may be replaced by a coupling component of formula (V); R<1> = H, hydroxysulfonyl (SO3H), halogen, hydroxyl (OH), methoxy, cyano (CN), carboxyl (COOH), 1-4 C alkoxycarbonyl, carbamoyl, sulfamoyl, mono- or di-(1-4 C)-alkyl-carbamoyl or -sulfamoyl; R<2> = H, SO3H or halogen; R<3> = H or 1-4 C alkyl, optionally substituted by OH, CN, COOH, SO3H, (m)ethoxycarbonyl or acetoxy; n = 1 or 2; R<4>, R<5> = OH, 1-4 C alkoxy, amino, morpholino, NHAlk or N(Alk)2; R<6> = H, COOH, SO3H, 1-4 C alkyl, 1-4 C alkoxy, 1-4 C alkoxycarbonyl, carbamoyl, sulfamoyl, mono- or di-(1-4 C)-alkyl-carbamoyl or -sulfamoyl, NHAlk or -N(Alk)2; and Alk = 1-4 C alkyl, optionally substituted by OH, CN, mono- or di-(1-4 C)-alkylamino, amino, COOH, SO3H, 1-4 C alkoxycarbonyl, carbamoyl, sulfamoyl, mono- or di-(1-4 C)-alkyl)-carbamoyl or -sulfamoyl or morpholinocarbonyl and optionally with one oxygen atom in the chain. An Independent claim is also included for the preparation of (I).

Description

The present invention relates to oligomeric azo dyes with an alternating structure of tetrazo components and coupling components containing at least 4 units of structure I in the molecule

- [DK] - (I)

in the D for a tetrazo component of the formula II

stands in which
R ^{1 is} hydrogen, hydroxysulfonyl, halogen, hydroxy, methoxy, cyano, carboxyl, C ₁ -C ₄ alkoxycarbonyl, carbamoyl, mono- or di- (C ₁ -C ₄ ) -alkylcarbamoyl, sulfamoyl or mono- or di- (C ₁ -C ₄ ) alkylsulfamoyl,
R ^{2 is} hydrogen, hydroxysulfonyl or halogen and
in which K is a divalent radical of a coupling component of the formula III

in which the variables have the following meaning:
R ^{3 is} hydrogen, C ₁ -C ₄ -alkyl, which can be substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, methoxycarbonyl, ethoxycarbonyl or acetoxy,
n 1 or 2,
where up to 80 mol% of component III by a coupling component of formula IV

in the
R ⁴ and R ⁵ independently of one another are hydroxy, C ₁ -C ₄ alkoxy, amino, morpholino or a radical NHAlk or N (alk) ₂ ,
R ^{6 is} hydrogen, carboxyl, hydroxysulfonyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carbamoyl, mono- or di- (C ₁ -C ₄ ) alkylcarbamoyl, sulfamoyl , Mono- or di- (C ₁ -C ₄ ) -alkylsulfamoyl or a radical -NHAlk or -N (alk) ₂ and
Alk C ₁ -C ₄ alkyl, optionally with hydroxy, cyano, mono- or di- (C ₁ -C ₄ ) alkylamino, amino, carboxyl, hydroxysulfonyl, C ₁ -C ₄ alkoxycarbonyl, carbamoyl, mono- or Di- (C ₁ -C ₄ ) -alkylcarbamoyl, sulfamoyl, mono- or di- (C ₁ -C ₄ ) -alkylsulfamoyl or morpholine carbonyl is sub-substituted and is optionally interrupted by 1 oxygen atom,
can be replaced
Processes for their preparation, their use for dyeing and printing natural or synthetic substrates and their mixtures.

DE-A-22 44 991 describes a process for the production of Tetrakisazo dyes, based on N-oxaloyl-1,4-phenylene diamine that doubles with 1-hydroxy-8-aminonaphthalene-3,6-disulfone acid was coupled, subsequent hydrolysis of the protective groups to amino groups, tetrazotization and coupling in a molar ratio of 1: 2 with anilines or phenols. The obtained by this method Dyes, however, have primarily in their use as leather dyes unsatisfactory fastness properties. In particular the wet and Sweat fastness is insufficient.

It was therefore an object of the present invention to provide new azo color to provide substances that are characterized by advantageous application technical properties especially good wet and sweat fastness distinguish units.  

Accordingly, the oligomeric azo specified in the introduction dyes found.

Because the oligomeric azo dyes have multiple hydroxysulfonyl groups and optionally also contain carboxy groups, are also their Salts encompassed by the invention.

