DE1906834A1 - Derivatives of 1-amino-anthraquinone and process for their preparation - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 659 2

Germany

Derivatives of 1-amino-anthraquinone and processes for their

Manufacturing.

The present invention relates to a process for the preparation of l-amino- ² i-nitro-anthraquinone-2-sulfonic acid, l, 4-diaminoanthrachinone-2-sulfonic acid and I ₃ 4 - = · Di amino 2,3-dicyano- anthraquinone.

The invention therefore relates to a process which is characterized in that 1-amino-anthraquinone-2-sulfonic acid or -2-sulfohalide, after introduction of a protective group on the 1-amino group, nitrated in the 4-position,

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splits off the protective group and optionally the -2-sulfohalide group hydrolyzed to the 2-sulfonic acid group, the 4-nitro group reduced to the amino group and the resulting l ^ -diamino-anthraquinone-S-sulfonic acid in per se known Way by reacting with cyanides, especially aqueous ones Solutions of water-soluble cyanides, in the 1,4-diamino-2,2-dicyan-anthraquinone implements.

If the present reaction is interrupted after the production of the l-amino-4-nitro-anthraquinone-2-sulfonic acid, this gives a valuable water-soluble acid dye, which in particular polyamides, such as wool and nylon, colors in vivid orange tones, and is also the subject of the present invention.

If the reaction leads to 1,4-diamino-anthraquinone-2-sulfonic acid, in this way a valuable intermediate is obtained, which was previously obtained from 1-amino-anthraquinone-2-sulfonic acid by bromination in the 4-position, reaction of the 4-bromine atom with e.g. p-toluenesulfonic acid amide and elimination of the p-Toluenesulfonsäuregruppe was accessible. Compared to this Production method, the production according to the invention has the advantage that one less step is required, and moreover does without the use of the expensive bromine.

The end product of the present process which is 1,4-diamino-2,5-dicyano-anthraquinone or 1,4-diaminoanthraquinone-2,3-dinitrile a valuable dispersion

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dye that dyes polyester fibers in blue tones.

The nitration of the 1-amino-anthraquinone-2-sulfonic acid is carried out with customary nitrating agents, such as nitric acid or nitrating acid. Nitrating acid, ie a mixture of sulfuric and nitric acid, is particularly suitable if the 1-aminoanthraquinone-2-sulfonic acid protected on the 1-amino group is already dissolved in sulfuric acid. In the nitration in sulfuric acid is preferably carried out at temperatures below 0 ⁰ C O or does not substantially exceed ^0C.

In a variant of the present process, the nitration is based on the reaction mixture, which one in the monosulfation of 1-amino-anthraquinone in 2 position. This monosulfation is more common Way done with oleum. This saves the isolation of the 1-amino-2-sulfonic acid or the -2-sulfohalide and also receives higher yields ("one-pot process"),

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Before the nitration of the l-amino-anthraquinone-2-sulfonic acid the 1-amino group is converted into a suitable one blocked group protected. For this purpose, the transfer to a Schiffsche .Base by adding is particularly suitable of formaldehyde or better paraldehyde for the solution of the l-amino-anthraquinone-2-sulfonic acid in concentrated form Sulfuric acid. In addition, higher aldehydes, such as Acetaldehyde, to protect the 1-amino group during nitration, or other protecting groups, e.g. Acyl groups.

In the case of Schiff’s bases, the protective groups are removed by treatment with dilute Mineral acid or alkali solutions in the heat. For example, you only need the acidic solution that is used in Poured out with sulfuric acid and made up in nitric acid Nitration mixture on ice. Arises to warm.

When the nitration mixture is treated with ice and / or water, the sulfochloride group becomes at the same time hydrolyzed to the sulfonic acid group.

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The l-amino-4-nitro-anthraquinone-2-sulfonic acid is conveniently isolated from aqueous solution by salting out. Usually, when the aqueous sulfuric acid solution is neutralized, a sufficiently high salt concentration of, for example, 5 $ is created. If necessary, additional salt, especially sodium salt, is added.

The reduction of l-amino-4-nitro-anthraquinone-2-sulfonic acid l to, 4-diamino-2-sulfonic acid is carried out with: in the Anthrachinonchemie customary reducing agents, especially with an excess of sodium sulfide or sodium hydrosulfide 3- ⁿ aqueous solution at Room tempeaifcur or at elevated temperature.

The further processing of 1,4-diamino-2-sulfonic acid the 2, j5-dinitrile takes place in a manner known per se by heating the aqueous solution in the presence of alkali metal cyanides, such as potassium or sodium cyanide until there is no more water-soluble product. Additional Measures are taken such as blowing air, adding persulfate, alkali vanadate, alkali acetate, alkali perborate, Potassium carbonate, etc.

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages by weight and temperatures are given in degrees Celsius.

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Example 1 ..

98 parts of the sodium salt of 1-aminoanthraquinones 2-sulfonic acid in 600 parts of 100 # iger with stirring Dissolved sulfuric acid and 13 * 5 parts of paraformaldehyde added to the solution cooled to 0 °. The resulting blue solution is warmed to 40, 15 minutes at that temperature further stirred and cooled to -5 ° to -10 °.

At this temperature 46.6 parts of a Mixture of equal parts of sulfuric acid and nitric acid added dropwise within 40 minutes. The reaction mixture is stirred at -5 ° to 0 ° for 1 hour and made up to 1500 parts Poured ice.

