DE1151334B - Process for the preparation of metallizable 4-oxy-5-carboxy-phenyl-2, 2'-dioxyazo dyes - Google Patents

Description

Process for the production of metallizable 4-oxy-5-carboxyphenyl-2,2'-dioxyazo dyes The invention relates to a process for the production of metallizable 4-oxy-5-earboxyphenyl-2,2'-dioxyazo dyes which contain at least one of the following atomic groupings where R denotes the remainder of a couplable compound in which the oxy group is in the ortho position to the couplable carbon atom.

Swiss Patent 365 163 describes a process for the preparation of 4-oxy-5-carboxyphenyl-2,2'-dioxyazo dyes, in which 1-amino-2-arylsulfonyloxy-4-oxybenzene-5-carboxylic acid is diazotized and the resulting Diazo compounds are coupled to components which have an oxy group in the ortho position to the carbon atom capable of coupling. The arylsulfonyl radical is subsequently split off in an alkaline medium from the arylsulfonyl esters of 4-oxy-5-carboxyphenyl-2,2'-dioxyazo dyes obtained in this way. The dyes according to formula 1 thus obtained can be converted into metal complex compounds and are mainly used for chrome printing on cotton. The dyeings and prints are distinguished by very good wet and light fastness properties.

However, there are various disadvantages associated with this method, in particular the tendency to undesired cleavage of the arylsulfonyl radical during manufacture of the aryl sulfonyl ester dye in an alkaline medium.

Furthermore, dyes that have no sulfonic acid groups in the molecule are Usually so sparingly soluble in water that they do not conform to the usual ones Color or print methods.

There is a further disadvantage of said arylsulfonyl ester dyes in that the metallization on the fiber remains practically insignificant, since the alkaline cleavage of the aryl sulfonyl esters fixed on the fiber with chromium runs slowly and fiber damage can occur as a result.

It has now been found that the valuable, metallizable 4-oxy-5-carboxyphenyl-2,2'-dioxyazo dyes which have the following atomic grouping at least once can be obtained contain, where R denotes the remainder of a couplable compound in which the oxy group is in the ortho position to the couplable carbon atom, can be produced in a simple manner in very good yield by the sulfuric acid mono- (5-oxy-4-carboxy- 2-aminophenyl) esters of the general formula diazotized and the diazo compound obtained on a coupling component, which has an oxy group in the ortho position to the coupling C atom, and the sulfuric acid monoester of 4-oxy-5-carboxyphenyl-2,2'-dioxyazo dye thus obtained, which at least once the following atom grouping where R has the above meaning, is subjected to saponification in an acidic to neutral medium in substance or on the fiber, with cleavage of the sulfuric acid monoester of the 4-oxy-5-carboxy-2,2'-dioxyazo dye, which has at least one atomic grouping contains according to formula 1 , is obtained.

The method according to the invention is particularly characterized by the use of sulfuric acid mono- (5-oxy-4-carboxy-2-an-iinophenyl) ester according to Formula II as the starting material.

This latter connection is new and can e.g. B. can be produced in very good yield as follows: a) Sulfuric acid mono- (3-oxy-4-earboxyphenyl) ester Dry 2,4 - dioxybenzoic acid is introduced into a mixture consisting of pyridine and chlorosulfonic acid with the exclusion of moisture. At a moderately elevated temperature, preferably 50 to 70 ° C., the esterification is completed in the course of 5 to 6 hours. The reaction product is discharged onto excess soda, carefully mixed with water and the pyridine is driven off by passing in steam.

A clear, alkaline solution of sulfuric acid mono- (3-oxy-4-carboxyphenyl) ester is obtained. b) 2- (4 '# chlorophenylazo) -phenyl- (1) -ester] sulfuric acid mono- [5-oxy-4-carboxy- 4-chloroaniline is diazotized as usual and coupled in the presence of excess soda to the sulfuric acid mono- (3-oxy-4-carboxyphenyl) ester obtained in accordance with paragraph a) above. Towards the end of the coupling, the mixture is heated to 50 to 60.degree. C., the partly precipitated ester dye going into solution. Impurities are filtered off and the ester dye is separated off by adding ox salt.

