DE1214347B - Process for the preparation of dyes of the anthraquinone and perylenetetracarboxylic acid diimide series - Google Patents

Description

Process for the preparation of dyes of the anthraquinone and perylenetetracarboxylic diimide series The invention relates to a process for the preparation of valuable dyes of the anthraquinone and perylenetetracarboxylic diimide series which are free of salt-forming, water-solubilizing groups and which have the general formula where A is a viable radical consisting of at least four fused rings, m is an integer not exceeding 4, n is an integer not exceeding 5, at least three of the radicals R are hydrogen atoms or optionally substituted alkyl or cycloalkyl radicals and one of the radicals R denotes a hydrogen atom, an optionally substituted alkyl or cycloalkyl radical or a benzene radical, where the radicals R1 and R2 or R3 and R4 together with the nitrogen atom can also form the radical of a heterocyclic ring system, for example a piperidine or morpholine ring.

Preferred alkyl or cycloalkyl radicals are those containing a maximum of 6 carbon atoms. The alkyl radicals can for example be substituted by halogen atoms, hydroxy, alkoxy or cyano groups, are, however expediently free from amino groups. Examples of alkyl radicals are the methyl, Ethyl, propyl, isopropyl, butyl, ß-hydroxyethyl, γ-hydroxypropyl, ß-chloroethyl, ß-Cyanäthyl- or ß-Methoxyäthylreste called. As an example of a cycloalkyl radical the cyclohexyl radical should be mentioned. The dyes should be free from salt-forming, water-solubilizing agents Groups, d. H. of sulfonic acid, carboxylic acid or aliphatic amino groups.

The new dyes can be obtained by using a linkable amine of the formula in which A and n have the specified terms, with a compound of the formula where -X is a chlorine atom, an amino or optionally substituted alkylamino, cycloalkylamino, phenylamino or dialkylamino group and Y is a chlorine atom, an amino or an optionally substituted alkyl or cycloalkylamino group or dialkylamino group, condensed in a proportion of approximately 1: 1 and in those of the condensation products obtained which still have chlorine atoms on the triazine radical, the latter is replaced by amino, alkylamino, dialkylarhino, hydroxyalkylamino or phenylamino groups, the starting materials being selected so that at most one phenylamino group is present in the finished dye molecule.

As relevant for the present proceedings Amines, consisting of at least four fused rings, are both mono- and also called diamines, for example amines derived from anthraquinones, which still fused, carbocyclic or: heterocyclic rings contain, for example the 4-aminoanthraquinone-2,1 (N) -acridone, the 5-amino-1,9-isothiazolanthrone, the 4- or 5-aminoanthrapyrimidine, the aminoacedianthrones, the 4- or 5-amino-1 ', 1-dianthrimide carbazole, the 4- or 5-amino-5'-ben2toylamino-dianthrimidcarbazole, the 4-amino-4'-benzoylamino - dianthrimidcarbazole, 4 - aminoanthrapyridone, aminodibenzanthrone, aminoisodibenzanthrone, Aminoanthanthrone, aminobenzanthrone, aminoflavanthrone, aminopyranthrone.

These compounds are to be condensed with a compound of the formula (3), for example with cyanuric chloride. In this case a condensation product is obtained which still contains 2 chlorine atoms on the triazine residue. These are implemented by using Ammonia or aliphatic amines replaced by NH2 or amine residues.

The amines which can be connected can also be mixed with dichlorotriazines of the formula in which R 1 and R 2 are hydrogen atoms or optionally substituted alkyl groups or at most one of the radicals R 1 and R 2 is a benzene radical, are condensed. The condensation products obtained, which still contain a chlorine atom on the triazine residue, are reacted with ammonia or an aliphatic amine. If R1 and R2 of the formula (4) are alkyl radicals, the condensation product can also be reacted with an aminobenzene.

Finally, the amines to be used according to the process can also be linked to monochlorotriazines of the formula wherein R1, R2, R3 and R4 have the same meaning as in the formula (1), are reacted.

The implementation of the connectable amine with the triazine of the formula (3) is advantageously carried out in an inert organic solvent, for example Nitrobenzene, chlorobenzene or o-dichlorobenzene, at an elevated temperature.

