DE1164004B - Process for the preparation of dyes of the tetrazaporphin series - Google Patents

Description

Process for the preparation of dyes of the tetrazaporphin series It is known that dyes can be prepared which have as substituents radicals of α, β-unsaturated aliphatic carboxylic acids, β-halogen or β-sulfatoethylaminosulfonyl groups or halotriazine groups. Such residues can also be present in phthalocyanine dyes, as the Belgian patents 565 447, 565 997 and 577 169 show.

It has now been found that valuable new dyes of the tetrazaporphin series with improved coloring properties are obtained if tetrazaporphin derivatives containing primary and / or secondary amino groups in the molecule are reacted with compounds which contain halogen atoms and groups of the general formulas which can react with amino groups contain, in which R1 and R2 are hydrogen atoms, alkyl, cycloalkyl, aralkyl and / or aryl groups, Z and Z2 are hydrogen atoms, halogen atoms and / or alkyl groups and X is a halogen atom or an ester group, and the reaction products, if desired, with tertiary amines, Reacts thioethers or thioureas or if you react with amino groups reactive halogen atoms in the molecule containing tetrazaporphin derivatives with compounds which carry primary and / or secondary amino groups and groups of the general formulas I or II in the molecule, and, if desired, the reaction products with tertiary amines, thioethers or thioureas .

The implementation of the amino-tetrazaporphine with the groups of the formula I or II bearing halides and the implementation of the tetrazaporphin derivatives with reactive halogen atoms with those carrying the groups of the formula I or 1I Amines are used in the usual way, e.g. B. in water or organic liquids or in mixtures of water and organic liquids, expediently in the presence acid-binding substances, such as alkali hydroxides, carbonates, hydrogen carbonates and acetates.

The resulting radicals of the general formulas I or II in the molecule bearing tetrazaporphin dyes can, if desired, with tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, triethanolamine, dimethylcyclohexylamine, Dimethylaminobenzene and pyridine or with thioureas such as thiourea, N-methylthiourea, N, N- and N, N'-dimethylthiourea, tetramethylthiourea or with thioethers be implemented, giving tetrazaporphin dyes that are quaternary in the molecule Contain ammonium groups, thiuronium groups or tertiary sulfonium groups. Farther one can use the tetrazaporphin dyes, which contain the groups of the above formulas, react with mereaptanes and treat the reaction products with alkylating agents, tetrazaporphin dyes with tertiary sulfonium groups also being obtained will.

The conversion of the tetrazaporphin dyes into those with quaternary Ammonium or sulfonium groups are particularly advantageous when the starting materials are not or only slightly soluble in water. With the introduction of the ammonium resp. Sulfonium groups increase the water solubility of the tetrazaporphine dyes or brought about.

Halides with groups of the general formulas I or 1I are for example Halobutenes and halobutines, such as 1,4-dichlorobutene- (2), 1,4-dibromobutene- (2), 1,3,4-trichlorobutene- (2) and 1,4-dichlorobutyne- (2). examples for Amines with residues of the formula 1 or II are 1-amino-4-chlorobutene- (2), 1-amino-4-chlorobutin- (2), 1-Amino-3,4-dichlorobutene- (2) and 1-amino-2,3-dimethyl-4-bromobutene- (2). The production such amines is z. B. in H o u b e n - W e y 1, "Methods of Organic Chemistry", 4th edition (Stuttgart 1957), Vol. 11/1, pp. 105 ff., In “Comptes rendus hebd. of Seances de 1'Academie des Sciences ", Vol. 241 (1955), pp. 752 ff., And" Annales de Chimie "(12), Vol. 3 (1948), p. 656.

Other amines that contain residues of the formulas I or II in bond, are for example 1-aminobenzene-4-sulfonic acid [3,4-dichlorobutene- (2) -ylamide], 1-aminobenzene-3-sulfonic acid [3,4-dichlorobutene- (2) -ylamide], 1-aminobenzene-4-sulfonic acid - [4-chlorobutene- (2) -ylamide], 1-aminobenzene-4-sulfonic acid [4-chloro-butyn- (2) ylamide] and the halobutenylamides and halobutynylamides of 1-aminobenzene-4-carboxylic acid, 1-amino-3-chloro-4-methylbenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid, 1-aminobenzene-2,4-, -2,5- and -2,6-disulfonic acid and 1-amino-2-methylbenzene-4,5- and -4,6-disulfonic acid. These amides can be prepared, for example, by reacting acylaminosulfonic acid halides with amines containing radicals of the formula I or II, and subsequent cleavage the acyl groups from the reaction products.

