DE1060522B - Process for the production of mono- and polyazo dyes - Google Patents

Description

Process for the preparation of mono- and polyazo dyes It was found that new mono- and polyazo dyes are obtained when using diazonium compounds with 1-aryl-3-alkyl-4-pyrazolones and the resulting dyes, if desired converted into their metal complex compounds.

As 1-aryl-3-alkyl-4-pyrazolones, for example, the 1-phenyl-3-methyl-4-pyrazolones are suitable for the new process; these can be substituted in the phenyl group by halogen atoms, alkyl, oxyalkyl, nitro, amino, carboxyl, sulfonic acid, sulfonic acid amide, alkyl sulfone and / or aryl sulfone groups. Such connections can be made, for example, according to the method of patent 1,029,827 .

Suitable diazo components are all diazotizable compounds, especially aniline, 1- and 2-aminonaphthalene and their diazotizable compounds, for example halogen atoms, alkyl, aryl, oxyalkyl, oxy, nitro, carboxylic acid, sulfonic acid, carboxylic acid and sulfonic acid amide -, alkylsulphone and arylsulphone, amino and acylamino groups substituted derivatives. Advantageously, diamines such. B. the 4,4'-diaminodiphenyl, or its bridging members between the two phenyl nuclei, such as -CH, - -Co-, -1VH-CO-NH-, -S- or SO2-, containing derivatives. Furthermore, diazotizable mono- and polyazo dyes are generally suitable as diazo components for the present process.

The reaction of the 1-aryl-3-alkyl-4-pyrazolones with these diazo compounds can in a known manner, namely preferably in an alkaline medium and / or under Acid-binding or acid-blunting agents can be added. As far as the Dyes produced according to the invention in positions adjacent to the azo bridge metal-sensitive groups such as hydroxyl, alkoxy, amino or carboxyl groups, can contain them in a known manner - in substance or on the fiber - in convert their metal complex compounds; as usual, here too, above all, they are Metals with ordinal numbers 24 to 30 are suitable. If the metal complex compounds thus obtained Each molecule of dye contains 1 atom of metal, they can also be known Way with other metallizable monoazo or azomethine dyes or - z. B. by the method of the patent 846142 - implemented with colorless complexing agents will. Finally, you can also use mixed complex compounds of the new dyes with one another or with known dyes by metallizing the corresponding Prepare dye mixtures under such conditions that for 1 metal atom more than 1 molecule of dye is omitted. The azo dyes obtained by the new process can be used as pigments or as dispersant dyes if they do not contain water-solubilizing groups. If, on the other hand, you have one or more of these Groups such as carboxylic acid or sulfonic acid groups carry, so they can be used for dyeing of natural or synthetic polyamides, such as wool, silk, leather, polycaprolactam, Polyhexamethylene diamine adipate, and natural and regenerated cellulose fibers are used, they have good fastness properties, in particular mostly very good lightfastness, show. The metal complex compounds that can be produced using the new process result on natural and synthetic polyamides such as wool, silk, polycaprolactam or polyhexamethylene diamine adipate, dyeings with excellent fastness properties. To the extent that they are free from groups which make them water-soluble, they are also suitable for coloring Zapon, nitro and acetyl cellulose lacquers and varnishes.

Of the isomeric dyes made with 1-aryl-3-alkyl-5-pyrazolone the new dyes differ by a considerable shift in their Light absorption after longer waves. While z. B. the dye from diazotized 1-aminobenzene-4-sulfonic acid and 1-phenyl-3-methyl-5-pyrazolone give yellow colorations, obtained brown with the corresponding 1-phenyl-3-methyl-4-pyrazolone dye Tints; the dye made from diazotized 1-aminonaphthalene-4-sulfonic acid and 1-phenyl-3-methyl-5-pyrazolone colors orange, which is made from the same diazo component and 1-phenyl-3-methyl-4-pyrazolone existing dye is black. This through the use of 4-pyrazolones Achieved bathochromic effect is very desirable, as it builds up brown, blue and allows black dyes of relatively small molecular size, while one allows such Color shades within many dye groups only with significantly larger molecular weights can get, in which the production is very expensive and often the Fiber affinity decreases.

