DE977257C - Process for the preparation of water-insoluble disazo dyes - Google Patents

Description

Process for the preparation of water-insoluble disazo dyes The invention relates to a process for the preparation of water-insoluble, new disazo dyes which, like the dye of the formula correspond to the general formula R2-N = N-Rl-N = N -R3 (2), in which R1 is an anthraquinone radical free of solubilizing groups in which the two azo groups are bonded directly to the anthraquinone nucleus and separated from one another by at least three carbon atoms, and R2 and R3 each denote a ß-ketocarboxamide radical which is free of solubilizing groups and is bonded to the azo group in the * -position.

According to the invention, these disazo dyes are obtained by Tetrazo compounds of diaminoanthraquinones, those of solubilizing groups are free and in which the two diazotized amino groups are attached directly to the anthraquinone nucleus are bound and separated from one another by at least 3 carbon atoms, and which in addition to the two amino groups at most halogen atoms, in particular chlorine or contain bromine atoms as substituents, with free of solubilizing groups Coupling compounds in substance which couple a single one in the oc position Contain ß-Ketocarbonsäureamidrest.

As can be seen from the above information, the amino groups can are not in the same six-membered ring of the anthraquinone nucleus. More suitable as examples Diaminoanthraquinones, the following compounds should be mentioned: i, 5-diaminoanthraquinone, i, 6-diaminoanthraquinone, i, 7-diaminoanthraquinone, 2,6-diaminoanthraquinone, 2,7-diaminoanthraquinone, 4,8-dichloro-i, 5-diaminoanthraquinone, 2, q., 6, 8-tetrachloro-i, 5-diaminoanthraquinone, 2,6-dibromo-i, 5-diaminoanthraquinone, 2,4, 6, 8-tetrabromo-i, 5-diaminoanthraquinone, i, 5-dichloro-2,6-diaminoanthraquinone, i, 5-dibromo-2, 6-diaminoanthraquinone, 3,7-dibromo-2,6 diaminoanthraquinone, i, 3,5,7-tetrabromo-2,6-diaminoanthraquinone, 3,6-dibromo-2,7-diaminoanthraquinone. As compounds which have a single ß-ketocarboxamide radical coupling in the a-position contain, acylacetylamino compounds such. B. the Benzoylacetylaminoarylverbindungen, but especially the acetoacetylaminoaryl compounds of the benzene series into consideration. The aryl radicals bonded to the acylacetylamino group can, in addition to this group contain other non-solubilizing substituents, e.g. B. low molecular weight Alkyl or alkoxy groups or halogen atoms, such as chlorine, and also acetylamino groups or sulfonic acid amide groups. There are also such acylacetylamino compounds in Consider whose acylacetylamino group on a carbon atom located in a hetero ring is bound. Examples of suitable azo components are i-Benzoylacetyläminobenzene, the i -B enzoylacetyl amino - 2 - methoxy - 5 - methylbenzene as well as those from the following amines of the benzene series are called acetoacetylamino compounds: Aminobenzene, i-amino-2-chlorobenzene, i-amino-4-methylbenzene, i-amino-2-methoxybenzene, i-amino-2,5-dichlorobenzene, i-amino-2,4-dimethyl-5-chlorobenzene, i-amino-2-chloro-q.-acetylamino-5-methoxybenzene, i-Amino-2-chloro-5-trifluoromethylbenzene, i-Amino-2,5-dimethoxy-4-chlorobenzene, i-aminobenzene-3-sulfonic acid amide, i-amino-2-methoxy-5-methylbenzene, i-amino-2,6-diinethylbenzene, i-amino-2-methylbenzene.

As acylacetylamino compounds with one to one carbon atom An example of a hetero ring bonded acylacetylamino group is 2-acetoacetylamino-6-methoxybenzthiazole mentioned.

