DE1223970B - Process for the preparation of water-soluble azo dyes - Google Patents

Description

Process for the preparation of water-soluble azo dyes It has been found that you get new, valuable, water-soluble azo dyes if you diazotized, optionally substituted 2-aryl-4-haloquinazolines, which are attached to the aryl radical and or or one or more diazotizable ones on the carbocyclic part of the quinazoline system Carry primary amino groups, with couplable compounds in the usual way combined to form azo dyes and the components selected in such a way that the diazo component and / or the coupling component has one or more water-solubilizing groups wear.

The invention thus relates to the preparation of water-soluble mono-, dis- or polyazo dyes which are derived from optionally substituted 2-aryl-4-haloquinazolines of the general formula derive, where A is an optionally substituted aromatic radical, X is a halogen atom and the carbocyclic ring D may optionally carry substituents.

Optionally substituted aromatic radicals A are, for example Residues that contain up to two benzene rings, such as the residues of benzene or naphthalene or of diphenyl, called. These aromatic radicals can be just like the carbocyclic Ring D the substituents customary in the chemistry of azo dyes, such as halogen atoms, low molecular weight alkyl groups, low molecular weight alkoxyl groups, aryl groups, aralkyl groups, ionogenic water-solubilizing groups, such as sulfonic acid groups or carboxyl groups, or contain non-ionic water-solubilizing groups, such as methylsulfonyl groups, Halogen atoms are, for example, fluorine, bromine, iodine and preferably chlorine atoms.

Couplable compounds are the coupling components customary in the chemistry of azo dyes, but preferably coupling components of the naphthalene series and coupling components of the pyrazolone series which carry at least one ionic water-solubilizing group, advantageously one or more sulfonic acid groups. Of these, the following coupling components may be mentioned individually: hydroxynaphthalene sulfonic acids, such as 1-hydroxynaphthalene-3-sulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid, 2-hydroxynaphthalene-6-sulfonic acid, 2-hydroxynaphthalene-3,6-disulfonic acid; Aminohydroxynaphthalene sulfonic acids, such as 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, and their N-acyl derivatives, such as 1- Acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid or 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid; 1-phenyl-3-methylpyrazolone- (5) -sulfonic acids, such as 1- (2-methyl-4-sulfophenyl) -3 -methylpyrazolone- (5), 1- (2-chloro-5-sulfophenyl) -3-methylpyrazolone - (5) or 1- (4-sulfophenyl) -3-methylpyrazolone- (5); 1-Phenyl-3-carboxypyrazolone- (5) and the 1- (sulfophenyl) -3-alkylpyrazolone- (4) known from German patent specification 1060 522.

Monoazo dyes of the general formulas are of particular technical interest for example the formulas Here, X denotes a halogen atom and E denotes the remainder of a coupling component bearing one or more water-solubilizing groups.

The new diazotizable aromatic amines of the 2-aryl-4-haloquinazoline series used as starting compounds according to the invention are obtainable in various ways, for example by reacting an optionally substituted 2-aminobenzenecarboxamide with a nitroarylcarboxamide to give the corresponding carboxamide, this in the usual way with the quinazoline ring closure by elimination of water, then the hydroxyl group on the heterocyclic ring of the quinazoline system is replaced by a halogen atom and finally the nitro group is advantageously reduced to the amino group by catalytic reduction or by proceeding in a similar manner, but starting from a 2-aminobenzenecarboxamide bearing a nitro group and an optionally substituted arylcarboxylic acid chloride. The methods customary for dyeing and / or printing textiles, such as fibers, threads, flocks, woven and knitted fabrics, made from native and / or regenerated cellulose with reactive dyes, give bright and clear dyeings and prints with excellent fastness properties with the new dyes .

The new dyes excel in their use for dyeing of cotton, rayon or linen according to the so-called exhaust process or according to the so-called cold dwell process (also pad-batch method called) from the known reactive dyes in that they are also with addition from small amounts of electrolytes already strong, brilliant, lightfast and wetfast Staining result.

