DE1100209B - Process for the preparation of imidazole dyes of the anthraquinone series - Google Patents

Description

Process for the preparation of imidazole dyes of the anthraquinone series It has been found that valuable vat dyes with very good wet fastness properties can be obtained obtained when 1,2-diaminoanthraquinone unsubstituted in the amino groups, the in the 3- or 4-position can carry halogen atoms or alkoxyl groups, with compounds of the general formula Xi-A-XZ, in which A is a phenyl radical and X1 and X2 in the m- or p-position a C 0 0 H-, C 0 0 R-, C 0 Y-, C H 0-, CHY2 or CY, 7 group, Y is a halogen atom, R is a simple alkyl, aralkyl or aryl radical and the phenylene radical A can in turn carry halogen atoms.

As 1,2-diaminoanthraquinones, the halogen atoms in the 3- or 4-position or carry alkoxyl groups, are for example 1,2-diamino-3-methoxyanthraquinone, 1,2-diamino-3-bromoanthraquinone or 1,2-diamino-4-chloranthraquinone called as Halogen atoms are, for example, chlorine or bromine atoms, as alkoxyl groups z. B. low molecular weight alkoxyl groups, such as methoxyl or ethoxyl groups, and as simple alkyl, aralkyl or aryl radicals are, for. B. low molecular weight alkyl, aralkyl or aryl radicals, such as the methyl, ethyl, benzyl or phenyl radical, mentioned.

Compounds of the general formula X1 - A - X2 are for example the benzene dicarboxylic acids, e.g. B. terephthalic acid, chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2,5-dibromoterephthalic acid, isophthalic acid, 4,6-dichloroisophthalic acid, 4,6-dibromoisophthalic acid, as well as the esters and acid halides of benzene dicarboxylic acids or benzene dialdehydes, z. B. terephthalaldehyde, 2,5-dichloroterephthalaldehyde, 2,5-dibromoterephthalaldehyde, Isophthalaldehyde, 4,6-dichloroisophthalaldehyde, trichloroisophthalaldehyde, tetrachloroisophthalaldehyde and also the co-halogenated xylenes, e.g. B. co, co, aj ', oo'-tetrachloro-para-xylene, w, u), co ', co'-tetrabromopara-xylene, 2,5, co, o), oj', u) '- hexachloro-para-xylene, 2,5, (o, o), co ', w'-hexabromo-para-xylene, 2,3,5,6, c "), a), co', co'-octachloro-para-xylene, co, a @, co ', co' - tetrabromo - meta - xylene, 2,4, w, oo, a) ', oo'-hexachloro-meta-xylene, 1,4-bis-trichloromethylbenzene, 4,6-dichloro-1,3-bis-trichloromethylbenzene, 2,5, a), co, co, co ', o,)' - heptachloro-para-xylene.

The new vat dyes are obtained in the for the production of imidazoles known manner by condensation of one mole each of a compound of the general Formula X1 - A - X2, in which A, X1 and X2 have the meaning given above, with 2 to 2.2 moles each of a 1,2-diaminoanthraquinone of the aforementioned type, expediently in solvents and / or diluents in the presence or absence of water or. acid binding agents. As a solvent and / or diluent and at the same time water-binding Agents are generally suitable, for example, sulfuric acid, sulfuric acid monohydrate and oleum. In organic solvents and / or diluents such as nitrobenzene, Trichlorobenzene, or naphthalene, can be used to conduct the condensation if one for example, starting from acid chlorides, aldehydes or a) -haloxylenes. Suitable Temperatures for the conversion into sulfuric acid and / or sulfuric acid monohydrate are generally 100 to 160 ° C, for the reaction in organic solvents 150 to 220 ° C. In some cases, the implementation takes place already during the heater the reaction mixture takes place at the temperatures indicated above and is with has already ended when these temperatures are reached. In other cases you have to Reaction mixtures for up to 8 hours at the temperatures given above hold when you can achieve complete condensation of the implementation participants want.