The dyes prepared according to the invention show during washing and Fulling has a noticeably better color retention and a significantly lower one Tendency to stain the accompanying material as similar 1-aryl-3-a.lkyl-5-pyra7olones obtained dyes.

The parts mentioned in the examples are parts by weight.

EXAMPLE 1 12.8 parts of 1-amino-4-chlorobenzene are stirred for 90 minutes in a mixture of 100 parts of water and 25 parts of 36.5% hydrochloric acid, then 100 parts of ice and a solution of 6.9 parts are added Sodium nitrite in 20 parts of water. The diazo solution obtained is then allowed to flow into a solution of 18.5 parts of 1-phenyl-3-methyl-4-pyrazolone, 15 parts of 40% sodium hydroxide solution and 5.5 parts of anhydrous sodium carbonate in 100 parts of water. After the coupling is complete, suction is carried out; the filter material washes with water and dries it at 70 ° C., a red-brown pigment being obtained.

Example 2 24.6 parts of the sodium salt of 1-aminonaphthalene-2-sulfonic acid are dissolved in 200 parts of water. This solution is first 100 parts of ice and a solution of 6.9 parts of sodium nitrite in 20 parts of water, then 25 parts of 36.5% with stirring Hydrochloric acid added. The mixture obtained is stirred for 2 hours at 3 to 5 ° C and leaves them in a prepared at 40 ° C and then by adding ice to 5 ° C cooled mixture of 18 parts of 1-phenyl-3-methyl-4-pyrazolone, 100 parts of water and 15 parts of 40% sodium hydroxide solution are poured in. After the coupling is complete, the The resulting dye was filtered off with suction and dried at 70.degree. He gives one on wool Coloring in brown tones and with very good fastness properties.

If 18.7 parts of 1-amino-2-methylbenzene-5-sulfonic acid are used as the diazotizing component or 1-amino-4-methylbenzene-3-sulfonic acid, dyes are obtained, as does wool color in brown tones. One leads the dyes in their calcium, barium or If manganese salts are used, brown lacquer pigments of good oil quality are obtained.

Example 3 25.6 parts of the potassium salt of 1-amino-4-nitrobenzene-2-sulfonic acid are in a mixture of 300 parts of water and 25 parts of 36.5% hydrochloric acid Dissolved with heating and at 5 ° C with a solution of 6.9 parts of sodium nitrite added in 20 parts of water. The diazo suspension is left in a solution of 18 Pour parts of 1-phenyl-3-methyl-4-py razolon in 100 parts of 6o / o strength sodium hydroxide solution. After the coupling has ended, the resulting dye is filtered off with suction with a little water washed and dried at 70 ° C. He dyes wool in black tones. example 4 The diazo solution of 7.1 parts of 1-amino-2-methyl-4-chlorobenzene obtained in a known manner is left into a solution of 13.1 parts of 1- (4'-sulfo) -phenvl-3-methyl-4-pyrazolone, 13 parts 40% sodium hydroxide solution and 2.5 parts of anhydrous sodium carbonate in 70 parts of water flow in. The resulting dye is filtered off with suction and dried at 70.degree. He dyes wool from an acid bath in brown tones.

The 1- (4'-sulfo) -phenyl-3-methyl-4-pyrazolone required for coupling or - depending on the reaction conditions - a mixture of this compound with 1- (2'-sulfo) -phenyl-3-methyl-4-pyrazolone you can z. B. by treating 1-phenyl-3-methyl-4-pyrazolone with chlorosulfonic acid obtain.

The following dyes can be produced in the same way: Diazo component Azo component I shade on wool 1 Aminolienzol-4-sulfonic acid 1-phenyl-3-methyl-4-pyrazolone brown 1-Amino-8-oxytiaphthalene-3,6-disulfonic acid like violet 1-aminolienzol-2-sulfonic acid - (\ T-benzoyl) - amide like brown 1 aminolietizol-2-stilfonic acid - (\ '- l) enzoyl) - amide 1- (4'-sulfo) -phenyl-3-methyl-4-pyrazolone brown red 1-Ami iiol) etizol-2-ätlivlsulfon desgl. Braun EXAMPLE 5 34.4 parts of 4,4'-diaminodiphenyl-2,2'-disulfonic acid and 11 parts of anhydrous sodium carbonate are dissolved in 300 parts of water with heating, the solution is cooled, 14 parts of sodium nitrite are added and the mixture is allowed to mix Pour in 150 parts of ice and 50 parts of 36.5% hydrochloric acid. The resulting diazo solution is allowed to flow after 30 minutes into a solution of 36.5 parts of 1-phenyl-3-methyl-4-pyrazolone, 30 parts of 40% sodium hydroxide solution and 5.5 parts of anhydrous sodium carbonate in 250 parts of water, and the reaction mixture is stirred over night. To precipitate the resulting dye, 400 parts of sodium chloride and 500 parts of water are added, the product is filtered off with suction and the filter material is dried at 70 ° C.