Suitable salts here are metal or ammonium salts. Metal salts are in particular the lithium, sodium or potassium salts. Ammonium salts in the sense of the invention are understood to mean those salts which have either unsubstituted or substituted ammonium cations. Substituted ammonium cations are e.g. B. monoalkyl, dialkyl, trialkyl, tetraalkyl or benzyltrialkylammonium cations or cations derived from nitrogen-containing five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium or piperazinium cations or their N-monoalkyl or N, N-dialkyl substituted products. Alkyl is generally straight-chain or branched C ₁ -C ₂₀ alkyl, which can be substituted by 1 to 3 hydroxyl groups and / or interrupted by 1 to 4 oxygen atoms in ether function.

When substituted alkyl radicals in the above formulas occur, they usually have 1 or 2, especially one, Substituents.

R ¹ and R ² are, for. B. fluorine, chlorine and bromine.

R ³ , R ⁶ and Alk are, for. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

R ¹ and R ⁶ are still z. B. methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, mono- or dimethyl carbamoyl, mono- or diethylcarbamoyl, mono- or dipropyl carbamoyl, mono- or dibutylcarbamoyl, mono- or dimethyl sulfamoyl, mono - Or diethylsulfamoyl, mono- or dipropyl sulfamoyl and mono- or dibutylsulfamoyl.

R ⁴ , R ⁵ and R ⁶ are also methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy or tert-butoxy.

R ³ 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, hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl, 2- or 4-hydroxysulfonylbutyl.

R ³ are still z. B. methoxycarbonylmethyl, methoxy carbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 4-meth oxycarbonylbutyl, acetoxymethyl, acetoxyethyl, 2- or 3-acetoxy propyl or 2- or 4-acetoxybutyl.

Residues Alk 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, 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, 2- or 4-acetoxybutyl, Carbamoylmethyl, 2-carbamoylethyl, 2- or 3-carbamoylpropyl, 2- or 4-carbamoylbutyl, mono- or dimethylcarbamoylmethyl, 2-mono- or 2-dimethylcarbamoylethyl, 2- or 3-mono- or 2- or 3-dimethylcarbamoylpropyl, 2- or 4-mono- or 2- or 4-dimethylcarbamoylbutyl, mono- or diethylcarbamoylmethyl, 2-mono- or 2-diethylcarbamoylethyl, 2- or 3-mono- or 2- or 3-diethylcarbamoylpropyl, 2- or 4-mono- or 2- or 4-diethylcarbamoylbutyl, sulfamoylmethyl, 2-sulfamoylethyl, 2- or 3-sulfamoylpropyl, 2- or 4-sulfamoylbutyl, mono- or Dimethylsulfamoylmethyl, 2-mono or 2-dimethylsulfamoylethyl, 2- or 3-mono- or 2- or 3-dimethylsulfamoylpropyl, 2- or 4-mono- or 2- or 4-dimethylsulfamoylbutyl, mono- or Diethylsulfamoylmethyl, 2-mono- or 2-diethylsulfamoylethyl, 2- or 3-mono- or 2- or 3-diethylsulfamoylpropyl, 2- or 4-mono- or 2- or 4-diethylsulfamoylbutyl, mono- or dimethyl aminomethyl, 2-mono- or dimethylaminoethyl, 2- or 3-mono- or Dimethylaminopropyl, 2- or 4-mono- or dimethylamino butyl, mono- or diethylaminomethyl, 2-mono- or diethylamino ethyl, 2- or 3-mono- or diethylaminopropyl, 2- or 4-mono- or Diethylaminobutyl, aminomethyl, 2-aminoethyl, 2- or 3-aminopropyl, 2- or 4-aminobutyl, 2-methoxyethyl or 2-ethoxyethyl.

In the following, aminonaphtholsulfonic acids were used as examples Coupling component III listed. In particular, e.g. B. 1-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxy naphthalene-4-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-di sulfonic acid, 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-8-hydroxy naphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-di  sulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 1-hydroxysulfonylmethylamino-8-hydroxynaphthalene-3,6-disulfone acid, 2-methylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl amino-8-hydroxynaphthalene-6-sulfonic acid, 2-hydroxysulfonylmethyl to name amino-8-hydroxynaphthalene-6-sulfonic acid.

Coupling components of Formula IV include 3-hydroxyphenylimino diacetic acid, especially resorcinol, 2- and 4-methylresorcinol, 1,3-phenylenediamine, 3-aminophenol, 4-methyl-3-aminophenol, 5-amino-2-methylphenol, 4-ethyl-3-aminophenol, 2,4-diamino toluene, 2,4-dihydroxybenzoic acid and 2,4-diaminobenzenesulfone acid.