The previously known imidazole dyes of the anthraquinone series adhere various defects, e.g. B. inadequate wet fastness properties and / or poor Color strength. In contrast, the new dyes are characterized by high color strength and have very good, in some cases excellent, wet fastness properties. the new imidazole dyes of the anthraquinone series are valuable yellow vat dyes for dyeing and / or printing structures such as fibers, threads, flakes, foils, Woven and knitted fabrics made from native and / or regenerated cellulose. You are suitable also for dyeing synthetic material, e.g. B. from linear polyamides.

The dyes obtainable according to the invention differ both from the imidazole dyes known from German patent 615 756 and from the thiazole dyes known from German patent 384 674 and from the oxazole dyes known from the US Pat. No. 2,415,938 by their greater color strength and because of their better lightfastness.

The parts in the following examples are parts by weight.

Example 1 To a solution of 10 parts of 1,2-diaminoanthraquinone 3.5 parts of terephthalic acid are added to 100 parts of concentrated sulfuric acid and heated the mixture to 150 to 160 ° C and holds it for 5 to 8 hours at this temperature. After cooling, the reaction mixture is poured into ice water and the precipitated is sucked off Precipitate, washes it acid-free and dries it.

If appropriate, you can also separate the dye that the sulfuric acid solution of the dye by carefully adding water adjusts to the acid concentration at which the dye separates out as sulfate. By breaking down the sulfate with water, the new dye is obtained in pure form. This type of separation of a dye from the reaction mixture is in the referred to as "fractionating" in the following examples.

The yellow dye obtained in very good yield is more concentrated Sulfuric acid readily soluble, but yellow in color in organic solvents sparingly soluble or insoluble. The dye dyes cotton from a purple-red vat in yellow tones.

If instead of 3.5 parts of terephthalic acid, 4.2 parts of dimethyl terephthalate are used and if the rest of the procedure is as indicated above, a good yield is obtained the same dye.

EXAMPLE 2 3.5 parts of isophthalic acid are introduced into a solution of 10 parts of 1,2-diarninoanthraquinone in 100 parts of sulfuric acid monohydrate, the mixture is heated to 150 to 160 ° C. and is kept at this temperature for 1 to 3 hours. After cooling, the reaction mixture is poured into ice water or the dye is fractionated as indicated in Example 1. The yellow dye obtained in very good yield is soluble in concentrated sulfuric acid with a yellow color. In organic solvents it does not dissolve or only slightly with a yellow color. The dye dyes cotton from an orange-red vat in yellow tones.

Example 3 To a solution of 10 parts of 1,2-diaminoanthraquinone in 100 parts of sulfuric acid monohydrate are added to 5 parts of 2,5-dichloroterephthalic acid, heats the mixture to 150 to 160 ° C and holds it for 3 hours at this temperature. After cooling, the reaction mixture is poured into ice water or fractionated the dye as described in Example 1. The yellow one obtained in good yield Dye is good in sulfuric acid, in organic solvents. not or only Slightly soluble with a yellow color and provides a blue-violet vat. The coloring of Cotton is yellow.

Example 4 In a solution of 10 parts of 1,2-diaminoanthraquinone in 100 parts of sulfuric acid monohydrate carry 6.8 parts of 2,5-dibromoterephthalic acid a, heats the mixture to 150 to 160 ° C and holds it for 3 hours at this Temperature. After cooling, the reaction mixture is poured onto ice water or fractionates the dye in the manner indicated in Example 1. The one in good yield yellow dye obtained is good in sulfuric acid, in organic solvents not soluble or only slightly soluble with a yellow color. He dyes cotton from a purple vat in yellow tones.

Example 5 To a solution of 10 parts of 1,2-diaminoanthraquinone in 100 parts of sulfuric acid monohydrate are added to 5 parts of 4,6-dichloroisophthalic acid and the mixture is heated the mixture to 150 to 160 ° C and holds it for 3 hours at this temperature. After cooling, the reaction mixture is poured into ice water or fractionated the dye as described in Example 1. The one obtained in very good yield yellow dye is readily soluble in sulfuric acid, in organic solvents not soluble or only slightly soluble with a yellow color and provides a red vat. The coloring of cotton is yellow.

