DE2838534A1 - SULPHONIC ACID GROUPS WITH OXDIAZOLYL RESIDUES - Google Patents

Description

The invention relates to compounds which, in the form of the free acids of the formula I I.

correspond in the

K is the remainder of a coupling component,

n the numbers 1, 2 or 3,

R [high] 1 hydrogen, chlorine, bromine, sulfonic acid ester, optionally substituted sulfamoyl or hydroxysulfonyl,

R [high] 2 hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl,

R [high] 3 hydroxy, C [low] 1- to C [low] 8-alkyl, aralkyl or optionally substituted aryl and

Z denotes C [deep] 1 to C [deep] 8-alkylene or aralkylene.

The radicals K of the coupling components come mainly from the phenol, aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole,

Pyridone, diaminopyridine, triaminopyridine, diaminopyrimidine, triaminopyrimidine, barbituric acid, quinoline, isoquinoline or indole series.

The coupling components correspond in detail, for example, to the formulas whereby

B [high] 1 and B [high] 2 independently of one another hydrogen, C [low] 1- to C [low] 4-alkyl, through hydroxy, cyano, C [low] 1- to C [low] 4-alkoxy, C [deep] 1- to C [deep] 4-alkanoyloxy or C [deep] 1- to C [deep] 4-alkoxycarbonyl substituted C [deep] 2- to C [deep] 4-alkyl, interrupted by oxygen and through Hydroxy, C [deep] 1- to C [deep] 4-alkoxy, phenoxy or benzyloxy substituted alkyl with 4 to 9 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenyl,

B [high] 3 hydrogen, hydroxysulfonyl, chlorine, methyl or C [low] 1- to C [low] 4-alkanoylamino,

B [high] 4 phenyl optionally substituted by hydroxysulfonyl, chlorine, bromine, methyl, ethyl, methoxy or ethoxy,

B [high] 5 hydrogen, C [low] 1- to C [low] 4-alkyl, cyclohexyl, benzyl or optionally by chlorine, bromine, methyl, ethyl or

Hydroxysulfonyl substituted phenyl,

B [high] 6 hydroxy or amino,

B [high] 7 hydrogen, methyl, carbamoyl, C [low] 1- to C [low] 4-alkoxycarbonyl or carboxyl,

B [high] 8 cyano or carbamoyl,

B [high] 9 hydrogen, hydroxy or methyl,

B [high] 10 a remainder B [high] 1 or

B [high] 11 a remainder B [high] 1 or

B [high] 12 methyl or phenyl,

B [high] 13 hydrogen, methyl, small beta-cyanoethyl, small beta-hydroxyethyl, small beta-carboxyethyl or small beta-carbamoylethyl and

p are 0, 1 or 2.

Individual remainders B [high] 1 and B [high] 2 are in addition to those already mentioned, for example:

CH [deep] 3, C [deep] 2H [deep] 5, C [deep] 3H [deep] 7, C [deep] 4H [deep] 9, C [deep] 2H [deep] 4OH, CH [deep] 2CHOHCH [deep] 3, CH [deep] 2CHOHCH [deep] 2Cl, CH [deep] 2CH [deep] 2CN, CH [deep] 2CH [deep] 2OCH [deep] 3, CH [deep] 2CH [deep] 2OC [ deep] 2H [deep] 5, CH [deep] 2CH [deep] 2OC [deep] 4H [deep] 9, CH [deep] 2CHCH [deep] 3, OCH [deep] 3,

