DE1248189B - Process for the production of metallizable reactive dyes and their copper and nickel complex compounds - Google Patents

Description

Process for the production of metallisable reactive dyes and their copper and nickel complex compounds The present invention provides a process for the production of metallisable reactive dyes and their copper and nickel complex compounds, which is characterized in that 1 mol of the diazo compound is obtained from an amine of the formula wherein one X is a sulfonic acid group, the other X is a group - NH - R, where R is a mono-, di- or trihalopyrimidyl radical bonded directly or via - CH2 -, optionally further substituted, with 1 mol of an azo component of the formula couples, in which W - OH or - NH.a, Y is an optionally further substituted mono- or disulfophenyl or mono-, di- or trisulfonaphthyl radical and Z is low molecular weight alkyl, carboxy, an alkyl carboxylate group or an optionally substituted carboxamide group, and in substance with one treated copper or nickel releasing agents, with dyes or copper or nickel complex compounds of dyes of the general formula wherein X, W, Y and Z have the meanings given, are formed.

A modification of this procedure is that 1 mole of the diazo compound from an amine of the formula wherein one X 'denotes a sulfonic acid group and the other X' denotes a nitro group, couples with 1 mol of an azo component of the formula (11) and reduces the nitro group X 'in the monoazo dye obtained and the aminomonoazo dye in any order on the one hand with a di-, tri- or Tetrahalopyrimidine and on the other hand with a copper or nickel releasing agent.

A second modification of the process according to the invention consists in that 1 mol of the diazo compound is obtained from an amine of the formula wherein one X "is a sulfonic acid group and the other X" is an acylamino group, couples with 1 mol of an azo component of the formula (II) and in the monoazo dye obtained the acylamino group X "is hydrolyzed and the aminomonoazo dye in any order on the one hand with a di-, tri- or Tetrahalopyrimidine and on the other hand with a copper or nickel releasing agent.

The nitro group is advantageous by heating with a solution of Sodium sulfide or sodium hydrogen sulfide reduced to 60 to 100 ° C.

The acylamino group (acetylamino, propionylamino, formylamino, Benzoylamino, carbomethoxyamino or carbethoxyamino) is z. B. by loosening in 10 to 20 times the amount of concentrated sulfuric acid and diluting with water up to a sulfuric acid concentration of about 801% in such a way that that the temperature rises to about 100'C, or by heating in an aqueous Mineral acid solution, preferably in an aqueous 3 to 10% hydrochloric acid solution at 90 to 100'C or in an aqueous solution of alkali metal hydroxides, preferably in a 5 to 10 °,! oigen sodium or potassium hydroxide solution, at 70 to 100 ° C hydrolyzed.

If the hydrolysis is carried out under alkaline conditions, can one also metallize the acylamino monoazo dye first and then the hydrolysis as the metal complex compound is resistant to alkali. But it will the metallized acylamino monoazo dye hydrolyzes under acidic conditions or the metallized nitromonoazo dye under first metallizing conditions reduced, it must be metallized again afterwards.

Possible di-, tri- or tetrahalopyrimidines are: 2,4,6-trichloropyrimidine and 2,4,6-tribromopyrimidine and their derivatives, which are in the 5-position, for example carry the following substituents: methyl, ethyl, carboxylic acid methyl or ethyl ester, Alkenyl, e.g. B. allyl, chlorovinyl, substituted alkyl, e.g. B. carboxymethyl, chlorine or bromomethyl, 2,4, 5,6-tetrachloro- or -Tetrabromopyrimidin, 2,6-dichloro- or -Dibromopyrimidine-4-carboxylic acid ethyl ester, 2,4,5-trichloropyrimidine, 2,6-dichloro or -dibromopyrimidine, 2,5,6-trichloro-4-methylpyrimidine, 2,4-dichloro-5-chloromethyl-6-methylpyrimidine and 2,6-dichloro-4-trichloromethylpyrimidine.

The condensation of the di-, tri- and tetrahalopyrimidines is advantageous at temperatures between 40 and 100`C and at pH values between 3 and 9. If temperatures higher than about 50-C have to be used, it is with a view to it indicated on the water vapor resistance of individual halopyrimidines, if necessary to work with vessels equipped with a reflux condenser. To keep things constant of the pH value, either an acid-binding agent is added to the reaction mixture at the beginning, such as sodium acetate or a phosphate buffer, added or added during the reaction in small portions of sodium or potassium carbonate or carbonate in solid, powdered form or as an aqueous solution. As a neutralizing agent but aqueous solutions of sodium or potassium hydroxide are also suitable. The addition of small amounts of a wetting or emulsifying agent to the reaction mixture accelerate the conversion reaction. The reaction is conducted so that only one Halogen atom of the halopyrimidine with an exchangeable hydrogen atom of Amino group reacts.