In general it is not necessary to use the chlorine-containing primary condensation products separate, but the two reactions can be carried out in the same vessel will.

The dyes obtained can be used for a wide variety of purposes in particular as vat dyes, pigments or as disperse dyes for synthetic fibers. Depending on the size of the anthraquinone residue or the nature of the substituents in the triazine residue, they are better suited for one or the other type of application.

Of particular interest as vat dyes are anthraquinones of the formula (1), in which A denotes a more highly condensed anthraquinone radical, for example a pyranthrone, acedianthrone, dibenzpyrenquinone, but in particular a dibenzanthrone or isodibenzanthrone radical: Dyes containing the dibenzanthrone radical represent Dye cellulose fibers in valuable deep black shades. Of particular interest are dyes of the dibenzanthrone series which contain at least one hydroxyalkylamino group in the triazine radical. Compared to the dye of Example 6 of US Pat. No. 2235480 , the next comparable dyes according to the invention have the advantage of dyeing cellulose fibers in deep black shades.

In the following examples, unless otherwise stated, parts are parts by weight, percentages are percentages by weight, and temperatures are given in degrees Celsius. Example 1 9.4 parts of aminodibenzanthrone are suspended in 200 parts of dry nitrobenzene with stirring and heated to 160 ° to 170 °. The solution of 6 parts of cyanuric chloride in 40 parts of nitrobenzene is then added, 0.5 part of pyridine is added and the mixture is stirred at 170 ° for 12 hours. After cooling to room temperature, the cyanuration product has the formula separated by filtration and washed with nitrobenzene. The filter material .wird is now entered in 100 parts of monoethanolamine in small portions at 150 to 160 ° and stirred for a further 2 hours at 150 °. After cooling, it is poured onto water and the dye of the formula filtered, washed thoroughly with water, then acetone and dried in vacuo at 60 to 70 °.

The new dye is a black powder when dry represents cotton and regenerated cellulose from alkaline hydrosulfite vat in dyes valuable black shades with excellent fastness properties.

The same dye is also obtained if the suspension is at 170 ° C of the primary cyanuration product in nitrobenzene in the course of one hour, 20 parts Monoethanolamine in 20 parts of chloroform are added dropwise and the batch still a few Stirring is continued for hours at 170 to 180 °.

If you use N-methyl-aminodibenzanthrone instead of the aminodibenzanthrone and otherwise follows exactly. the information in paragraph 1, you get a Vat dye, the cotton in brownish black tones of excellent Dyes fastness properties.

Example 2 The cyanuration product described in Example 1, first section, is introduced as filter material in small portions of 100 parts of diethanolamine at 150 to 160 ° with thorough stirring and stirred for a further 1 hour. The dye of the formula is, as described in Example 1, separated. It dyes cotton and regenerated cellulose from a red-blue hydrosulfite vat in rich, black tones with excellent fastness properties. Example 3 6.2 parts of the dichlorotriazine product of aminodibenzanthrone described in Example 1 are suspended in 200 parts of nitrobenzene and heated to 160 °. Then 12 parts of cycllohexylamine are added dropwise over a period of 2 to 3 hours and the mixture is stirred for a further 6 hours at 150 to 160 °. After cooling, the dye becomes of the formula by filtration, separated off, washed with nitrobenzene, then methanol and finally with water and dried in vacuo at 70 to 80 °.

Cotton and regenerated cellulose are made from red-blue hydrosulfite vat colored in very real blue-gray tones.

Leaving this example. a solution instead of cyclohexylamine of 5.5 parts of hydroxylamino hydrochloride in 30 parts of pyridine or 8 parts of hydrazine hydrate add dropwise in 30 parts of pyridine, the result is dyes with similarly good properties.

Example -4 The dichlorotriazine product of aminodibenzanthrone described in Example 1, first section, is introduced as nitrobenzene-moist filter material in small portions of 100 parts of N-methylethanolamine with thorough stirring at 140 ° to 150 ° and stirred for 2 hours at this temperature. The dye of the formula _ is, as described in Example 1, separated. Cotton and regenerated cellulose are dyed from the hydrosulfite vat in greenish black shades with very good fastness properties. . EXAMPLE s The dichlorotriazine product of aminodibenzanthrone described in Example 1, first section, is suspended as filter material in a pressure vessel in 200 parts of nitrobenzene and 20 parts of diethylamine and heated to 100 to -110 for 12 hours: the dye of the formula is separated off by filtration, washed with nitrobenzene, then methanol and finally with water and dried in vacuo.