The dried disodium salt of the yellow-colored ester dye gives, calculated as an anhydrous and salt-free product, the following analytical results: Q3H7O7N2C1SNa2 (Mol 416.5): Calculated . . . N 6.73%, Ci 8.53 1 / o, S 7.69 1 / o; found ... N 6.76%, Cl 8.47%, S 7.76%. c) Sulfuric acid mono- (5-oxy-4-ca # boxy-2-aminophenyl) ester The ester dye obtained according to section b) above is z. B. treated in the presence of excess sodium hydroxide solution with sodium hydrosulfite at a temperature of 75 to 95'C. The solution, decolorized by reduction, is freed from 4-chloroaniline by steam distillation and cooled to O'C.

The crystalline decomposition products of sodium hydrosulfite are separated off and hydrochloric acid is added to the clear solution at a temperature of about -5'C, the sulfuric acid mono (5 - oxy - 4 - carboxy - 2 - aminophenyl) ester precipitating as the inner salt. After filtering, washing neutral and drying, a light gray powder is obtained in excellent yield, which, calculated as a salt- and anhydrous product, gives the following analytical results: C7H707NS (249): Calculated ... N 5.63%, S 12.85% ; found ... N 5.59%, S 12.86%. The diazotization of the sulfuric acid mono- (5-oxy-carboxy-2-aminophenyl) ester to be carried out according to the invention is advantageously carried out at a temperature below O'C in order to avoid premature cleavage of the sulfuric acid ester and possibly nitrosation. The best way to proceed is the so-called indirect method and allow a solution consisting of the disodium salt of sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester and sodium nitrite to flow onto a mixture of ice, table salt and hydrochloric acid, so that the temperature does not rise above -5'C. The diazo body precipitates out as an inner salt and can optionally be filtered and washed neutral with ice water. The diazo compound thus obtained is stable in a neutral or alkaline medium.

The coupling of the diazotized sulfuric acid mono- (5-oxy-4-earboxy-2-aminophenyl) ester with couplable compounds which are in the ortho position to the couplable carbon atom have an oxy group or an enolizable keto group after the usual methods in the presence of alkalis. If necessary, the Coupling reaction accelerated by adding small amounts of pyridine or by heating will.

The compounds customary for azo dyes are used as azo components into consideration, in the ortho position to the couplable carbon atom, an oxy group or a have enolizable keto group.

A. Among the azo components which lead to monoazo dyes, there may be mentioned, for example: 1,3-dioxybenzene, 2,4-dioxybenzoic acid, acetoacetylaminobenzene, 4-acetoacetylamino-1-chlorobenzene, 3-acetoacetylaminobenzenesulphonic acid, 5-acetoacetylamino-2-oxybenzoic acid - (3'-carboxy-4'-oxyphenyl) -3-methyl-5-pyrazolone, 2-oxynaphthalene, 2-oxynaphthalene-3,6-disulfonic acid, 1 oxy-8-aminonaphthalene-3-sulfonic acid, 1-oxy -8-aminonaphthalene-3,6- and -4,5-disulfonic acid and their acylation products.

B. It is also possible to use 2 molecules of the diazotized sulfuric acid mono (5 - oxy - 4 - carboxy - 2 - aminophenyl) ester with 1 mol of a component which can be coupled twice, each having an oxy group or a group which can be converted into an enolizable group in the ortho position contains to the couplable C atom, are combined.

Examples of such components are: 1,3-dioxybenzene, 1,8-dioxynaphthalene-3,6-disulfonic acid, 1-oxy-8-acetoacetylaminonaphthalene-3,6-disulfonic acid, 5,5'-dioxydinaphthyl- (2.2 ') -aminodisulfonic acid- (7.7 #. C. As azo-group-containing azo components which have an oxy group or a group which can be converted into an enolizable group in the ortho position to the couplable carbon atom, azo dyes are to be understood that are formed by diazotizing an aromatic amino -. or aminoazo compound and acid coupling are obtained on aminonaphtholsulfonic acids, e.g., the acidic coupling product of diazotized 4-nitroaniline and 1-amino-8-naphthol-3,6-disulfonic acid, and coupling products of 1 molecule of a twice detachable component, eg. B. 4 ', 2'-Dioxy-1,1 "-azobenzene-4-sulfonic acid.