The diazotization of the amine of the formula (1I) is after the direct or indirect method carried out at temperatures of, for example, 0 to 10 ° C. The coupling is carried out in a weakly acidic, neutral or alkaline medium, preferably in the pH range from 6 to 12, and at low temperatures, e.g. B. at 0 to 15 ° C, optionally carried out in the presence of organic bases such as pyridine or pyridine base mixtures.

Suitable azo components are, for. B. 1-Phenyl-3-methyl-5-pyrazolone-2'- or -3'- or -4'-sulfonic acid, 1-phenyl-3-methyl-5-pyrazolone-2 ', 4'- or -2', 5'-disulfonic acid, 1- (2'-chlorophenyl) -3-methyl-5-pyrazolone-4'- or -5'-sulfonic acid, 1- (2'-methylphenyl) - 3 - methyl - 5 - pyrazolone - 4 '- sulfonic acid, 1- (2'-chloro-6'-methylphenyl) -3-methyl-5-pyrazolone-4'-sulfonic acid, 1- (2 ', 5'-dichlorophenyl) -3-methyl-5-pyrazolone-4'-sulfonic acid, 1-phenyl-3 -carboxy-5-pyrazolone-4'-sulfonic acid, 1- (2 ', 5'-dichlorophenyl) -3 - ethyl - 5 - pyrazolone - 4'-sulfonic acid, 1 - phenyl-3-aminocarbonyl-5-pyrazolone-4'-sulfonic acid, 1-phenyl-3-carbomethoxy- or -carbethoxy-5-pyrazolone-4'-sulfonic acid, 1- (2'-naphthyl) -3-methyl-5-pyrazolone-5'- or -6'- or -8'-sulfonic acid, 1- (1'-naphthyl) -3-methyl-5-pyrazolone-4'- or -5'- or -6'- or -7'-sulfonic acid, 1- (2'-naphthyl) -3-methyl-5-pyrazolone-5 ', 7'-disulfonic acid, or -4,8'- or -6 ', 8'-disulfonic acid, 1- (1' - naphthyl) - 3 - methyl - 5 - pyrazolon-3 ', 6'-, -3 ', 7'-, -4', 6'- or -4 ', 7'-disulfonic acid, 1- (2'-naphthyl-3-methyl-5-pyrazolone-3', 6 ', 8'- or -4 ', 6', 8'-trisulfonic acid, 1-phenyl-3-methyl-5-aminopyrazole-2 ', 4'- or -2', 5'-disulfonic acid, 1-phenyl-3-methyl-5-aminopyrazole-2'-, -3'- or -4'-sulfonic acid.

After the end of the condensation or the coupling, the reactive dye becomes from its previously neutralized solution or suspension with sodium or potassium chloride salted out or precipitated with acid, then suctioned off, washed and dried.

The conversion of the monoazo dyes into the copper or nickel complex dyes is advantageously carried out in aqueous solution, in weakly acidic (e.g. acetic acid) to slightly alkaline medium at temperatures from 20 to 70 ° C and with addition an aqueous solution of an alkali metal hydroxide, an alkali metal carbonate or an alkali metal salt of a low molecular weight aliphatic monocarboxylic acid. Here, for 1 molecule of dye, the amount of a copper containing 1 atom of metal or nickel-releasing agent used.

The metal complex compounds obtained are obtained from an aqueous medium deposited by adding salt, then filtered off, washed if necessary and then dried.

The new metal-free and metal-containing reactive dyes are suitable for dyeing, padding and printing fibers of animal origin, e.g. B. wool, Silk, synthetic polyamide fibers, leather, cellulose fibers, e.g. B. Cotton, Linen and regenerated cellulose fibers, e.g. B. viscose rayon or rayon, Copper reyon or viscose wool as well as mixtures and / or structures the end these fibers. The optimal application conditions depend on the type of fiber and the dyes used are different. The new copper or nickel-containing reactive dyes which have three or more sulfonic acid groups, have good solubility in water, good stability in printing pastes and block solutions, good compatibility with salts and hard water, good reactivity with vegetable Fibers, animal and synthetic polyamide fibers; they are insensitive to Heavy metal ions, such as copper, iron and chromium ions, and reverse acetate, Triacetate, polyester, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate and Polyalkylene fibers. Thanks to their only moderate substantivity, the unfixed dye component is Easily washable from the prints or dyeings on cellulose fibers.