The dyes obtainable according to the invention can also be used for Dyeing and / or printing of various types of material, for example of Sheets made from regenerated cellulose, from films made from polyvinyl alcohol or from textiles made of natural or synthetic linear polyamides, such as natural silk, wool, polycaprolactam, Polylaurolactam, polyaminoundecanoic acid or based on adipic acid and Hexamethylenediamine are used and are also used for dyeing fibers such as leather and Paper, usable.

Compared to one from British patent specification 305 487, example 1, second paragraph, known, containing a 2-chloro-3-methoxyquinoxalinyl radical The azo dye provides the corresponding 2-phenyl-4-chloroquinazolinyl radical obtainable according to the invention containing dye deeper dyeings on cotton.

The parts and percentages mentioned in the examples are so far not otherwise specified, weight units. The parts of space relate to the parts by weight like the liter to the kilogram measured under normal conditions.

EXAMPLE 1 In a slurry of 70 parts of 2- (4-aminophenyl) -4-chloroquinazoline in 350 parts of water and 90 parts of concentrated acetic acid, 160 parts of concentrated aqueous hydrochloric acid are added at 0 to + 5 ° C. within 15 minutes stirred in small portions of 19.6 parts of sodium nitrite in 140 parts of water. The mixture is then stirred at 5 ° C. for 1 hour. Then 350 parts of concentrated acetic acid are added. After stirring for a further 15 minutes, the mixture is dissolved in a solution of 80 parts of 1- (2-chloro-5-sulfophenyl) -3-methylpyrazolone- (5), 300 parts of sodium acetate and 70 parts of sodium hydroxide in 2800 parts of water over the course of 15 minutes registered. The temperature should not rise above 10 ° C. The mixture is then stirred at 5 to 10 ° C. for a further 20 minutes. 240 parts of concentrated aqueous hydrochloric acid are added at the same temperature. The reaction mixture is then filtered off with suction, washed with water and dried at 30.degree. C. under reduced pressure. The yield is approximately 150 parts. The new dye in the formula dyes cotton in brilliant reddish yellow tones. The dyeings have excellent dyeing properties.

The starting material used in paragraph 1 2- (4-aminophenyl) -4-chloroquinazoline is available in the following way 100 parts of 2-aminobenzoic acid amide are available in 500 Parts by volume of glacial acetic acid and 500 parts by volume of saturated aqueous sodium acetate solution dissolved with stirring at room temperature (i.e. at about 15-30 ° C). In these The solution is a solution of 135 parts of 4-nitrobenzoyl chloride in 90 parts by volume of acetone registered in small portions. After stirring for 1 hour at room temperature suctioned off the reaction mixture, washed with water and dried.

74 parts of the 2- (p-nitrobenzoylamino) benzoic acid amide thus obtained are in a boiling mixture of 1000 parts by volume of 2 normal aqueous sodium hydroxide solution and 50 parts by volume of pyridine entered. Then the solution of impurities filtered off, cooled and weakly acidified with acetic acid. The departed one Precipitate is then filtered off with suction, washed free of acid with water and dried.

Into a slurry of 100 parts of the 2- (4-nitrophenyl) -4-hydroxy-1,3-quinazoline thus obtained in 300 parts of dichlorobenzene and 45 parts of dimethylformamide at 100 to 110.degree Phosgene passed in with stirring until no more starting material can be detected. The reaction mixture is then cooled to 10 ° C. and the crystal slurry obtained is then cooled suctioned off, washed with methanol and dried. 90 to 95 parts of 2- (4-nitrophenyl) -4-chloroquinazoline are obtained from melting point 188 to 190 ° C.