The dye obtained dyes leather in brown shades.

If the diazo compound prepared in the usual way is coupled from 24.4 parts of 4,4'-diamino-3,3-dimethoxydiphenyl with 36 parts of 1-phenyl-3-methyl-4-pyr azolone in the presence of sodium hydroxide solution, a blue-black pigment is obtained of good fastness properties.

Example 6 22.3 parts of 4,4'-diaminodiphenyl sulfide are in a mixture dissolved in 100 parts of water and 51.5 parts of 36.5% hydrochloric acid. The solution sets man first 150 parts of ice and then a solution for 15 minutes of 14.2 parts of sodium nitrite in 40 parts of water. After 45 minutes one sets the diazo solution by adding 15% sodium carbonate solution to a pH value of 3.5 and leaves a neutral solution of 36.3 parts within 1 hour of the sodium salt of 1-amino-8-oxynaphthalene-4,6-disulfonic acid in 300 parts of water flow in. The reaction mixture is stirred overnight and left for 1/2 hour a diazo solution is poured in at 5 ° C., which can be obtained by stirring in 13.8 parts of 1-amino-4-nitrobenzene in 40 parts of water, addition of 40 parts of 36.5% hydrochloric acid, stirring for 11/2 hours with ice cooling, addition of 200 parts of ice and - in one pour and with stirring - A solution of 7.25 parts of sodium nitrite in 20 parts of water, 11 / 2stfindiges Stir and then filter. Then the clutch mix brought to a pH of 8.5 with 15% sodium carbonate solution and at 10 ° C stirred for 2 to 3 hours. A solution of 18.4 parts of 1-phenyl-3-methyl-4-pyrazolone is now used in a mixture of 100 parts of water and 13 parts of 40% sodium hydroxide solution and stir again overnight. The resulting dye is made by adding 500 parts Sodium chloride precipitated, filtered off with suction and dried at 70 ° C. It is soluble in water and dyes leather in dark blue tones.

If the same procedure is used instead of 1-amino-4-nitrobenzene the same molecular amount of 1-aminobenzene-4-sulfonic acid, a dye is obtained the coloration results in tones shifted slightly more towards green.

Example 7 18.4 parts of 4,4'-diaminodiphenyl are dissolved in a mixture of 200 parts of water and 25 parts of 36% strength hydrochloric acid at 70 ° C., the solution is cooled to 20 to 30 ° C and place another 25 parts of a 36, so / oigen one after the other Hydrochloric acid, 100 parts. Ice, a solution of 13.8 parts of sodium nitrite in 40 parts Water and - after 1/2 hour stirring at 0 to -I-5 ° C - finally to the Congo violet Reaction to sodium bicarbonate. In the diazo solution obtained in this way, one is left on 0 to 5 ° C cooled solution of 35 parts of the sodium salt of 2-oxynaphthalene-3,6-disulfonic acid pour in 250 parts of water and make the coupling mixture by careful Addition of 10% sodium carbonate solution, weakly alkaline. After 2 to 3 hours a solution, cooled to 0 ° C., of 17.9 parts of 1-phenyl-3-methyl-4-pyrazolone is left pour in a mixture of 100 parts of water and 15 parts of 40% sodium hydroxide solution and stir the reaction mixture for 12 hours. Then the resulting precipitate becomes suctioned off and dried at 70 ° C. It consists of 7.3 parts of a dark powder, that dyes cotton in red-brown tones.