The reactive dyes containing copper or nickel, which have two sulfonic acid groups wear, are particularly suitable for the so-called exhaust process for cellulose fibers and for weakly acidic dyeing of wool, silk and synthetic polyamide fibers.

The dyeings and prints obtained on animal fibers and synthetic Polyamide fibers have good light, washing, sweat, fulling, water, sea water, Potting, acid, alkali, friction, flue gas, chlorine bath water, bleach (peroxide) and dry cleaning fastness properties (organic solvents).

The dyeings and prints on cellulose fibers are particularly notable due to good resistance to anti-crease finishes and alkaline or weak acidic hydrolytic influences as well as excellent wet fastness properties (washing, perspiration, Water, sea water, rubbing, alkali, vulcanizing, chlorine bathing water, bleach and Dry cleaning fastnesses).

Compared to the closest comparable copper complex dyes known from French patent specification 1225 282, the copper complex dyes obtainable according to the invention are distinguished by the better washability of their prints on cotton.

In the following examples, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius. Example 1 234 parts of 2-amino-6-nitro-1-hydroxybenzene-4-sulfonic acid are used in 1000 Parts of water with the addition of 242 parts of a 30% sodium hydroxide solution at 65 - ' and pH 5.0 dissolved. With thorough stirring, 218 parts of 2,4,5,6-tetrachloropyrimidine are obtained added and condensed at 65 °. The pH is through during the condensation Dropwise addition of 20% soda solution kept between 4.5 and 5.0. After 2 hours the condensation has ended and part of the condensation product is crystalline Form failed.

The warm condensation mass is then left within a Hour with stirring at 10 to 20 "to a slurry of 300 parts iron powder add dropwise in 700 parts of 20% acetic acid and stir for a further 30 minutes 80- after. The one consisting of the reaction product and iron sludge is filtered Precipitate and wash it with a little dilute acetic acid. He will be at 10- suspended in 1500 parts of water, mixed with 270 parts of a 30% sodium hydroxide solution and filtered after stirring briefly. The filtrate is with 350 parts of a 30o / oigVn Hydrochloric acid made Congo acid and the deposited precipitate filtered off.

385 parts of the starting amine obtained according to the above information are stirred in 1000 parts of water, 150 parts of 30% sodium hydroxide solution and a solution of 70 parts of sodium nitrite in 250 parts of water are added and the resulting solution is stirred over the course of 2 hours at 0 to 5 ° to 400 parts of a 20% hydrochloric acid was added dropwise. The resulting diazo suspension is added at 0 to 5 'to a solution of 335 parts of 1-phenyl-3-methyl-5-pyrazolone-2', 4'-disulfonic acid and 200 parts of soda in 2000 parts of water. After the coupling has ended, 1000 parts of a 16% copper sulfate solution are added to the dye solution at 60 'and pH 5.0, and the copper-containing dye formed is salted out with sodium chloride and filtered off. The dye, dried in vacuo, is a red-brown powder which dissolves in water with a yellow-brown color and, when printing on mercerized cotton satin, gives a yellow-brown print with very good wet fastness properties and excellent light fastness. Example 2 234 parts of 2-amino-6-nitro-1-hydroxybenzene-4-sulfonic acid are dissolved in 1000 parts of water and diazotized at 0-5 'by adding 145 parts of 30% hydrochloric acid and 292 parts of 4N sodium nitrite solution. The suspension obtained is at 5 'to a well-stirred solution of 276 parts of 1-phenyl-3-methyl-5-pyrazolone-2'-sulfonic acid sodium and 110 parts of anhydrous sodium carbonate in 1000 parts of water. After the coupling has ended, the monoazo dye is salted out, filtered off with suction and washed with a dilute sodium chloride solution.

The paste of the nitro-monoazo dye is dissolved in 1500 parts of water of 60 ", this solution is mixed with about 750 parts of a 27% sodium hydrogen sulfide solution, heated to the boil and held at about 100 'for 1 hour. The pH of the solution is about 10 to 11. When the reduction is complete, about 90 = 850 parts are added dropwise 30% hydrochloric acid is added. The sodium thiosulfate present in the solution decomposes in sulfur dioxide which escapes and sulfur which separates out. Filter the sulfur suspension at 90, salting out the amino monoazo dye in the filtrate, filter it off and wash it with a dilute sodium chloride solution.