Other usable as starting materials amines can be, for. B. by Implementation of molar amounts of amines containing groups of the formulas I or II, 1,3-diaminobenzene-3- or -4-sulfonic acid and dihalotriazine or dihalopyrimidine derivatives or by reacting di- or polyhalobutenes or -butynes with one side acylated diamines in molar amounts and subsequent cleavage of the acyl groups manufacture from the conversion products. Suitable diamines acylated on one side are for example 1-acetylamino-3- and -4-aminobenzene and 1-acetylamino-3-aminobenzene-4-sulfonic acid.

The tetrazaporphin derivatives used as starting materials with primary or secondary amino groups or reactive halogen atoms can, for example of tetrazabenzoporphines, such as metal-free phthalocyanine or iron, nickel, Cobalt, copper and aluminum phthalocyanine or substituted tetrazabenzoporphines such as mono-, di- or tetrachloro copper phthalocyanine, alkyl and aryl phthalocyanines such as di-, tetra- and octaphenyl copper phthalocyanine, also from benzoyl, phenoxy, Phenyl mercapto- and phenylsulfonyl phthalocyanines such as tetrabenzoyl copper phthalocyanine, Di- and tetraphenylsulfonyl copper phthalocyanine or azaphthalocyanines or naphthophthalocyanines and those tetrazaporphines that are less than contain four or no benzo rings in the molecule, e.g. B. tetramethyltetraphenyl and Octaphenyl nickel and copper tetrazaporphines, tetramethyl and tetraphenyl tetrazadibenzoporphines.

It is particularly advantageous to use those containing amino groups Tetrazaporphin derivatives, which, in addition to the amino groups, also make them water-soluble Groups, e.g. B. sulfonic acid groups contained in the molecule, such as tetrakisaminocopper phthalocyanine tetrasulfonic acid, Bis-, tris- and tetrakisaminomethyl copper phthalocyaninedi-, -tri- and -tetrasulfonic acids, Bis- (4-aminobenzoyl) -, bis- (4-aminophenylmercapto) - and bis- (4-aminophenyl-sulfonyl) -copper phthalocyanine sulfonic acids, and the tetrazaporphines obtained by the process of German patent 1,066,683.

Tetrazaporphin derivatives containing amino groups come as Starting materials continue to be produced by the reaction of Tetrazaporphinsulfonsäurehalogeniden with aromatic di- or polyamino compounds or aromatic nitroamino or Aminoacylaminoverbindungen obtained compounds into consideration, wherein in the case of Nitroamino and aminoacylamino compounds after the reaction with the tetrazaporphinsulfonic acid halides the second amino group has to be generated by reduction or saponification.

Tetrazaporphinabkömmlinge with reactive halogen atoms are, for example, those with carboxylic acid halide, sulfonic acid halide and / or imide halide groups, where the imide halide groups can also be components of heterocyclic systems, eg. B. tetrazaporphinecarboxylic acid halides, such as copper phthalocyanine tetracarboxylic acid tetrachloride, and tetrazaporphine sulfonic acid halides, such as copper phthalocyanine di, tri and tetrasulfonic acid chloride, nickel phthalocyanine trisulfonic acid chloride, metal-free phthalocyanine disulphonic acid chloride and tetraphenyl copper phthalate. The dyes in the following table are suitable as tetrazaporphin derivatives with imide halide groups: The halides of carboxyarylaminotetrazaporphines and sulfoarylaminotetrazaporphines and the tetrazaporphinmethylene thioalkyl and thioaryl carboxylic acids which can be prepared by the process of German patent specification 878 686 can also be used as starting materials.

The new dyes of the tetrazaporphin series are suitable for coloring and printing of structures such as fibers, flakes, woven, knitted, nonwovens and molded articles of wool, silk, synthetic polyamides and polyurethanes and of leather, in particular of structures made of natural or regenerated cellulose.

Compared to a corresponding dye according to the Belgian patent 565 447, the new dyes have the advantage that they can be used at a lower temperature, z. B. by simply drying the alkaline padded cotton goods in proportion fix deep notes. The same advantage exists over the Belgian dyes U.S. Patent 565,997; In addition, there is a better resistance of the alkaline Dye or padding liquors. Compared to the corresponding dye according to the Belgian Patent specification 577 169 are the superiority of the dyes according to the invention when dyeing from the liquor, e.g. B. after the exhaust process, and the available to highlight stronger colors.