In one embodiment of the present invention, the oligomeric azo dyes only bivalent residues K of the coupling components of formula III. However, oligomers are preferred Azo dyes, whose bivalent radicals K differ from coupling compo derived from the formula III and the formula IV, the Share of the latter up to 80 mol% of the total of all couplings components can be.

Preference is given to oligomeric azo dyes in which the proportion of Coupling component IV 10 to 60 mol% of the bivalent radical K is 10 to 60 mol% of component III through the compo nente IV are replaced.

Particularly preferred are oligomeric azo dyes in which 20 to 50 mol% of the aminonaphtholsulfonic acids III through the Component IV are replaced.

Preference is given to oligomeric azo dyes in which the two Azo bridges in the 1,3- or 1,4-position on the phenyl ring of the tetrazo component II stand.

Also preferred are oligomeric azo dyes in which R ^{1 represents} hydrogen, hydroxysulfonyl, carboxyl or sulfamoyl, in particular hydrogen or hydroxysulfonyl.

Oligomeric azo dyes with 1-amino-8-hydroxynaphthalene-4,6-di sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 3-amino-8-hydroxynaphthalene-6-sulfonic acid and especially with 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid as a coupling Components III are generally preferred.

One can be used in the preparation of the oligomeric azo dyes individual tetrazo component as well as a mixture of different tetra zo components of the formula II are used. Likewise are  oligomeric azo dyes by mixing several couplings components III and / or coupling components IV are obtained, covered by the invention. The use of an aminonaphthol acidic mixture enables a nuance of the black color of the products.

The oligomeric azo dyes are obtained by adding a total of 1 molar equivalent of a diamine of the formula V

and / or the formula VI

in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n have the meaning given in claim 1, tetrazotized and coupled with a total of 0.8 to 1.2 mol equivalents of the coupling components III and / or IV , wherein the combined proportion of components VI and IV is not more than 80 mol% of the starting materials III, IV, V and VI.

The diamines of the formulas V and VI can be prepared step by step be put.

According to a process variant which also includes the synthesis of the diamines of the formulas V and VI, the dyestuffs are obtained by 1.95 to 2.05 molar equivalents of an amine of the formula VII

in which X represents nitro or a protected amino group and R ¹ and R ^{2 have} the meaning given in claim 1, diazotized and coupled with a total of one molar equivalent of coupling components III and / or IV, then the radical X by reduction or hydrolysis into an amino group transferred, this diazotized and coupled with a total of 0.8 to 1.2 molar equivalents of the coupling components III and / or IV, with the proviso that no more than 80 mol% of component III is replaced by component IV over the entire reaction are.

The rest X was one with a protecting group provided amino group or preferably the nitro group. The About leadership of these residues in free amino groups by reduction or Hydrolysis is carried out in the usual way.

Protective groups Z for the protected amino group -NH-Z are, for example, hydroxysulfonylmethyl and acid residues such as benzoyl, benzoyl substituted with methoxy, nitro, methyl or halogen, oxaloyl, N-maleinoyl, N-fumaroyl and preferably C ₁ -C ₄ -acyl, ins special formyl and acetyl.

Suitable amino compounds of the formula VII are, for example N-formyl-1,4-phenylenediamine and the corresponding N-acetyl, N-propionyl, N-benzoyl, N-3-sulfobenzoyl, N-3-nitrobenzoyl, N-4-nitrobenzoyl, N-oxaloyl, N-maleinoyl and N-fumaroyl Links; N-sulfo-1,4-phenylenediamine; 1-amino-4-acetylamino benzene-2-sulfonic acid; 1-amino-4-acetylamino-benzene-2,5-disulfone acid and -2,6-disulfonic acid; 1-amino-4-oxaloylaminobenzene-3- sulfonic acid; 1-amino-4-formylamino-2-chlorobenzene, -3-chlorobenzene, -2,5-dichlorobenzene; 1-amino-4-acetylamino-2-chlorobenzene, -3-chlorobenzene, -2,5-dichlorobenzene; 1-amino-4-propionylamino-2- chlorobenzene, -3-chlorobenzene, -2,5-dichlorobenzene; 1-amino-4-oxa loylamino-2-chlorobenzene, -3-chlorobenzene, -2-5, -dichlorobenzene; 1-amino-4-formylamino-2-methyl- or -3-methyl- or 2-carboxy-, 3-carboxy-, 2-methoxy- or 3-methoxybenzene and the ent speaking 4-acetylamino, 4-benzoylamino or 4-oxaloylamino Links.

