DE1151076B - Process for the preparation of monoazo dyes - Google Patents

Description

Process for the production of monoazo dyes It has been found that valuable monoazo dyes are obtained if 2,4,6-trihalo-1,3,5-triazines in any order on the one hand with primary or secondary amino groups containing, preferably water-soluble monoazo dyes or their precursors and on the other hand Reacts with optionally substituted hydrazines to binary condensation products, optionally the halogen atom still on the triazine ring in a customary manner replaced by a simple inorganic or organic radical and in the case of Use of the dye precursors, the compounds obtained in a customary manner added to dyes.

The invention accordingly relates to a process for the preparation of preferably water-soluble monoazo dyes which are bound at least once via an imino group to the group of the all-Lyemeine formula where X is the radical of an optionally substituted hydrazine and Y is a halogen atom, such as a chlorine or bromine atom, or a simple inorganic or organic radical.

Examples of simple inorganic or organic radicals are primary, secondary or tertiary ammo groups, the hydroxyl group, the sulfhydryl group, Ether groups, thioether groups or optionally substituted hydrazine radicals called. The secondary or tertiary amino groups, the ether groups, the thioether groups or the substituted hydrazine radicals can be of aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic in nature and can optionally carry further substituents. You can for example and in particular as low molecular weight Alkylamino, ether or thioether groups, such as mono- or dimethylamino groups, Ethoxyl groups, tertiary butyhnercapto groups, diethanolamino groups, isopropylamino groups or n-butylamino groups are present. Examples of aromatic groups are Amino, ether or thioether groups that contain up to two benzene rings, such as Phenoxy groups, o-, m- or p-chloroanilino groups or toluidino groups are suitable. Cycloaliphatic, araliphatic or heterocyclic amino, ether or thioether groups are z. B. phenylethyl ether groups, N-methyl-N-cyclohexylamino groups or benzothiazolyl thioether groups.

For the conversion of 2,4,6-trihalo-1,3,5-triazines, such as cyanuric acid chloride or bromide, with monoazo dyes containing primary or secondary amino groups or their precursors are preferably water-soluble dyes or their Pre-products into consideration. These compounds expediently contain ionogenic water-solubilizing agents Groups such as sulfonic acid groups, carboxyl groups, sulfuric acid ester groups or Aryl carboxylic acid ester groups which have at least one sulfonic acid group attached to the aryl radical wear.

Monoazo dyes in the part of the molecule corresponding to the diazo component and / or primary or secondary in the part of the molecule corresponding to the azo component Have amino groups are, for example, those obtained by coupling diazotized aminobenzene or its sulfonic acids with 1-phenyl-3-methylpyrazolon- (5), the one on the phenyl radical customary substituents such as halogen atoms, low molecular weight alkyl groups or sulfonic acid groups can carry, obtainable monoazo dyes or those by coupling of diazotized 1-methyl-4-aminobenzene-2-sulfonic acid with 2-amino-5 - hydroxynaphthane - 7 - sulfonic acid, 2 - Amino-8-hydroxynaphthalene-6-sulfonic acid or 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid available in alkaline liquid. Further be here the one by combining diazotized aminonaphthalenesulfonic acids with in the para position derivatives of aminobenzene coupling to the amino group, such as 1-methyl-3-aminobenzene, 1-methyl-3-amino-4-methoxybenzene, 1-methoxy-3-aminobenzene or 1-acetylamino-3-aminobenzene, available dyes mentioned. Azo dyes are also used as starting materials for the process into consideration, which can be obtained by coupling diazotized 1-amino-3- or -4-acetylaminobenzene-2-sulfonic acid with amino, hydroxy or hydroxyacylaminonaphthalene sulfonic acids, such as 2-aminonaphthalene-5-sulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid or 1 - (2,5 - dichlorobenzoylamino) - 8 - hydroxynaphthalene - 4,6 - disulfonic acid, and subsequent cleavage of the acetyl radical on the diazo component Acetylamino group win by boiling with 5% aqueous sodium hydroxide solution can.

Azo dye precursors containing primary or secondary amino groups are, for example, compounds capable of coupling, such as 1-amino-8-hydroxynaphthalene-3,6- and -4,6-disulfonic acid or 2-amino-5-hydroxynaphthalene-8-sulfonic acid.

Substituted hydrazines are, for example, methylhydrazine, N, N ' - Dimethylhydrazine, acetylhydrazine, phenylhydrazine, phenylhydrazine sulfonic acid, semicarbazide, Thiosemicarbazide, aminoguanidine, hydrazodicarboxamide, 2, 3, 6, 7, 9, 10-hexaazadecahydronaphthalene, Maleic acid hydrazide, phthalic acid hydrazide, N-aminoethyl urethane, N-aminopiperazine, 2,4,6-trihydrazino-1,3,5-triazine, pyrazoline and piperidazine called.

