DE3940081A1 - Azo dyes with 1,3,4-thia:di:azole and julolide residues - give fast red to blue shades e.g. on wool and polyamide(s) - Google Patents

Abstract

Azo dyes of formula (I) are new, in which R1 = -SR5, -COOR6 or opt. substd. phenyl; R2 = H, halogen, opt. substd. 1-8C alkyl, 1-8C alkoxy, phenoxy or 2-4 C alkanoylamino, R3 = H or opt. substd. 1-8 C alkyl, R4 = H, opt. substd. 1-8 C alkyl, halogen, -OH, 1-8 C alkoxy, phenoxy, -SO3H, -OSO3H or -S2O3H, X = a direct bond, -O- or -CHR7-, R5 = opt. substd. 1-8 C alkyl or opt. substd. benzyl, R6 = opt. substd. 1-8 C alkyl, R7 = H or opt. substd. 1-8 C alkyl, with the proviso that the cpd. contains at least one sulpho-, sulphato- or thiosulphato gp. Claimed cpds. (I) have X = -O- or -CHR7- where R7 = H or 1-4 C alkyl, exp. Me; R2 = H, 1-4 C alkyl, esp. Me, or 1-4 C alkoxy, esp. OMe; R3 = 1-4 C alkyl, esp. Me; R4 = H, 1-4 C alkyl, esp. Me, OH, -SO3H or -OSO3H; R1 = -SR5 where R5 = 1-4C alkyl which is opt. substd. by -SO3H, -S-(CH2)2-4-SO3H or -S-(CH2)2-3-H. Specifically claimed cpds. (I) have R1 = -SCH2CH2R8, R2 = H, Me or OMe, R3 = H or Me, R4 = -SO3H, -OSO3H or OH, R8 = H or -SO3H and X = -O- or a gp. of formula (i). USE/ADVANTAGE - e (I) are useful for dyeing and printing of fibres, yarns, fabrics and knitware made from OH- or N-contg. materials such as cellulose, silk and esp. wool and synthetic polyamides. (I) give level blue and red shades with good general fastness, esp. good light fastness, rub resistance and wet resistance.

Description

The present invention relates to new azo dyes, processes for their Production and use of these dyes for dyeing and printing Fiber materials, in particular textile fiber materials.

The present invention relates to azo dyes of the formula

wherein R₁-SR₅, -COOR₆ or optionally substituted phenyl, R₂ is hydrogen, halogen, optionally substituted C₁-C₈ alkyl, C₁-C₈-alkoxy, phenoxy or C₂-C₄-alkanoylamino, R₃ is hydrogen or optionally substituted C₁-C₈ alkyl, R₄ hydrogen, optionally substituted C₁-C₈ alkyl, halogen, hydroxy, C₁-C₈ alkoxy, phenoxy, -SO₃H, -OSO₃H or -S₂O₃H, X the direct bond, -O- or -CHR₇-, R₅ optionally substituted C₁-C₈ alkyl or optionally substi tuated benzyl, R₆ optionally substituted C₁-C₈ alkyl, R₇ is hydrogen or optionally substituted C₁-C₈ alkyl, and which contain at least one sulfo, sulfato or thiosulfato group.

As C₁-C₈ alkyl for R₂, R₃, R₄, R₅, R₆ and R₇ in formula (1) independently z. B. into consideration: methyl, ethyl, propyl, iso propyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, Octyl, and the corresponding radicals, the z. B. by hydroxy, C₁-C₄- Alkoxy such as e.g. B. methoxy or ethoxy, phenyl, sulfo, sulfato, thio sulfato, cyan or halogen are substituted.  

As optionally substituted phenyl for R₁ in formula (1) z. B. by hydroxy, C₁-C₄ alkoxy, such as. B. methoxy or ethoxy, sulfo, Sulfato, thiosulfato, cyan, halogen, or C₁-C₄-alkyl, such as. B. methyl or ethyl, substituted phenyl.