Example 8 18.9 parts of 4,4'-diaminodiphenyl are dissolved in a mixture of 200 parts of water and 27.5 parts of 36.5% hydrochloric acid, the solution cools, add another 27.5 parts of 36.5% hydrochloric acid one after the other with 100 Parts of ice, with a solution of 14.2 parts of sodium nitrite in 40 parts of water and after 30 minutes with a solution of 7.2 parts of anhydrous sodium acetate in 30 Share water. In this diazo solution one leaves a little in the course of 30 minutes dilute sodium carbonate solution 'neutralized solution of 37.4 parts of the sodium salt the 1-amino-8-oxynaphthalene-3,6-disulfonic acid are poured into 300 parts of water. Man stirs the coupling mixture 11/2 hours at 10 ° C, then sets him a solution of 6.4 parts of anhydrous sodium acetate in 30 parts of water are added and the mixture is stirred overnight. The next day, a diazo suspension is added to the mixture, which is then dissolved of 17.3 parts of 1-aminobenzene-4-sulfonic acid in a mixture of 200 parts of water and 10 parts of 40% sodium hydroxide solution, addition of a solution of 6.9 parts of sodium nitrite in 20 parts of water, pouring the resulting solution into a mixture of 100 Parts of ice and 25 parts of 36.5% hydrochloric acid with stirring and stirring for 1 hour made. The coupling mixture is anhydrous with a solution of 33 parts Brought sodium carbonate in 250 parts of water to a pH of 8.5 and 2 hours stirred at 10 ° C. A solution of 18.3 parts of 1-phenyl-3-methyl-4-pyrazolone is then left pour in a mixture of 100 parts of water and 16 parts of 40% sodium hydroxide solution and stir again overnight. The resulting dye is by adding 700 Parts of sodium chloride and 85 parts of concentrated hydrochloric acid precipitated, filtered off with suction and dried at 70 ° C. He dyes cotton and leather in Russian green tones.

If 1-nitrobenzene-4-diazonium chloride is used instead of diazotized 1-aminobenzene-4-sulfonic acid, thus a dye is obtained which dyes cotton in just such shades. example 9 18.4 parts of 4,4'-diamino, diphenyl are, as described in Example 7, tetrazotized. The clear diazo solution is allowed to pour into one of 26.1 parts of des over the course of 1 hour Sodium salt of 2-amino, -5-oxynaphthalene-7-sulfonic acid by dissolving in 200 parts Water with the addition of 30 parts of 40% sodium hydroxide solution and 37 parts of 15% Sodium carbonate solution flow into the solution obtained, the coupling mixture is stirred over Night, then sucks off the resulting precipitate and washes it with a little water after. The dye thus obtained is suspended in 300 parts of water and washed with ice chilled. 70 parts of 36.5% hydrochloric acid and 100 parts of ice are then added to the suspension and then leaves a solution of 6.9 parts of sodium nitrite within 1/2 hour pour in 20 parts of water. After 2 hours the mixture is made by adding Sodium bicarbonate and neutralized with a solution of 36.5 parts of 1-phenyl-3-methyl-4-pyrazolone in a mixture of 200 parts of water and 22 parts of 40% sodium hydroxide solution. The reaction mixture is stirred for 2 days, and the resulting dye is filtered off with suction dries it at 70 ° C. It dyes cotton in blue tones.

Example 10 A mixture of the solutions of 37.0 parts of 4,4'-diaminostilbene-2,2'-disulfonic acid is left in a mixture of 200 parts of water and 21 parts of 40% sodium hydroxide solution and of 13.8 parts of sodium nitrite in 40 parts of water in a mixture of 200 parts of ice and 50 parts of 36% hydrochloric acid pour in with stirring. The diazo suspension obtained after stirring for 2 hours, it is left in a solution of 36.5 parts of 1-phenyl-3-methyl-4-pyrazolone flow in a mixture of 200 parts of water and 32 parts of 40% sodium hydroxide solution and stir that . -upplication mixed overnight. The resulting dye is filtered off with suction, washed with a little water and dried at 70.degree. He dyes cotton in; rough shades.

Example 11 42.6 parts of the dye from 1-amino-2,5-dimeth-) xybenzene-4-sulfonic acid amide and 1-phenol-3-methyl-1-pyrazolone are at 140 ° C to a solution of 30 parts Chromium chloride hexahydrate in 600 parts of ethylene glycol was added. You heat it up To-3-etch mixture 6 hours to 140 to 145 ° C, let it cool down, it carries 5000 Part in 20% sodium solution and stir the resulting mixture for some time. then The resulting chromium-plated dye is suctioned off and dried at 70 ° C.