CH [deep] 2CH [deep] 2OCOCH [deep] 3, CH [deep] 2CH [deep] 2OCOC [deep] 2H [deep] 5, CH [deep] 2CH [deep] 2COOCH [deep] 3, CH [deep] 2CH [deep] 2COOC [deep] 2H [deep] 5, CH [deep] 2CH [deep] 2COOC [deep] 4H [deep] 9, CH [deep] 2CH [deep] 2OCH [deep] 2CH [deep] 2OH, (CH [deep] 2) [deep] 3OCH [deep] 2CH [deep] 2OH, (CH [deep] 2) [deep] 3O (CH [deep] 2) [deep] 4OH, (CH [deep] 2) [deep] 3OC [deep] 2H [deep] 4OCH [deep] 3, (CH [deep] 2) [deep] 3OC [deep] 2H [deep] 4OC [deep] 2H [deep] 5, (CH [deep] 2) [deep] 3OC [deep] 2H [deep] 4OC [deep] 4H [deep] 9, (CH [deep] 2) [deep] 3OC [deep] 2H [deep] 4OCH [deep] 2C [deep] 6H [deep] 5, (CH [deep] 2) [deep] 3OC [deep] 2H [deep] 4OC [deep] 6H [deep] 5, (CH [deep] 2) [deep] 3O (C [deep] 2H [deep] 4O) [deep] 2CH [deep] 3 or (CH [deep] 2) [deep] 3O (C [deep] 2H [deep] 4O) [deep] 2C [deep] 2H [deep] 5.

Preferred diazo components are, for example:

Preferred coupling components correspond, for example, to the formulas

or

In addition to hydroxy, radicals R [high] 3 are for example:

CH [deep] 3, C [deep] 2H [deep] 5, C [deep] 3H [deep] 7, C [deep] 4H [deep] 9, C [deep] 5H [deep] 11, C [deep] 6H [low] 13, C [low] 8H [low] 17,

CH [deep] 2C [deep] 6H [deep] 5, C [deep] 2H [deep] 4C [deep] 6H [deep] 5, C [deep] 6H [deep] 5, C [deep] 6H [deep] 5, C [deep] 6H [deep] 4Cl or C [deep] 6H [deep] 4CH [deep] 3.

For example, Z are or to be mentioned, where n can be 1 to 6.

Sulfonic acid ester and optionally substituted sulfamoyl radicals for R [high] 1 are, for example, SO [deep] 2R, where R is preferably phenoxy optionally substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy or a radical of the formulas N (CH [deep] 3 ) [deep] 2, N (C [deep] 2H [deep] 5) [deep] 2, N (C [deep] 3H [deep] 7) [deep] 2, N (C [deep] 4H [deep] 9) [deep] 2, N (C [deep] 6H [deep] 13) [deep] 2, N (C [deep] 8H [deep] 17) [deep] 2,

N (CH [deep] 2CH [deep] 2OH) [deep] 2, N (CH [deep] 2CH [deep] 2OCH [deep] 3) [deep] 2, N (C [deep] 2H [deep] 4OC [ deep] 2H [deep] 5) [deep] 2,

or is.

The dyes of the formula I produce yellow to red dyeings with very good light and wet fastness properties on natural and synthetic polyamides. The color strengths and the clear tones, which can be achieved with many dyes, should be emphasized. The dyes can be used in the form of their alkali salts (Li, Na, K) or ammonium salts (optionally substituted).

Dyes of the formula Ia are of particular industrial importance Yes in the

R [high] 4 hydrogen, chlorine, optionally substituted sulfamoyl or hydroxysulfonyl,

R [high] 5 hydrogen, chlorine or trifluoromethyl,

Z C [deep] 1- to C [deep] 3-alkylene or aralkylene,

m 1 or 2 and

K [high] 1 is a coupling component of the aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole, pyridone, diaminopyridine, diaminopyrimidine or indole series.

A diazonium compound of amines of the formula I can be used to prepare the dyes of the formula I with a coupling component of the formula

HK

convert, the n sulfonic acid groups are in the diazo and / or coupling component.

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

example 1

The solution of 29 parts of the sodium salt of the formula (3) in 200 parts of water is added to a mixture of 300 parts of ice and 35 parts by volume of 10 mol of hydrochloric acid. In this mixture, 30 parts by volume of a 23 percent aqueous sodium nitrite solution are allowed to under the surface at 0 to 5 ° C pour in, stir for 3 hours at 0 to 5 ° C and destroy excess nitrous acid, as usual, by adding sulfamic acid.

