DE2727383A1 - AZO DYES OF THE PYRIDONE SERIES - Google Patents

Description

The invention relates to compounds in one of the possible tautomeric forms of the formula I correspond in the

D is a remainder of the formula n

R is hydrogen, optionally substituted alkyl, cycloalkyl, aralkyl or aryl,

R [high] 1 hydrogen, alkyl, trifluoromethyl, alkoxy, chlorine, bromine, alkylsulfonyl, phenylsulfonyl, benzoyl, optionally substituted carbamoyl or sulfamoyl or cyano,

R [high] 2 hydrogen, chlorine, bromine, alkyl, hydroxy, alkoxy, nitro or optionally substituted carbamoyl or sulfamoyl,

R [high] 3 hydrogen, chlorine, alkyl or alkoxy,

R [high] 4 hydrogen, chlorine, bromine or alkyl,

R [high] 5 hydrogen, chlorine, bromine or alkyl or

R [high] 4 and R [high] 5 complement the naphthalene ring,

T methyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl or nitro,

X cyan or carbon ester,

Y methyl or carbon ester and

Z denotes hydrogen, chlorine or bromine.

R radicals are in addition to hydrogen z. B. C [deep] 1- to C [deep] 16-alkyl, which is still interrupted by oxygen and by hydroxy, C [deep] 1- to C [deep] 8-alkoxy, cyano, chlorine, bromine, phenoxy or phenyl may be substituted, cyclohexyl, norbornyl, phenyl-C [deep] 1- to C [deep] 4-alkyl or phenyl optionally substituted by methyl, ethyl, methoxy, ethoxy, acetylamino or chlorine.

Examples include:

Methyl, ethyl, n- and iso-propyl, n-butyl, iso-butyl, n-octyl, 2-ethylhexyl, stearyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3 - (2-Ethylhexoxy) propyl, 2-hydroxyethyl, 2-chloroethyl, cyclohexyl, 2-methylcyclohexyl, benzyl, 2-phenylethyl, 2-phenylpropyl, norbornyl, 3-phenoxypropyl, 3- (2'-phenoxyethoxy) propyl, Benzyloxypropyl, phenyl, 2-chlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2-methylphenyl, 2,5-dimethylphenyl, 2,4-dimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxy-4-chlorophenyl, 4-acetylaminophenyl, 1-naphthyl.

Alkyl and alkoxy radicals R [high] 1 have, for example, 1 to 8 carbon atoms, preferably 4 to 8 carbon atoms. In particular, let CH [deep] 3, C [deep] 2H [deep] 5, C [deep] 3H [deep] 7, C [deep] 4H [deep] 9, OCH [deep] 3, OC [deep] 2H [deep] 5, OC [deep] 3H [deep] 7, OC [deep] 4H [deep] 9 and especially C [deep] 5H [deep] 11, C [deep] 6H [deep] 13, C [deep] 8H [deep] 17, OC [deep] 5H [deep] 11, OC [deep] 6H [deep] 13 or OC [deep] 8H [deep] 17.

Alkylsulfonyl radicals R [high] 1 are z. B. methyl, ethyl, propyl or butylsulfonyl.

The optionally substituted carbamoyl and sulfamoyl radicals R [high] 1 and R [high] 2 correspond to the formulas n.

R [deep] 6 and R [deep] 7, which can be the same or different, have the same meaning as R; in addition, together they can represent a complement to a morpholine, pyrrolidine or piperidine ring.

The alkyl and alkoxy radicals R [high] 2 to R [high] 5 preferably have 1 to 4 carbon atoms. In particular, methyl, ethyl, methoxy or ethoxy come into consideration.

Carbon ester groups X and Y are preferably COOCH [deep] 3, COOC [deep] 2H [deep] 5, COOC [deep] 3H [deep] 7, COOC [deep] 4H [deep] 9, COOC [deep] 2H [deep] 4OCH [deep] 3, COOC [deep] 2H [deep] 4OC [deep] 2H [deep] 5 or COOC [deep] 2H [deep] 4OC [deep] 4H [deep] 9.