100 parts of 2- (4-nitrophenyl) -4-chloroquinazolone are suspended in 1500 parts by volume of acetone and, after addition of 10 parts of Raney nickel, hydrogenated with hydrogen at 20 to 30 ° C. As soon as the calculated amount of hydrogen has been absorbed, the catalyst is suctioned off and the acetone solution of the amine is poured into 5000 parts by volume of water. The amine precipitates in the process. The reaction material is then filtered off with suction, washed with water and dried at 30 ° C. under reduced pressure. 88 parts of 2- (4-aminophenyl) -4-chloroquinazoline are obtained in the form of a yellow powder. EXAMPLE 2 A diazonium salt solution prepared as described in Example 1, paragraph 1, is allowed to slowly run into a solution of 63 parts of 1-hydroxynaphthalene-4-sulfonic acid in 3400 parts of abnormal aqueous sodium hydroxide solution with thorough stirring. The temperature is kept between 5 and 10 ° C. Thereafter, the reaction mixture is stirred for 15 minutes. 240 parts of concentrated aqueous hydrochloric acid are then added at 5 ° to 10 ° C., the reaction material is filtered off with suction, washed with water and dried at 30 ° C. under reduced pressure. The yield is 125 parts. The new dye in the formula dyes cotton in bright scarlet shades. A diazonium salt solution prepared as described in Example 1, paragraph 1, is dissolved in a solution of 74 parts of 1- (2-methyl-4-sulfophenyl) -3-methylpyrazolone- (5), 300 parts of sodium acetate and 70 parts within 15 minutes Sodium hydroxide is stirred into 2800 parts of water. The temperature should not rise above 10 ° C. After stirring for 15 minutes, 240 parts of concentrated aqueous hydrochloric acid are added at 5 to 10 ° C., and the reaction material is filtered off with suction, washed and dried at 30 ° C. under reduced pressure. The yield is approximately 135 parts. The new dye in the formula provides brilliant reddish yellow dyeings with very good fastness properties on cotton. Example 4 A diazonium salt solution prepared as described in Example 1, paragraph 1, is stirred into a solution of 118 parts of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid in 5000 parts of 2N aqueous sodium hydroxide solution within about 30 minutes. The temperature should not rise above 10 ° C. To complete the reaction, the mixture is stirred for a further 15 minutes at 5 to 10 ° C. and then 240 parts of concentrated aqueous hydrochloric acid are added. The reaction material is then filtered off with suction, washed with water and dried at 30. ° C. under reduced pressure. The yield is 180 parts. The new dye in the formula dyes cotton in brilliant red-violet tones. The dyeings have very good fastness properties.

Example s The diazonium salt solution prepared as described in Example 1, paragraph 1, is stirred into a solution of 88 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 5000 parts of 2N aqueous sodium hydroxide solution within about 30 minutes. The temperature should not rise above 10 ° C. After stirring for 10 minutes at 5 to 10 ° C., 240 parts of concentrated aqueous hydrochloric acid are introduced into the mixture, the reaction material is filtered off with suction, washed with water and dried at 30 ° C. under reduced pressure. The yield is approximately 140 parts. The new dye in the formula stains cellulose tissue in purple tones. Example 6 A diazonium salt solution prepared as described in Example 1, paragraph 1, is slowly stirred at 5 to 10 ° C. into a solution of 88 parts of 1,8-dihydroxynaphthalene-3,6-disulfonic acid in 5000 parts of 2N aqueous sodium hydroxide solution. 240 parts of concentrated aqueous hydrochloric acid are then added to the mixture at 5 to 10 ° C. The reaction mixture is then filtered off with suction, washed with water and dried at 30 ° C. in a vacuum. The yield is approximately 100 parts. The new dye in the formula dyes linen fabrics in red-violet tones. Example ? A diazonium salt solution prepared as described in Example 1, paragraph 1, is stirred into a solution of 84 parts of 2-hydroxynaphthalene-3,6-disulfonic acid in 4000 parts of abnormal aqueous sodium hydroxide solution at 5 to 10 ° C. After the reaction has ended, 240 parts of concentrated aqueous hydrochloric acid are added to the mixture at 5 to 10 ° C. The reaction mixture is then filtered off with suction, washed with water and dried at 30 ° C. in a vacuum. The yield is approximately 120 parts. The new dye in the formula dyes cotton in clear red tones. The dyeings have good fastness properties. Example 8 In a slurry of 25.6 parts of 2- (3-aminophenyl) -4-chloroquinazoline in a mixture of 150 parts of water, 60 parts of concentrated aqueous hydrochloric acid and 50 parts of concentrated acetic acid, a solution of 7 parts of sodium nitrite in 30 parts of water are slowly stirred in. When the diazotization is complete, 300 parts of concentrated acetic acid are added, the mixture is stirred for a further 15 minutes and the mixture is poured into a solution of 27 parts of 1- (2-methyl-4-sulfophenyl) -3-methylpyrazolone- (5), 100 parts Sodium acetate and 20 parts of sodium hydroxide in 1200 parts of water. The temperature should not rise above 10 ° C. After stirring for 15 minutes, 100 parts of concentrated aqueous hydrochloric acid are added. The reaction material is then filtered off with suction, washed with water and dried at 30 ° C. under reduced pressure. The yield is 45 to 50 parts. The new dye in the formula dyes cotton greenish yellow with very good fastness properties.