The dye obtained in this way can still be manufactured by the method of the patent React 846 142 with 2-oxybenzoic acid-5-sulfonic acid phenylamide, a complex compound receives, which dyes wool from weakly acidic bath in very even, real blue tones.

Example 12 23.5 parts of that obtained in Section 1 of Example 11 Dye with 14.6 parts of the azomethine dye from 2-oxybenzaldehyde and 1-Oxy-2-aminobenzene-4-sulfonic acid amide in 150 parts of formamide for 3 hours with stirring heated to 115 ° C. The cooled conversion mixture is carried in 1000 parts 20% Sodium chloride solution, sucks off the resulting precipitate and washes it with dilute sodium chloride solution. The dye obtained is dissolved in a Mixture of 700 parts of water and 7 parts of 40% sodium hydroxide solution, the solution is filtered, the dye is precipitated by adding 400 parts of saturated sodium chloride solution again, sucks it off and dries it at 80 ° C. It dyes wool from weakly acid bath in green tones with good fastness properties.

Example 13 50.3 parts of that from nitrodiazoxy acid (= diazo anhydride from 1-amino-2-oxy-6-nitronaphthalene-4-sulfonic acid) by coupling with 2-oxynaphthalene The dye obtained is pasted with 100 parts of water, 175 parts of aqueous, 6.7 parts of chromium-containing chromium (III) formate solution and heated the obtained Mixture 3 hours at 135 ° C in an autoclave with stirring. Then you dilute that Reaction mixture with 1000 parts of water, sucks off the precipitated dye, washes it with a little dilute sodium chloride solution and dries it at 60 ° im Vacuum. This gives 55 parts of a dark colored powder, which is mixed with 43 parts of the monoazo dye 1- oxy-2-amino -4,6-dinitrobenzene- @ 1-phenyl-3-methyl-4-pyrazolone intimately ground in a ball mill. The mixture of the two dyes produced in this way behaves during dyeing like its uniform mixed complex compound; it yields very pure black dyeings on wool and synthetic polyamide fibers good wet and light fastness properties.

The following table shows dye mixtures obtained in the same way and having analogous dyeing properties No. 1: 1 chromium complex component Non-metalated dye component a fr ol e 1,4-dimethoxy-2-aminobenzene-4-sulfone- 1-oxy-2-amino-4-chlorobenzene-6-sulfone- 1 acid amide .- @ acid --- @ blue 1-phenyl-3-methyl-4-pyrazolone 2-oxynaphthalene-3-carboxylic acid (I \ T-oxy- ethyl) -ami d 1-Oxy-2-amino-4-nitrobenzene-6-sulfone-1-oxy-2-amino-4,6-dinitrobenzene . @ 1 acid -> 2 2-Oxynaphthalene-3-carboxylic acid- (1 \ T-me- 1-phenyl-3-methyl-4-pyrozolone black tliyl -. \ - oxv äthyl) -ami d 1 Ainiiio-2-oxy-6-nitronaphthalene- 1-oxy-2-amino-5-nitrobenzene .- @ 3 4-sulfonic acid - # - Black lt 2-oxynaphthalene 1-phenyl-3-methyl-4-pyrazolone 1-oxy-2-amino-4-nitrol) enzene-6-sulfone-1-oxy-2-amino-4-chlorobenzene.-a 4 acid .- @ black 2-Oxynal) litlialin-3-carl) onic acid (N-oxy-1-phenyl-3-methyl-4-pyrazolone ethyl) -ami d EXAMPLES 14 15, -I parts of 1-oxy-2-amino-4-nitrobenzene are dissolved in a mixture of 200 parts of water and 25 parts of 36.5% strength hydrochloric acid and at -I-8 ° C. with a solution of 6, 9 parts of sodium nitrite in 20 parts of water are added. The yellow diazo suspension obtained is allowed to flow into a solution of 18 parts of 1-phenyl-3-methyl-4-pyrazolone in a mixture of 300 parts of water and 25 parts of 400% sodium hydroxide solution. After coupling is complete, 150 parts of sodium chloride are added to the reaction mixture, it is heated to 70 to 80 ° C. for 1 hour, and after cooling, the dyestuff which has precipitated out is filtered off with suction and washed with dilute sodium chloride solution.