The sulfuric acid monoesters of 4 - oxy - 5 - earboxyphenyl - 2,2 ' - dioxyazo dyes obtained in this way, which contain at least one atomic grouping according to formula III, can be isolated by the customary methods and can optionally be subjected to purification.

The dyes which contain at least one atomic grouping according to formula III combine in the same molecule a complexable group and a system which can be converted into a complexable group, in that the atomic grouping according to formula III is converted into atomic grouping according to formula I by treatment with acids with cleavage of the sulfuric acid ester (Ester cleavage). The dyes can be applied according to the following scheme, namely by ester cleavage on the fiber, i. H.

a) dyeing, ester cleavage on the fiber and metallization, b) dyeing, metallization, ester cleavage on the fiber and renewed metallization, c) metallization, dyeing, ester cleavage on the fiber and renewed metallization, or by ester cleavage in substance, d. H. d) bulk ester cleavage, dyeing and metallicization, or e) bulk ester cleavage, metallization, dyeing and renewed metallization. The dyes, which contain at least one atom group according to formula III, depending on their constitution, are absorbed in different shades on animal, vegetable and synthetic fibers, and some of them are also suitable for coloring anodically oxidized aluminum. The dyeings are generally strong and bright, but with moderate fastness properties. In chrome printing, chromium plating on the fiber or dyeing on pre-chromium-plated fiber, while maintaining the atomic grouping according to formula III, complex formation of the o-oxycarboxyphenyl group results in significantly better wet fastness properties and in some cases better light fastness properties than was previously the case.

The same effect can also be achieved with a short treatment these ester dyes, at a moderately elevated temperature, with chromium donating agents, like chromium acetate. The chromium enters the o-oxycarboxyphenyl group, whereby the ester grouping according to formula III is retained. Complex compounds of these Art are characterized by very good solubility and good fixability.

One treats dyes that at least once the atom grouping according to formula III, with acids, the sulfuric acid ester is obtained with cleavage Dyes which contain the atom grouping according to formula I at least once. With strong acids such as hydrochloric or sulfuric acid, the ester cleavage takes place at room temperature, while with weak acids such as acetic acid, the cleavage only occurs runs at a noticeable rate at higher temperatures.

If the ester cleavage is carried out on the fiber, one uses in order to prevent bleeding, it is advantageous to use chromium-fixed colors. Post-treatment with metal-releasing agents gives colorations that are characterized by very good wet and light fastness properties.

If the ester cleavage is carried out in bulk, 4-oxy-5-carboxyphenyl-2,2-dioxyazo dyes which contain the atomic grouping according to formula 1 at least once are obtained. The colorations of these dyes can be aftertreated by the customary methods with metal-releasing agents, in particular copper and chromium compounds, as a result of which the general fastness properties are significantly improved.

The dyes, which at least once the atom grouping according to Formula I can contain also in substance according to known methods be converted into metal complex compounds with meta-donating compounds. The metal-containing dyes prepared in this way are suitable if they contain sulfonic acid groups for dyeing animal, vegetable and synthetic fibers such as also for coloring anodically oxidized aluminum. Unless in the dyes, which contain the metal bound by the o-dioxyazo group, which are capable of complexing o-Oxycarboxyphenyl group is not yet occupied by a heavy metal, the Coloring of these dyes with metal donating agents, preferably chromium compounds, post-treated, the wet fastness properties are significantly improved. Special The metal-containing, sulfonic acid group-containing dyes are of interest for chrome printing. When printed on cotton, they deliver color tones of very good wet- and lightfastness and in some cases of remarkable purity.

A particularly advantageous embodiment is that one the dyes which contain at least one atom group according to formula III, in substance or preferably on the fiber, at the same time the ester cleavage and subject to metallization. This is achieved by keeping the dyes in neutral to weakly acidic medium at temperatures from 40 to 95'C with metal-releasing Means treated. Both simple metal salts, such as sulfates, chlorides or acetates, as well as those compounds which Contain metals bound in complexes, such as aromatic and aliphatic oxycarboxylic acids, Dicarboxylic acids and aminocarboxylic acids. Particularly good results are obtained if the dyes fixed with chromium on the fiber, which at least once contain the atom grouping according to formula III, in neutral to weakly acidic Medium can be post-treated with copper salts at elevated temperatures.

