DE1544393A1 - Process for the production of metal complex dyes - Google Patents

Description

Process for the preparation of metal complex dyes

It has been found that new metal complex dyes are obtained if you have heterocyclic disazo dyes of the general Formula I.

A-N = N-B

N = N-HC

(I)

in the η the numbers 1 to 4 and A and B are aromatic-isocyclic or aromatic-heterocyclic radicals which are in the ortho position to the azo group connecting them each contain a hydroxyl group, and in the R for a carbon-containing group The remainder stands alone or in admixture with one another or in admixture with other metallizable Αζοτ or azomethine dyes with metal-donating agents to form the metal-containing dyes, or if dyes (I) are used in the case of production, of 1: 2 chromium complexes to 1: 1 chromium complexes of another Dye (I) or of other azo or azomethine dyes accumulates, or if you dyestuffs (I) with chromium abgebäuden Means to 1; I ^ converts chromium complexes and others

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Dyes (I) or other complex-forming azo or azomethine dyes with the formation of 1: 2 complexes av.

The starting dyes of the formula I are obtained if one Dyes of the formula II

(HO, S)

A-N = N-B

NH,

(II)

diazotized and with pyvazolone derivatives of the formula III

HO

-R

(III)

clutch.

The monoazo dyes serving as diazo components of Formula II can be obtained by various processes, for example by reducing nitro group-containing dyes from Formula IV

(HO-S)

3 'n

A-N = N-B

(IV)

by means of sodium o <3 ammonium sulfide in per se known Hot. The dyes of the formula IV are obtained, for example, by coupling 2-hydroxy-1-aminobenzenes containing nitro groups or 2-hydroxy-i-aminonaphthalenes with coupling

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treatment components which are in the ortho position to the hydroxyl group couple, with the diazo and coupling components so selects that at least one of the components is a sulfonic acid group contains. Examples of such nitro-group-containing diazo components are:

4-nitro-2-hydroxy-1-aminobenzene 5-nitro-2-hydroxy-1-aminobenzene 5-nitro-2-hydroxy-1-aminobenzene-3-sulfonic acid 3-nitro-2-hydroxy-1-aminobenzene-5-sulfonic acid 6-nitro-2-hydroxy-1-aminonaphthalene-4-sulfonic acid.

Aminoazo dyes of the formula II can also be prepared by that the diazo compounds of optionally containing sulfonic acid groups 2-hydroxy-i-arainobenzenes or 2-hydroxy-1-aminonaphthalenes in an alkaline medium with hydroxyaminonaphthalenesulfonic acids capable of coupling in the ortho position to the hydroxyl group united. These include:

1-hydroxy-6-aminonaphthalene-3-sulfonic acid 1-hydroxy-7-aminonaphthalene-3-sulfonic acid 2-hydroxy-3-aminonaphthalene'-6-sulfonic acid 1-hydroxy-8-aminonaphthalene-4-sulfonic acid i-hydroxy e-aminonaphthalin- ^, 6-disulfonic acid 1-hydroxy-8-aminotaphthalene-3,5-disulfonic acid ^a * " ^{? <Mv} i-hydroxy-S-aminonaphthalene-S, 7-disulfonic acid.

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A particular coupling component of the formula III is 3-methylpyrazolone to call. Furthermore, for example: 3-ethyl- and 3-butyl-pyrazolone, 3-phenylpyrazolone, Pyrazolone-3-carboxylic acid, pyrazolone-3-carboxylic acid amide, pyrazolone-3-carboxylic acid hydrazide and 3-cyanpyrazolone. In general, the substituents R in (III) are carboxyl, carbonamide, Cyano or aryl or alkyl groups with 1 to 8 carbon atoms are possible.

The disazo dyes obtained in this way are with metal donating Means, the metals comprising the atomic numbers 24 to 30, in a manner known per se in aqueous solution or slurry, in organic solvents or in mixtures from water and organic solvents, preferably at elevated temperature, optionally reacted under pressure. Preferred metals are copper and cobalt, and above all Chrome. Especially with chromium-releasing compounds, metal-containing ones can initially also be used, depending on the chosen reaction conditions Dyes are obtained which contain only one dye molecule bound to a chromium ion complex. To these 1: 1 metal complex dyes are in aqueous, weakly acidic, neutral or weakly alkaline medium, optionally with additive organic solvents or alone in organic solvents, metal-free disazo dyes of the formula I or other dyes capable of complex formation with normal or deposited at elevated temperature, whereby one expediently

