DE1150474B - Process for the preparation of basic azo dyes - Google Patents

Description

Process for the preparation of basic: "Azo dyes It has been found that" valuable basic azo dyes are obtained if aminophenylhydr_azones of the general formula. or their salts of the general formula diazotized, coupled with compounds capable of coupling which are free from sulfonic acid groups and treated the coupling products, optionally with alkylating or aralkylating agents, where R1 is a hydrogen atom, a short-chain alkyl radical, an aralkyl radical or an aryl radical, R2. Hydrogen atom or a short-chain alkyl radical; R3, 11.1, RS and R6 are hydrogen atoms or non-ionic substituents and X is the equivalent of an anion.

The aminophenylhydrazones mentioned or their salts are obtained when aminonitröbenzenes or aminoacylaminobenzenes are diazotized with methylene compounds of the general formula in which Rl, R3 and R4 have the meanings given above, couples, optionally treats the coupling products with alkylating or aralkylating agents and reducing the nitro or acylamino compounds obtained, e.g. B. with ammonium, alkali or alkaline earth metal sulfides; or saponification, e.g. B. with dilute mineral acids, converted into the corresponding inocompounds.

As aminonitrobenzenes, for example, 1-amino-4-nitrobenzene, 1-amino-2-methoxy-4-nitro-benzene, 1-amino-2-chloro-5-nitrobenzene, 1-amino, 3-nitrobenzene, -As: Aminoacylaminobenzenes can be z. B. 1-Amino-4-formylaminobenzene, 1-Aminoz 3-acetylaminobenzene, 1-amino-4-acetylaminobenzene, 1-amino-4-oxalylaminobenzene and Use 1-amino-2,5- @ diT methoxy-4-acetylaminobenzene.

. As non-ionic, substituents in the formulas above are designated with R3, R4, RS and RB, come z. B. alkyl, alkoxy, acylamino radicals or halogen atoms.

Of the methylene compounds used as azo components: the Examples of formula III are: 3,3-dimethyl-2-methyleneindoline, 1,3; 3-trimethyl - 2 - methylene indoline, 3,3 - dimethyl - 2 - nie; ethylene - 5 - chlorine phenol, 1.3, 3 - trimethyl - 2 - methylene-5-methoxyindoline, 3,3-dimethyl-2-methylene-5-carbethoxyindoline, 1- ethyl - 3,3 - dimethyl - 2 - methylene-5-carbethoxyindoline, 1-methyl-2-methylene-3,3-tetramethyleneindoline, 3, 3 - dimethyl - 2 - methylene -1, 7 - trimethylene indoline.

Alkylating or aralkylating agents are e.g. B. dimethyl sulfate, Diethyl sulfate, benzyl chloride, methyl iodide, ethyl bromide or methyl toluenesulfonate. The alkylation takes place in organic diluents; like benzene, toluene, den Chlorine, benzenes, methylene chloride, chloroform, tetrachlor: carbon or: tetrahydrofuran in the usual way: preferably at elevated temperature and in ane essence acid binding agents such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, Potassium hydrogen carbonate, magnesium oxide or calcium carbonate. , -The diazotization takes place one, in the usual way in an aqueous mineral acid solution with cooling with sodium nitrite before.

Couplings capable of coupling free of sulfonic acid groups can be @`z.`B: - Such `` the benzene, naphthalene or heterocychic series continue to use cyclic or open-chain enols are suitable. Examples of such azo components are hydroxybenzene, 1,3-dihydroxybenzene, methylhydroxy benzenes; Dimethylhydroxybenzenes, 4-tert-butyl-1-hydroxybenzene, 1- or 2-hydroxynaphthalene, 2-hydroxy-8-acetylaminonaphthalene, 1,5-Dihydroxynaphthahn, 1-Hydroxy-3-aminobenzol, 1-Hydroxy-3-Diethylaminobenzol, 3-hydroxydiphenylamine, 1-hydroxy 2- or -3-acetylaminobenzene, 1-hydroxymethyl benzene-2-carboxylic acids, Dimethylaminobenzene, 1-dimethylamino-3-aminobenzene, 1- [N, N-bis (2-hydroxyethyl) amino] -3-chlorobenzene, N, N-bis (2-cyanoethyl) aminobenzene, N-butyl-N-carbomethoxyethylamino-benzene, N-ethyl-N- (2-dimethylaminoethyl) aminobenzene; 1 = or 2-aminonaphthalene, 2-ethylaminonaphthalene, 1-amino-5-hydroxynaphthalene, N-ethyl diphenylamine, 3 - methylpyrazolone - (5), 1 - phenyl-3-methylpyrazolone- (5), 1-phenyl-3-carbäthoxypyrazolon- (5), 1- (2-methylphenyl) -3-methylpyrazolon- (5), 2,4-dihydroxyquinoline, 4-hydroxyindazole, 8-hydroxyquinoline, 3 - hydroxythionaphthene - 2 - carboxylic acid, Imidazole, 4,5-diphenyhmidazole, 1,3,3-trimethyl-2-methyleneindoline, 2-phenylindole, 1-methyl-2-phenylindole, 2-methylindoline.