The process according to the invention has the following advantages over the process described in Swiss Patent 365 163 : The sulfuric acid mono (5 - oxy - 4 - carboxyaminophenyl) ester and the ester dyes made from it are stable in an alkaline medium even at elevated temperatures. The alkali resistance makes the production of the dyes much easier and in some cases also leads to better dye yields.

Another advantage of the method according to the invention is that it is good Solubility of the intermediate ester dyes and their ease Metallizability on the fiber.

Sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester is coupled on components that do not contain sulfonic acid groups, e.g. B. 1,3-Dioxybenzene, this gives dyes which are readily soluble in water and without difficulty can be fixed on the fiber with chrome printing. A follow-up treatment of a few minutes with copper sulfate or other copper salts are obtained with cleavage of the sulfuric acid ester and with the simultaneous formation of the o, o-dioxyazo-copper complex compound washable prints of excellent lightfastness. The inventive method is illustrated by the following examples; under parts are in the Follow parts by weight understood.

Example 1 24.9 parts of the sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester (mol 249) are dissolved in 100 parts of cold water with 20 parts by volume of aqueous sodium hydroxide solution (30%) and mixed with 25 parts by volume 4 n -Nitrite solution mixed. The clear solution is slowly poured into a mixture consisting of 400 parts of ice, 100 parts by volume of saturated sodium chloride solution and 60 parts by volume of hydrochloric acid (30%) with stirring so that the temperature does not rise above -5'C. The diazotization is over after 10 to 20 minutes. The precipitated diazo compound is isolated and added to a prepared solution consisting of 200 parts of water, 60 parts by volume of aqueous sodium hydroxide solution (30%), 10 parts of pyridine, 100 parts of ice and 35 parts of the disodium salt of 2-oxynaphthalene-3,6-disulfonic acid ( Mol 348). The mixture is stirred until the coupling has ended, the pH of the coupling solution is adjusted to 9 by adding acetic acid and the mixture is heated to 40 to 50.degree. The dye is precipitated by adding 300 parts of sodium chloride, filtered and dried at 60 to 80 ° C. in vacuo.

The ester dye thus obtained has the structural formula in the form of the free acid and is a red-brown powder that dissolves in water and concentrated sulfuric acid with a red color. The chrome print on cotton gives a blue-violet coloration which, after treatment with copper acetate-acetic acid at 90 ° C., with cleavage of the sulfuric acid ester and the simultaneous formation of the o, o'-dioxyazo-copper complex compound, gives a washable red-violet of excellent lightfastness.

The same result can be achieved by post-treatment with copper sulphate at 60 to 70 ° C. Example 2 50 parts of the ester dye obtained in Example 1 are dissolved in 750 parts of water at room temperature, and 60 parts by volume of hydrochloric acid (30%) are added. A clear red-orange solution is obtained which has a distinct mineral acidic reaction. The mixture is left to stand for 48 hours at room temperature, after which the cleavage of the sulfuric acid ester has ended. 75 parts of calcined sodium carbonate are carefully added.

The now intensely blue-violet solution is heated to 40 to 50 ° C and the dye is deposited by adding sodium chloride. The isolated and dried dye has the structural formula in the form of the free acid and represents a violet-brown powder that dissolves in water with a reddish-tinged blue color, and in concentrated sulfuric acid with a bluish-tinged-red color. Chrome printing on cotton gives a violet coloration which, on aftertreatment with copper acetate with formation of the o, o-dioxyazo-copper complex compound, gives a very lightfast red-violet, on wool a violet and on anodically oxidized aluminum a bluish red. Example 3 50 parts of the o, o # -dioxyazo dye obtained according to Example 2 are dissolved in 500 parts of water at 90 to 95.degree. 100 parts of a chromium acetate solution containing 5.5 parts of chromium are added dropwise with stirring. The mixture is stirred until the formation of the o, o "-dioxyazo-chromium complex compound has ended, and the very readily soluble metal-containing dye is isolated by evaporating to dryness in vacuo.

The chromium-containing monoazo dye thus obtained is a dark one purple-tinged powder that dissolves in water and concentrated sulfuric acid dissolves with purple paint. In the chrome print on cotton you get a real blue-violet.

If the chromium solution is replaced by the corresponding amount of cobalt solution, so you get a gray-violet in the chrome print on cotton.