As optionally substituted benzyl for R₅ in formula (1) z. B. by hydroxy, C₁-C₄ alkoxy, such as. B. methoxy or ethoxy, sulfo, Sulfato, thiosulfato, cyan, halogen or C₁-C₄-alkyl, such as. B. methyl or ethyl, benzyl substituted in the phenyl ring.

As C₁-C₈ alkoxy for R₂ and R₄ in formula (1) is independent of one another e.g. B. methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, heptoxy and octoxy into consideration.

As C₂-C₄ alkanoylamino comes for R₂ in formula (1) z. B. acetylamino, Propionylamino, Butyrylamino, Isobutyrylamino and Isovalerylamino in Consider.

Halogen comes independently for R₂ and R₄ in formula (1) e.g. B. fluorine, chlorine, bromine or iodine into consideration.

Preference is given to azo dyes of the formula (1), in which X is -O- or -CHR₇- and R₇ is hydrogen or C₁-C₄ alkyl, especially methyl.

Also preferred are azo dyes of formula (1), wherein R₄ water substance, C₁-C₄-alkyl, especially methyl, hydroxy, -SO₃H or -OSO₃H means. Furthermore, azo dyes of the formula (1) are preferred, in which R₂ Hydrogen, C₁-C₄-alkyl, in particular methyl, or C₁-C₄-alkoxy, especially methoxy. Azo dyes are also preferred of formula (1), wherein R₃ is hydrogen or C₁-C₄ alkyl, in particular Methyl means.

Furthermore, azo dyes of the formula (1) are preferred, in which R₁ -SR₅ means and R₅ optionally substituted by -SO₃H C₁-C₄ alkyl is, in particular wherein R₁

means.  

Azo dyes of the formula (1) in which R 1

R₂ is hydrogen, C₁-C₄ alkyl, especially methyl, or C₁-C₄ alkoxy, especially methoxy, R₃ Hydrogen or C₁-C₄-alkyl, in particular methyl, R₄ hydrogen, C₁-C₄-alkyl, especially methyl, hydroxy, -SO₃H or -OSO₃H, X -O- or -CHR₇- and R₇ is hydrogen or C₁-C₄ alkyl, especially methyl, and which contain at least one sulfo or sulfato group.

Azo dyes of the formula are very particularly preferred

wherein R₈ is hydrogen or -SO₃H, R₂ is hydrogen, methyl or methoxy, R₃ Hydrogen or methyl, R₄ -SO₃H, -OSO₃H or hydroxy and X -O- or -CHCH₃- is.

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

wherein R₁ has the meanings given by formula (1), diazotized and to a coupling component of the formula

wherein R₂, R₃, R₄ and X have the meanings given under formula (1) have, couples, the diazo component of formula (3) at least one  Sulfo group and / or the coupling component of formula (4) at least contains a sulfo, sulfato or thiosulfato group.

The diazotization of the diazo component of the formula (3) is generally carried out by the action of nitrous acid in aqueous mineral acid solution, e.g. B. by the action of nitrosylsulfuric acid in sulfuric acid / acetic acid or acetic acid / propionic acid solution, at low temperature, the coupling on the coupling component of formula (4) in acidic to neutral pH values.

Preferred for the process according to the invention for the production of Azo dyes of the formula (1) coupling components of the formula (4) used, wherein X is -O- or -CHR₇- and R₇ is hydrogen or C₁-C₄-alkyl, especially methyl.

Couplings are also preferred for the method according to the invention Components of the formula (4), wherein R₄ is hydrogen, C₁-C₄-alkyl, in particular special methyl, hydroxy, -SO₃H or -OSO₃H means. Furthermore, for the Process according to the invention coupling components of formula (4) before moves where R₂ is hydrogen, C₁-C₄-alkyl, especially methyl, or C₁-C₄ alkoxy, especially methoxy means. Preferred for the he Methods according to the invention are also coupling components of the Formula (4) in which R₃ is hydrogen or C₁-C₄alkyl, in particular methyl, means.