One dissolves 245 parts of the amino-monoazo dye (as 100% free acid calculated) corresponding amount of the paste obtained in 1500 parts warm Water, mixed with 125 parts of crystallized copper sulfate and sets the temperature to 50 to 55 - and by adding solid sodium carbonate the pH to 5. Man stir at 50 - until the metallization is finished, then gives 110 parts at once 2,4,5,6-Tetrachloropyrimidine and condenses at 70 to 80 ". The pH value is during the condensation by adding dropwise 20% soda solution between 5.0 and 6.0 held. After stirring for 2 hours, the condensation has ended. You salt that Dye off, sucks it off, washes him with a dilute sodium chloride solution and dries it in a vacuum at about 60 °. A red-brown powder is obtained which dissolves in water with a brown color and on wool a wash-, sweat-, water- and provides walkeehte as well as lightfast, level brown coloring.

Example 3 A suspension of 24.6 parts of 2-amino-1-hydroxy-6-acetylaminobenzene-4-sulfonic acid in 100 parts of water, 100 parts of ice and 5 parts of 30% hydrochloric acid is through Addition of 29.5 parts of 4N sodium nitrite solution at 3 to 5 diazotized. After completion after the diazotization, 38 parts of 1-phenyl-3-methyl-5-pyrazolone-2 ', 5'-disulfonic acid are gradually added Sodium and 10 parts of sodium carbonate at 10 to 15 ° and stir for 4 hours, to end the clutch. The acetylamino monoazo dye is made by acidification deposited with 20 to 25 parts of 30% hydrochloric acid (pH value 0.5 to 1.0) and salting out, suctioned off and washed with sodium chloride solution. The moist residue is carried in 150 parts of 10% hydrochloric acid and heated to 90 to 100 ° until the acetyl group is split off. The hydrolysis solution is allowed to cool to about 60 ° and is added with 25 parts of crystallized copper sulfate and then at 50 to 55 ° with 30o / oiger Sodium hydroxide solution until pH is 5. The solution is stirred for a Hour at 50 to 55 ° and provides by adding 20% sodium carbonate solution, that the pH remains between 5 and 6. 22 parts of finely powdered 2,4,5,6-tetrachloropyrimidine are added added, the reaction mixture heated under reflux to 70 to 80 ° and stirred it about 75 to 80 °, with the addition of dilute sodium carbonate solution constantly a weakly acidic reaction is provided. After 2 to 3 hours it is brought to the boil the solution without a reflux condenser a small amount of unreacted tetrachloropyrimidine removed. Then the dye is salted out by adding sodium chloride and sucked off. After drying in vacuo at 80 to 100 °, the dye is ground. It is a dark powder that dissolves in water with a brownish-red color.

Replace the 25 parts of crystallized copper sulfate in this example 28 parts of crystallized nickel sulfate gives a similar dye: On a fabric made of mercerized cotton, dyeing with the above is obtained Copper complex dye has a reddish brown color, which is excellent light and is wet fast.

Example 4 47 parts of the 2-amino-1-hydroxy-4-carbethoxyaminobenzene-6-sulfonic acid obtained by coupling diazotized to 1-phenyl-3-methyl-5-pyrazolone-3'-sulfonic acid and subsequent alkaline saponification of the carbethoxyamino available amino monoazo dye are in 600 parts Dissolved water at 80 °. This is added with vigorous stirring and reflux cooling Reaction mixture with a solution of 22 parts of 2,4,5,6-tetrachloropyrimidine dropwise in 200 parts of acetone and the mixture is stirred at 60 to 65 ° further, by adding of dilute sodium carbonate solution constantly ensured a weakly acidic reaction will. After 2 to 3 hours the reflux condenser is removed and the acetone as well a small amount of unreacted tetrachloropyrimidine by boiling the solution and condensing the vapors distilled off.

The solution of the condensation product obtained in this way is added dropwise 70 to 80 ° slowly a solution of 25 parts of crystallized copper sulfate in 250 Share water. By allowing dilute sodium carbonate solution to flow in at the same time the pH of the medium is constantly kept at 6.0 to 6.5. After the metallization is finished the dye is salted out by adding sodium chloride and then suctioned off. After drying in vacuo at 80 to 100 °, the dye is ground. Created a dark powder that dissolves in water with a brownish-red color and on a mercerized Cotton satin provides a light and wet-fast reddish brown color.