If the chromium solution is replaced by the corresponding amount of copper acetate or copper tetramine, a dye is obtained which, when printed on chrome on cotton, gives a pure red-violet with very good lightfastness. Example 4 If in Example 1 the 2-oxynaphthalene-3,6-disulfonic acid is replaced by the equivalent amount of 1-oxynaphthalene-4-sulfonic acid, a sulfuric acid monoester dye with similar properties is obtained.

The corresponding o, o-dioxyazo dye is formed by cleavage of the sulfuric acid ester according to Example 2. The o, o'-dioxyazo dye thus obtained is metallized according to Example 3 , the following metal-containing azo dyes being obtained: The dyeings are distinguished by good fastness to light and washing. Example 5 24.9 parts of the sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester (mol 249) are diazotized according to Example 1. The diazo suspension is introduced into a prepared solution consisting of 16 parts of 2,4-dioxybenzoic acid (Moll54), 100 parts by volume of aqueous sodium hydroxide solution (30%), 20 parts of pyridine, 50 parts of water and 50 parts of ice. The mixture is stirred at room temperature until the coupling has ended, the pH of the coupling solution is adjusted to 8.5 by adding 25 parts of acetic acid (80%) and the mixture is heated to 40 to 50.degree. After 300 parts of sodium chloride have been added, the dye precipitates, is filtered and dried at 60 to 80 ° C. in vacuo.

The easily soluble dye has the structural formula in the form of the free acid and is a dark brown powder which dissolves in water with a yellow-brown color and in concentrated sulfuric acid with a brown color. Chrome printing on cotton gives a rich, brown color. After treatment with copper sulphate for 5 to 10 minutes. at 60 to 70 ° C. , with cleavage of the sulfuric acid ester and the simultaneous formation of the o, o # -dioxyazo-copper complex compound, a purple-tinged brown with excellent wash and lightfastness is obtained.

The same result is obtained by a 5 to 10 minute post-treatment with copper acetate in acetic acid solution at a temperature of 90 to 95.degree. Example 6 24.9 parts of the sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester (mol 249) are diazotized according to Example 1. The diazo suspension is introduced into a solution consisting of 11 parts of 1,3-dioxybenzene ( 110 moles), 20 parts of pyridine, 85 parts by volume of aqueous sodium hydroxide solution (30%) and 100 parts of water. After the coupling has ended, the dye is precipitated with sodium chloride at pH 9.5 , isolated and dried. A red-brown powder is obtained which dissolves in water with a yellow color and in concentrated sulfuric acid with a yellow-brown color. The chrome print on cotton gives a strong reddish brown which, on aftertreatment with copper sulphate, changes to a rich, real brown with excellent lightfastness, with cleavage of the sulfuric acid ester and the simultaneous formation of the o, o-dioxyazo-copper complex compound. Example 7 24.9 parts of the sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester (mol 249) are diazotized according to Example 1. The diazo suspension is introduced into a solution consisting of 18 parts of acetoacetylaminobenzene ( 177 mol), 200 parts of water, 50 parts of pyridine and 120 parts of calcined sodium carbonate. At the end of the coupling reaction, the mixture is heated to 40 to 50 ° C. and the dye is separated off by adding 180 parts of sodium chloride. After isolation and drying, a yellow powder is obtained which dissolves in water and concentrated sulfuric acid with a yellow color. Chrome printing on cotton gives a bright yellow with good wash fastness, which turns into a brownish yellow with very good lightfastness when re-coppering with copper sulfate with cleavage of the sulfuric acid ester and with simultaneous formation of the o, o'-dioxyazo-copper complex compound.

Dyes with similar properties are obtained when used as azo components 1-chloro-4-acetoacetylaminobenzene or 3-acetoacetylaminobenzene-1-sulfonic acid is used will.

Example 8 If the procedure of Example 7 is followed and 5- acetoacetylamino - 2 - oxybenzoic acid (mol 237) is coupled to 24 parts, a yellow-brown powder is obtained which dissolves in water and concentrated sulfuric acid with a yellow color. The dye has the following constitutional formula in the form of the free acid: 49.7 parts of this dye (mol 497) are dissolved in 500 parts of water. The clear yellow solution is mixed with 100 parts of a chromium acetate solution containing 15 parts of chromium. The mixture is heated to 80 to 85 ° C. for 5 minutes. The very easily soluble dichromium complex compound of the dye is obtained without the sulfuric acid ester being cleaved, the chromium being bound by the two o-oxycarboxy groups.