Furthermore, diazo components are for the process according to the invention Formula (3) preferred, wherein R₁ is -SR₅ and R₅ is optionally by -SO₃H is substituted C₁-C₄ alkyl, especially where R₁

means.

Diazo are particularly preferred for the process according to the invention components of formula (3), wherein R₁

is, diazotized and on coupling components of formula (4), wherein R₂ Hydrogen, C₁-C₄-alkyl, in particular methyl, or C₁-C₄-alkoxy, in particular methoxy, R₃ hydrogen or C₁-C₄ alkyl, in particular Methyl, R₄ hydrogen, C₁-C₄ alkyl, especially methyl, hydroxy, -SO₃H  or -OSO₃H, X -O- or -CHR₇- and R₇ hydrogen or C₁-C₄-alkyl, especially methyl, is coupled, the diazo component being the Formula (3) at least one sulfo group and / or the coupling component of the formula (4) contains at least one sulfo or sulfato group.

One is very particularly preferred for the method according to the invention Diazo component of the formula

wherein R₈ has the meanings given under formula (2), diazotized and to a coupling component of the formula

wherein R₂, R₃, R₄ and X have the meanings given under formula (2) have coupled.

The diazo components of the formula (3) and the coupling components of the Formula (4) are known per se and can be made analogously to known ones Connections are made.

Examples of diazo components of the formula (3) are: 2-amino-5-sulfomethyl-, -5- β -sulfoethyl-, -5- γ -sulfo-n-propyl-5-methyl-, -5-ethyl- , -5-n-propylthil-1,3,4-thiadiazole, 2-amino-5-phenylthio-1,3,4-thiadiazole.

The coupling components of formula (4) are prepared by a compound of the formula

wherein R₂, R₃ and X have the meanings given under formula (1), with a compound of the formula

or

wherein X₁ and Y₁ represent an anionic leaving group and Q is hydrogen, an anionic leaving group or the radical R₄ means to one Compound of formula

implements, wherein R₂, R₃ and X have the meanings given under formula (1) and Q has the meaning given under formula (8), and given if the rest Q, if Q is an anionic leaving group, into one of the converts for R₄ called substituents.

As X₁ and Y₁ in formula (8) and (9) come independently z. B. Halogen, such as chlorine or bromine and toluenesulfonate.

The following may be mentioned as examples of the compounds of the formula (8) or (9): Epichlorohydrin, epibromohydrin, 1,3-dichloropropane, 1-bromo-3-chloropropane.

For example, the compound of formula (4), wherein R₄ sulfato or C₁-C₈ alkoxy is, by sulfation or alkylation of the hydroxyver get loyalty.

The introduction of the substituent R₄ in the meaning of sulfo takes place by nucleophilic substitution, so that the position for the Substi tuenten R₄ depends on the respective reaction conditions.  

The compounds of the formula (4) and the azo dyes of the formula (1) except those where R₄ is hydrogen are stereoisomers, i.e. H. it are always mixtures of Get stereoisomers.

The dyes of the formula (1), which contain at least one sulfo-, sulfato- or contain thiosulfato group, are either in the form of their free acid or preferably as its salts.

The salts include, for example, the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine.

The sodium, lithium, potassium or ammonium salts are an example or called the salt of triethanolamine.

The azo dyes of the formula (1) according to the invention are suitable for known methods for dyeing and printing, especially of nitrogen-containing or hydroxyl-containing fiber materials, such as. B. textile fiber materials made of cellulose, silk and in particular wool and synthetic polyamides. You get level dyeings in blue and red tones with good general fastness properties, especially good rubbing, Wet and light fastness. Furthermore, the invention Dyes can be combined very well with other dyes. The above Textile material mentioned can be in a variety of processing forms are present, such as. B. as fiber, yarn, woven or knitted fabric.