Cotton and regenerated cellulose are made from alkaline hydrosulfite vat colored in very real blue-gray to blue-black tones.

In the above example, ammonia is used instead of diethylamine in the pressure vessel pressed up to a pressure of 6 to 8 atmospheres, a dye is obtained ' with similar characteristics.

Example 6 9.4 parts of aminodibenzanthrone are suspended in 200 parts of dry nitrobenzene and heated to 160 ° to 170 °. The warm solution of 7.6 parts of 2-N-methylanilino-4,6-dichloro-1,3,5-triazine in 50 parts of nitrobenzene is then added, and 2.24 parts of N-dimethylaniline are left in for one hour with thorough stirring slowly drip in. The mixture is stirred for a further 7 hours at 190 to 200 °, then cooled to room temperature, filtered and washed with nitrobenzene. The filter material is then introduced in small portions of 100 parts of boiling monoethanolamine and stirred for 2 hours. Then it is poured onto water and the dye 'of the formula separated by filtration, washed neutral and dried in vacuo at 70 to 80 °. Cotton and regenerated cellitlose are dyed from the hydrosulfite vat in black shades with excellent fastness properties.

In this example, instead of the 7.6 parts of 2-N-methylanilino-4,6-dichloro-1,3,5-triazine an equimolecular amount of the 2-cyclohexylamino-4,6-dichloro-1,3,5-triazine is used, a dye with similarly good fastness properties is obtained in this way.

Example? 9.4 parts of aminodibenzanthrone are mixed with 5.8 parts of 2-dimethylamino-4,6-dichloro-1,3,5-triazine in nitrobenzene, as described in Example 6, reacted and then with monoethanolamine treated and severed.

The dye 'of the formula dyes cotton and regenerated cellulose from the hydrosulfite vat in reddish black tones with excellent fastness properties.

In this example, instead of 5.8 parts, 2-dimethylamino-4,6-dichloro-1,3,5-triazine is used an equimolecular amount of the 2-diethylamino-4,6-dichloro-1,3,5-triazine is obtained a dye 'with similar properties.

Example 8 50.4 parts of 5-amino-1,9-isothiazolanthrone are condensed in 500 parts of nitrobenzene with 74 parts of cyanuric chloride and the product thus obtained is stirred in 1200 parts of nitrobenzene in a pressure vessel. Then dry ammonia gas is injected until the pressure is about 6 atmospheres. The mixture is heated to 140 ° to 150 ° and kept at this temperature for 15 hours. After cooling, it is filtered off, washed with benzene, alcohol and water and dried under vacuum at 90 to 100 °. A dye of the formula is obtained in this way which, in polyvinylchloride-orange dyeings, results in excellent fastness properties. Example 9 23 parts of 5; 5'-l) iamino = 1,1'-dianthrimidecarbazole are heated to 160 ° with 6E30 parts of nitrobenzene with 37 parts of cyanuric chloride for 20 hours. After 4 hours, 1 part of pyridine is added to the reaction mixture. After cooling, the product is filtered off, washed with nitrobenzene, benzene and chloroform and dried at 100 ° under vacuum.

70 parts of the condensation product thus obtained are condensed in 1200 parts of nitrobenzene according to Example 8 with ammonia. A dye of the presumed formula is obtained in this way which; Dyed from alkaline hydrosulphite vat on cotton and regenerated cellulose, gives real rust-brown colorations.

EXAMPLE 10 28.5 parts of bis-p-aminophenylimide of perylenetetracarboxylic acid are heated in 1000 parts of nitrobenzene with 38 parts of cyanuric chloride with the addition of 1 part of dimethylformamide to 190 to 195 ' for 17 hours and to 200 to 205' for 4 hours. After cooling to 50 °, it is filtered off, washed with nitrobenzene and acetone and dried under vacuum at 60 to 70 °.