A diazonium compound of amines of the formula I can be used to prepare the dyes of the formula I

D-NH [deep] 2

with a coupling component of the formula II II

implement in a manner known per se.

The coupling components of the formula II can, for. B. be prepared according to the method described in the patent (patent application P).

The dyes of the formula I are yellow to red, very extensive (strongly colored) and produce corresponding dyeings on synthetic fibers, in particular polyester, which are generally characterized by very good light, heat-setting and wet fastness properties. The dyeing behavior is also very favorable, and fluctuations in pH and temperature have only a minor influence.

Compounds of the formula I a are of particular importance I a,

in the

D [high] 1 is a remainder of the formulas n

B C [deep] 1- to C [deep] 8-alkyl,

B [high] 1 C [low] 4- to C [low] 8-alkoxy or optionally substituted sulfamoyl,

B [high] 2, B [high] 3 and B [high] 4 hydrogen, nitro, chlorine or methyl,

Z [high] 1 hydrogen or bromine,

T [high] 1 methoxy, ethoxy or nitro and

Y [high] 1 is methyl, carbomethoxy or carboethoxy.

In the following examples, parts and percentages are based on weight, unless otherwise stated.

example 1

49 parts of p-aminoazobenzene are stirred with 1.25 parts of an oxyethylation product of a long-chain saturated alcohol mixture in 250 parts of water overnight. 160 parts of half-concentrated hydrochloric acid are then added and the mixture is stirred for one hour at room temperature. After adding 900 parts of a water / ice mixture, 83 parts of 23% sodium nitrite solution are added dropwise at 0-5 ° C. The mixture is stirred for 3 hours at 0-5 ° C. and the excess nitrite is destroyed with 1.8 parts of sulfamic acid. A filtered solution of 48 parts of 1,4-dimethyl-3-acetyl-6-hydroxypyrid-2-one in 600 parts of 5% sodium hydroxide solution is added to the diazo solution thus prepared. The pH is adjusted to 5-6 by adding 10% sodium hydroxide solution. After the coupling has ended, the product is filtered off with suction, washed salt-free with water and, after drying, 97 parts of the dye of the formula are obtained ,

the polyester fibers dyes in golden yellow tones with very good fastness properties.

Example 2

12 parts of the coupling product of p-chloroaniline on o-toluidine are rubbed with 60 parts of concentrated hydrochloric acid. After standing for 2 hours, 500 parts of a water / ice mixture are added and 20 parts of a 23% strength sodium nitrite solution are added dropwise. The mixture is stirred for 3 hours at 10-20 ° C., filtered and the solution of 8.2 parts of 2,6-dihydroxy-3-acetyl-4-methylpyridine in a mixture of 150 parts of water and 25 parts of 10% sodium hydroxide solution is left with cooling come in. The pH is adjusted to 5.6 by adding 10% sodium hydroxide solution. After uncoupling, it is suctioned off, washed salt-free with water and dried. 18 parts of the dye of the formula are obtained ,

the polyester fabric dyes in an orange shade with very good fastness properties.

Example 3

18 parts of 3,5-dibromo-4-aminoazobenzene are dissolved in 250 parts of 96% strength sulfuric acid. 15 parts of nitrosylsulfuric acid (40-42%) are added dropwise and the mixture is stirred at 10 ° C. for 2 hours. Then it falls onto 500 parts of ice, the excess nitrite is destroyed with a little sulfamic acid and a solution of 10 parts of 1-ethyl-3-acetyl-4-methyl-6-hydroxypyrid-2-one in 250 parts of 10% strength is left Run in sodium hydroxide solution with cooling. The pH is adjusted to 3-4 by adding 10% sodium hydroxide solution. The clutch is finished very quickly. It is filtered off with suction, washed salt-free with water, dried and 28 parts of the dye of the formula are obtained ,

the polyester fabric dyes a reddish yellow with very good fastness properties.

In the following examples, the procedure is analogous to that of Examples 1-3. The diazo and coupling components indicated in the table are used and dyes are obtained whose hue on polyester fabric is listed in the last column.