The resulting suspension is heated to 70 and, after the addition of 300 parts of sodium chloride, cool left, suctioned off and washed the suction filter with a 10 ^ igen sodium chloride solution until the washing solution is acid-free is. The product is made by dissolving in water at 90 ° and salting out again with 10 $ sodium chloride, based on the weight of the solution, purified. After filtering the on 25 cooled suspension, washing with the above sodium chloride solution and drying, the sodium salt of l-amino-4-nitroanthraquinone-2-sulfonic acid is obtained in good yield

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Example 2.

90 parts of 1-aminoanthraquinone and 78 parts of anhydrous Sodium sulfate is introduced into 290 parts of 100% sulfuric acid within 1 hour with stirring. Included the temperature rises to 35 ° · During 50 minutes leaves 5 parts of 65% oleum are added dropwise at 35 ° to 45 °. then the mixture is heated to 110 ° over the course of one hour and to 120 ° over the course of a further hour. This temperature becomes 2 Held for hours, then, after cooling to 50 °, 100 parts of 80% sulfuric acid are added dropwise. After further cooling to 0 to -5 °, 17 parts of paraformaldehyde are introduced into the reaction mixture and the mixture is stirred for 1 hour. At -5 ° to -10 are 58 parts of a mixture within 40 minutes from equal parts sulfuric acid and nitric acid were added dropwise. At -5 to 0 °, stirring is continued for 1 hour. The reaction mixture is then discharged onto about 3OOO parts of ice the suspension obtained is heated to 70 and the resulting suspension Solution filtered clear and treated with 400 parts of sodium chloride. After cooling down, the crystallized The product is filtered off, washed with saturated sodium chloride solution until the washing solution reacts neutrally and in 1500 parts of a 5 $ aqueous sodium carbonate solution hot solved. This solution is stirred boiling with activated charcoal for 1 hour, filtered until clear and treated with 200 parts of sodium

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Chloride added. After cooling down, the sodium salt becomes the l-Amino-4-nitroanthraquinone-2-sulfonic acid filtered off, with. washed with an oxygenated sodium chloride solution and dried.

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Example 3.

l-Amino ^ -nitro-anthraquinone ^ -sulfonic acid will dissolved in water. The aqueous solution is with a conc. Solution of sodium sulfide added and at room temperature Stirred for 5 hours until the 4-position nitro » group is reduced. Salting out gives 1,4-diaminoanthraquinone-2-sulfonic acid.

5 parts 1,4-diamino-anthraquinone-2-sulfonic acid were added at 60 to a solution of 4 parts of sodium cyanide in 85 parts of water. The solution was slowly rising Heated to 85 ° and kept at this temperature while blowing through air until the water-soluble starting material has disappeared was. 1,4-Diamino-2,3-dicyanoanthraquinone was isolated by suction.

The conversion of 1,4-diamino-2-sulfonic acid to 1,4-diamino-2,5-dicyanoanthraquinone was repeated, wherein but as in Example 1 of French Patent No.1 475 was proceeded.

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Dyeing of wool. .

In a dyebath containing 150 parts of crystallized sodium sulphate, K% concentrated sulfuric acid and 20 parts of l-amino - ^ - nitro-anthraehinone ^ -sulphonic acid in 1000 parts of water, 20 parts of woolen fabric are entered at 60, slowly heated to the boil and 1 Boiled for an hour, the liquor finally reaching a p “value of 2.5. The woolen fabric is then thoroughly rinsed with water and dried. An orange color is obtained.

Coloring of nylon.

In a dyebath which in 1000 parts of water J> 0 parts of 80 # acetic acid and 20 parts of 1-amino-4-nitro-anthraquinone-2-sulfonic acid is entered at room temperature with nylon tricot fabric and at a liquor ratio of 1:40 to Boil heated and cooked for 1 hour. The nylon tricot fabric is then thoroughly rinsed with water. A vivid orange color is obtained.

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Claims (1)

Claims. ( 1. A process for the preparation of derivatives of 1-amino-anthraquinone, characterized in that 1-amino-anthraquinone-2-sulfonic acid or -2-sulfohaiogenide, after introducing a protective group on the 1-amino group, is nitrated in the 4-position , splits off the protective group and optionally hydrolyzes the -2-sulfohalide group to the 2-sulfonic acid group, reduces the 4-nitro group to the amino group, and the resulting 1,4-diamino-anthraquinone-2-sulfonic acid in a manner known per se by reaction with cyanides, in particular aqueous solutions of water-soluble cyanides, converted into 1,4-diamino-2,5-dicyano-anthraquinone. 2. The method according to claim 1, characterized in that that the reaction is carried out at the level of 1,4-diamino-anthraquinone-2-sulfonic acid breaks off. 5. The method according to claim 2, characterized in that that you can get the reaction without isolation the intermediates. 4. The method according to claim 1, characterized in that the reaction is carried out at the stage of the l-amino-4-nitro- 909839/1418 anthraquinone-2-sulfonic acid breaks off. 5. The method according to claim 4, characterized in that the reaction is performed in the ^r-pot process without isolation of the intermediates. 6. The method according to claims 1 to 5, characterized in that one starts from the crude mixture of the monosulfonation of 1-aminoanthraquinone, which contains the free 2-sulfonic acid and / or the 2-> sulphate chloride. . 7. l-Amino-4-nitro-anthraquinone-2-sulfonic acid. 8. Process for dyeing natural or synthetic polyamides with l-amino-4-nitro-anthraquinone-2-sulfonic acid. 909839/141 «