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selects stoichiometric proportions. Likewise, the 1: 1 chromium complexes of other azo or azoraethine dyes preferably reacted with the metal-free disazo dyes of the formula I at elevated temperature. The complex formation can also be carried out on the fiber in a known manner will. Others suitable for the preparation of mixed 1: 2 complexes Azo and azomethine dyes are "e.g .:

Azomethine dye. 2-Hydroxy-3-sulfo-5-nitroaniline +

Salicylaldehyde

Azomethine dye from 2-hydroxy-4-sulfonamidoaniline +

2-hydroxy-i-naphthaldehyde

Azo dyes azo dyes azo dyes

Azo dyes azo dyes Azofajebetöff

from 2-hydroxy-4-nitroaniline -—- ^ 2-amino-. -5-sulfonaphthalene-

from 2-hydroxy-4-chloroaniline ^ 2-

Hydroxy-6-sulfonaphthalene

from 2-hydroxy-3-sulfo-chloro-aniline • '■ 2-Hydroxy-6-sulfonaphthalene

from ^ -hyäroxy ^ -sulfo-t-nitroaniline

■> ■■ 1-phenyl-3-methylpyrazolone (5)

from ^ -hydroxy ^ -sulfo-S-nitraniline - «^ 2-Hydroxynaphthalin

from 2 "Hydroxy-4-siüfö-6-nitraiiiliii 2-Hydroynaphthalide

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The dyes according to the invention are more or less easily soluble in water. They are suitable for dyeing and printing from a wide variety of textile materials such as wool as well as cotton or rayon with the use of polyfunctional ones reactive compounds, e.g. according to the procedure of the German Auslegeschriften 1 155 088 and. (Registration B 65 722 IVc / 8m - O.Z. 21 680).

The parts given in the examples are parts by weight. Parts of space relate to parts by weight as liters to kilograms under normal conditions.

example 1

30 parts by volume of 23% sodium nitrite solution are added to a solution of 22.35 parts of 5-chloro-2-hydroxy-1-aminobenzene-3-sulfonic acid in 220 parts by volume of 2 strength sodium hydroxide solution. This mixture is gradually poured into a mixture of 30 parts by volume of concentrated hydrochloric acid and 250 parts of ice at 0-5 ° C. The whole is 2 hours at 0 - 5 ⁰ C and then stirred slowly to a mixture of 30 parts of 1-amino-8-hydroxynaphthalene - 3 »6-disulfonic acid, 110 parts by volume of 4- # sodium hydroxide solution, 50 parts of ice and 35 parts of Sodium carbonate added. After the coupling has ended, the coupling product is precipitated by adding 80 parts by volume of concentrated hydrochloric acid and 200 parts by volume of saturated sodium chloride solution and filtered off with suction.

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The filter cake - is made in 500 parts. 1 $ solution of sodium hydroxide solution * This solution is gradually poured into a mixture of 70 parts by volume of concentrated hydrochloric acid, 300 parts of water and 400 parts of ice together with 30 parts by volume of 23% sodium hydroxide solution. After stirring for 2 hours at 0 - 5 ⁰ O are employed the diazotization mixture, a solution of 11 parts of 3-methylpyrazolone in 220 parts by volume of 2 $ aqueous sodium hydroxide are added and then is gradually by addition of 200 parts by volume of 10 $ aqueous sodium hydroxide solution to p '6. The disazo dye thus obtained is filtered off with suction, washed with dilute sodium chloride solution and dried. A black-brown powder is obtained which dissolves in hot water with a red-brown color and, when chromium-plated on wool in an acid bath, gives olive-colored shades of very good fastness properties.

Example 2

The total amount of the dye obtained according to Example 1 is 25 $ ammonia with stirring to 50 with 750 parts water and 30 parts by - heated 60 ⁰ C "After the addition of 27 parts of copper sulfate pentahydrate dissolved in the mixture of 150 parts of water and 60th Parts of 25 # ammonia are stirred for 2 hours at 50-60.degree. C. and the copper-containing dye is then precipitated by adding 2000 parts by volume of acetone ° Q _; . The ■ received dark-colored! -Powder dissolves with cloudy purple

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Color in water and gives gray dyeings of very good fastness properties on cellulose fibers according to the DAS 1 155 088 process.

Example 3

The total amount of the dye obtained according to Example 1 is stirred together with 750 parts of water, 30 parts of 25 # strength ammonia and 100 parts of a cobalt salt solution, their preparation is given below, 3 hours at 50-60 ° C. and the whole is evaporated to dryness, a brown one is obtained Powder which dissolves in water with an olive-brown color and which is applied to tissue containing cellulose in accordance with the specifications of DAS 1 155 088 Provides brownish gray dyeings and prints with very good fastness properties.