The starting material 2- (3-aminophenyl) -4-chloroquinazoline used in paragraph 1 can be obtained in the following way , the 2- (3-nitrophenyl) -4-hydroxyquinazoline is obtained. Phosgene is introduced into a suspension of the 2- (3-nitrophenyl) -4-hydroxy-1,3-quinazoline in 250 parts of nitrobenzene and 45 parts of dimethylformamide at 90 ° to 100 ° C. with stirring until starting material is no longer detectable is. The reaction mixture is then cooled to 10 ° C. and the precipitated crystal slurry is filtered off with suction, washed with methanol and dried. The 2- (3-nitrophenyl) -4-chloroquinazoline obtained melts at 182 to 183 ° C. The yield is 92 parts.

100 parts of 2- (3-nitrophenyl) -4-chloroquinazoline are suspended in 1500 parts by volume of tetrahydrofuran and, after addition of 10 parts of Raney nickel, hydrogenated with hydrogen at room temperature. As soon as the hydrogenation has ended, the catalyst is filtered off and the filtrate is poured into 5000 parts by volume of water. The amino compound precipitates in the process. It is filtered off with suction, washed with water and dried at 30 ° C. under reduced pressure. 85 parts of 2- (3-aminophenyl) -4-chloroquinazoline are obtained in the form of a pale yellow powder. Example 9 A diazonium salt solution prepared as described in Example 8, paragraph 1, is converted into a solution of 29 parts of 1- (2-chloro-5-sulfophenyl) -3-methylpyrazolone- (5), 100 parts, at 5 to 10 ° C Sodium acetate and 25 parts of sodium hydroxide are stirred into 1,300 parts of water. After 15 minutes, 100 parts of concentrated aqueous hydrochloric acid are added to the mixture, and the reaction material is filtered off with suction, washed with water and dried. The yield is about 40 parts. The new dye in the formula dyes cellulose fabric greenish yellow with very good fastness properties. EXAMPLE 10 A diazonium salt solution prepared as described in Example 8, paragraph 1, is slowly stirred into a solution of 43 parts of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid in 3000 parts of 2-normal aqueous sodium hydroxide solution at 5 to 10 ° C. After stirring for 15 minutes, 100 parts of concentrated aqueous hydrochloric acid are introduced into the mixture, the reaction material is filtered off with suction, washed with water and dried. The yield is approximately 60 parts. The new dye of dyes cotton textiles in brilliant ruby red tones.

