DE656381C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the production of vat dyes Valuable vat dyes are obtained according to the processes of patents 643 083 and 65 i 75o, if, on Pz-Dioxyquinoxaline, Pz-Halogenoxyquinoxaline or Pz-Dihaloquinoxaline, i.e. on compounds of the general formula where R is an aromatic ring system, X and Y are halogen atoms or hydroxyl groups and can be identical or different from one another, organic amino compounds are allowed to act, the starting materials being chosen so that at least one of them can be vetted.

It has now been found that such vat dyes can also be prepared by adding aromatic amines to compounds of the general formula where R is an aromatic ring system, X is a halogen atom, a hydroxyl group or another radical which can be replaced by an arylamino group, Y is a radical different from halogen and hydroxyl and which can be replaced by an arylamino group, the starting materials also being chosen so that at least one of them can be linked.

Examples of compounds of the general formula mentioned are the monoalkyl, -aryl- and -acyl compounds of Pz-Dioxyquinoxalinen, also Pz-Oxymercapto-, -s.eleno- and -amino-, Pz-halogen mercapto-, -seleno- and aminochi: called noxaline. The mercapto, seleno and amino compounds can be attached to the sulfur, selenium or Nitrogen atom also contain organic residues.

Example i A mixture of i part of Pz-oxymercapto-1,2-pyrazinoanthraquinone (her- adjustable by converting P -Chloroxv- i, 2-pyrazinoanthraquinone with f a- kob, oli t; , n w) enj Sodium sulfide and conversion of the sodium mercaptide thus obtained into the free mercaptan by treatment with hydrochloric acid; red-brown powder, which dissolves in alkalis with a red-violet color) and 10 parts of i-amino-3-methylbenzene to boiling for about an hour. In the process, hydrogen sulfide escapes =. When the initially yellow-brown color of the solution does not shift any further to red, the mixture is allowed to cool, the dye is filtered off with suction, washed off with alcohol and dried. It is practically correct in its chemical and coloring properties. iÜit, the dye described in Patent 651,750, Example i, No. 4'd @ P table.

If instead of the Pz-Oxymercaptoi, 2-pyrazinoanthraquinone is used thioether obtainable therefrom by methylation with dimethyl sulfate or the from this sulphoxide which can be produced by oxidation with ammonium persulphate in sulfuric acid, this gives the same dye.

Example 2 A mixture of 10 parts of Pz-oxyaminoi, a-pyrazinoanthraquinone (Can be produced by introducing ammonia into a solution heated to around 150 ° from. Pz-chloroxy-1,2-pyrazinoanthraehinone in nitrobenzene; red-brown powder that dissolves in sulfuric acid with a brown color and forms a yellow sulfate) and -12o parts of i.-amino-2-methylbenzene are heated for so long. to simmer until no ammonia more. escapes. After the red-colored solution has cooled down, the red-yellow solution is separated Needle the resulting dye in the manner described in Example i. The dye is practical in its chemical and coloring properties identical to that in patent .651.75o, example i under. No. 3 of the table Dye.

If you use it instead of the Pz-oxyäminopyrazinoanthraquinone Pz-oxybenzoylaminopyrazinoanthraquinone which can be prepared by benzoylating in nitrobenzene, this gives the same dye. . . Example 3 A mixture of 10 parts of Pz-Oxymethylamino-i, 2-pyrazinoanthraquinone. (can be produced in the same way as in the example 2 starting material used when methylamine is used instead of ammonia; yellow-red needles,. which are soluble in sulfuric acid with a yellow-red color and a yellow sulfate), iö parts i-amino-3-methylbenzene and. 100 parts nitrobenzene it is heated to the boil for 1 to 2 hours and worked up after cooling. The dye thus obtained is identical to that described in Example i. . Example 4 10 parts of Pz-oxyethoxy, 2-pyrazinoanthraquinone (e.g. -available by heating Pz-Chloroxyi, 2-pyrazinoanthraquinone with alcoholic potassium hydroxide solution; yellow needles from ° @ E sessi.g) with ten times the amount of aniline } 'for about i hour to boil and works = @ täs mixture on the in the examples i to 3 described manner. The dye thus obtained in the form of red-brown needles agrees with the dye which can be prepared according to example i, paragraph i of the patent 65 = -75o match.

Example If one uses in Example 4 instead of the Pz-Oxyäthoxy-z, 2-pyrazinoanthraquinones the same amount of the reaction compound from Pz-dichloro-i, 2-pyrazinoanthraquinone with excess sodium sulphide in boiling alcohol (violet-black crystalline powder, mostly in dilute aqueous alkalis, in aqueous sodium sulfide solution prak-: t @ sch completely soluble, according to properties and. Analysis of the Pz-Dimercapto-i, 2-pyrazinoanthraquinone, mixed with smaller amounts, of the corresponding tetrasulfide), so 'one obtains --a bluish-tinged vat dye.

- A very similar dye is obtained from the reaction compound that is obtained when Pz-dichloro, 2-pyrazinoanthraquinone suspended in nitrobenzene is treated with ammonia until a processed sample is practically chlorine-free. On the other hand, if one proceeds in the same way but at a lower temperature, e.g. B. at iio to 120 °, produced, strongly chlorine-containing reaction compound of Pz-dichloro-i, 2-pyrazinoanthraquinone with ammonia, one obtains a much more dyed dye. _. - Example 6 A mixture of 10 parts of the methyl sulfoxide which can be prepared from Pz-oxymercapto-i, 2-pyrazinoanthraquinineQri in the manner indicated in the second paragraph of Example 1 is heated,. Boil 20 parts of r-amino-5-benzoylaminoanthraquinone and 100 parts of diphenyloxide until no more methyl mercaptan escapes, which takes 1 to 2 hours. The dye separated in the usual way corresponds to that described in patent 651750 under No. 2g of the list of example i. Example 7 A solution of 5 parts of the pyridinium compound obtainable by gently heating Pz-chloroxy-1,2-pyrazinoanthraquinone with pyridine, probably of the following structure: (pale yellow, water-soluble needles) in 50 parts of nitrobenzene are heated to boiling with 2 parts of z-amino-3-methylbenzene for about 1 hour. After working up in the usual manner, a dye is obtained which corresponds to the dye described in example r.

The implementation succeeds even without the supply of heat, only then it works correspondingly slower.

Claims (1)

PATENT CLAIM: Process for the preparation of vat dyes, characterized in that aromatic amines are based on compounds of the general formula wherein R is an aromatic ring system, X is a halogen atom, a hydroxyl group or another radical which can be replaced by an arylamino group, Y is a radical different from halogen and hydroxyl, which can be replaced by an arylamino group, the starting materials being chosen so that at least one can be linked by them.