The tetrazotization of the diaminoanthraquinones can be known per se Appropriately done in concentrated sulfuric acid by means of alkali metal nitrite. As a rule, it is advisable to separate and isolate the tetrazo compounds.

The coupling of the tetrazo compounds thus obtainable with the ß-ketocarboxamides of the specified type is advantageous in weakly acidic, z. B. acetic acid agent carried out, it generally proves to be expedient, the coupling mixture add a wetting or dispersing agent. Wetting agents and dispersants are used here ionogenic and non-ionogenic type into consideration. As a dispersing agent of an ionic type For example, turkey red oil can be used, but not as a dispersing agent Ionic type polyglycol ethers of higher molecular weight fatty alcohols may be mentioned.

The new disazo dyes corresponding to the formula (2) given at the outset are valuable pigments and are usually characterized by particularly good migration fastness and also by temperature resistance and solvent fastness. This is z. B. valuable for so-called pigment printing, d. H. for printing processes that point to it based, pigments using suitable adhesives, such as casein, curable plastics, in particular urea or melamine-formaldehyde condensation products, polyvinyl chloride or polyvinyl acetate solutions or emulsions or other emulsions (e.g. oil-in-water or water-in-oil emulsions) on a substrate, in particular on a textile fiber, but also on other flat structures such as paper (e.g. wallpaper) or Fabrics made of fiberglass to fix. The new pigments can also be used for other purposes, z. B. in finely divided form for dyeing rayon rayon or cellulose ethers and -esters or from superpolyamides or super-polyurethanes in the spinning mass as well for the production of colored lacquers or lacquer formers, solutions and products Acetyl cellulose, nitrocellulose, natural resins or synthetic resins, such as polymerization or condensation resins, e.g. B. aminoplasts, phenoplasts, polyvinyl chloride, polystyrene, Polyethylene, polyacrylic, rubber, casein, silicone, and silicone resins, serve well. They can also be used to advantage in the production of colored pencils, cosmetic Use specimens or laminating plates.

The new dyes can normally be used in bulk or preparations of the type mentioned can be easily distributed and this expediently at a time since these masses or preparations do not yet have their definitive shape. the Measures required for shaping, such as spinning, pressing, hardening, casting, gluing i.a. m., can then easily in the presence of the pigments present be carried out without any chemical reactions of the substrate, such as others Polymerizations, condensations, etc., are hindered.

The new dyes have compared to that according to Example 13 of the United States patent 2,457,823 obtained product which, like the new dyes, contains azo groups, on the one hand to anthraquinone nuclei and on the other hand to enolized or enolizable Ketomethylene groups are bound, the advantage of a significantly better lightfastness on.

British Patent 396 431 describes a dye that by coupling tetrazotized i, 5-diamino-4,8-diphenylamirioanthraquinone with 3,3'-dimethyl-4,4'-diacetoacety laminodiphenyl on the fiber. In contrast to the dyes according to the invention, however, this dye is after cannot be produced in substance using the usual methods.

Compared to that according to Example 3 of French Patent 471 799 by coupling diazotized 1,5-dianlinoanthraquinone with 2 moles of ß-oxynaphthoic anilide available disazo dyes are distinguished by the disazo dyes obtainable according to the process by a significantly better migration fastness.

In the following examples, parts are parts by weight and percentages are percentages by weight. EXAMPLE I 40o parts 98% sulfuric acid are cooled to 0 ° C. and 28 parts 10% sodium nitrite are introduced at 5 to 100 ° C. with stirring. The mixture is then heated to 55 to 60 ° C. until a clear solution occurs, then cooled to 30 ° C. and 47.6 parts of 1,5-diaminoanthraquinone are introduced at 30 to 40 ° C. with stirring. A thick yellow suspension forms. After the end of the introduction, the mixture is slowly heated to 50 to 60 ° C. until a clear solution occurs, and it is kept at this temperature for a further 30 minutes. The mixture is then allowed to cool to 30 ° C. and the solution is poured onto 600 parts of ice and 100 parts of water. The tetrazo compound crystallizes out in yellowish-white crystals. The mixture is stirred for a further 30 minutes at from 0 to 5 ° C., filtered and pressed off thoroughly. The tetrazo compound can be kept unchanged for several weeks in a moist state in the cold and with the exclusion of light.