This dark brown dye solution dyes natural silk, wool, polyamide fibers, Cotton and anodized aluminum in clear, reddish-yellow tones.

By NacA treatment of the above dyeings with copper sulfate at 60 to 70 ° C. , with cleavage of the sulfuric acid ester and the simultaneous formation of the o, o * -dioxyazo-copper complex compound, yellow-brown shades of partly very good lightfastness are obtained.

Example 9 24.9 parts of the sulfuric acid mono- (5-oxy-4-carboxy-2-anünophenyl) ester (mol 249) are diazotized according to Example 1 and 23.5 parts of 1- (4 # -oxy-3'- carboxyphenyl) -3-methyl-5-pyrazolone (Mol 234) coupled. After isolation and drying, the dye is obtained as an orange powder which is soluble in water with an orange color and in concentrated sulfuric acid with a red-orange color.

In the chrome print on cotton, a clear, real orange of good lightfastness obtained; re-coppered with cleavage of the sulfuric acid ester and with simultaneous formation of the o, o "-dioxyazo-copper complex compound a brownish orange of excellent lightfastness.

According to Examples 1 to 8 , further valuable metal-containing monoazo dyes can be prepared. Some examples are summarized in the table below. Example 18 24.9 parts of the sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester (mol 249) are diazotized according to Example 1. The diazo suspension is introduced into a solution consisting of 5.5 parts of 1,3-dioxybenzene ( 110 moles), 72 parts by volume of aqueous sodium hydroxide solution (30%), 20 parts of pyridine and 150 parts of ice water. The mixture is stirred at room temperature until the coupling has ended, the pH of the dye solution is adjusted to 8.5 by adding acetic acid, heated to 40 to 50 ° C. and the dye is separated off by adding sodium chloride. The dye that has the structural formula in the form of the free acid possesses, is filtered and dried in vacuo at 60 to 70'C. The easily soluble dye is a gray-black powder that dissolves in water with a brown color, and in concentrated sulfuric acid with a brown-violet color.

In chrome printing on cotton, the dye gives a dark brown color. When re-coppering with copper sulphate at 50 to 70'C or with copper acetate at 90 to 100'C one obtains, with cleavage of the sulfuric acid esters and with simultaneous formation of the o, o-dioxyazo-copper complex compounds or the di-o, o "- dioxyazo-copper complex compound, a deep black with excellent light and wash fastness.

If the dye is dyed on anodically oxidized aluminum, it is obtained after treatment with aqueous copper sulphate solution (metal sealing), with cleavage the sulfuric acid ester and with simultaneous formation of the o, o # -dioxyazo-copper complex compounds, a brownish black with excellent lightfastness.

The colors on pre-chromed silk, wool and viscose result in the Post-coppering with cleavage of the sulfuric acid esters and with simultaneous formation the o, o-dioxyazo-copper complex compounds washfast gray to black shades partly very good lightfastness. Colored in the same way on pre-chromed Polyamide fibers, the brown color is obtained by an alkaline treatment turns black in an aqueous medium at elevated temperature (alkaline wash). The dyeing is characterized by very good wet and light fastness.

If 12.6 parts of the ester dye prepared according to Section 1 of this example (mole 630) are dissolved at 60 to 80 ° C. in 400 parts of aqueous chromium acetate solution containing 3.5 parts of chromium and stirred for some time, the result is obtained without the Schwefelsäureester are cleaved, the readily soluble o - Oxycarboxy - Dichrom - complex compound of Esterfarbstoffes. The dichromium complex compound is isolated as a brown-violet powder by evaporation in vacuo at 40 to 50 ° C.

The aqueous solutions of the o-oxycarboxy-dichromium complex compound can directly for dyeing silk, wool, viscose, polyamide fibers and anodically oxidized Aluminum can be used. When re-coppering you get the same color tones as described above.