The dye paste prepared in this way is made into a paste with 600 parts of water and gives a chromium formate solution, which can be obtained by dissolving 4 parts of chromium (III) oxide containing chromium oxide hydrate paste in a mixture of 7.0 parts of anhydrous Formic acid and 10 to 20 parts of boiling water, and then 20 parts of crystallized sodium acetate. The implementation mix is now heated in an autoclave to 130 to 135 ° C for 5 to 10 hours. Then you suck the formed dye from and dries it at 70 ° C. It dyes wool and synthetic polyamide fibers from neutral to weakly acidic bath in black Tones. It can also be used to make dark brown zapon varnishes.

To convert into the cobalt complex compound, the one according to section 1 of this example prepared dye paste with 150 parts of fozn amide and 150 parts Parts of water are added to a solution of 15 parts of cobalt acetate in a little water and heat the reaction mixture in an autoclave to 140 ° C for 5 to 8 hours. The dye formed is filtered off with suction and dried at 80.degree. He dyes wool or synthetic polyamide fibers from a weakly acidic bath in dark brown tones.

Is used in Section 1 instead of 1-phenyl-3-methyl-4-pyrazolone 26.1 parts of 1- (4'-sulfonic acid amido) -phenyl-3-methyl-4-pyrazolone or 21.5 parts of 1- (3'-chloro) -phenyl-3-methyl-4-pyrazolone as azo components, dyes are obtained, the chromium complex compounds of which are wool color in brown-black tones.

The following dyes can also be prepared in the manner described Shade (on wool) the Diazo component azo component chromium complex cobalt complex connection connection 1-oxy-2-amino-4-chlorobenzene 1-phenyl-3-methyl-4-pyr- black dark brown azolone 1-Oxy-2-amino-4-chloro-6-nitrobenzene like violet 1-oxy-2-amino-4,6-dichlorobenzene like violet 1-Oxy-2-amino-4,6-dinitrobenzene like brown-black brown-black 1-Amino-2-methoxy-5-methylbenzene-4-sul- like violet fonsäureamid 1-Oxy-2-amino-5-nitrobenzene like black 9.-aminobenzene-2-carboxylic acid like dark brown brown 1-Oxy-2-aminobenzene-4-sulfonic acid amide, like brown, red-brown Example 15 15.4 parts of 1-oxy-2-amino-4-nitrobenzene are diazotized as indicated in Example 14. The resulting diazo suspension is added at 0 ° C. to a solution of 23.0 parts of 2-oxynaphthalene-6-sulfonic acid amide in a mixture of 200 parts of water and 25 parts of 40% sodium hydroxide solution, the coupling mixture is stirred for a few hours and the precipitate formed is filtered off with suction and washes it with water. A mixture of the dye thus obtained with the dye prepared according to Example 14 is partially stirred into a mixture of 400 parts of formamide, 400 parts of water and an aqueous solution of chromium formate containing 9.0 parts of chromium (III) oxide and placed in an autoclave 5 to Heated to 130 to 135 ° C for 8 hours. The reaction mixture is then introduced into 1500 parts of 10% sodium chloride solution, the resulting dye is filtered off with suction and dried at 70 ° C. It dyes wool in black shades with very good fastness properties.

Example 16 18.8 parts of 1-oxy-2-aminobenzene-4-sulfonic acid amide become in a mixture of 100 parts of water and 25 parts of 36.5% hydrochloric acid 0 ° C with a solution of 6.9 parts of sodium nitrite in 20 parts of water. Furthermore, by dissolving 17.8 parts of 1-phenyl-3-methyl-4-pyrazolone and 10 parts of anhydrous sodium carbonate in a mixture of 180 parts of water and 15 parts of 40% sodium hydroxide solution produce a coupling solution into which the diazo solution pour in while cooling with ice. After the coupling is finished, the resulting Precipitate sucked off; the dye paste thus obtained is mixed with the same Way from 18.8 parts of 1-oxy-2-amino-4-chloro-6-nitrobenzene and 1-phenyl-3-methyl-4-pyrazolone produced dye and chromed the mixture as described in Examples 14 and 15. The chromium compound thus obtained dyes wool or polyamide fibers from neutral to weakly acidic bath in black tones with very good fastness properties.