16 parts of the condensation product thus obtained are reacted in 1000 parts of nitrobenzene according to Example 8 with ammonia. A dye of the formula is obtained in this way which from alkaline hydrosulphite vat on cotton and regenerated cellulose results in real red colors. Red plaques with good fastness properties are obtained in plasticized polyvinyl chloride. EXAMPLE 11 22.9 parts of bis-m-aminophenylimide of perylenetetracaic acid are condensed in 1000 parts of nitrobenzene with 22 parts of cyanuric chloride according to Example 10, paragraph 1.

5 parts of the condensation product thus obtained are heated in 200 parts of nitrobenzene with 4.2 parts of N-methylethanolamine for 7 hours at 150 ° to 160 ° with stirring. After cooling, it is filtered off with suction, washed with nitrobenzene; Alcohol and water and dried under vacuum at 100 °. A dye of the formula is obtained in this way which from alkaline hydrosulfite vat on cotton and regenerated cellulose gives strong red dyeings with good fastness properties.

If one condenses with mono- or diethanolamine instead of N-methylethanolamine, this gives dyes with similar properties.

Example 12 15 parts of aminoacedianthrone are condensed in 250 parts of nitrobenzene with 13 parts of cyanuric chloride according to Example 11 and the product thus obtained is reacted with ammonia in 500 parts of nitrobenzene according to Example 8. A dye of the formula is obtained in this way which, dyed from an alkaline hydrosulphite vat on cotton and regenerated cellulose, gives real brown colorations.

Example 13 A fine suspension of 9.4 parts of aminodibenzanthrone in 180 parts of dry nitrobenzene is heated to 170 ° with thorough stirring. To this is added the warm solution of 7.5 parts of 2-N-cyclohexylamino-4,6-dichloro-1,3,5-triazine in 50 parts of nitrobenzene and, after addition of 0.2 part of pyridine, condenses at 200 bis for 16 hours 210 °. After cooling to room temperature, the precipitated monocondensation product is filtered off and washed with nitrobenzene. The filter material is then added in small portions to 100 parts of aniline and stirred for 10 hours at 160 to 170 °. Then, to remove the excess aniline, steam distillation is carried out and the residue is separated off by filtration and dried at 100 °.

The dye of the formula thus obtained dyes cotton and regenerated cellulose from the alkaline hydrosulfite vat in very real black tones.

Claims (3)

Claims: 1. Process for the preparation of dyes of the anthraquinone and perylenetetracarboxylic diimide series which are free from salt-forming, water-solubilizing groups and which have the general formula correspond, in which A is a group consisting of at least four fused rings, can be linked, m is an integer not exceeding 4, n is an integer not exceeding 5, at least three of the radicals R are hydrogen atoms or optionally substituted alkyl or cycloalkyl radicals and one of the R radicals denote a hydrogen atom, an optionally substituted alkyl or cycloalkyl radical or a benzene radical, where the radicals R1 and R2 or R3 and R4 can also form the radical of a heterocyclic ring system together with the nitrogen atom, characterized in that a viatable amine is used formula wherein A and n have the meaning given, with a compound of the formula where X is a chlorine atom, an amino or optionally substituted alkylamino, cycloalkylamino, phenylamino or dialkylamino group and Y is a chlorine atom, an amino, an optionally substituted alkyl or cycloalkylamino group or a dialkylamino group, condensed in a proportion of approximately 1: 1 and in those of the condensation products obtained which still have chlorine atoms on the triazine radical, the latter is replaced by amino-alkylamino, dialkylamino or phenylamino groups, the starting materials being chosen so that at most one phenylamino group is present in the finished dye molecule. 2. The method according to claim 1, characterized in that that a monoaminodibenzanthrone or a monoaminoisodibenzanthrone is used as an amine that can be connected used. 3. The method according to claim 2, characterized in that the reaction is carried out in the presence of a high-boiling organic solvent at temperatures above 100 °. Documents considered: German Patent No. 390 201; Swiss Patent No. 181720; French Patent No. 1178 224; U.S. Patent No. 2,235,480. When the application was made public, a coloring chart was displayed with explanations.