The basic azo dyes formed by the coupling are appropriately isolated from below. Addition of mineral acids, whereby they are in the form of the salts of the general formula are obtained, where .R1, R2, R $, R4, R5, R, and X have the abovementioned meanings and Y is the radical of an azo component: "In those azo dyestuffs of the above formula in which the substituents Ry and R2 are hydrogen atoms the water solubility of the dyes is increased considerably by a subsequent alkylation .. -The .Isolation of the -alkylation products takes place, if necessary after adding water, for example by distilling off the organic solvent It falls with neutral salts, such as sodium chloride or sodium sulphate, or with zinc chloride ... The basic azo dyes are suitable for dyeing textile materials such as fibers, threads, flakes, woven or non-woven textiles or foils made from pickled native or regenerated cellulose, wool, leather , Paper, jute, coconut or acetyl cellulose. They can also be used as:. Dyes in lacquers or graphic materials . The new dyes are particularly suitable for dyeing synthetic fiber-forming substances - such as polyamides, polyethylene terephthalate, polyhexahydroterephthalyl terephthalate, polyacrylonitrile and mixed polymers of acrylonitrile, e.g. B. with vinyl acetate, in which the coloring character of the copolymers is determined by the acrylonitrile content. In particular on the last-mentioned materials, the basic dyes give vivid colorations with excellent fastness properties.

The parts named in the examples are, unless otherwise specified, Parts by weight. Parts of space relate to parts by weight as liters to kilograms under normal conditions. Percentages relate to percentages by weight.

Example 1 15 parts of 1-amino-4-acetylaminobenzene are diazotized in a conventional manner in an aqueous hydrochloric acid solution. A solution of 20 parts of 5-chloro-2,3,3-trimethylindolenine in 250 parts of ethanol is added to the filtered diazo solution. The coupling is completed by flowing in a solution of 28 parts of crystallized sodium acetate in 120 parts of water. The mixture is diluted with about 500 parts of water and the deposited dye is filtered off, washed on the filter with water and dried at 50 ° C. under reduced pressure: the coupling product of the formula is obtained in practically quantitative yield.- The total amount of this compound is powdered together with 4.2 parts of magnesium oxide and the mixture is stirred with 300 parts by volume of chloroform. 31 parts of dimethyl sulfate are allowed to run into this suspension at 40 ° C. and then heated to 70 ° C. for several hours until a sample taken from the mixture is uniform in the paper chromatogram -.] St and by acids or. Bases in color is no longer changed. The resulting reaction mixture is diluted with 500 parts of benzene, filtered and evaporated at about 100.degree. The dye powder obtained is stirred in .550 parts of water and, after the addition of 80 parts of 5N hydrochloric acid, refluxed for 3 hours. The resulting solution containing the color salt of the formula contains, is diazotized at O 'C with a solution of 7 parts of sodium nitrite in 30 parts of water. After removing excess nitrous acid with urea, the diazo solution is added to a cooled solution of 18 parts of 1-phenyl-3-methylpyrazolone- (5), 4.4 parts of sodium hydroxide and 42 parts of crystallized sodium acetate in 400 parts of water. After several hours of stirring, the coupling is complete; it is filtered off, the filter residue is washed with water and dried at 50.degree. 64 parts of a dye which dissolves in alcohols or ketones with a yellowish red color are obtained.

When hydrochloric acid is added, a red solution is obtained in hot water. from which one can look at the color salt of the formula with sodium chloride receives. This dyes polyacrylonitrile fibers from an acetic acid or sulfuric acid bath in lively, red shades of good lightfastness and very good wetfastness properties. .