The implementation of the 2,4,6-trihalogeno-1,3,5-triazine with primary or secondary amino groups containing monoazo dyes or their precursors and with hydrazine or substituted hydrazines can, as usual, in any order in water or in organic solvents, e.g. B. in alcohols such as ethanol, in Ketones, such as acetone, in polar solvents, such as N, N-dimethylformamide or N-methylpyrrolidone, or their mixtures with one another and / or with water and expediently in the presence of acid-binding agents, e.g. B. of alkali metal acetates, carbonates or hydrogen carbonates, such as sodium acetate, potassium carbonate or sodium bicarbonate.

In the bonded via an imino group, the group of the general formula containing binary condensation products in which X is the radical of an optionally substituted hydrazine and Y is a halogen atom, such as a chlorine or bromine atom, the halogen atom Y on the triazine ring can be exchanged in the usual way for a simple inorganic or organic radical, e.g. B. by hydrolysis against an OH group or by treatment with ammonia, primary or secondary aliphatic or aromatic amines or their sulfonic acids, aliphatic or aromatic mercaptans, hydrazine or hydrazine derivatives against optionally substituted amino, ether, thioether or hydrazine residues.

In the case of using dye precursors, e.g. B. of couplable Compounds, the condensation products obtainable according to the invention in usual way, e.g. B. by treating with diazotized amines such as diazotized Aminobenzene or diazotized 1-aminobenzene-2- or -4-sulfonic acid or -2-carboxylic acid, added to dyes.

The dyes advantageously contain one to four times the group of, depending on the size of the molecule where X is the radical of an optionally substituted hydrazine and Y is a halogen atom or a simple inorganic or organic radical, and preferably up to four ionogenic water-solubilizing groups. If they are water-soluble, they are used for dyeing and printing textiles made of natural or synthetic linear polyamides, such as wool, natural silk or polycaprolactam, and for dyeing leather and paper.

From French patents 1,182,633, 1,184,700 and 1,184 701 it is already known that monoazo dyes can be prepared by 2,4,7-trihalo-1,3,5-triazines on the one hand with monoazo dyes and on the other hand with hydrazine or thiosemicarbazide. The dyes obtainable according to the process stand out from those described in the examples of the patent documents mentioned Dyes not only because of the better washing and milled fastness, but especially also due to the significantly better sweat and sea water fastness of their dyeings on wool. The dyes according to the invention are also those from the examples of the prior art patents known by means of dyes the much greater color strength of their colorations on fabrics made of polycaprolactam think.

In the form of their methylol compounds, which can be obtained in a conventional manner, for. B. obtained by reaction with formaldehyde, as well as in the form of the corresponding methylene ester or ethers, the dyes obtainable according to the invention are outstandingly suitable for dyeing and / or printing structures, for example textiles such as fibers, Threads, flakes, woven and knitted fabrics made from native and / or regenerated cellulose.

Furthermore, the dyes or their optionally esterified or etherified methylol compounds in the usual manner in the presence of acids or acidic compounds, z. B. of salts of strong acids and weak bases such as ammonium chloride along with curable aminoplast-forming Substances or the precursors of such substances, possibly together with aldehydes or aldehydes, e.g. B. formaldehyde, releasing compounds on the goods to be colored applied and fixed with the help of a heat treatment. This can be done at the same time a usual treatment, for example a high-quality finish, such as a crease-proof, Chintz or shrink fit equipment. Of course, at This process also includes leveling, wetting, water repellent, plasticizing and Finishing agents and plastic dispersions are added, and the colored and / or Printed goods can still undergo mechanical treatment, e.g. B. embossing, calendering, Friction and, if necessary, subjected to post-heating to higher temperatures will. Textiles made from natural, regenerated or synthetic fibers can colored in this way with the help of the dyes in a single operation. can be printed, finished and finished. The invention make it possible Dyes to dye the goods with excellent wet fastness within a few minutes and to refine at the same time. With the previously known dyes there is one considerably longer time required.

The parts and percentages given in the examples are units of weight. Example 1 20 parts of the dye obtained by coupling diazotized 1-aminobenzene-2-sulfonic acid with 2- (8-hydroxy-3,6-disulfonaphthyl-1-amino) -4,6-di-35 chloro-1,3 , 5-triazine is available, are added with stirring to a mixture of 200 parts of ice water and 20 parts of hydrazine hydrate. The mixture is stirred for about 20 hours at room temperature until the starting dye can no longer be detected by paper chromatography and the paper chromatogram instead shows a new dye of the same shade but with a lower RF value. The mixture is then acidified with 40 parts of 30% acetic acid, the dye is separated off using 80 parts of saturated aqueous sodium chloride solution, filtered off with suction, washed with 5% aqueous sodium chloride solution and dried at 50.degree. The dye has the following structure: It can be used for dyeing textiles in the following way: Cotton fabric is padded with an aqueous solution containing 20 parts of the aforementioned dye, 50 parts of 1,3-dimethylol-5-methylperhydrotriazon- (2) and 8 parts of monoammonium phosphate in 1000 parts contains. After squeezing and drying at 70 ° C, the fabric is heated to 145 ° C for 8 minutes. After soaping, a bluish-tinged red dyeing with excellent wet fastness properties is obtained.