Nitroanilines such as 2-sulfo-4-nitroaniline, 3-nitro- 4-sulfoaniline and 1,3- and 1,4-nitroaniline used themselves.

In principle, the reaction consists of several steps together. In the first step, a diazotized amine in the mol ratio of about 2: 1 to a coupling component K twice coupled. Then the latent amino groups released and the diamine tetrazotized. In one Another coupling step is the tetrazo component in the mol ratio of about 1: 1 again to a coupling component K basic coupled. This last basic coupling step with its stoichiometry leads to polycondensation.  

In the coupling steps in which the coupling component is completely or partially is a hydroxyaminonaphthalenesulfonic acid to take into account that a full double clutch, such as generally known, first by an acidic and one by itself closing basic coupling step is achieved.

The coupling component can be added in portions. The diazotization or tetrazotation of the amines or diamines follows in a manner known per se, e.g. B. with sodium nitrite acidic conditions usually at temperatures from -5 ° C to 25 ° C. The nitrite is usually used in excess and the Excess nitrite after di- or tetrazotation, for example destroyed with sulfamic acid.

For the coupling steps, it is advisable to work in aqueous Medium. The temperature in both steps is usually from -5 to 25 ° C.

In the acidic coupling step, the pH is in the range of 0 to 4, preferably a pH <2. The coupling time is at least 15 minutes, with a duration of 15 hours is not normally exceeded. As a rule, it is after 2 to 3 hours ended.

The alkaline coupling step is at a pH above 7, preferably carried out in a range from 7.5 to 13. The Setting the desired pH values in the direction of higher values, and, if necessary, keeping constant during the clutch takes place as is generally known by adding ammonium or Alkali metal bases, e.g. B. sodium or potassium hydroxide, carbonate or acetate.

The alkaline coupling is carried out until complete conversion by. By decreasing the diazo or tetrazo component easily determine the end of the reaction. Usually it is End point after approx. 15 minutes to 2 hours after the last addition reached.

Longer stirring times are possible, but usually have the last coupling step has no influence on the polymerization grad. For security reasons, it is recommended that the reaction medium After coupling, the temperature briefly increases to around 50 ° C heat to destroy the last traces of the tetrazo component.  

The chain termination occurs in the polycondensation step e.g. B. by further coupling to a coupling component before no longer has a reactive end, or by decomposition of diazonium salt.

In a preferred process variant, 1.95 to is diazotized 2.05 molar equivalents of an amine of formula VII and couples 1 mol equivalent of a coupling component III, where up to 60, preferably up to 20 mol% of component III by a compo nente IV can be replaced and then transfers the rest X ß by reduction or hydrolysis in an amino group, diazo tiert these and couples them with 0.8 to 1.2 molar equivalents a coupling component IV. Particular preference is given to the first Coupling step only component III used.

According to another process variant, the oligomeric azo dyes made by adding 1.95 to 2.05 molar equivalents of an amine of formula VII diazotized and with one molar equivalent a coupling component IV couples, then the rest X converted into an amino group by reduction or hydrolysis, this diazotized and with 0.8 to 1.2 molar equivalents Coupling component III couples, with up to 60 mol% of Component III can be replaced by a component IV.

In all process variants that link the diamonds to V and VI, is preferably 1 mol in this step equivalent coupling component 1.98 to 2.02 molar equivalents particularly preferably coupled equimolar amounts of amine VII.

In all process variants, polycondensation step 1 Molar equivalent of diamine V and / or VI with preferably 0.95 to 1.05 mole equivalent, especially equimolar amount of coupling component coupled.

The preferred oligomeric azo dyes in which the proportion of component IV less than 50 mol% of the total coupling component K is obtained by the first or second Coupling step a mixture of components III and IV is set and in the other step pure component III.

The degree of polycondensation of the azo dyes according to the invention is dependent on synthesis conditions, feed materials and their Stoichiometry. However, it is believed that the polycondden degree of termination due to termination reactions does not exceed 100.

Particularly preferred are oligomeric azo dyes, their re collection unit is at least 5 on average.  

The azo color obtainable by the methods described above substances are mixtures with an average polycondensation grad. Their separation is possible, but not necessary. Before those obtained by the method according to the invention are partially obtained union dye mixtures used without further separation.

The oligomeric azo dyes according to the invention are at pH values well water soluble above 8.

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 coloring and recording liquids such as inks, especially for the Inkjet, suitable.

You get dyeings on leather with good wet and sweat fastness units.