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Example 46

17.3 parts of 4-chloro-2-nitroaniline are dissolved warm in 100 parts of 46% strength sulfuric acid. After adding 300 parts of ice, 32 parts of a 23% strength sodium nitrite solution are added and the mixture is stirred at 0-5 ° C. for 3 hours. The solution of 18.5 parts of 1,4-dimethyl-3-acetyl-6-hydroxypyrid-2-one in 200 parts of 5% sodium hydroxide solution is allowed to flow into the diazo solution thus prepared. The pH is adjusted to 4 - 5 by adding dilute sodium hydroxide solution. After the coupling has been removed, the product is filtered off with suction, washed free of salt and dried, and 35 parts of the dye of the formula are obtained .

It dyes polyester fibers in brilliant, greenish yellow tones.

Example 47

13.5 parts of 2-nitro-4- (2-ethylhexyloxy) aniline are diazotized in 150 parts of a mixture of formic acid and propionic acid (1: 1) with 15 parts of nitrosylsulfuric acid at 0-5 ° C. The diazo solution is added to a solution of 9 parts of 1,4-dimethyl-3-acetyl-6-hydroxypyrid-2-one in 250 parts of 5% sodium hydroxide solution. The coupling is left at pH 4-5, the product is filtered off with suction, washed free of salt and, after drying, 20 parts of the dye of the formula are obtained ,

dyes the polyester fibers with very good fastness properties in a reddish yellow.

In the following examples, the instructions in Examples 46 or 47 are used. The tabulated diazo and coupling components give dyes which dye polyester fabrics in the specified shades.

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Example 76

18.5 parts of 3-nitro-4-aminobenzenesulfonic acid-2-ethylhexylamide are dissolved in 200 parts of a formic acid / propionic acid mixture (1: 1) with 15 parts of nitrosylsulfuric acid (40-42%) at 0-5 ° C in Diazotized for 3 hours.

The diazo solution thus obtained is filtered and poured into a solution of 9.1 parts of 1,4-dimethyl-3-acetyl-6-hydroxypyrid-2-one in 200 parts of 5% sodium hydroxide solution and 500 parts of ice. The pH is adjusted to 6 with dilute sodium hydroxide solution, the coupling is disengaged, suctioned off and dried. 22 parts of the dye of the formula are obtained ,

the polyester fabric dyes in brilliant, greenish yellow tones with very good lightfastness.

The dyes listed in the next table are prepared analogously to Example 76.

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Example 125

13.7 parts of 3-amino-5-nitro-7-bromo-2,1-benzisothiazole are diazotized in 250 parts of a formic acid / propionic acid mixture (1: 1) at 0-5 ° C. with 15 parts of nitrosylsulfuric acid in 3 hours. The diazo solution is added dropwise to a cooled solution of 9.1 parts of 1,4-dimethyl-3-acetyl-6-hydroxypyrid-2-one in 250 parts of 5% sodium hydroxide solution. The pH is adjusted to 6 by adding dilute sodium hydroxide solution. After uncoupling, it is suctioned off, washed neutral and dried. 19 parts of the dye of the formula are obtained ,

the polyester fabric with very good fastness properties dyes in scarlet shades.

The dyes listed in the table below are prepared analogously to Example 125.

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Example 155

7.5 parts of 2-amino-5-nitro-thiazole are dissolved in 29 parts of 96% strength sulfuric acid by heating to 90 ° C. for 30 minutes. After cooling to 0 ° C., 40 parts of a mixture of glacial acetic acid and propionic acid (17: 3) are added, and 15 parts of nitrosylsulfuric acid (40-42%) are added dropwise. The mixture is subsequently stirred at 0-5 ° C. for 3 hours. The solution of 10 parts of 1-ethyl-3-acetyl-4-methyl-6-hydroxypyrid-2-one in 200 parts of glacial acetic acid is added to the diazo solution thus prepared, with cooling. After stirring for 1 hour at room temperature, the coupling is complete. It is poured into 500 parts of water, filtered off with suction, washed neutral and dried. 6 parts of the dye of the formula are obtained ,

the polyester fabric dyes yellow-brown.