When dyeing with the new dyes you can proceed, for example, that one z. B. structure made of cellulose with a solution of the new dyes and after drying leads through a bath, the basic agents, such as alkali hydroxides, carbonates and bicarbonates, and optionally neutral salts such as sodium chloride and sodium sulfate, with 100 parts of water, mix this dough with 500 parts of methanol and add so much aqueous sodium hydroxide solution that a pH of about 8.5 is established in the mixture. 20 parts of 1,3,4-trichlorobutene- (2) are gradually added at 0 ° C. with stirring, the mixture is allowed to warm to room temperature and after some time is added to the mixture by adding 10% aqueous sodium carbonate solution a pH of about 7. By occasionally adding more 10% aqueous sodium carbonate solution, the mixture is kept at the same pH value until it is no longer there. The dyes are fixed on the item to be dyed by briefly steaming them. Instead of steaming, treatment with hot air at 50 to 150 ° C can also be used. The basic agents and optionally the neutral salts can also be added to the pad bath. It is also possible, for example, to treat structures made of cellulose with solutions of basic substances, then pad them with the new dyes and fix them on them.

When printing structures such. B. made of cellulose, the new ones Dyes are advantageous together with customary thickeners and basic thickeners Materials, if necessary applied to the print material with the usual printing auxiliaries, this dried and steamed briefly. You can also use the new dyes on the fabric and customary thickeners, optionally together with customary printing auxiliaries print, dry, run through a bath filled with alkaline substances, then dry and steam again. Finally you can put the dyes together with the usual thickeners to a treated with basic substances Print on fabric, then dry and steam.

The processes mentioned give dyeings and prints with excellent quality Wet fastness properties.

The parts mentioned in the examples are parts by weight. The relationship from parts by volume to parts by weight is that from liters to kilograms under normal conditions. The percentages are percentages by weight. Example 1 You dough 30 parts of the compound of the formula no more without the addition of sodium carbonate solution changes. The alcohol is then distilled from the reaction mixture under reduced pressure from, 250 parts of saturated aqueous sodium chloride solution are added to the residue and the mixture is filtered the separated reaction product. After drying under reduced pressure a water-soluble dye is obtained, cotton in turquoise-blue tones dyes of excellent fastness properties.

If, instead of 1,3,4-trichlorobutene- (2) 1,4-dichlorobutene- (2) or 1,4-dichlorobutyne- (2) or, instead of the copper phthalocyanine compound, the above formula the corresponding nickel, aluminum or metal-free compound is obtained Dyes of similar properties.

A cotton fabric is padded with an aqueous solution in 1000 Volume parts 20 parts of the dye from Section 1 of this example and 20 parts Contains sodium hydrogen carbonate, squeezes the tissue and steams it for 8 minutes 100 ° C and rinses and soaps it. A strong turquoise blue color of very is obtained good wet fastness properties. Example 2 A mixture of 65 parts of monochloro copper phthalocyanine and 600 parts of chlorosulfonic acid are heated to 130 to 135 ° C for 3 hours. After this When cooling, the mixture is stirred into ice water and the reaction product is filtered and washes it with ice water. 440 parts of the still moist reaction product dough one with 300 parts of ice and a solution of 40 parts of the hydrochloride of 1-amino-3,4-dichlorobutene- (2) in 200 parts of water, add enough saturated aqueous sodium acetate solution to this dough, that a pH of about 5 is reached, and the mixture is stirred at room temperature until the pH value no longer changes even without the addition of sodium acetate solution changes. Excess sodium chloride is then added and the resulting product is filtered off Dye off and dry it under reduced pressure at 40 to 45 ° C. He solves immersed in water with a turquoise blue color.

Similar dyes that are greenish turquoise blue in water Dissolve color is obtained in the same way if, instead of monochloro copper phthalocyanine Copper tetrachloride, nickel or iron phthalocyanine is used. Using of an aza copper phthalocyanine, which is composed of molar amounts of quinolinic acid and phthalic acid in the urea melt, instead of monochloro copper phthalocyanine reddish turquoise blue dyes are obtained.