42.3 parts of i-acetoacetylamino-2-chlorobenzene are achieved with 3o parts 3oo / cent sodium hydroxide solution in 3oo parts of water at 30 "C. A dispersant is added, e.g. B. Turkish red oil is added and the solution is adjusted to a volume of 800 parts and a temperature of 5 ° C. by adding ice and water. Then it is acidified with dilute acetic acid until the lacquer acid reaction is reached, 60 parts of crystallized sodium acetate are added and a solution of the tetrazo compound of 23.8 parts of i, 5-diaminoanthraquinone in 10000 is left with thorough stirring for about 30 minutes. Add parts of water to it. The mixture is stirred for 2 hours at 5 to 8 ° C. and then heated in 1 hour to 35 to 40 ° C. and stirred at this temperature for a further 4 hours. The water-insoluble yellow dye formed is then filtered off, washed salt-free with plenty of water and dried in vacuo at 50 ° C. A yellow powder is obtained which dissolves in concentrated sulfuric acid with a reddish-yellow color. Rolled into polyvinyl chloride, strong, yellow colorations with very good migration and lightfastness are obtained.

If the i-acetoacetylamino-2-chlorobenzene is replaced in the above example by 55.9 parts of i-acetoacetylamino-2-chloro-5-trifluoromethylbenzene, one obtains a dye that dissolves in concentrated sulfuric acid with a yellow color and that, rolled into polyvinyl chloride, has strong, pure, greenish-yellow colorations of very good properties.

The table below lists some additional disazo dyes which can be obtained from 1 mol of tetrazotized I, 5-diaminoanthraquinone and 2 mol of the azo components given in column I, as described in example i, and which, when rolled into polyvinyl chloride, give the colors shown in column II . I azo component I II color shade i Acetoacetylaminobenzene pure yellow 2 I-acetoacetylamino-4-methyl-pure, very Benzene bright yellow 3 i-acetoacetylamino-2-methoxy- yellowish- benzene orange 4 i-acetoacetylamino-2,5-dichloro green benzene pungent yellow i-Acetoacetylamino-2,4-dimethyl- pure yellow 5-chlorobenzene 6 i-acetoacetylamino-2-chloro-orange 4-acetylamino-5-methoxybenzene 7 I-acetoacetylamino-2-chloro yellow 5-trifluoromethylbenzene 8 2-acetoacetylamino-6-ethoxy- yellowish- benzthiazole orange 9 i-acetoacetylamino-2,5-dimeth-orange oxy-4-chlorobenzene io i-acetoacetylaminobenzene orange 3-sulfonic acid amide il i-acetoacetylamino-2-methoxy- reddish- 5-methylbenzene yellow i2 i-Benzoylacetylamino-2-methoxy- reddish- 5-methylbenzene yellow Example 2 42.3 parts of i-acetoacetylamino-2-chlorobenzene are dissolved with 30 parts of 30% sodium hydroxide solution in 300 parts of water. After adding a dispersant, e.g. B. Turkish red oil, one sets the solution with ice and water to 800. Parts by volume and 5 'C a. Then dilute acetic acid is added until a lacquer acid reaction occurs, and 60 parts of crystallized sodium acetate are added.

At the same time, 23.8 parts of 2,6-diaminoanthraquinone are tetrazotized as described in Example i, Paragraph i, and the separated tetrazo compound is dissolved in 1,000 parts of water. The clear solution of the tetrazo compound is allowed to flow into the suspension of i-acetoacetylamino-2-chlorobenzene in 30 minutes with thorough stirring and stirred for 2 hours at 5 to 8 ° C. The mixture is then slowly warmed to 40 to 50 ° C. and stirred for a further hour at this temperature. The dye formed is then filtered off and washed free of salt with water. After drying in vacuo, a yellow powder is obtained which dissolves in concentrated sulfuric acid with a yellow color. Rolled into polyvinyl chloride, this dye gives strong, greenish yellow colorations with very good migration and lightfastness.