The following table contains further reactive dyes which can be prepared according to the invention and which can be obtained according to the information in Examples 1 to 4 and in the metal-free state of the formula correspond. With Ri R = Ur ZY metal color play cotton 5 dichloropyrimidyl- - S03H - OH -CHa 4-sulfophenyl Cu yellow brown amino 6 Dibromopyrimidyl- - SO3H - OH - CH3 desgl. Cu desgl. amino 7 Trichloropyrimidyl- - S03H -OH - CHa 4-sulfonaphthyl-1 Cu desgl. amino 8 - S03H dichloropyrimidyl- - OH - CH3 like Cu red-brown amino 9 - SO3H like - OH - CH3 3-sulfophenyl Cu like. 10 '- SO3H like - OH - CH3 like Ni like. continuation At-hue on play Ri R2 WZY metal cotton 11 Trichloropyrimidyl- - S03H - OH - CH3 2-methyl-4-sulfo- Cu yellow-brown amino phenyl 12 the same. The same -OH - CH3 2-sulfophenyl Cu the same. 13 the same. The same - OH - CH3 3-sulfophenyl Cu desgl. 14 the same. The same. -OH - CH3 2-chloro-4-sulfo- Cu the same. phenyl 15 the same. The same - OH - CH3 2,5-dichloro - Cu the same. 4-sulfophenyl 16 the same. The same -OH - CH3 2-chloro-6-methyl- Cu the same. 4-sulfophenyl Ni desgl. 17 the same. The same -OH - COOH 4-sulfophenyl Cu red-brown 18 dichloropyrimidyl like - OH - CH3 2,5-disulfophenyl Cu yellow brown amino 19 Trichloropyrimidyl like - NH2 - CH3 like Cu like. amino 20 the same. The same -OH - COOH 5,7-disulfo-Cu red-brown naphthyl-2 21 the same. The same - OH - CO - NH-2 the same. Cu the same. 22 the same. The same - OH - COOC2H5 the same. Cu the same. 23 Dibromopyrimidyl like -OH - CH3 2,5-disulfophenyl Cu yellow-brown amino 24 Tribromopyrimidyl like -OH - CH3 like Cu like. amino 25 - S03H 5-methyl-dichloro - OH - CH3 like Cu red-brown pyrimidylamino 26 5-Ethyl-dichloro- - SO3H -OH - CH3 like Cu yellow-brown pyrimidylamino 27 5-Carboxymethyl- like - OH - CH3 4,6,8-Trisulfo- Cu like. dichloronaphthyl-2 pyrimidylamino 28 6-methyl-2,4-di- like -OH - CH3 2,5-disulfophenyl Cu like. chloropyrimidyl 5-methylene amino 29 5-Carbomethoxy- like - OH - CH3 6,8-Disulfo- Cu like. dichloronaphthyl-2 pyrimidylamino

Claims (4)

Claims: 1. A process for the preparation of metallizable reactive dyes and their copper and nickel complex compounds, characterized in that 1 mol of the diazo compound is obtained from an amine of the formula wherein one X is a sulfonic acid group, the other X is a group - NH - R, where R is a mono-, di- or trihalopyrimidyl radical bonded directly or via - CH-, -, with 1 mol of an azo component of the formula couples, where W is - OH or - NH2, Y is an optionally further substituted mono- or disulfophenyl, mono- or di- or trisulfonaphthyl radical and Z is low molecular weight alkyl, carboxy, a carboxylic acid alkyl ester group or an optionally substituted carboxylic acid amino group, and in substance with a copper- or nickel-releasing agents, with dyes or copper or nickel complex compounds of dyes of the general formula wherein X, W, Y and Z have the meanings given, are formed. 2. A process for the preparation of metallizable reactive dyes or their copper and nickel complex compounds of the type obtainable according to claim 1 as a modification of the process according to claim 1, characterized in that 1 mole of the diazo compound is obtained from an amine of the formula wherein one X 'is a sulfonic acid group and the other X' is a nitro group, with 1 mole of an azo component of the formula wherein W, Y and Z have the meanings given in claim 1, couples and reduces the nitro group X 'in the monoazo dye obtained and reacts the amino monoazo dye in any order on the one hand with a di-, tri- or tetrahalopyrimidine and on the other hand with a copper- or nickel-releasing agent . 3. A process for the preparation of metallizable reactive dyes or their copper and nickel complex compounds of the type obtainable according to claim 1 as a modification of the process according to claim 1, characterized in that 1 mol of the diazo compound is obtained from an amine of the formula wherein one X "signifies a sulfonic acid group and the other X" signifies an acylamino group, with 1 mole of an azo component of the formula where W, Y and Z have the meaning given in claim 1, couples and hydrolyzes the acylamino group X "in the monoazo dye obtained and reacts the aminomonoazo dye in any order with a di-, tri- or tetrahalopyrimidine on the one hand and with a copper or nickel-releasing agent on the other . 4. The method according to claim 1 to 3, characterized in that at least 1 atom of copper or nickel-containing amount of a copper or nickel-releasing agent is allowed to act on 1 mole of the metallizable monoazo dye. Documents considered: French patent specification No. 1225 282. When the application was published, a coloring table with explanations was laid out.