The solution of 25 parts of acetoacetic-2,4-dimethoxyanilide in 250 parts by volume of glacial acetic acid and then another 750 parts by volume of a 55 percent aqueous sodium acetate solution are allowed to flow into the diazotization mixture thus obtained. The dye, a yellow powder, which has been sucked off and washed with dilute sodium chloride solution, dissolves in hot water with a greenish yellow color. On fabrics made of synthetic polyamide or wool, greenish yellow dyeings with excellent light and wet fastness properties are obtained.

Example 2

The solution of 19 parts of 1-phenyl-3-methyl-5-aminopyrazole in 20 parts of 10 mol of hydrochloric acid and 500 parts of water is slowly added to the diazotization mixture obtained as described in Example 1, paragraph 1, at 0 to 5 ° C pour in, then 400 parts by volume of a 55 percent aqueous sodium acetate solution. The dye thus obtained is filtered off with suction, washed with dilute sodium chloride solution and then with water. After drying at 100 ° C., a yellow powder is obtained which dyes synthetic polyamide fibers in yellow shades which have very good light and wet fastness properties.

Example 3

A solution of 25 parts of 2,6-bis- (2-hydroxyethylamino) -3-cyano-4-methylpyridine in 15 parts by volume is gradually added to the diazotization mixture prepared according to the instructions in Example 1, paragraph 1 conc. Hydrochloric acid and 500 parts of water and then as much saturated sodium acetate solution until a pH range of 4 to 5 is reached. The dye which is suctioned off after the coupling has ended is washed with a little water and dried at 100.degree. An orange powder is obtained which dissolves in hot water with a golden yellow color and dyes textile structures made of synthetic polyamide in yellow-orange shades which have very good light and wet fastness properties.

Example 4

The diazotization mixture obtained according to Example 1, paragraph 1, is added at 0 to 5 ° C. to a solution of 32 parts of N-ethyl-N-benzyl-aniline-3'-sulfonic acid in 10 parts of 50 percent sodium hydroxide solution and 500 parts of water with the addition of 500 Parts of ice and 20 parts of sodium carbonate. The dye is precipitated from the dye solution obtained by adding 1000 parts by volume of saturated sodium chloride solution, filtered off with suction, washed with dilute sodium chloride solution and dried. The yellow-brown powder dissolves easily in water and gives threads of synthetic polyamide orange dyes with very good light and wet fastness properties.

Example 5

37.5 parts of the compound of formula (3) are dissolved in 250 parts of glacial acetic acid and 50 parts of propionic acid. 32 g of nitrosylsulfuric acid (40 percent) are added dropwise at 0 to 5 ° C. and the mixture is stirred at 0 to 5 ° C. for a further 2 hours. Then the excess nitrous acid is destroyed by adding urea, as usual.

The diazotization mixture thus obtained is added to the following mixture at 0 to 5 ° C:

26 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid are dissolved with 7.5 parts by volume of 50 percent sodium hydroxide solution in 300 parts of water. Then add 60 parts of space to the solution

10 percent hydrochloric acid and 300 parts of ice.

Sufficient saturated sodium acetate solution is then slowly added dropwise to the coupling mixture until a pH range of 2 to 3 is reached.

After coupling has ended, it is neutralized with 50 percent sodium hydroxide solution (pH = 6-8), then the dye is filtered off with suction, washed with water and dried. A black powder is obtained which dissolves in hot water with a blue-violet color and dyes synthetic polyamide fabric in blue shades which have good light and wet fastness properties.