The table below lists some further disazo dyes obtainable according to the information in Example 2 from 1 mol of tetrazotized 2,6-diaminoanthraquinone and 2 mol of the azo components of column I. I azo component II shade Polyvinyl chloride r i-Acetoacetylaminobenzene greenish yellow 2 i-acetoacetylamino-2,5-di- greenish yellow chlorobenzene 3 1-acetoacetylamino- greenish yellow 4-methylbenzene 4 i-acetoacetylamino pure yellow 2-methoxybenzene 5 i-acetoacetylamino-2,5-di- pure yellow methoxy-4-chlorobenzene EXAMPLE 3 160 parts of concentrated sulfuric acid are cooled to 0 ° C., and 14 parts of 100% sodium nitrite are then introduced at 0 to 100 ° C. The mixture is then slowly heated to 50 to 60 ° C. until a clear solution has entered, then cooled to 30 ° C. and 39.6 parts of 2,6-diamino-3,7-dibromoanthraquinone are introduced with stirring at 30 ° to 40 ° C. The mixture is then stirred for 1 hour at 50 to 55 ° C., cooled to 15 ° C. and the solution is poured onto 300 parts of ice. The tetrazo compound crystallizes out in yellow crystals. The mixture is stirred for 1 hour at 0 to 5 ° C., filtered off and washed with a little ice water.

42.3 parts of i-acetoacetylamino-2-chlorobenzene are mixed with 3o parts of 3o% Sodium hydroxide solution dissolved in 300 parts of water at 30 ° C. A dispersant is added like Turkish red oil, and the solution is made up by adding ice and water a volume of 800 parts by volume and a temperature of 100 C. Then you acidify with dilute acetic acid up to the lacquer acid reaction, there are 60 parts crystallized Sodium acetate is added and, with thorough stirring, leaves in iooo parts for about one hour Add water dissolved tetrazo compound. The mixture is stirred for 2 hours at 10 to 15 ' C., then heated to 40 to 50 ° C. and stirred for 4 hours at this temperature. then the water-insoluble, yellow dye formed is filtered off and washed with salt-free hot water and dry in vacuo at 50 to 60 ° C. A yellow color is obtained Powder that dissolves in concentrated sulfuric acid with a red-yellow color and that, Rolled into polyvinyl chloride, strong yellow colors with good properties results.

Dyes with similar properties are obtained if one in the above Example, the 2,6-diamino-3,7-dibromoanthraquinone by the corresponding amount of 2,6-diamino-i, 3,5,7-tetrahromanthraquinone or 2,6-diamino-i, 5-dichloroanthraquinone replaced.

Claims (1)

Claim: Process for the preparation of water-insoluble disazo dyes, characterized in that one tetrazo compounds of diaminoanthraquinones which are free of solubilizing groups and in which the two diazotized amino groups are bonded directly to the anthraquinone nucleus and separated from one another by at least 3 carbon atoms, and those other than the two Amino groups still contain at most halogen atoms, in particular chlorine or bromine atoms as substituents, couples on both sides with compounds free of solubilizing groups in substance which contain a single ß-hetocarboxamide radical coupling in the α-position. Documents considered: German Patent Specifications Nos. 261 872, 26i 873; U.S. Patent No. 2,457,823; French Patent Nos. 471 799, 659 026; British Patent Nos. 309 879, 310 779, 310 827, 396 412, 396 430, 396 431; Chemical Abstracts, Volume 25 [193i], p.27185; Reports of the German Chemical Society, Vol. 37 [19041, p.4187.