DE1205212B - Process for the production of metal-containing azo dyes - Google Patents

Description

Process for the production of metal-containing azo dyes It has been found that valuable metal-containing azo dyes are obtained when using the diazo compound a 1-amino-2-oxy-4-cyannaphthalins, which can be further substituted with a Pyrazolone coupling component combined and the resulting azo dyes on one Substrate or, optionally in a mixture with other metallizable dyes, converted in substance into their metal complex compounds.

The coupling of the starting components takes place depending on the type of use Compounds in aqueous or organic, acidic, neutral or alkaline range.

The 1-amino-2-oxy-4-cyanaphthalenes can be prepared, for example, by the process given in British Patent 381602 .

For coupling with 1-diazo-2-oxy-4-cyanonaphthalene (4-cyanonaphthoquinone-1,2-diazid-1) or its substitution products are, for example, the following pyrazolones used: 1-phenyl-3-methylpyrazolon-5; 1-phenyl-3-carboxylic acid pyrazolone-5, 1- Phenyl-5-pyrazolone-3-carbonamide, 1- (2'-sulfophenyl) -3-methyl-pyrazolone - 5, 1- (3'-sulfonamidophenyl) -3-methyl-pyrazolon-5, 1- (4'-sulfonamidophenyl) -3-methyl-pyrazolon-5, 1- (2'-chloro-5'-sulfophenyl) -3-methyl-pyrazolone-5, 1- (4'-sulfophenyl) -3-methyl-pyrazolone-5, 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-pyrazolone-5, 1- (3'-aminophenyl) -3-methylpyrazolone-5, 1- (2'-methyl-4'-sulfophenyl) -3-methylpyrazolone-5, 1- (2'-methyl-3'-amino-S'-sulfophenyl) -3 - methyl - pyrazolone - 5, 1- (6 '- sulfonaphthyl - [2']) - 3-methyl-pyrazolone-5 and 1- (2'-sulfophenyl) -3-phenyl-pyrazolone-5.

The metal-free dyes can be obtained in substance by methods known per se Convert processes into their metal complex compounds. Appropriate procedures for this For example, the reaction with salts of trivalent cobalt is preferred ammoniacal medium and the reaction with salts of hexavalent chromium in the presence of reducing agents such as tartaric acid or preferably carbohydrates, or with chromium formate in solvents such as glycol, glycol monomethyl ether, formamide or other acid amides, or with CrZQ3 in dilute alkalis or with chromium complex compounds aromatic carboxylic acids.

The dyes can also be mixed with other metal complexing agents Dyes are metallized.

In comparison with the chromium-containing monoazo dye known from Example 3 of German Patent 564 820, the chromium complex of the monoazo dye obtainable according to the process shows greater color strength and better washfastness of the wool dye.

While the dye 1-diazo-2-oxynaphthalene-4-sulfonic acid -> 1- (Y- sulfophenyl) - 3 - methyl - 5 - pyrazolone known from German patent specification 404 647 does not absorb on wool by the monochrome process, the invention shows Dye 1-diazo-2-oxy-4-cyanonaphthalene -> 1- (3'-sulfophenyl) -3-methyl-5-pyrazolone in the monochrome process excellent drawability on wool. Example 1 2.7 parts by weight of 1-amino-2-oxy-4-cyanaphthalene are dissolved at 20 to 50 ° C. in about 12 parts by volume of glacial acetic acid containing 1.2 parts by weight of anhydrous sodium acetate. Then 1 part by weight of sodium nitrite is added to the vigorously stirred solution at room temperature and the mixture is stirred at room temperature until nitrous acid is no longer detectable. The reaction mixture is then poured into 2000 parts by volume of ice water, and the precipitated quinonediazide is filtered off. The quinonediazide is suspended in a little water and the suspension at 0 to 5 ° C with 100 parts by volume of an aqueous solution containing 10 parts by weight of soda, 1.15 parts by weight of sodium hydroxide and 3.7 parts by weight of 1- (2'-sulfophenyl) -3-methyl -pyrazolon-5 contains, combined. After 10 to 12 hours, the resulting dye is deposited by adding sodium chloride, filtered off and dried.

The red dye powder dyes wool, silk and similar materials coloring behavior in very clear Bordo tones after the chromium plating process. The dyeings are distinguished by very good fastness properties.

If instead of 3.7 parts by weight of 1- (2'-sulfophenyl) -3-methyl-pyrazolone-5, the coupling components given in the table below are used in equivalent amounts, dyes are obtained which, according to the post-chrome plating process, wool, silk and materials dye similar coloring behavior in the specified shades: 1- (4'-sulfophenyl) -3-methylpyrazolon-5. . . . . . . . . . . . . . . bluish bordo 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-pyrazolon-5 ....... clear red-tinged bordo 1- (2'-chloro-5'-sulfophenyl) - 3-methyl-pyrazolon-5 ....... red-stinging Bordo 1- (2'-methyl-4'-sulfophenyl) -3-methyl-pyrazolone-S ....... red-stinging Bordo 1- (3 '-Sulfophenyl) -3-phenylpyrazolon-5 ............... clear Bordo 1- (6'-sulfonaphthyl- [2']) - 3-methyl-pyrazolon-5 .. ..... red-sticky Bordo Example 2 If, instead of 1- (2'-sulfophenyl) -3-methyl-pyrazolon-5, the coupling component used is the equivalent amount of 1- [3'-methylpyrazolone- (5 ') - yl- (1 ')] - benzenesulfonic acid- (3) - (2 "-carboxyanilide), a red dye powder is obtained which dyes wool, silk and materials with similar dyeing behavior in Bordo shades using the one-bath chromating process very good fastness properties.