Example 17 That from 18.8 parts of 1-oxy-2-aminobenzene-4-sulfonic acid amide as in Example 16 obtained diazo solution is left in the solution prepared at 45.degree of 9.3 parts. 1-phenyl-3-methyl-5-pyrazolone and 9.3 parts of 1-phenyl-3-methyl 1-4-pyrazolone in a mixture of. 200 parts of water and 15 parts of 40% sodium hydroxide solution pour in, sets a solution of 10 parts of sodium carbonate in 80 parts of water and cools to 5 ° C. After the coupling is finished, the resulting precipitate is sucked off. The dye paste obtained is stirred with one as indicated below prepared solution of chromium formate in formamide and heated the mixture for 5 hours to 145 ° C. The cooled reaction mixture is filtered off with suction and the filtrate is poured in 1000 parts of 15% sodium chloride solution. The dye which has precipitated out is suctioned off and dried at 70 ° C. He dyes wool with a very good brown color Authenticity properties.

The solution of chromium formate in formamide used above is provided by making a chromium oxide hydrate paste that contains 3.8 parts of chromium (III) oxide, in a mixture of 5 parts of anhydrous formic acid and 15 parts of water Dissolves boiling temperature, the solution is poured into 200 parts of formamide and the reaction mixture Heated in an open vessel until the evacuating vapors react alkaline.

The following azo dye mixtures can also be converted into their metal complex compounds in the same way: Shade (on wool) the Dye 1 Dye 2 Chromium Cobalt complex- complex- connection connection i 1-Oxy-2-amino-4-chloro-6-nitrobenzene - @ 1-Oxy # -2-amino-4-chloro-6-nitrobenzene @ Violet- 1-phenyl-3-methyl-4-pyrazolone 2-oxyiiaphthalene-6-sulfonic acid amide black 1-Oxy-2-amino-4-chloro-6-nitrolienzol - @ 1-Oxy -? - aininobenzene-4-sulfonic acid- Black 1-phenyl-3-methyl-4-pyrazolon arid - @ 1-phenyl-3-methyl-4-pyrazolone 1-Oxy-2-amino-1,6-dichlorobenzene. @ 1-Oxy-2-amino-4,6-dichlorobenzene - @ Violen 1-phenyl-3-methyl-4-pyrazolone 2-oxynaphthalene-6-sulfonic acid amide 1-oxy-2-aniino-1,6-dichlorobenzene. -> 1-Oxy-2-aminobenzene-4-sulfonic acid amid - @ black 1-phenyl-3-methyl-4-pyrazolone 1-phenyl-3-methyl-4-pyrazolone 1-oxy-2-amino-4,6-dinitrobenzene .- @ 1-oxy-2-aminobenzene-4-sulfonic acid- 1 black- arid .- @ brown dark brown 1-phenyl-3-methyl-4-pyrazolone 1-phenyl-3-methyl-4-pyrazolone 1-Ox@#-2-amino-4.6-dinitrobenzene - @ 1-Oxy-2-aminobenzene-4-sulfonic acid- amid - # - black reddish brown 2-oxynaphthlialine-6-sulfonic acid amide 1-phenyl-3-methyl-4-pyrazolone 1-Oxy-2-amino-4,6-dinitrobenzene .- @ 1-Oxy-2-aminobenzene-4-sulfonic acid- amid _ # - black red-brown 2-oxynaphthalene in 1-phenyl-3-methyl-4-pyrazolone 1-Oxy-2-amino-4-nitro-6-chlorobenzene - @ 1-Oxy-2-aminobenzene-4-sulfonic acid- amid - # - black 1-phenyl-3-methyl-4-pyrazolone 1-phenyl-3-methyl-4-pyrazolone 1-Oxv-2-am ino-5-nitrolienzol - @ 1-Oxy-2-aminobenzene-4-sulfonic acid- arid .- @ Black 1-phenyl-3-methyl-4-pyrazolone 1-phenyl-3-methyl-4-pyrazolone 1-Oxv-2-amino-5-nitrobenzene - # - 1-Oxy-2-amino-5-nitrobenzene - + - 1-phenyl-3-methyl-4-pyrazolone 2-oxynaphthalene-6-sulfonic acid - dark blue (N'N-dimethyl) amide 1-Oxy-2-amino-4-nitrobenzene - @ 1-Oxy-2-amino-4-nitrobenzene .-> 1-phenyl-3-methyl-4-pyrazolone 2-oxynaphthalene} Black 1-Oxy-2-amino-4-nitrobenzene -> 1-Oxy-2-amino-4-nitrobenzene - @ 1-plienyl-3-methyl-4-pyrazolone, 2-oxynaphthalene-6-sulfonic acid, dark purple (N, N-dimethyl) amide 1-oxy-2-amino-4-nitrol> enzol .-- @ 1-oxy-2-amino-4-nitrobenzene .- @ 1- (3'-Chlorophenyl) -3-methyl-4-pyr-2-oxynaphthalene-6-sulfonic acid - dark purple azolone (N, N-dimethyl) arid 1-oxy-2-amino-4-nitrobenzene -> 1-oxy-2-aminobenzene-4-sulfonic acid amid .- -, black dark brown 1-phenyl-3-nietliyl-4-pyrazolone 1-phenyl-3-methyl-4-pyrazolone 1-oxy-2-amino-4-chlorobenzene -> 1-oxy-2-amino-4-chlorobenzene - > dark 1-phenyl-3-methyl-4-pyrazolone 2-oxynaphthalene-6-sulfonic acid amide} Black, red-brown 1-Oxy-2-amino-4-chlorobenzene .- @ 1-Oxy-2-aminobenzene-4-sulfonic acid- amid - black dark brown 1-phenyl-3-methyl-4-pyrazolone 1-phenyl-3-methyl-4-pyrazolone Example 18 The diazo compound is prepared from 22.3 parts of 1-oxy-2-amino-4-chlorobenzene-6-sulfonic acid and coupled with 17.9 parts of 1-phenyl-3-methyl-4-pyrazolone with the addition of sodium hydroxide solution . The resulting dye is filtered off with suction and washed with a little water. Then it is stirred with 400 parts of water and 50 parts of aqueous chromium (III) formate solution containing 10 parts of chromium (III) oxide are added to the suspension. The reaction mixture is then heated to 120 ° for 4 hours in an autoclave equipped with a stirrer, then 200 parts of saturated sodium chloride solution are added and the mixture is filtered off with suction. The dye obtained in this way dyes wool from an acid bath in pure purple tones.