The dyes in the following table can be obtained in a manner similar to that explained in the first paragraph. You dye textiles made of cotton or rayon in the specified shades. The dyes described above can be converted into the corresponding methylol compounds or the corresponding methylene ethers as follows: are introduced into 113 parts of a 30% aqueous formaldehyde solution. The pH of the mixture is adjusted to 7.5 by adding 10% aqueous sodium carbonate solution. The mixture is then stirred at room temperature for 24 hours. The dye carrying methylol groups is separated off by adding excess sodium chloride, filtered off with suction, washed with saturated aqueous sodium chloride solution and with methanol and dried at ordinary temperature.

To etherify the methylol groups, the dye is in the form of methanol-moist filter material with stirring in a mixture of 400 parts of methanol and added 20 parts of concentrated aqueous hydrochloric acid. After 15 Minutes while standing, the mixture is made by adding anhydrous sodium bicarbonate neutralized. After the methanol has been removed under reduced pressure, it is then added aqueous sodium chloride solution saturated with the residue of the reaction mixture sucks the deposited dye and dry it at ordinary temperature.

When dyeing textiles with methylol or methylene ether groups Carrying dyes can be done as follows: A bleached cotton fabric is impregnated on the padder with a liquor containing 20 parts of dye in 1000 parts and contains 12 parts of ammonium nitrate, squeezed, dried and held for 5 minutes heated to 150 ° C. After soaping and drying, a strong yellow color is obtained of good wet and light fastness.

A cotton fabric that has been bleached and treated with caustic soda is used impregnated on the padder with a liquor containing 20 parts of dye in 1000 parts, 80 parts of methylol melamine methyl ether, 1.5 parts of the ammonium salt of polyacrylic acid, 5 parts of polyglycol ether, 1 part of isopropylnaphthalene sulfonic acid and 8 parts contains a mixture of diethanolamine and triethanolamine hydrochloride, and squeezed off. The material to be dyed is then dried on a flat frame at 120 ° C. for 5 minutes long after-heated to 145'C. A yellow dyeing with good fastness properties is obtained. The fabric is also crease-resistant. Example 2 38.7 parts of the primary condensation product of 1 mole of cyanuric acid chloride with 1 mole of 2-amino-5-hydroxynaphthalene-7-sulfonic acid are mixed with 40 parts of hydrazine hydrate and about 8 to 12 hours at Maintained 85 to 95 ° C. The mixture is then diluted with 200 parts of water and filtered the reaction material from, washes it with water and dries it.

28 parts of the 2- (4,6-dihydrazino-1,3,5-triazinyl-2> amino-5-hydroxynaphthalene-7-sulfonic acid obtained in this way) are dissolved in 500 parts of ice water together with 6 parts of 50% aqueous sodium hydroxide solution and after Addition of 10 parts of sodium bicarbonate is coupled with a diazo compound prepared in the customary manner from 12 parts of 1-aminobenzene-4-sulfonic acid. The coupling product is then precipitated with 400 parts of saturated aqueous sodium chloride solution, filtered off and dried. About 43 parts of the dye of the formula are obtained which can be fixed on cotton fabric in the presence of aminoplast-forming substances and acids or acidic compounds in wet-fast orange tones. Example 3 38.7 parts of the primary condensation product of 1 mole of cyanuric acid chloride with 1 mole of 2-amino-5-hydroxynaphthalene-7-sulfonic acid are mixed with 50 parts of phenylhydrazine. After the vigorous reaction has subsided, the mixture is kept at 85 to 95 ° C. for 20 hours and then diluted with 300 parts of water and 20 parts of 10 normal hydrochloric acid. The reaction material is now suctioned off, washed acid-free with water and dried.

47 parts of the compound obtained in this way are dissolved in 300 parts of ice water together with 12 parts of 500% strength aqueous sodium hydroxide solution. After addition of 17 parts of sodium acetate, the mixture is acidified with 30 parts of 30% aqueous acetic acid and a diazo compound prepared in the usual way from 13.5 parts of 1-aminobenzene-4-sulfonic acid is allowed to flow into the resulting slurry. After the coupling has ended, the dye of the formula is obtained by adding 300 parts of sodium chloride precipitated, suctioned off and dried. The dye dyes cellulose tissue in the presence of aminoplast-forming substances and acids or acidic compounds in shades of orange. The dyes in the following table can be obtained in a similar manner. You dye textiles made of cotton or rayon in the specified shades.

Claims (1)

Claim: Process for the production of monoazo dyes, characterized in that 2,4,6-trihalo-1,3,5-triazines are added in any order on the one hand with primary or secondary amino groups, preferably water-soluble monoazo dyes or their precursors, and on the other hand with optionally substituted hydrazines converts binary condensation products, if necessary the halogen atom still present on the triazine ring is replaced in the usual way by a simple inorganic or organic radical and, if the dye precursors are used, the compounds obtained are added to dyes in the usual way. Considered publications French patent specifications No. 1 182633, 1 18.4700, 1 184701. When the application was published, two coloring tables with explanations were laid out.