In the following examples, parts represent parts by weight. The tempera doors are degrees Celsius. The relationship between parts by weight and Parts by volume is the same as that between grams and cubic centi meter.

Example 1

30 parts of glacial acetic acid, 10 parts of propionic acid and 1.5 parts of sulfuric acid are placed in a beaker at about 10 ° with stirring. Then 3.4 parts of 2-amino-5- β -sulfoethylthio-1,3,4-thiadiazole (68%) are added and the mixture is cooled to 0 °. The mixture is then diazotized at -2 to 0 ° with 3.4 parts of nitrosylsulfuric acid (40%) and stirred at -2 to 0 ° for 2 hours. The excess nitrosylsulfuric acid is destroyed by adding a part of sulfamic acid and stirring is continued briefly. Then 2.6 parts of 6-hydroxy-1,3,3,8-tetramethyl julolidine, dissolved in 10 parts of ethanol, are added dropwise at 0 ° over the course of 2 minutes. The mixture is stirred at 0 ° for 5 minutes and 24 parts of sodium acetate are added in 4 equal portions within 20 minutes. At a temperature of 0 °, stirring is continued for about 1 hour and then a solution consisting of 6 parts of sodium acetate, 2.5 parts of sodium carbonate and 25 parts of water is added dropwise over the course of 30 minutes, the temperature not exceeding 5 °. The ice bath is removed and 150 parts of a 15% strength aqueous sodium chloride solution are added dropwise in the course of 30 minutes. The dye is suctioned off and dried in vacuo at 50 °. 3 parts of violet powder of a dye are obtained, in the form of the free acid of the formula

corresponds. The dye obtained strongly stains polyamide 6.6 fabric bluish tones of red.

Examples 2 to 7

The procedure is as given in Example 1, used however, instead of 2.6 parts of 6-hydroxy-1,3,3,8-tetramethyljulolidine one equimolar amount of those given in table 1 in column 2 Coupling components, so you get the column 3 in the form of free Acids specified azo dyes, the polyamide-6,6 fabrics in the in Color the shades listed in column 4.  

Table 1

Example 8

In a beaker, 35 parts of glacial acetic acid, 10 parts Propionic acid and 1.8 parts sulfuric acid (98%) at about 10 ° with stirring submitted. Then 2 parts of 2-amino-5-ethylthio-1,3,4-thiadiazole admitted. At -2 to 0 ° 4.25 parts of nitrosylsulfuric acid (40%) added, stirred at this temperature for 2 hours and then 1 part of sulfamic acid added. The solution obtained becomes a solution consisting of 7 parts dimethylformamide and 4.1 parts 6-sulfato-1,3,3,8- Tetramethyljulolidin added dropwise, the temperature not higher than 3 ° increases. The mixture is stirred for 5 minutes and then 24 parts of sodium Acetate added in 4 equal portions within 20 minutes. On finally stirring is continued for 45 minutes at -2 to 0 ° and a solution consisting of 8 parts sodium acetate, 4 parts soda and 45 parts water added dropwise within 30 minutes, the temperature not higher than 5 ° rises. The mixture is then 15% in 200 parts aqueous saline solution entered, the dye is suctioned off and in Vacuum dried at 45 °. 4 parts of reddish powder are obtained Dye in the form of the free acid of the formula

corresponds. The dye obtained strongly stains polyamide 6.6 fabric bluish red hues.

Examples 9-26

The procedure is as given in Example 8, but instead of 4.1 parts of 6-sulfato-1,3,3,8-tetramethyljulolidine, an equimolar amount of the coupling components shown in Table 2 in column 2 and, if appropriate, instead of 2 parts of 2-amino- 5-ethylthio-1,3,4-thiadiazole an equimolar amount of 2-amino-5- β -sulfoethylthio-1,3,4-thia diazole, 2-amino-5-n-hexylthio-1,3,4-thiadiazole , 2-Amino-5- β- hydroxyethyl thio-1,3,4-thiadiazole or 2-amino-5-benzylthio-1,3,4-thiadiazole, the azo color indicated in column 3 in the form of the free acids is obtained fabrics that dye polyamide 6,6 fabrics in the colors listed in column 4.