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

example 1

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

• a) 6.9 g (0.05 mol) of 4-nitroaniline were in 75 ml of water and 25 ml of 5N hydrochloric acid submitted. 100 g of ice and 15.5 ml a 3.3 molar sodium nitrite solution was added. You let Stir for 45 min at 0-5 ° C and then removed the nitrite excess with sulfamic acid.
• b) 8.53 g (0.025 mol) were added to this diazonium salt solution Given 1-amino-8-naphthol-3,6-disulfonic acid. It was left for 90 min Stir at 5-10 ° C. The pH was then 0.3. Then 0.8 g of sodium acetate were added and 20% by weight Sodium hydroxide solution adjusted to pH 5. After half an hour at 5-10 ° C was adjusted to pH 7-8 with 20% by weight sodium hydroxide solution and then left to stir for 15 hours at room temperature.
• c) The reaction mixture was at room temperature with a solution of 11.33 g of sodium sulfide in 40 ml of water. After a stirring time of one hour was left within a mixture of 13.9 g of hydrogen for half an hour  Add peroxide and 18 ml of water so that the temperature did not rise above 33 ° C.
• d) After one hour, the reaction mixture was cooled to 0 ° C and gave 17 ml of a 3.3 molar sodium nitrite solution as well Add 25 ml of concentrated hydrochloric acid. It was left for 90 minutes Stir in 0-5 ° C and then removed the excess nitrite with Amidosulfonic acid. 2.75 g were added to this diazo suspension 0.025 mol resorcinol, which with the help of 50 wt .-% Sodium hydroxide solution had been dissolved in 150 ml of water. You asked with 20% by weight sodium hydroxide solution, a pH of 9.5-10 and left two hours at 5 ° C and fifteen hours at room stir temperature. Then with concentrated salt acid adjusted to pH 1.5 and the failed dye filtered off and dried. 16.9 g (98% of the Theory) of a black dye powder. The dye was suitable for the production of black, lightfast Leather dyes.

Analogously to Example 1, 4 mmol of 4-nitroaniline, 25 mmol 1-amino-8-naphthol-3,6-disulfonic acid (Ex. 1.1 and 1.2) or 1-amino-8-naphthol-4,6-disulfonic acid (Ex. 1.3, 1.4 and 1.5) and 25 mmol of the coupling components IV listed in Table 1 Obtain dyes that dye leather with good fastness properties.

Table 1

Example 2

• a) 0.025 mol of 3-nitroaniline were as in Example 1a diazotized. 0.025 mol were added to this mixture at 0-5 ° C Given 1-amino-8-naphthol-3,6-disulfonic acid. Two were stirred Hours at 5-10 ° C and then raised the pH with Sodium acetate 2. It was two under the same conditions Stirred for an additional twelve hours at room temperature. Then another 0.025 mol of diazotized 3-nitroaniline was added given. The pH was then 20% by weight with sodium hydroxide solution set to 7-8 before stirring at 5-10 ° C for two hours has been.  
• b) 11.3 g of sodium sulfide dissolved in 40 ml of water were added and 13.9 g of hydrogen dripped within half an hour peroxide 30 wt .-%, dissolved in 18 ml of water without a Temperature of 33 ° C was exceeded. It became another stirred for half an hour at room temperature.
• c) The mixture was cooled to 0-5 ° C. There were 17 ml a 3.3 molar sodium nitrite solution and 25 ml hydrochloric acid 37 wt .-% added, stirred at 0-5 ° C for one and a half hours and the excess nitrite is removed with amidosulfuric acid. To the reaction mixture was 0.025 mol resorcinol, with sodium lye 50 wt .-% dissolved in 150 ml of water, added and the pH adjusted to 9-10. It was only two hours ago 5-10 ° C then stirred for a further 12 hours at room temperature. The mixture was heated to 50 ° C. for two hours and the mixture was made up to 37% by weight Hydrochloric acid adjusted the pH to about 1.5 and isolated it fallen solid.

Analogously to Example 2, 1-amino-8-naphthol-3,6- disulfonic acid and 50 mmol of the amine VII listed in Table 2 and 25 mmol coupling components IV obtained dyes that Dye leather with good fastness properties.

Table 2

Example 3

0.050 mol of 4-nitroaniline-2-sulfonic acid as described under 1a) diazotized. 0.050 mol of 3-amino were added to this mixture at 0-5 ° C phenol (coupling component IV), dissolved in 75 ml of water let run. The mixture was at 0-5 ° C and two hours stirred for a further 12 hours at room temperature. Then became white tere 0.050 mol of diazotized 4-nitroaniline-2-sulfonic acid was added. The pH was then adjusted to 4-5 with 20% strength by weight sodium hydroxide solution put before one hour at 0-5 ° C and 12 hours at room temperature was stirred.  