A cotton fabric is padded with an aqueous solution which contains 20 parts of the dye described in the first paragraph of this example in 1000 parts by volume, it is squeezed to a moisture content of 80% and dried. The fabric is then passed through a second pad bath containing 15 parts of sodium hydroxide and 300 parts of sodium sulfate in 1000 parts by volume, it is squeezed off, dried for 1/2 hour at 70 ° C. or steamed for eight minutes Example s For a paste of 40 parts of a mixture of copper phthalocyanine and trisulfonic acid chloride, 100.degree. After rinsing and soaking, a turquoise-blue dye of very good washfastness is obtained.

Example 3 To an aqueous paste of 250 parts of ice, 250 parts Water and 50 parts of copper phthalocyanine-4,4 ', 4 ", 4"' - tetrasulfonic acid chloride is stirred a solution of 30 parts of the hydrochloride of 1-amino-4-chlorobutyn- (2) in 150 parts of water and makes the mixture by adding 10% aqueous Sodium carbonate solution has a pH of about 7. The mixture is stirred several times Hours at room temperature and gives when the pH is even without adding Sodium carbonate solution no longer changes, so much dilute hydrochloric acid to that a pH of 2 to 3 is reached, the deposited dye is filtered off and dry it under reduced pressure at low temperature. He gives up Cotton in the presence of alkaline substances, blue dyeings of excellent Fastnesses.

A green dye with similar properties is obtained if instead of copper phthalocyanine tetrasulfonic acid chloride, tetraphenyl copper phthalocyanine tetrasulfonic acid chloride used.

EXAMPLE 4 370 parts of an aqueous paste are pasted, the 100 parts Copper phthalocyanine 3,3 ', 3 ", 3"' - contains tetrasulfonic acid chloride, with 250 parts Ice and add a suspension to this dough, which is made by stirring in 65 parts of the hydrochloride of 1- (4-aminobenzenesulfonylamino) -3,4-dichlorobutene in 650 parts hot water and then cooling this mixture to 0 ° C. By Saturated aqueous sodium acetate solution is added to the reaction mixture a pH of 5 and maintains this while stirring the mixture for several hours upright until it no longer changes even without the addition of sodium acetate solution. The resulting dye is precipitated with excess sodium chloride and filtered it off and dry it under reduced pressure at about 45 ° C. 165 parts are obtained of a water-soluble dye, cotton in the presence of basic substances dyes in blue shades of good washfastness.

Similar dyes are obtained if one proceeds in the same way the copper phthalocyanine 3,3 ', 3 ", 3"' - tetrasulfonic acid chloride with the amines or reacts with the hydrochlorides of the amines of the following table: 150 parts of ice and A solution of 25 parts of the hydrochloride is added to 200 parts of water with stirring of 1-amino-3,4-dichlorobutene- (2) in 400 parts of tetrahydrofuran. to This mixture is added as much dilute aqueous sodium hydroxide solution, saturated aqueous sodium carbonate solution or saturated aqueous sodium hydrogen carbonate solution, that a pH of about 7 is established at which the mixture is stirred lasts for several hours. The mixture is then weakly acidified with dilute hydrochloric acid on, filtered off the resulting dye and dried it under reduced pressure Pressure at low temperature.

20 parts of this dye are stirred with 100 parts of pyridine and this mixture is left at room temperature or at a moderately elevated temperature until a sample of it dissolves completely in a little water. Then the reaction mixture is added Can produce turquoise blue to greenish blue dyes.

10 parts of the dye from the first paragraph of this example and 50 parts of tetramethylthiourea are heated to 100 ° C for several hours. Then stirred the reaction mixture is added to acetone or it is taken up in water and salted out. The dye precipitate is filtered off and dried at low temperature. A water-soluble blue dye is obtained. Example 6 One is heated Mixture of 15 parts of tetrakischloromethyl copper phthalocyanine and 15 parts of 1-amino-3-hydroxybenzene and 150 parts of sulfuric acid monohydrate gradually to 100 ° C and keeps the mixture several hours at 100 to 110 ° C. A solution of 7 parts of sulfur trioxide is then added in 30 parts of sulfuric acid and the mixture is heated for a further 2 to 3 hours 120 ° C. The mixture is allowed to cool, poured onto ice and the reaction product is filtered away.

The total amount of the still moist filter residue is dissolved together with so much diluted Acetone, filter off the precipitated dye and dry it.

The dye dissolves in water with a turquoise blue color and stains Cotton in the presence of basic-looking fabrics in turquoise-blue tones is good Washfastness.