The cobalt salt solution used is obtained if you mix with a solution of 250 parts of cobalt (II) acetate tetrahydrate, Tillen ammonium acetate and 300 parts by volume of a 25 $ ammonia solution in 1000 parts of water with intensive soaking a stream of air passes through and then this solution fills up with water to 2000 parts of the room.

Example 4

If you use in Example Ί instead of 22.35 parts of 5-chloro-2-hydroxy-1-aminobenzene-3-sulfonic acid 18.8 parts of 2-hydroxy-1-amino-

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benzene-5-sulfonsäureamiä and proceed as described there, so receives matt a disazo dye, which is in water dissolves with red-brown color and the greenish gray color tones on wool after chrome-plating are very good. Results in fastnesses.

Example 5

If the total amount of the dye obtained according to Example 4 is used according to the information in Example 3 for the cobalt complex, this results in a gray-brown powder after evaporation dissolves in water with a brownish-purple color and cellulose fibers according to the procedure of DAS 1 155 088 in real gray

tinted brown tones.

Example 6

The total amount of the dye obtained according to Example 4 is stirred at 40 ⁰ O 400.4Ieilen with water and 10 parts 25 # ammonia. The equivalent amount of the 1: 1 chromium complex of the dye 4-nitro-2-hydroxy-1-aminobenzene-2-aminonaphthalene-5-sulfonic acid, which is accessible in a known manner, is then added. When the accumulation is over, which can easily be determined by chromatography, the whole thing is steamed to the surface. The black powder dissolves in water with a muted green color and dyes tissue made of Colluloaefaserii in true gray-green tones according to the method of DAS 1 155 088. ·

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If, instead of the specified 1: 1 chromium complex, the 1 ': 1 chromium complexes of the following dyes are converted into 1: 2 chromium complexes obtained with similar coloring properties.

Table examples according to Example 6

At- ι ι nu ι -ι hue of the additive

game ¹ · '1-chromium complex of products on cotton

7 5-nitro-2-hydroxy-1-araino-

benzene-3-sulfonic acid brown

1-phenyl-3-methylpyrazolone- (5)

5-nitro-2-hydroxy-1-amino

8 benzene-3-sulfonic acid> Gray

2-hydroxynaphthalene

6-nitro-2-hydroxy-1-amino

9 naphthalene-4-sulfonic acid - ^ gray-2-hydroxynaphthalene

Example 10

The dye from Example 4 is refluxed for a few hours with 500 parts of water, 20 parts of 25 # strength ammonia and 150 parts by volume of a chromium-containing solution, the preparation of which is given below. After a complete conversion has been determined by chromatography , the dark green dye solution is evaporated to dryness on a water bath.

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The green-gray powder dissolves easily in water and stains fabric made of cotton or regenerated cellulose according to DAS 1 155 in real greenish gray tones.

The chromium-containing solution used is prepared as follows:

533 parts of Ohrom (III) chloride hexahydrate are dissolved in 1000 parts by volume of hot water and this solution is poured into a mixture of 552 parts of salicylic acid, 220 parts by volume of 5Obiger sodium hydroxide solution and 1000 parts of water. This mixture is heated to 90-10O ⁰ C for one hour, 300 parts by volume of 50% sodium hydroxide solution and 200 parts by volume of 25% ammonia solution are added and the whole is made up to 5000 parts by volume with water.

Example 11

The mixture of 19 parts of i-ATnino ^ -hydroxybenzol-S-sulfonic acid amide, 75 parts water, 15 parts of concentrated hydrochloric acid and 100 parts of ice at 0 - 5 ⁰ O was added at once 30 parts of a 23 $ IGEU sodium nitrite solution. This diazotization mixture is gradually added, with external cooling, to the mixture of 24 parts of 5-hydroxy-2-aminonaphthalene-7-sulfonic acid dissolved in 100 parts of 5 strength sodium hydroxide solution, 100 parts of ice and 30 parts of sodium carbonate. After the coupling has ended, the dye obtained is precipitated by adding 30 parts of concentrated hydrochloric acid, filtered off with suction and washed with a little water.

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The coupling product is mixed with 12 parts by volume of 50% sodium hydroxide solution dissolved in 700 parts of water and then indirectly diazotized in the usual way. In the diazotization mixture thus obtained gradually gives a solution of 10 parts of 3-methylpyrazolone- (5) in 6 parts of 50% sodium hydroxide solution and 120 parts of water. Then slowly leave 250 parts of volume 50% Pour in sodium acetate solution. The disazo dye is filtered off with suction and washed with a little water. That after drying The blue-gray powder obtained dissolves in water with a blue color and gives blue-gray colorations on wool after it has been chrome-plated with very good fastness properties.