By coupling the same diazo component with the components of the table below, similar dyes are obtained which color polyacrylonitrile in the shades indicated on the right. Azo components hue of the coloring on polyacrylonitrile 2,4-dihydroxyquinoline ....... bluish red Acetoacetanilide: ........ Red-orange 1-Hydroxy-2-acetylaminobenzene red orange imidazole (coupling product with Dimethyl sulfate aftertreated) Red Hydroxybenzene ............... Orange 1-phenyl-3-methyl-5-amino- pyrazole ................... bluish tinge red 2-hydroxynaphthalene ......... Bordo 1-hydroxynaphthalene ......... red-violet 1- (Diethylarnino) -3-methylbenzene violet blue Example 2 A diazo solution prepared in a customary manner from 15 parts of 1-amino-4-acetylaminobenzene is combined with a cooled solution of 17.5 parts of 1,3,3-trimethyl-2-methyleneindoline and 22 parts of 5N hydrochloric acid in 120 parts of water. The coupling is terminated by flowing in a solution of 42 parts of crystallized sodium acetate in 150 parts of water. The resulting dye is precipitated with 100 parts of sodium chloride, filtered off, dried at 50 ° C. under reduced pressure and mixed with 4.4 parts of magnesium oxide in 300 parts by volume of chloroform. 19 parts of dimethyl sulfate are allowed to flow in with stirring and the mixture is heated to 60 ° C. until the reaction product is uniformly yellow in color. The dye is separated off by adding 300 parts of benzene, filtered, the residue is washed with benzene and dried.

To saponify the acetyl group, the product obtained is heated to boiling for 4 hours in a mixture of 400 parts of water and 80 parts of 5N hydrochloric acid until a sample taken from the reaction mixture gives a uniform red paper chromatogram. The mixture is cooled with ice to 0 ° C., an aqueous solution of 7 parts of sodium nitrite is run in and it is coupled with an ice-cold solution of 12 parts of 1-hydroxy-3-methylbenzene, 4.4 parts of sodium hydroxide and 16 parts of sodium carbonate in 400 parts Water. When the diazo compound can no longer be detected in the mixture, it is acidified with 35 parts of 5N hydrochloric acid, filtered off and the residue is dried at 50.degree. 24 parts of the dye of the formula are obtained which dissolves in aqueous ethanol with a yellowish red color and dyes polyacrylonitrile fibers in very light and wet-fast orange tones.

Example 3 A diazo solution prepared in a customary manner from 15 parts of 1-amino-4-acetylaminobenzene is combined with a solution of 17.5 parts of 2,3,3-trimethylindolenine and 28 parts of crystallized sodium acetate in 250 parts of ethanol; After the coupling has ended, the mixture is diluted with 400 parts of water and the coupling product is filtered off. The filter residue is heated to boiling with 800 parts of water and 80 parts of 5N hydrochloric acid until the acetylamino group has been split off. The solution in which the amine of the formula is present, is cooled to 0 ° C and diazotized with 7 parts of sodium nitrite. The diazo solution is allowed to flow into an ice-cooled solution of 17.5 'files of 1-phenyl-3-methylpyrazolone- (5), 4.2 parts of sodium hydroxide and 4.5 parts of crystallized sodium acetate in 400 parts of water while stirring. The coupling is ended after a short time; it is filtered off, dried at 50 ° C. and 46 parts of the compound of the formula are obtained which is insoluble in water and dissolves in alcohol with a bluish red color.

23 parts of this compound are mixed with 300 parts by volume - chloroform. No addition - of 4.5 parts of magnesium oxide - is added 16 parts of dimethyl sulphate and the mixture is heated to 70 ° C. for 6 hours. The methylation product precipitated with - 500 parts of benzene - is filtered off with suction, dissolved in 80O parts of 50% aqueous ethanol, treated with 60 parts of -5N hydrochloric acid and filtered. The dye which crystallizes out after prolonged stirring is filtered off and dried at 50.degree. It is obtained in a yield of 26 parts. It dissolves in hot water with a red color and colors polyacrylonitrile in yellowish red tones; in terms of dyeing behavior, it is very similar to the dye obtained according to Example 1.

Is used instead of the above-mentioned 1-amino-4-acetylaminobenzene the 1-amino-3-acetylaminobenzene, one obtains an isomeric dye 'which on Polyacrylonitrile gives real yellow colorations:

Claims (1)

PATENT CLAIM: Process for the preparation of basic azo dyes, characterized in that aminophenylhydrazones of the general formula or their salts of the general formula diazotized, coupled with compounds capable of coupling which are free from sulfonic acid groups and optionally treated the coupling products with alkylating or aralkylating agents, where Rz is a hydrogen atom, a short-chain alkyl radical, an aralkyl radical or an aryl radical, R2 is a hydrogen atom or a short-chain alkyl radical, R3, R4, R , and R, hydrogen atoms or non-ionic substituents and X is the equivalent of an anion. When the registration was announced, a coloring table with an explanation was displayed.