Using the same procedure instead of 1-oxy-2-amino-4-chlorobenzene-6-sulfonic acid 23.4 parts of 1-oxy-2-amino-4-nitrobenzene-6-sulfonic acid, this gives a dye the wool dyes in more reddish purple tones than the previous one. With 1-oxy-2-amino-6-nitrobenzene-4-sulfonic acid arises corresponding to a dye, the wool in brown tones colors.

Example 19 The diazo solution of 7.7 parts obtained in a known manner 1-Oxy-2-amino-5-nitrobenzene is left in a solution of 13.1 parts of 1- (4'-sulfo) -phenyl-3-methyl-4-pyrazolone, 12.5 parts of 40% / a: sodium hydroxide solution and 6.5 parts of anhydrous sodium carbonate: nat pour in 100 parts of water; the coupling mixture is stirred for 12 hours, then set then 140 parts of sodium chloride and 10 parts of concentrated hydrochloric acid are added, sucks the resulting precipitate was washed with dilute sodium chloride solution and dries it. This is how you get a black colored powder, the wool after the chromium plating process dyes in black tones with excellent fastness properties. The dye can also be converted into the chromium complex compound using chromium formate solution as in Example 18 be transferred. The dye thus obtained also dyes wool in black Tones.

Claims (1)

PATENT CLAIM: Process for the production of - if necessary metallized - Mono- and polyazo dyes, characterized in that, B is diazonium compounds with 1-aryl-3-alkyl-4-pyrazo: ion and the resulting dyes, if desired converted into their metal complex compounds. Considered publications: German patent specification No. 959 394. When the application is published, a Coloring table has been laid out.