Example 6

146 parts of the diazo component of the formula are dissolved at 30 to 50 ° C in 2500 parts by volume of water at a pH of 8 to 9. 160 parts by volume of a 23 percent aqueous sodium nitrite solution are added, followed by 2000 parts by weight of ice. Then 180 parts by volume of an aqueous 36 percent hydrochloric acid solution are quickly added. After stirring for two hours at 0 to 5 ° C., the suspension obtained is combined with the solution obtained from 146 parts of the coupling component of the formula

2000 parts by volume of water and 100 parts by volume of 36 percent concentrated hydrochloric acid and subsequent addition of 2000 parts of ice is obtained. The mixture is mixed with 600 parts of sodium chloride and then brought to a pH of 3.5 to 3.7 by adding sodium acetate. The mixture is stirred for 30 minutes and then the pH is raised to 5 to 5.5. The coupling is complete after stirring overnight. The mixture is then heated to 50 to 70 ° C., 100 g of sodium chloride are added, the dyestuff which has precipitated out is filtered off and washed with a little cold water. After drying, 296 parts of the dye of the formula are obtained

This dissolves in water with a yellow color and dyes polycaprolactam fabric in strong, extremely lightfast reddish yellow shades with very good wet fastness properties. The dyeings on wool also have good lightfastness.

Example 7

18, 2 parts of the diazo component of the formula are dissolved in 280 parts by volume of water at pH 8 to 9.

14 parts by volume of a 23 percent sodium nitrite solution are added and the mixture is cooled to 0 to 5 ° C. with ice. After the addition of 15 parts by volume of concentrated hydrochloric acid, the mixture is stirred at 0 to 5 ° C. for 2 hours. Excess nitrous acid is then destroyed with sulfamic acid and buffered to pH 4.7 with sodium acetate. After adding a solution of 10.4 parts of the coupling component of the formula in 50 parts by volume of dimethylformamide, the mixture is allowed to stir for 3 hours and then the pH is increased to 5.5. After stirring overnight, the suspension is brought to pH 6.5 with sodium hydroxide solution and heated to 80 ° C. with steam. The unusual dye of the formula is filtered off, washed with a little cold water and dried. 29 parts of a red-brown powder are obtained which dissolve in water with a golden yellow color and dyes polycaprolactam and wool with excellent fastness properties in yellow shades. The dye also dyes leather in orange tones that are lightfast and wetfast.

Table 1

Table 2

Table 3

Table 4

Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas Continuation of the table with formulas

Claims (4)

1. Azo dyes containing sulfonic acid groups with oxdiazolyl radicals, which are in the form of the free acids of the formula correspond in the K is the remainder of a coupling component, n the numbers 1, 2 or 3, R [high] 1 hydrogen, chlorine, bromine, sulfonic acid ester, optionally substituted sulfamoyl or hydroxysulfonyl, R [high] 2 hydrogen, chlorine, bromine, nitro, methyl or trifluoromethyl, R [high] 3 hydroxy, C [low] 1- to C [low] 8-alkyl, aralkyl or optionally substituted aryl and Z C [deep] 1- to C [deep] 8-alkylene or aralkylene Mean. 2. Dyestuffs according to Claim 1 of the formula in the R [high] 4 hydrogen, chlorine, optionally substituted sulfamoyl or hydroxysulfonyl, R [high] 5 hydrogen, chlorine or trifluoromethyl, Z C [deep] 1- to C [deep] 3-alkylene or aralkylene, m 1 or 2 and K [high] 1 denotes a coupling component of the aniline, naphthol, naphthylamine, aminonaphthol, acetoacetarylide, pyrazolone, aminopyrazole, pyridone, diaminopyridine, diaminopyrimidine or indole series. 3. Process for the preparation of dyes according to Claim 1, characterized in that a diazonium compound of amines of the formula with a coupling component of the formula HK reacted, the n sulfonic acid groups in the diazo and / or coupling component. 4. Dyestuff preparations for dyeing natural and synthetic polyamides, containing, in addition to the usual constituents, dyestuffs according to Claim 1. i