DE955176C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the production of vat dyes In the German patent specification 589 639 a process for the production of vat dyes is described, which consists in that halogen compounds of the acedianthrone of the formula (in which one or more X is halogen) with compounds which contain at least one exchangeable hydrogen atom bonded to nitrogen. Amino compounds of the anthraquinone series are particularly suitable as such “anthrimide components”.

The German patent 83o 69o describes the treatment of the reaction products of tetrahaloacedianthrones with aminoanthraquinones in the presence of acidic condensing agents.

A similar process. is also in the German patent 84q.779 described, whereby halogenaoedianthrones with amines of the Phthaloylacridon- or phthaloylthioxanthone series are not used.

In most cases the reaction products are haloacedianthrones with aminoanthraquinones dyes from. muted red-brown, yellow-brown to black-brown nuances; this is the case without exception when using i-Aminoanthraquinone or i-Amino-5-benzoylaminoanthraquinone as anthrimide components. Also the one in the last paragraph of. Example 6 of patent 589,639 described The dye shows a reddish, gray shade.

It has now surprisingly been found that a special group of halogen compounds of the acedianthrone series in the implementation with the above-mentioned Anthrimidkomponen.ten. not brown to reddish gray, but racing gray to strong bluishichiggrau.e dyes, which are therefore out of the scope of the previous avowed anthrimids fall out of the acedianthrone row.

These haloacedianthrones used as starting material according to the invention can be obtained from the brominated derivatives of the Obtain dianthronethylenes of unknown constitution by treating these blue bodies. B. boils with high-boiling solvents or with acidic condensing agents treated.

The haloacedianthrones used must be at least contain a bromine atom in a - r (as yet unknown) preferred position, whereby the strong shift in nuances of the anthrimides is caused.

In place of the amino compounds of the anthraquinone series there are also others Compounds that have an exchangeable hydrogen atom bonded to nitrogen have, can be used for implementation, e.g. B. amines of the benzene series (aniline) or p-toluenesulfaxnide.

The reaction products obtained are either themselves vat dyes or can serve as a starting material for such. As dyes, they have good fastness properties and are particularly suitable for stuff printing.

Your differences from the. Known condensation products from haloeedianthrones and amino compounds show the following comparisons: One obtains from that which can be represented according to patent 915 604, example i, paragraph 2. Halogenacedianthrone, which contains 3 bromine atoms according to the analysis, by reaction with i-aminoanthraquinori according to the present invention, a strongly bluish gray anthrimide, while one is off. a tribromacedianthrone obtainable in the usual way by brominating acedianthrone is given a strong red-tinged, muted brown. A neutral gray is obtained from the halogenacedianthrone obtainable according to patent 9156o4, example 2, last section, which is derived from 2,2'-dichlorodianthrone-ethylene and contains 2 atoms of chlorine and 1 atom of bromine, and i-Aminoan.thraquinone, while the Anthrimide, obtained according to patent 589 639 from the dichloroacedianthrone obtainable according to patent 550 7i2 from the same: dichlorodianthrone ethylene, red-brown. colors.

To achieve shades of gray that are as bluish as possible. is it appropriate Halogenacedianthrone and aminoanthraquinone Lm molar ratio 1: 3 to be used. At reduced Aminoanthrachi @ non amount shift the nuances of the obtained Anthrimide towards reddish gray and brown, whereby one dyes with valuable blackish brown. and similar deep tones. By using substituted aminoanthraquinones the gray tones can be varied further, e.g. B. on the green side when using from i Amino-4-benzoy laminoanthraquinone. The ones obtainable by the above procedure AnthrimIde let @gidh -in -a known way (German patent specification 61i 512) by treatment with condensing agents into the corresponding compounds transfer the carbazole series, whereby you get very strong, real vats, dyes, which sometimes color very peculiar, violet-gray to violet-brown tones. example i In 70o parts of nitrobenzene are 21 parts of the brown dye, which is after Patent 91,5604, example i, para. 2, wins and contains 3 atoms of bromine, with 37 Parts i-aminoanthraquinone, 15 parts. Soda, 3 parts of copper acetate and 1 part of copper oxide Heated to 2o5 to 2o8 '°' for about 24 hours. The melt is sucked off, the one obtained Product washed with alcohol. and to remove the copper with dilute sulfuric acid boiled out.