• b) 22.66 g of sodium sulfide dissolved in 80 ml of water were added and dripped 27.8 g within half an hour 30% by weight hydrogen peroxide, dissolved in 36 ml of water, without exceeding a temperature of 33 ° C. On finally it was half an hour at room temperature stirred. The mixture was cooled to 0-5 ° C.
• d) 34 ml of a 3.3 molar sodium were added to this mixture nitrite solution and 50 ml of 37% by weight hydrochloric acid are added, stirred for one and a half hours at 0-5 ° C and the excess nitrite removed with amidosulfuric acid. In the reaction mixture 0.050 mol of 1-amino-8-naphthol-3,6-disulfonic acid was added and stirred for half an hour at pH <1 and 0-5 ° C. The pH was slowly adjusted to 7-8 with 20% by weight sodium hydroxide solution posed. First it was an hour at 5-10 ° C then more Stirred for 12 hours at room temperature. Then heated it was set at 50 ° C. for two hours, with 37% by weight salt acid the pH to about 1.5 and isolated the falling solid.

Analogously to Example 3, 4-nitroaniline-2-sulfone was converted from 100 mmol acid, 50 mmol of the coupling components listed in Table 3 IV and 25 mmol 1-amino-8-naphthol-3,6-disulfonic acid dyes receive that dye leather with good fastness properties.

Table 3

Example 4

• a) 0.050 mol of 4-nitroaniline-2-sulfonic acid were as in 1a) described diazotized. This mixture was at 0-5 ° C. 0.025 mol and 0.025 mol 1-amino-8-naphthol-3,6-disulfonic acid given. The mixture was at pH <1 for three hours at 0-5 ° C and stirred for a further 12 hours at room temperature. Then was the further 0.050 mol of diazotized 4-nitroaniline-2-sulfonic acid admitted. The pH was then adjusted with 20% by weight sodium bicarbonate alkali set to 4-5 before one hour at 0-5 ° C was stirred. The pH was raised to 7-8 and stirred for 12 hours at room temperature.  
• b) 22.66 g of sodium sulfide dissolved in 80 ml of water were added and dripped 27.8 g within half an hour 30% by weight hydrogen peroxide, dissolved in 36 ml of water, without exceeding a temperature of 33 ° C. It was stirred for half an hour at room temperature. The mixture was cooled to 0-5 ° C.
• c) 34 ml of a 3.3 molar sodium nitrite solution and 50 ml of 37% strength by weight hydrochloric acid were added, the mixture was stirred at 0-5 ° C. for one and a half hours and the excess nitrite was removed with amidosulfuric acid. 0.050 mol of resorcinol, dissolved in 75 ml of water, was run into the reaction mixture and the mixture was stirred at pH <1 and 0-5 ° C. for half an hour. The pH was slowly adjusted to 8-9 with 20% by weight sodium hydroxide solution.
  The mixture was first stirred at 5-10 ° C. for two hours and then at room temperature for another twelve hours. The mixture was heated to 50 ° C. for two hours, the pH was adjusted to about 1.5 with 37% strength by weight hydrochloric acid and the precipitated solid was isolated.

Analogously to Example 4, 25 mmol of resorcinol, 25 mmol of 1-amino naphthol-3,6-disulfonic acid, 100 mmol 4-nitroaniline-2-sulfonic acid and 50 mmol of the coupling components IV listed in Table 4 in c) obtain dyes that dye leather with good fastness properties.

Table 4

Example 5

• a) 0.05 mol of 4-nitroaniline-2-sulfonic acid were as in Example 1a) described diazotized. To this mixture were 0-5 ° C 0.01875 mol 1-amino-8-naphthol-3,6-disulfonic acid and Given 0.00625 mol. The mixture was stirred at 0-5 ° C for one and a half hours and then raised the pH with sodium acetate and 20% by weight sodium hydroxide solution to 4.5-5. Staying the same the conditions were stirred for a further half an hour. The pH was then adjusted to 8-9 with 20% strength by weight sodium hydroxide solution adjusted before stirring at room temperature for 12 hours has been.  
• b) 11.3 g of sodium sulfide dissolved in 40 ml of water were added and dripped 13.9 g within half an hour 30% by weight hydrogen peroxide, dissolved in 18 ml of water, without exceeding a temperature of 33 ° C. It was stirred for half an hour at room temperature. The mixture was cooled to 0-5 ° C.
• c) 17 ml of a 3.3 molar sodium were added to this mixture nitrite solution and 25 ml 37% by weight hydrochloric acid added, stirred for one and a half hours at 0-5 ° C and the excess nitrite removed with amidosulfuric acid. To the reaction mixture 0.025 mol of resorcinol was added half an hour after stirred and the pH adjusted to 9-10. It was only two Hours at 5-10 ° C then another 12 hours at room temperature touched. The mixture was heated to 50 ° C. for two hours and then put into the oven 37 wt .-% hydrochloric acid, the pH to about 1.5 and iso gelled the precipitated solid.