Other valuable disazo dyes can be prepared in a similar way, such. B .: Hue of By-copied Component colorations in game chrome print on cotton 19 1,8-dioxynaphthalene blue-violet 3,6-disulfonic acid 20 5,5'-dioxydinaphthyl- (2,2 ') violet amine disulfonic acid (7.7 ') 21 8-acetoacetylamino- 1 -oxy- violet- naphthalene-3,6-disulfonic acid Brown Example 22 46.8 parts of the monoazo dye prepared in a known manner from diazotized 4-nitro-1-aminobenzene (mol 468) by coupling in an acidic medium to 1- amino -8- oxynaphthalene-3,6-disulfonic acid are dissolved in 500 parts of water, 50 parts of pyridine and 60 parts by volume of aqueous sodium hydroxide solution (30%) dissolved. 24.9 parts of the sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester (mol 249) diazotized according to Example 1 are added to the solution. The mixture is stirred until the coupling has ended, the dye is isolated as usual and purified by dissolving from dilute sodium chloride solution. The dye thus obtained has the structural formula in the form of the free acid: In the chrome print on cotton, the re-coppered dyeing results in navy blue tones of very good lightfastness. Example 23 24.9 parts of the sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester (mol 249) are diazotized according to Example 1 and coupled to 29.4 parts of the monoazo dye, which was prepared by alkaline coupling of diazotized 4-aminobenzene-1-sulfonic acid on 1,3-dioxybenzene.

After isolation and drying of the disazo dye thus obtained you get a dark brown powder, which is concentrated in water with brown and in Dissolves sulfuric acid with a purple-brown color.

In chromium printing on cotton, deep brown tones of very good lightfastness are obtained in post-copper plating with cleavage of the sulfuric acid ester and the simultaneous formation of the o, o'-dioxyazo-copper complex compound. Example 24 24.9 parts of the sulfuric acid mono- # 5-oxy-4-carboxy-2-aminophenyl) ester (mol 249) are diazotized according to Example 1 and coupled to 66.7 parts of the disazo dye, prepared by weakly acidic coupling of diazotized 4-Oxy-3-carboxy-3 * '- amino-1,1'-azobenzene-4-sulfonic acid on 1-amino-8-naphthol-4,6-disulfonic acid.

The trisazo dye thus obtained is precipitated at pH 7 to 8 by adding sodium chloride, filtered and purified by recrystallization from dilute sodium chloride solution. The dye, dried in vacuo, has the following structural formula in the form of the free acid: and is a gray-black powder that dissolves in water with blue, in concentrated sulfuric acid with green color.

The chrome print on cotton gives a dark green coloration, the when re-coppering with cleavage of the sulfuric acid ester and with simultaneous Formation of the o, o '# dioxyazo-copper complex compound a neutral gray with very good Results in lightfastness.

Claims (2)

PATENT CLAIMS: 1. Process for the preparation of metallizable 4-oxy-5-earboxyphenyl-2,2-dioxyazo dyes which have at least one atom grouping according to the formula where R denotes the radical of a couplable compound in which the oxy group is in the ortho position to the couplable carbon atom, characterized in that the sulfuric acid mono- (5-oxy-4-carboxy-2-aminophenyl) ester is used formula diazotized and the diazo compound obtained can act on a couplable compound which has an oxy group in the ortho position to the couplable carbon atom and the 4 - oxy - 5 - carboxyphenyl - 2 - monosulfuric acid ester-2'-oxyazo dye obtained at least once the atom grouping according to the formula where R has the above meaning, is subjected to saponification in an acidic to neutral medium in substance or on the fiber, with cleavage of the sulfuric acid monoester of the 4-oxy-5-carboxy-2,2'-dioxyazo dye, which has at least one atomic grouping according to formula I contains, is obtained. 2. The method according to claim 1, characterized in that the couplable compound is an azo component of the series acetoacetylarylamide, pyrazolone, benzene, naphthalene. 3. The method according to claim 1, characterized in that the couplable compound contains at least one azo group. 4. The method according to any one of claims 1 to 3, characterized in that the 4-oxy-5-carboxy-2,2'-dioxyazo dyes, which contain at least once the atomic grouping according to formula I, in substance or on the fiber with metal donating Means treated. 5. The method according to any one of claims 1 to 4, characterized in that the saponification of the sulfuric acid ester dyes according to formula III and the metallization of the resulting 4-oxy-5-carboxyphenyl-2,2'-dioxyazo dyes according to formula I in substance or on the fiber carried out at the same time. Documents considered: German Patent No. 842 379, French Patent No. 1 108 146.