One receives a. black dye powder that is concentrated in Sulfuric acid dissolves purple. It colors the vegetable fiber from the reddish-brown vat in strong blue-tinged gray tones with good ones. Authenticity properties and provides, after it has been processed in the usual way on fine dough, level, blue-gray Prints.

By treating with a sodium chloride-aluminum chloride melt with the addition of gaseous sulphurous acid at 80 °, the product becomes one real, reddish-gray vat dye over. Example 2 13 parts of the example i Starting material used are in 7oo parts of nitrobenzene together with 21 Teildn.i-Amino-5-benzoylaminoanthraquinone, 12 parts of soda, 2 parts of copper acetate and 1 part of copper oxide for about 24 hours Stirred from 2o5 to 2o8 ° 'and worked up as in Example i.

One obtains a dye that is strong from a reddish-brown vat, something dyes bluish gray tones with good fastness properties. The solution paint in concentrated Sulfuric acid is red-violet.

If this product is stirred in chlorosulfonic acid for a few hours at 50 to 55 °, a dye with a reddish, dark brown shade is obtained from it.

If, in the above example, the i-amino-5-benzoylaminoanthraquinone is replaced by the i-amino-4-benzoylaminoanthraehinone, one obtains. the end the Nitrobenzene melt a dye with a greenish-gray shade.

EXAMPLE 3 19 parts of the acedianthrone dye, which is obtained according to patent 915 604, Example 2, last section, and which, according to analysis, contains 1 atom of bromine and 2 atoms of chlorine, are naphthalene in 700 parts together with 30 parts of i-aminoanthraquinone, 15 parts Soda, 3 parts of copper acetate and 2 parts of copper oxide are stirred for 24 hours at 2o5 to 23o ° and the melt is filtered off with suction after dilution with o-dichloro, lorbienzol.

Eiri black dye powder is obtained, which is concentrated in Sulfuric acid dissolves turbid-violet and can be evaporated with a red-brown color. It dyes and prints the vegetable fiber in real, neutral gray tones. example 4 10 parts of the starting material used in Example 3 are divided into 700 parts Nitrobenzene together with 3o parts of i-amino-5-benzoylaminoanthraquinone., Io parts Soda, 2 parts copper acetate and 1 part copper oxide for about 24 hours at 2o5 to 2o8 ° heated and worked up as in Example i. A dye, cotton, is obtained and related fibers from reddish-brown vat dyes olive-gray, real tones.

A very similar dye can be found when using i-amino-4-benzoylaminoanthraquinone obtain.

Both dyes can be converted into new products by exposure to chlorosulfonic acid at 50 to 55 ° C, which dye reddish-black-brown tones on cotton from the vat.

Replacing the dichlorobromacedianthrone in paragraph i of this example by that obtainable in an analogous manner from ß, ß, ß ', ß'-Tetrachlordianthronäthylen Acedianthrone derivative, is obtained in the reaction with i-amino-5-benzoylaminoanthraquinone a vat dye that produces neutral, very strong gray tones.

Example 5 In 600 parts are nitrobenzene. 25 parts of the example i used starting material, 3o parts p-Toluals.ulfamid, 15 parts soda and 3 Parts of copper acetate and 1 part of copper oxide heated to 20 ° C for about 24 hours at the zoo. The reaction product isolated in the usual way, which is a toluenesulfamino compound is, by treatment with 7o ° warm concentrated sulfuric acid to Amino compound saponified, which from the red-brown vat a violet-tinged Dunlml # brew # n colors.

If aniline is used instead of toluenesulfamide (whereby one, expediently does not work in nitrobenzene, but in an excess of aniline), so receives one has a blue-gray body that is very difficult to dissolve in the vat.

Claims (1)

PATENT CLAIM: Process for the production of vat dyes, thereby marked that one. bromine-containing dyes of the acedianthrone series, which are made up of the brominated derivatives of the dianthronethylenes obtainable according to patent 915604 by heating in solvents or treatment with acidic condensing agents are obtained, with compounds that implement at least one. exchangeable, contain hydrogen atom bonded to nitrogen. Considered publications: German patent specification No. 589 639.