EXAMPLE 11 A diazonium salt solution prepared as described in Example 8, paragraph 1, is slowly stirred into a solution of 32 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 3000 parts of 2N aqueous sodium hydroxide solution at 5 to 10 ° C. When the reaction has ended, 100 parts of concentrated aqueous hydrochloric acid are stirred into the mixture, and the material to be reacted is filtered off with suction, washed with water and dried. The yield is approximately 45 parts. The new dye in the formula dyes cotton in purple tones. EXAMPLE 12 A diazonium salt solution prepared as described in Example 8, paragraph 1, is stirred at 5 to 10 ° C. into a solution of 23 parts of 1-hydroxynaphthalene-4-sulfonic acid in 3000 parts of 2N aqueous sodium hydroxide solution. When the reaction has ended, 100 parts of concentrated aqueous hydrochloric acid are introduced into the mixture, the material to be reacted is filtered off with suction, washed with water and dried. The yield is about 40 parts. The new dye in the formula dyes cotton fabric orange-red with good fastness properties.

Example 13 A slurry of 10.2 parts of 2-phenyl-4-chloro-6-aminochinazoline in a mixture of 80 parts of water and 20 parts of concentrated aqueous hydrochloric acid is diazotized with a solution of 2.8 parts of sodium nitrite in 20 parts of water. Then 120 parts of concentrated acetic acid are added and, after stirring for 15 minutes, the mixture is added to a solution of 11.6 parts of 1- (2-methyl-4-sulfophenyl) -3-methylpyrazolone- (5), 50 parts of sodium acetate and 100 parts Part 2 normal aqueous sodium hydroxide solution in 400 parts of water. The temperature should not exceed 10 ° C. The reaction material is separated off as described above. The yield is 18 parts. The new dye in the formula dyes cotton fabric in a reddish yellow with good fastness properties.

The starting material used in paragraph 1 2-phenyl-4-chloro-6-aminochinazoline 185 parts of 2-amino-5-nitrobenzoic acid amide can be obtained in the following manner dissolved in 1000 parts by volume of N-methylpyrrolidone at room temperature. In this solution 150 parts of benzoyl chloride are entered in small proportions. Now you stir that Mixture for a further 2 hours at room temperature and then pour it into 4000 parts by volume Water. The precipitate is then filtered off with suction, washed with water and dried.

150 parts of the 2-benzoylamino-5-nitrobenzoic acid amide thus obtained in 3000 parts by volume of normal aqueous sodium hydroxide solution at 60 ° C for that long stirred until the amide is dissolved. This usually requires about 11/2 to 2 hours. The reaction material is then filtered off with suction, mixed with water and mixed with 10% aqueous sulfuric acid strongly acidified. Now the slurry becomes more Stirred for 2 hours and then filtered off with suction, washed acid-free and dried.

40 parts of the 2-phenyl-4-hydroxy-6-nitroquinazolite obtained in this way are suspended in 150 parts by volume of nitrobenzene. After adding 20 parts by volume of dimethylformamide, phosgene is passed into the mixture at 150 ° C. with thorough stirring. As soon as the reaction has ended, the mixture is allowed to cool, the reaction material is filtered off with suction, washed with nitrobenzene and then with methanol and dried. The 2-phenyl-4-chloro-6-nitroquinazoline obtained in this way has a melting point of 200 to 201.degree .

100 parts of 2-phenyl-4-chloro-6-nitroquinazoline are suspended in 1500 parts by volume of dioxane and, after addition of 10 parts of Raney nickel, hydrogenated with hydrogen at room temperature.

As soon as the hydrogenation has ended, the catalyst is filtered off and the filtrate poured into 5000 parts by volume of water. The amino compound falls in the process the end. It is filtered off with suction, washed with water and at 30 ° C. under reduced pressure dried. 85 parts of 2-phenyl-4-chloro-6-aminochinazoline are obtained in the form of a light yellow powder.

Claims (1)

Claim: Process for the production of water-soluble azo dyes, thereby marked = h: net; that one diazotized, optionally substituted, 2-aryl-4-haloquinazolines, the one on the aryl radical and / or on the carbocyclic part of the quinazoline system or carry several diazotizable primary amino groups, with compounds capable of coupling combined in the usual way to form azo dyes and the components selected in such a way that that the diazo component and / or the coupling component is one or more Wear water-solubilizing groups. Publications Considered: British Patent Specification No. 305,487. At the notice of application is a staining board has been laid out with explanations,