The dyes obtained by the method of Examples 1 and 2 can also be prepared in such a way that the coupling takes place in the presence of Pyridine, other organic bases and / or formamide. Example 3 used in Example 1 instead of 1- (2'-sulfophenyl) -3-methyl-pyrazolone-5 as the coupling component the equivalent amount of 1- (4'-sulfonamidophenyl) -3-methyl-pyrazolon-5 is obtained a red dye powder.

The dye is dissolved in order to convert it into the chromium complex compound in 60 parts by volume of ethylene glycol, gives 1 part by volume of anhydrous formic acid and 0.55 Parts by weight of Cr203 and keeps the solution at a temperature of 125 to 130 ° C, until no more metal-free dye can be detected. After cooling down, you wear the reaction mixture in 15% saline solution, filtered the deposited Dye off and dry at 100 ° C.

The chromium complex dye dyes wool, silk and similar materials Dyeing behavior from neutral and weakly acidic dye baths in clear Bordeaux tones with very good fastness to light, washing and carbonization. For conversion into the cobalt complex compound the metal-free dye is dissolved in a mixture of 30 parts by volume 10% sodium hydroxide solution and 2 parts by volume of 20% ammonia solution. The dye solutions are combined at room temperature with a solution of 2.04 parts by weight of cobalt sulfate in 10 parts by volume Water and 10 parts by volume of 20% ammonia solution. The cobalt sulfate solution will vigorously turbinated beforehand for about 1/2 hour with access to air. The cobalt complex compound The dye is formed at the boiling point and can be removed by adding table salt separate completely. The dye powder obtained after filtering and drying dyes wool, silk and materials with similar dyeing behavior in clear red tones with excellent fastness properties. Example 4 is used in Beispie13 as a coupling component 1- (3'-sulfonamidophenyl) -3-methyl-pyrazolon-5 and converts the azo dye like described there in the cobalt complex compound, one obtains a dye, behavior in clear red tones with very similar behavior to wool, silk and materials good fastness properties.

The chromium complex compound of the same dye is obtained by dissolving the dye paste obtained after coupling in 50 parts by volume of 10% sodium hydroxide solution and combining it with a solution of 1.06 parts by weight of K, Cr207 in 10 parts by volume of water. The amount of glucose or tartaric acid necessary to reduce the hexavalent chromium is added to the bichromate dye solution heated to 80 ° C., then allowed to cool and the chromium complex compound is completely separated off by adding sodium chloride. The metal complex dye obtained in this way dyes wool, silk and materials with similar dyeing behavior in lively Bordo tones. The dyeings have excellent fastness properties. Example 5 In a 40 to 45 ° C. hot dyebath containing 100 /, Glauber's salt and 501, acetic acid (30 ° / oig) and 2 g of the well-dissolved dyestuff from the table in Example 1, first component containing 100 g of woolen fabric brought in. The dyebath is slowly heated to the boil and left at the boiling temperature for 1/2 hour. The dyebath is exhausted by adding 20% sulfuric acid (960%) and boiling again for 1/2 hour.

The dyebath is then cooled by adding fresh water and the color is developed with 1-Chromkali at the boil for 1/2 hour. A bluish tint is obtained Bordo staining. Example 6 26.4 parts by weight of 1-amino-2-oxy-4-cyanaphthalene-6-sulfonic acid are diazotized as usual with 6.9 parts by weight of NaN02. The diazo solution combined one with a solution of 18.2 parts by weight of 1-phenyl-3-methyl-5-pyrazolone in 50 Parts by volume of pyridine and add 100 parts by volume to the reaction mixture at 0 to 5 ° C 20% sodium hydroxide solution. After the coupling is complete, the dye formed is precipitated with hydrochloric acid, filtered off and dried. The dye dyes wool, Silk and materials similar to dyeing behavior in very clear blue tinges Bordo tones after the chromium plating process. The dyeings have very good fastness properties.

Claims (1)

Claim: Process for the production of metal-containing azo dyes, characterized in that the diazo compound of an optionally further substituted 1-amino-2-oxy-4-cyanaphthalene is combined with a pyrazolone coupling component and the resulting azo dye on a substrate or, optionally in a mixture other metallizable dyes, converted in substance into the metal complex compound. Considered publications: German Patent Specifications No. 564 820, 673 025, 842982. When the application was announced, two color tables were laid out with explanations.