Table 2

Dyeing Instructions I

10 parts of polyamide 6.6 fabric are dyed in 500 parts of an aqueous Broth containing 2 g / l ammonium acetate and to pH 5 with acetic acid is provided. The proportion of the dye according to Example 1 is 0.7% based on the fiber weight. The dyeing time at one temperature from 98 ° is 30 to 90 minutes. The dyed polyamide 6.6 fabric then removed and washed and dried as usual.

One obtains a strong bluish red-dyed polyamide 6.6 fabric, the one pure shade and good overall fastness.  

Staining instructions II

10 parts of polyamide 6.6 fabric are dyed in 500 parts of an aqueous Fleet containing 1 g / l monosodium phosphate and with disodium phosphate is adjusted to pH 6. The proportion of the dye according to Example 8 is 1%, based on the fiber weight. The dyeing time for one Temperature of 98 ° is 30 to 90 minutes. The colored polyamide-6,6- Tissue is then removed and washed as usual and dried.

One obtains a strong bluish red-dyed polyamide 6.6 fabric, the one pure shade and good overall fastness.

Staining instructions III

10 parts of wool are dyed in 500 parts of an aqueous liquor. Based on the fiber weight, the proportions of dye are 0.8% according to Example 8, calcium on Glauber's salt. 5% and 80% acetic acid 2%. The dyeing time at a temperature of 98 ° is 30-60 minutes. The strongly bluish red, washed and dried as usual Wollstück has very good general fastness properties.

Manufacturing examples Production Example 1

142 parts of 1,2,3,4-tetrahydro-2,2,4,7-tetramethyl quinoline, 149.6 parts epichlorohydrin and 300 parts absolute ethanol are stirred in an autoclave at 150 ° for 24 hours, where a pressure of 5 to 10 bar is established. After cooling down excess epichlorohydrin and ethanol distilled off in vacuo and the residue was distilled in vacuo. 156.1 parts of one are obtained Stereoisomer mixture of the compound of the formula

(1,3,3,8-tetramethyl-2,3,6,7-tetrahydro-1H, 5H-benzo [ÿ] quinolizin-6 - ol) with the boiling point: 145-150 ° at 10 ^-1 mbar.

If one proceeds as indicated in Example 1, but instead of 142 parts of 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline an equimolar Amount of 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline used and instead of ethanol chlorobenzene used as a solvent and a reaction temperature of 170 °, you get the compound of formula

Production Example 2

11.4 parts of the preparation example 1 obtained 1,3,3,8-tetramethyl-2,3,6,7-tetrahydro-1H, 5H-benzo [ÿ] chino lizin-6-ol in 30 parts of toluene are added within 15 minutes 9.1 parts of phosphorus oxychloride are added, the temperature being Ice / water cooling is kept below 45 °. After the addition is warmed up one at 90 ° for 90 minutes with simultaneous stirring. Subsequently is allowed to cool and 25 parts of a 30% strength are added dropwise with stirring Sodium hydroxide solution so that the temperature does not rise above 35 °. Then the organic phase is separated, the aqueous phase twice with Extracted dichloromethane and the combined organic phases over Dried sodium sulfate. This is obtained after the dichlor has been distilled off methane 11.3 parts of a red oil, which the stereoisomer mixture of Compound of formula

corresponds.  