Analogously to Example 5, 1-amino-8-naphthol-3,6- disulfonic acid and y mmol resorcinol in substep a) in the Amounts to be taken in Table 5, 50 mmol of 4-nitroaniline-2-sufone Acid and 25 mmol resorcinol dyes obtained with leather dye good fastness properties.

Table 5

Example 6

• a) 0.100 mol of 4-nitroaniline-2-sulfonic acid were as in Bei game 1a) described diazotized. To this mixture given at 0-5 ° C 0.050 mol resorcinol. One stirred one and a half Hours at 5-10 ° C and then raised the pH with 20% by weight sodium hydroxide solution on 9-10. It has been 12 hours stirred at room temperature.  
• b) 22.6 g of solution dissolved in 80 ml of water were added to this mixture Sodium sulfide and dripped within half an hour 27.8 g of 30% by weight hydrogen peroxide, dissolved in 36 ml Water without exceeding a temperature of 33 ° C has been. It was still half an hour at room temperature stirred. The mixture was cooled to 0-5 ° C.
• c) Then 34 ml of a 3.3 molar sodium nitrite Solution and 50 ml of 37 wt .-% hydrochloric acid added, one and a half Stirred at 0-5 ° C for hours and the excess nitrite with amido removed sulfuric acid. To the reaction mixture 0.025 mol resorcinol and 0.025 mol 1-amino-8-naphthol-3,6-di added sulfonic acid and after half an hour at pH <1 touched. Then the pH with 20 wt .-% sodium hydroxide solution raised to 9-10 and then two more hours at 5-10 ° C Stirred for 12 hours at room temperature. Two were heated Hours at 50 ° C, adjusted the pH with 37 wt .-% hydrochloric acid to about 1.5 and isolated the precipitated solid.

Analogously to Example 6, 100 mmol of nitroaniline-2-sulfonic acid were used and 50 mmol resorcinol in substep a) and Table 6 taking x mmol coupling component IV and y mmol coupling Component III in sub-step c) receive dyes, the leather dye with good fastness properties.

Table 6

Example 7

0.05 mol of acetparamic acid were stirred in 100 g of ice water and dissolved with sodium hydroxide solution at pH <7. 15.5 ml a 3.3 molar sodium nitrite solution and then 25 ml 5 molar hydrochloric acid added. After stirring for three hours at 0-5 ° C the excess nitrite was removed with amidosulfonic acid. (Diazo solution).

0.05 mol of 1-amino-8-naphthol-3,6-di were added to the diazo solution sprinkled sulfonic acid and the pH within 0.5 hours raised to 2 with sodium acetate. After one hour at 0-5 ° C the pH was raised to 4 and raised for 16 hours Warmed up to room temperature.

A further 0.05 mol of acetparamic acid was described according to the above benen manner and the reaction cooled to 0-5 ° C. mixture added. The pH was initially at 7.5 and after 1.5 hours to 9. The clutch was on during sixteen hour stirring at room temperature completed.  

30 g of solid sodium hydroxide were added to this mixture and the temperature raised to 80-85 ° C for 2.5 hours.

After cooling to room temperature, 100 g Cooled ice to 0-5 ° C and adjusted the pH to 1 with hydrochloric acid lowers. Then 41 mL portions of a 3.3 molar were added in portions Sodium nitrite solution added and 2.5 hours with this Temperature stirred. The excess nitrite was treated with amidosulfone acid removed.

0.05 mol resorcinol, dissolved in 50 mL water, was added and stirred for half an hour. The pH was adjusted with sodium hydroxide solution 50% set to 9-10 and the clutch by 16 hours Stir complete. The reaction mixture was two hours heated to 50 ° C before pH with concentrated hydrochloric acid reduced to 1-2 and the precipitated solid was isolated. After drying, 77.4 g of a black powder were obtained Dyes leather in a greenish black shade.