In a similar manner, using tetramethyltetrazadibenzonickel porphine disulfonic acid chloride is obtained Instead of copper phthalocyanine di- or trisulfonic acid chloride, a reddish-tinged blue color Dye, while using copper phthalocyanine tris (methylene thioacetic acid chloride), -tetrakis- (methylene thiobutyric acid chloride), -tris- (methylene hydroxybenzoic acid chloride) or the phthalocyanine derivative of the following formula: aqueous sodium hydroxide solution, that the solution has a pH of about 8, and adds a at 0 ° C with stirring Solution of 28 parts of 1,3,4-trichlorobutene- (2) in 200 parts of methanol. By adding the pH of the mixture is maintained by saturated aqueous sodium carbonate solution at about 7 and stir the mixture at room temperature until the px value of the solution no longer changed even without the addition of sodium carbonate solution. then is added so much dilute hydrochloric acid that the mixture has a pH of adjusts about 4, and falls the resulting dye with excess potassium chloride the end. After filtering and drying under reduced pressure, one is obtained water-soluble dye that is found in cotton in the presence of alkaline substances dyes green-blue shades of excellent wet fastness properties.

Similar dyes are obtained by following the same way Tetrakisamino copper phthalocyanine tetrasulfonic acid, bis (aminomethyl) copper phthalocyanine disulfonic acid or the phthalocyanine derivatives of the following table with 1,3,4-trichlorobutene- (2) implements. Example ? 50 parts of copper phthalocyanine tetrasulfonic acid chloride, 200 parts of water and 200 parts of ice are stirred well and then mixed with 10% strength aqueous sodium hydroxide solution neutralized. A solution of 22 parts of the Hydrochloride of 1- (4-aminophenoxy) -3,4-dichlorobutene- (2) in 110 parts of water; which was previously brought to a pH of 1 with dilute hydrochloric acid, and a solution of 136 parts of crystallized sodium acetate over the course of 2 hours in 150 parts of water and the mixture is stirred for 20 hours at room temperature. Filter the reaction product and dried under reduced pressure at 35 ° C. It will about 65 parts of a dye obtained in the presence of basic agents Cotton dyes in wet-fast turquoise-blue tones.

Used instead of copper phthalocyanine sulfonic acid chloride the corresponding nickel compound and instead of the hydrochloride of 1- (4-aminophenoxy) -3,4-dichlorobutene- (2) the hydrochloride of 1- (3-aminophenoxy) -3,4-dichlorobutene- (2) is obtained cyan dye of similar properties. Example 8 30 parts of monochloro copper phthalocyanine are in 250 parts of chlorosulfonic acid at 120 ° C for 1 hour and at 130 ° C for 5 hours heated. The solution is poured onto ice, filtered off and the residue is washed with cold water until the filtrate is pale blue in color. The filter residue will Made into a paste with 100 parts of water and 200 parts of ice and with 10% sodium hydroxide solution neutralized. A hydrochloric acid solution of 14 parts of the is added to this mixture Hydrochloride of 1- (4-aminophenoxy) -4-chlorobutyn- (2) in 100 parts of water and a solution of 50 parts of crystallized sodium acetate in 50 parts of water. Under Addition of a 10% aqueous sodium carbonate solution in small proportions is kept the reaction mixture for 24 hours at room temperature at a pH of 6.0 to 6.4. 100 parts of potassium chloride are then added and the reaction product is filtered off and dry it at room temperature under reduced pressure. A water-soluble one is obtained turquoise blue dye.

Claims (2)

Claims 1. A process for the preparation of dyes of the tetrazaporphin series, characterized in that tetrazaporphin derivatives containing primary and / or secondary amino groups in the molecule are reacted with compounds containing halogen atoms and groups of the general formulas which can react with amino groups contain, in which R1 and R2 are hydrogen atoms, alkyl, cycloalkyl, aralkyl and / or aryl groups, Z1 and ZZ are hydrogen atoms, halogen atoms and / or alkyl groups and X is a halogen atom or an ester group, and the reaction products, if desired, with tertiary amines, thioethers or thioureas, or that one reacts with amino groups reactive halogen atoms in the molecule containing tetrazaporphin derivatives with compounds which carry primary and / or secondary amino groups and groups of the general formulas I or 11 in the molecule, and, if desired, the reaction products with tertiary amines, thioethers or thioureas . 2. Continuing education of the method according to claim 1, characterized in that instead of the thioethers Mercaptans are used and the reaction products are treated with alkylating agents. Publications considered: Belgian patents nos. 565 447, 565 997, 577 l69.