If you proceed as indicated, but instead of 11.4 parts 1,3,3,8-tetramethyl-2,3,4,7-tetrahydro-1H, 5H-benzo [ÿ] quinolizine-6-o-l an equimolar amount of 3,8-dimethyl-6-hydroxy-1-oxajulolidine used, so a mixture of stereoisomers of the compound of the formula is obtained

Production Example 3

20.7 parts of 1,3,3,8-tetramethyl-2,3,6,7- tetrahydro-1H, 5H-benzo [ÿ] quinolizin-6-ol (92%) in 15 parts of dimethyl formamide at 30 to 35 ° with stirring and dropwise 11.4 parts of chlorine sulfonic acid so that the temperature does not exceed 45 °. To when the addition is complete, the mixture is stirred at 50 ° for a further 75 minutes. After this The reaction solution is cooled at 5 ° into a solution consisting of 13.5 parts of potassium hydroxide and 15 parts of potassium chloride in 70 parts Water entered, the potassium salt of the sulfate ester precipitates. To Filtering and drying in the air you can easily get 39 parts of one reddish substance, 69% of the stereoisomer mixture of the compound of the formula

corresponds.

If you proceed as indicated, but instead of 20.7 parts 1,3,3,8-tetramethyl-2,3,6,7-tetrahydro-1H, 5H-benzo [ÿ] quinolizine-6-o-l an equimolar amount of 1,3,3-trimethyl-2,3,6,7-tetrahydro-1H, 5H-benzo [ÿ] quinolizin-6-ol or 1,3,3-trimethyl-8-methoxy-2,3,6,7-tetrahydro- 1H, 5H-benzo [ÿ] quinolizin-6-ol used, so you get a steroiso mer mixture of the compound of formula  

or a stereoisomer mixture of the compound of the formula

Production Example 4

At 70 to 75 °, 43.1 parts of that according to Production Example 2 obtained compound of formula (129) submitted with stirring and within 5 minutes, 21.1 parts of sodium sulfite, which in 90 parts Water were dissolved, metered. The solution is then 24 hours at 95 ° Internal temperature stirred and after cooling the red colored Solution mixed with 100 parts of water and three times with cold dichlor methane (75 parts each) extracted. The aqueous phase is then on the Rota evaporator evaporated. The residue of a total of 45.6 parts forms a slightly reddish powder.  

Production Example 5

40.8 parts of 1,2,3,4-tetrahydro-2,2,4-trimethyl-7-methoxyquinoline together with 46.2 parts of epichlorohydrin and 170 parts of chlorobenzene for 30 hours at 185 ° and a pressure of approx. 5 bar in an autoclave touched. After cooling, it is distilled. You get 38 parts of one red oil that crystallizes in the refrigerator. The product matches of the formula (135). Melting point: 98-100 °.

Production Example 6

49 parts of 3,6-dimethylbenzoxazine are stirred in an autoclave together with 67.8 parts of epichlorohydrin and 240 parts of isopropanol at 140 ° and 5 bar for 24 hours. After cooling, isopropanol and excess epichlorohydrin are first distilled off in a water jet vacuum and then distilled in a high vacuum (10 ^-1 mbar). The distilled orange oil is after cooling with good stirring in a solution of 150 parts of petroleum ether (40 to 60 °) and 15 parts of ethyl acetate. The precipitated crystals are filtered off and washed with 150 parts of petroleum ether (40 to 60 °). Drying takes place in the air. 41.5 parts of light, light brown solid substance (purity: 97%) are obtained. The compound of formula (136) has a melting point at 79 ° -81 °.

Production Example 7

In a sulfonation flask with reflux condenser, stirrer and internal thermometer 12.6 parts of 3,8-dimethyl-6- hydroxy-1-oxajulolidine (95%), cf. Formula (136), in 16 parts abs lutem Dimethylformamid registered. You drip within 15 minutes 8.4 parts of chlorosulfonic acid (97%) so that the internal temperature is 45 ° does not exceed. After the complete addition of chlorosulfonic acid is stirred for 90 minutes at 50 °. The cooled viscous Solution is then slowly at 10 ° to a solution consisting of 8.4 parts of potassium hydroxide and 8 parts of potassium chloride and 40 parts Water dripped. The potassium salt of the sulfate ester falls after a few Time out in the cold. After drying in a vacuum, it is obtained cabinet at 55 ° 24.8 parts of a yellow powder, which the compound corresponds to the formula (137).