Example 8

Instead of acetparamic acid, Acet metamic acid used. 79.8 g of a black were obtained Powder that dyes leather in a dark brown shade.

Claims (9)

1. Oligomeric azo dyes with an alternating structure of tetrazo components and coupling components, containing at least 4 units of structure I in the molecule
- [DK] - (I)
in the D for a tetrazo component of the formula II
stands in which
R ^{1 is} hydrogen, hydroxysulfonyl, halogen, hydroxy, methoxy, cyano, carboxyl, C ₁ -C ₄ alkoxycarbonyl, carbamoyl, mono- or di- (C ₁ -C ₄ ) -alkylcarbamoyl, sulfamoyl or mono- or di- (C ₁ -C ₄ ) alkyl sulfamoyl,
R ^{2 is} hydrogen, hydroxysulfonyl or halogen and
in which K is a divalent radical of a coupling component of the formula III
in which the variables have the following meaning:
R ^{3 is} hydrogen, C ₁ -C ₄ -alkyl, which can be substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, methoxycarbonyl, ethoxycarbonyl or acetoxy,
n 1 or 2,
where up to 80 mol% of component III by a coupling component of formula IV
in the
R ⁴ and R ⁵ independently of one another are hydroxy, C ₁ -C ₄ alkoxy, amino, morpholino or a radical NHAlk or N (alk) ₂ ,
R ^{6 is} hydrogen, carboxyl, hydroxysulfonyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carbamoyl, mono- or di- (C ₁ -C ₄ ) alkylcarbamoyl, sulfamoyl , Mono- or di- (C ₁ -C ₄ ) -alkylsulfamoyl or a radical -NHAlk or -N (alk) ₂ and
Alk C ₁ -C ₄ alkyl, optionally with hydroxy, cyano, mono- or di- (C ₁ -C ₄ ) alkylamino, amino, carboxyl, hydroxysulfonyl, C ₁ -C ₄ alkoxycarbonyl, carbamoyl, mono- or Di- (C ₁ -C ₄ ) -alkylcarbamoyl, sulfamoyl, mono- or di- (C ₁ -C ₄ ) -alkylsulfamoyl or morpholine carbonyl is substituted and is optionally interrupted by 1 oxygen atom,
can be replaced. 2. Oligomeric azo dyes according to claim 1, in which 10 to 60 mol% of coupling component III through a coupling component IV are replaced. 3. Process for the preparation of oligomeric azo dyestuffs according to Claim 1 or 2, characterized in that a total of 1 mol equivalent of a diamine of the formula V
and / or the formula VI
in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n have the meaning given in claim 1, tetrazotized and coupled with a total of 0.8 to 1.2 molar equivalents of coupling components III and / or IV, the combined proportion of components VI and IV being no more than 80 mol% of the starting materials III, IV, V and VI. 4. A process for the preparation of oligomeric azo dyes according to claim 1 or 2, characterized in that 1.95 to 2.05 molar equivalents of an amine of the formula VII
in which X represents nitro or a protected amino group and R ¹ and R ^{2 have} the meaning given in claim 1, diazotized and coupled with a total of one molar equivalent of coupling components III and / or IV, then the radical X by reduction or hydrolysis into an amino transferred group, this diazotized and coupled with a total of 0.8 to 1.2 molar equivalents of coupling components III and / or IV, with the proviso that no more than 80 mol% of component III are replaced by component IV over the entire reaction . 5. Process for the preparation of oligomeric azo dyes Claim 4, characterized in that one 1.95 to 2.05 molar equivalents of an amine of the formula VII diazotized and with a molar equivalent of a coupling component III, where up to 60 mol% of component III by a compo nente IV can be replaced, couples, then the rest x by reduction or hydrolysis into an amino group leads, diazotized and with 0.8 to 1.2 molar equivalents Coupling component IV couples.   6. Process for the preparation of oligomeric azo dyes Claim 3, characterized in that 1.95 to 2.05 molar equivalents of an amine of the formula VII diazotized and with one mole equivalent of a coupling component IV couples, then the rest X by reduction or Hydrolysis converted into an amino group, this diazotized and with 0.8 to 1.2 mole equivalent of a clutch compo nente III couples, with up to 60 mol% of component III can be replaced by a component IV. 7. Process for the preparation of oligomeric azo dyes Claim 3, characterized in that the radical X is nitro means. 8. Oligomeric azo dyes obtainable according to the methods of Claims 3 to 7. 9. Use of the oligomeric azo dyes according to the claims chen 1, 2 or 8 for dyeing and printing natural or synthetic substrates.