Example 6 10 parts of 1,2-diaminoanthraquinone are dissolved in 150 parts of nitrobenzene dissolved with warming. 0.1 part of pyridine is then added to the solution, followed by it 4.3 parts of terephthaloyl chloride in small portions at 120 ° C. Then heated if the solution is raised to 180 ° C. within 1 to 2 hours, the temperature is maintained for 1 hour at 180 ° C, heated further to 200 ° C, holds the temperature for 1 hour at 200 ° C and then cools down to 120 ° C. At this temperature the reaction material is sucked off, washed with hot nitrobenzene at 120 ° C., then washed free of nitrobenzene with methanol and dried. The dye obtained in very good yield is with the after Example 1 identical dye prepared.

Example 7 In example, the terephthaloyl chloride is replaced by the same amount of isophthaloyl chloride gives one in very good yield Dye which is identical to the dye obtainable according to Example 2.

Example 8 If instead of 4.3 parts of terephthaloyl chloride starting from 5.8 parts of 2,5-dichloroterephthaloyl chloride and otherwise, as in the example 6 indicated, proceeds, a yellow dye is obtained in good yield, the is identical to the dye prepared according to Example 3.

Example 9 10 parts of 1,2-diaminoanthraquinone are dissolved in 200 parts of nitrobenzene dissolved with warming. 0.1 part of pyridine is then added to the solution, followed by it 7.6 parts of 2,5-dibromoterephthaloyl chloride in small portions at 120 ° C. then If the mixture is heated to 180 ° C. within 1 to 2 hours, the temperature is maintained for 1 hour at 180 ° C, heated further to 200 ° C, holds the temperature for 1 hour at 200 ° C and then cools down to 120 ° C. At this temperature, the reaction material is sucked off and washed with hot nitrobenzene at 120 ° C., then washed free of nitrobenzene with methanol and dried. The dye obtained in very good yield is with the after Example 4 identical dye prepared.

Example 10 10 parts of 1,2-diaminoanthraquinone are used in 150 parts Nitrobenzene dissolved by heating. 0.1 part of pyridine is added to the solution and then carries 5.8 parts of 4,6-dichloroisophthaloyl chloride in small proportions at 120.degree a. The solution is then heated to 180 ° C. within 1 to 2 hours, the Temperature 2 hours to 180 ° C and then cools to 120 ° C. At this temperature, the reaction material is suctioned off with hot nitrobenzene at 120 ° C washed, then washed free of nitrobenzene with methanol and dried. The one in good Yield obtained dye is with the dye prepared according to Example 5 identical.

Example 11 10 parts of 1,2-diaminoanthraquinone are used in 100 parts Dissolved nitrobenzene with heating. At about 100 ° C you then set in small Adding 2.9 parts of terephthalaldehyde, the solution heats within 1 to 2 hours to 180 ° C and hold the temperature for 1 hour at 180 ° C. After the Cooling to 120 ° C, the reaction material is suctioned off and washed with 120 ° C hot Nitrobenzene. The dye is then washed free of nitrobenzene with methanol and dried. The dye obtained in very good yield is the same as that according to the example 1 or 6 produced identical dye.

Example 12 10 parts of 1,2-diaminoanthraquinone are in 150 parts Dissolved nitrobenzene with heating. At about 100'C one sets now in small proportions 4.3 parts of 2,5-dichloroterephthalaldehyde are added, the solution is heated within 1 to 2 hours and keep the temperature at 180 ° C for 1 hour. After cooling down 120 ° C, the reaction material is suctioned off, washed with 120 ° C hot nitrobenzene, then washed free of nitrobenzene with methanol and dried. The one in very good yield The dye obtained is identical to the dye prepared according to Example 3 or 8.

Example 13 Used in Example 13 instead of 150 parts Nitrobenzene 200 parts nitrobenzene and instead of 4.3 parts 2,5-dichloroterephthalaldehyde 6.2 parts of 2,5-dibromoterephthalaldehyde are obtained in good yield Dye which can also be obtained according to Examples 4 or 9.