Production Example 8

39.9 parts of 2-methylindoline, 55.5 parts of epichlorohydrin and 155 parts absolute ethanol in an autoclave for 24 hours at 130 ° stirred, a pressure of 7 bar. After cooling down excess epichlorohydrin and ethanol distilled off in vacuo and the residue was distilled in vacuo. 44.2 parts of a stereo are obtained isomeric mixture of the compound of formula (138).

Claims (12)

1. Azo dyes of the formula wherein R₁ -SR₅, -COOR₆ or optionally substituted phenyl, R₂ is hydrogen, halogen, optionally substituted C₁-C₈-alkyl, C₁-C₈-alkoxy, phenoxy or C₂-C₄-alkanoylamino, R₃ is hydrogen or optionally substituted C₁-C₈-alkyl, R₄ hydrogen, optionally substituted C₁-C₈-alkyl, halogen, hydroxy, C₁-C₈-alkoxy, phenoxy, -SO₃H, -OSO₃H or -S₂O₃H, X the direct bond, -O- or -CHR₇-, R₅ optionally substituted C₁- C₈-alkyl or optionally substituted benzyl, R₆ is optionally substituted C₁-C₈-alkyl, R₇ is hydrogen or optionally substituted C₁-C₈-alkyl, and which contain at least one sulfo, sulfato or thiosulfato group. 2. Azo dyes according to claim 1, wherein X is -O- or -CHR₇- and R₇ Is hydrogen or C₁-C₄ alkyl, especially methyl 3. azo dyes according to any one of claims 1 and 2, wherein R₂ is water substance, C₁-C₄-alkyl, especially methyl, or C₁-C₄-alkoxy, in particular Methoxy means. 4. azo dyes according to any one of claims 1 to 3, wherein R₃ is hydrogen or C₁-C₄ alkyl, especially methyl. 5. azo dyes according to any one of claims 1 to 4, wherein R₄ water substance, C₁-C₄-alkyl, especially methyl, hydroxy, -SO₃H or -OSO₃H means.   6. Azo dyes according to any one of claims 1 to 5, wherein R₁ -SR₅ means and R₅ optionally substituted by -SO₃H C₁-C₄ alkyl is. 7. azo dyes according to any one of claims 1 to 5, wherein R₁ means. 8. azo dyes according to any one of claims 1 to 7, wherein R₁ R₂ is hydrogen, C₁-C₄-alkyl, especially methyl, or C₁-C₄-alkoxy, especially methoxy, R₃ is hydrogen or C₁-C₄-alkyl, especially methyl, R₄ hydrogen, C₁-C₄-alkyl, especially methyl, hydroxy, -SO₃H or -OSO₃H, X -O- or -CHR₇- and R₇ is hydrogen or C₁-C₄-alkyl, in particular methyl, and which contain at least one sulfo or sulfato group. 9. Azo dyes according to claim 1 of the formula wherein R₈ is hydrogen or -SO₃H, R₂ is hydrogen, methyl or methoxy, R₃ is hydrogen or methyl, R₄ -SO₃H, -OSO₃H or hydroxy and X is -O- or -CHCH₃-. 10. A process for the preparation of azo dyes according to claim 1, characterized in that an amine of the formula wherein R₁ has the meaning given in claim 1, diazotized and on a coupling component of the formula wherein R₂, R₃, R₄ and X have the meanings given in claim 1, couples, and wherein the diazo component of the formula (3) contains at least one sulfo group and / or the coupling component of the formula (4) contains at least one sulfo, sulfato or thiosulfato group . 11. Use of the azo dyes according to claims 1 to 9, or Azo dyes obtained according to claim 10 for dyeing or printing. 12. Use of the azo dyes obtained according to claim 11 for dyeing or printing on natural or synthetic polyamide fiber materials lien.