Example 156

The procedure is as described in Example 155, but the N-ethyl compound is replaced by the analogous 1-butyl-3-acetyl-4-methyl-6-hydroxypyrid-2-one. A brown dye with comparable properties is obtained.

Example 157

10 parts of 4-amino-7-nitro-1,2-benzisothiazole are diazotized with 15 parts of nitrosylsulfuric acid (40-42%) at 0-5 ° C. in 190 parts of 96% strength sulfuric acid. The diazo solution thus prepared is added dropwise with ice cooling to a solution of 8.1 parts of 2,6-dihydroxy-3-acetyl-4-methyl-pyridine in 100 parts of 10% sodium hydroxide solution, 300 parts of water and 600 parts of ice. The coupling takes place at pH 1. It is filtered off with suction, washed free of salt and dried. 17 parts of the dye of the formula are obtained ,

the polyester fabric dyes in brilliant yellow tones.

The following dyes are prepared analogously to Example 157:

Example 165

13.5 parts of 2'-nitro-2,5-dimethyl-4-amino-azobenzene are heated to 60 ° C. for 15 minutes with 60 parts of concentrated hydrochloric acid and 250 parts of water. After cooling, 250 parts of water are added and 15 ml of a 23% strength sodium nitrite solution are added dropwise. The mixture is stirred for 4 hours at room temperature, 200 parts of glacial acetic acid are added to the diazo solution and it is poured into a solution of 9.8 parts of 1-ethyl-3-acetyl-4-methyl-6-hydroxy-2-pyridone in 1000 parts while cooling with ice Water and 25 parts of 50% sodium hydroxide solution. The pH is adjusted to 4-5 by adding dilute sodium hydroxide solution, stirring is continued for 3 hours at room temperature and the mixture is filtered off with suction. After drying, 20 parts of the dye of the formula are obtained ,

the polyester fibers dyes yellowish red with good fastness properties.

The dyes listed in the next table are prepared analogously to Example 165.

Claims (4)

1. Azo dyes of the pyridone series, which are in one of the possible tautomeric forms of the formula I. correspond in the D is a remainder of the formula n R is hydrogen, optionally substituted alkyl, cycloalkyl, aralkyl or aryl, R [high] 1 hydrogen, alkyl, trifluoromethyl, alkoxy, chlorine, bromine, alkylsulfonyl, phenylsulfonyl, benzoyl, optionally substituted carbamoyl or sulfamoyl or cyano, R [high] 2 hydrogen, chlorine, bromine, alkyl, hydroxy, alkoxy, nitro or optionally substituted carbamoyl or sulfamoyl, R [high] 3 hydrogen, chlorine, alkyl or alkoxy, R [high] 4 hydrogen, chlorine, bromine or alkyl, R [high] 5 hydrogen, chlorine, bromine or alkyl or R [high] 4 and R [high] 5 complement the naphthalene ring, T methyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl or nitro, X cyan or carbon ester, Y methyl or carbon ester and Z denotes hydrogen, chlorine or bromine. 2. Dyestuffs according to Claim 1 of the formula in the D [high] 1 is a remainder of the formulas n B C [deep] 1- to C [deep] 8-alkyl, B [high] 1 C [low] 4 to C [low] 8-alkoxy or optionally substituted sulfamoyl, B [high] 2, B [high] 3 and B [high] 4 hydrogen, nitro, chlorine or methyl, Z [high] 1 hydrogen or bromine, T [high] 1 methoxy, ethoxy or nitro and Y [high] 1 is methyl, carbomethoxy or carboethoxy. 3. Process for the preparation of azo dyes according to claim 1, characterized in that a diazonium compound of amines of the formula D-NH [deep] 2 with a coupling component of the formula II II implemented in a manner known per se. 4. Use of the dyestuffs according to Claim 1 for dyeing synthetic fibers, in particular polyesters.