Example 12 .::

The metal-free disazo dye obtained according to Example 11 is cobalted according to the instructions in Example 3. You get after evaporation on the water bath and drying a dark colored Powder that dissolves in water with a purple color, and cotton fabric according to the specifications of DAS 1 155 088 in dyes gray-violet shades with very good light and wash fastness properties.

Example 13

The total amount of the disazo dye of Example 11 becomes as given in Example 10 converted to the chromium complex. That after

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the powder obtained after evaporation of the dye solution cellulose-containing fabrics according to the specifications of DAS 1 155 088 in blue-gray tones with very good light and wash fastness properties.

Example H

The coupling product of diazotized 3-nitro-2-hydroxy-T-amiobenzene-5-sulfonic acid and 3-methylpyrazolone is in a known manner in aqueous solution with sodium sulfide with addition Treated by ammonium chloride until no more starting dye can be detected by chromatography.

31 parts of this amino-azo dye are indirectly diazotized and with the solution of 15 parts of 2-hydroxynaphthalene in Share 2 # sodium hydroxide solution with the addition of ice and so much Sodium carbonate combined that a p «of 8.5 to 9 im Coupling mixture consists. The isolated and dried dye dissolves in water with a blue color and gives up Re-chilled wool, gray dyeings with good fastness properties.

Example 15

0.02 mol of the disazo dyes obtained according to Example H are dissolved in 100 parts of water and 5 parts by volume of 25 # strength ammonia with the equivalent amount of the 1s1-Ohrom complex of 4 ^ nitro-2-hydroxy-i-aminobenzene ··· 2-naphthylamine-5 sulfonic acid

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has stirred for 60 ⁰ C, held until complete addition - as long as at 50th The dye is precipitated by adding 5 parts of 30% acetic acid and 1000 parts of saturated sodium chloride solution, washed with a little water and dried. The dark gray powder obtained dissolves in water with a cloudy blue color and gives blue-gray dyeings of good fastness properties on cotton according to DAS 1,155,088.

Example 16

The disazo dye obtained in Example 14 is converted into the chromium complex according to Example 10. The obtained aqueous Solution is made with 200 parts of saturated sodium chloride solution offset. The isolated dye gives on cotton fabrics in accordance with DAS T 155 088 gray-violet dyeings which are good lightfast and wetfast.

Example 17

The diazo compound of 51 parts of the aminoazo dye mentioned in Example 14, Section 1, is mixed with a solution of 32 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid combined in 220 parts of 2 strength sodium hydroxide solution with the addition of 250 parts of ice and 70 parts of sodium carbonate. The received The dye is isolated by suction filtration and dried.

All of the dye is converted into a cobalt (HX) complex as in Example 3. The solution thus obtained becomes dry

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steamed. Easily soluble in water with a cloudy blue color

dark gray powder gives way to cellulose-containing fabrics

the procedure of DAS 1 155 088 very good light and wet fastness gray prints and dyeings.

Example 18

In the diazotization mixture of 31 parts of the in Example H, Section 1, indicated aminoazo dye is left one Solution-of 10 parts of 3-methylpyrazolone- (5) in 150 parts Pour in 3 # sodium hydroxide solution and then add slowly Add 300 parts of 50 $ sodium acetate solution. The isolated one Dye Is cobalted as in Example 3. By adding 25 parts of 30% acetic acid, 75 parts of sodium chloride and 250 parts of saturated sodium chloride solution is the cobalt-containing one Dye like. The brown-red powder obtained after suctioning off and drying dissolves with a bluish red tinge Color in water and gives on cotton according to the indications of the DAS 1 155 088 real dyeings in Bordo shades.

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Claims (1)

Patent request Process for the preparation of Metallfconiplex dyes, characterized in that one heterocyclic disazo dyes of the general formula (HO, S) A-N = N-B HO in which η denotes the numbers 1 to 4 and A and B denote aromatic-isocyclic or aromatic-heterocyclic radicals which each contain a hydroxyl group in the ortho position to the connecting azo group, and in which R stands for a carbon-containing radical, alone or in a mixture with one another or in Gemi.?ch with other metallizable azo or azomethine dyes with metal donating agents to the metal-containing dyes, or if dyes (I) in the case of the preparation of 1: 2 chromium complexes to 1: 1 chromium complexes other dyestuff (I) or other azo or azomethine dyestuffs, or if dyestuffs (I) are reacted with chromium-releasing agents to form 1: 1 chromium complexes and other dyestuffs (I) oil other complex-forming azo or azomethine dyestuffs with the formation of 1 ' . 2 complexes. BADISCHE ANILIN- & SODA-FABRIK AG n) 00981 1/0692 '