Example 14 10 parts of 1,2-diaminoanthraquinone are used in 150 parts Dissolved nitrobenzene with heating. At about 150 ° C one carries in the solution in small portions 6.6 parts 2.5, o, co, co ', oo'; Hexachloro-para-xylene, heated in In the course of 1 hour to 180 ° C, the temperature is kept at 180 ° C for 1 hour, heated to 200 ° C, hold the temperature at 200 ° C for 1 hour and cool the mixture 120 ° C. At this temperature, the reaction mixture is suctioned off and washed first with 120 ° C hot nitrobenzene, then with methanol nitrobenzene-free and dry it. A dye is obtained in a very good yield which is identical to that of Example 3, 8 or 13 is identical.

Replace the 6.6 parts of 2.5, o, co, co ', co'-hexachlorop-xylene with 12.5 parts of 2,5-dichloro-co, co, uo ', o'-tetrabromo-xylene are obtained in very good Yield the same dye.

Example 15 In Example 14, the 2,5, o, co, co ', co'-hexachloro-para-xylene is replaced by 12.2 parts of 2.5, o, o, cv ', o'-hexabromo-para-xylene, you get very good Yield a dye made with the dye prepared according to Example 4, 9 or 13 is identical. Example 16 To a solution of 10 parts of 1,2-diaminoanthraquinone in 100 parts of sulfuric acid monohydrate are 8.9 parts of co, co, co ', co'-tetrabromo-meta-xylene, heats the mixture to 125 to 130 ° C and holds it for 2 hours at this temperature. After cooling, the reaction mixture is poured into ice water or fractionated the dye as indicated in Example 1. The one obtained in very good yield The dye is identical to the dye prepared according to Example 2 or 7.

Example 17 In a solution of 10 parts of 1,2-diaminoanthraquinone in 100 parts of sulfuric acid monohydrate carry 6.6 parts of 2.5, co, o, o) ', co'-hexachloro-para-xylene a, the mixture is heated to 100 ° C and held for 2 hours at this temperature. After cooling, the reaction mixture is poured into ice water or fractionated the dye as described in Example 1. A very good yield is obtained a dye made with the dye prepared according to Example 3, 8, 12 or 14 is identical.

Replace the 1,2-diaminoanthraquinone with the same amount by weight 1,2 - diamino - 3 - methoxyanthraquinone and uses 5.9 parts of 2.5, co; cv, o) ', oo'-hexachloro-p-xylene, a yellow dye is obtained in a very good yield, and in a concentrated form Sulfuric acid is well soluble with yellow color. The new dye dyes cotton from blue-violet vat in yellow tones.

Replace the 1,2-diaminoanthraquinone with the same amount by weight 1,2-diamino-4-chloroanthraquinone and uses 5.8 parts of 2.5, (,), w, «) ',«)' - hexachloro-p-xylene, in this way a yellow dye is obtained in good yield, which in concentrated sulfuric acid is well soluble with yellow color. The new dye dyes cotton from blue-violet Vat in yellow tones.

Example 18 If instead of 1,2-diaminoanthraquinone one goes from 10 Parts of 1,2-diamino-3-bromoanthraquinone and instead of 6.6 parts of 4.8 parts 2.5, co, co, co ', o'-hexachloroparaxylene and the rest of the procedure as in the example 17 indicated, a yellow dye is obtained in very good yield, which is found in concentrated sulfuric acid is readily soluble. The new dye is in organic Solvent-insoluble or only slightly soluble with a yellow color and stains cotton from purple vat in yellow tones.

Claims (1)

PATENT CLAIM: Process for the production of imidazole dyes the anthraquinone series, characterized in that there is unsubstituted in the amino groups 1,2-diaminoanthraquinone, which is in the 3- or 4-position halogen atoms or alkoxy groups can carry, reacts with compounds of the general formula Xl-A-X2, in which A is a Phenylene radical and Xl and X2 in the m- or p-position a C O O H-, C O O R-, C 0Y-, C H O, C H Y2 or C Y3 group, Y a halogen atom, R a simple alkyl, aralkyl or aryl radical and the phenylene radical A can in turn carry halogen atoms. Considered publications German Patent Nos. 384674, 615756; U.S. Patent No. 2,415,938. At the notice of application are two Coloring boards have been laid out.