DEC0005704MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration day : April 18, 1952 - docked on May 30, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 22b GROUP S ₁₇

C 5704 IVb / 22b

Dr. Emil Schwamberger, Frankfurt / M.- Fechenheim

has been named as the inventor

Cassella Farbwerke Mainkur Aktiengesellschaft, Frankfurt / M.- Fechenheim

Process for the production of vat dyes

In the German patent specification 589 639 is a Process for the production of vat dyes described, consisting therein. that he. Halogen compounds of the acedianthrone of the formula

X O

X O

(in which one or more X is halogen) with compounds which have at least one nitrogen contain bound exchangeable hydrogen atom. As such "anthrimide components" In particular, amino compounds, the anthraquinone series, come into consideration.

The German patent 830 690 describes the treatment of the reaction products of Tetrahalogenacedi anthrones with aminoanthraquinones in the presence of acidic surfactants.

A similar procedure is also used in the German, Patent 844,779. described, whereby Halogenaoedianthrone with amines, the Phthaloylacridon, - or phthaloylthioxanthone series are implemented.

In most cases, the reaction products are haloacedianthrones, with aminoanthraquinones Dyes of, muted red

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brown, yellow-brown to black-brown nuances; without exception, this is the case when using I-aminoanthraquinone or T-amino-5-benzoylaminoanthraehinön as anthrimide components. Also the im. last paragraph of example 6 of the The dye described in patent specification 589 639 shows a reddish-gray shade.

It has now surprisingly been found that ■ that a special group of halogen compounds of the acedianthrone series when reacted with the above-mentioned anthrimide components brown to reddish gray; but pure gray to very bluish gray dyes, i.e. the In terms of nuances, they fall outside the framework of the previously known anthrimides of the Acedianthron series.

This fiction according to the starting material

Haiogenadeianthrones used can be derived from the brominated ones obtainable according to patent 915,604 Derived from dianthronethylene of unknown constitution can be obtained by treating these blue Bodies, ß. boils with high-boiling solvents or treated with acidic condensation agents.

The Halogenaeedianthrones used must have at least one bromine atom in one , 25 (as yet unknown) preferred position, whereby, the strong shift in nuances the anthrimide is effected.

Instead of the amino compounds of the "Anthra, -. Quinone series are also other 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 ρ-toluenesulfamide. .

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

Their differences compared to the known condensation products from haloacedianthrones and amino compounds show the following comparisons:

One obtains from the example according to patent 915,604 i, para. 2, representable halogenacedianthrone: which contains 3 bromine atoms according to the analysis Implementation with 1-aminoanthraquinone according to the present Invention of a strongly bluish gray anthrimide, while one can be made by bromination from Acedianthron obtained in the usual way, Tribromaeedianthron a strongly reddish tinted, muted brown. From that available according to Patent 915604, Example 2, last paragraph Halogenacedianthrone, which is derived from 2, 2'-Dichlordianthronäthylen and 2 atoms of chlorine and ι atom contains bromine, and 1-aminoanthraquinone, you get a neutral gray, while the anthrimide, that one. according to patent 589639 from dem.ge; Patent 550712 for the same dichlorodianthrone ethylene obtainable, dichloroacedianthrone is obtained, turns reddish brown.

To achieve shades of gray that are as bluish as possible, it is advisable to use Halogenacedianthron and to use aminoanthraquinone in a molar ratio of 1: 3 ;. At; decreased amount of aminoanthraquinone the nuances of the anthrimides obtained shift towards reddish gray and brown, whereby you can get dyes with valuable black-brown, and similar deep tones. By using substituted aminoanthraquinones, the gray tones can be varied further, e.g. B. after the green side when using i-amino-4-benzoylaminO'änthraquinone. The anthrimides obtainable by the above process can be found in known way (German Patent 611 512) by treatment with condensing agents into the corresponding compounds of the carbazole series, using very strong, receives real vat dyes, some of which are very peculiar,; purple-gray to purple-brown tones to dye.

example 1

In 700 parts of nitrobenzene, 21 parts of the brown dye, which is obtained according to Patent 915 604, Example 1, Paragraph 2, and which contains 3 atoms of bromine, with 37 parts of 1-aminoanthraquinone, 15 parts of soda, 3 parts of copper acetate and 1 Part of copper oxide heated ^{to 205 to 208 101 for about 24 hours.} The melt is suctioned off, the product obtained is washed with alcohol and boiled with dilute sulfuric acid to remove the copper.

A black dye powder is obtained which dissolves purple-red in concentrated sulfuric acid. It dyes the vegetable fibers from the reddish-brown vat in shades of gray with a strong bluish cast and good fastness properties and, after being processed in the usual way on fine dough, produces level, blue-gray prints.

• By treatment with a sodium chloride-aluminum chloride melt with the addition of gaseous sulphurous acid at 80 °, the product turns into a real, reddish-gray vat dye over.

Example 2

13 parts of the starting material used in Example 1 are, together in 700 parts of nitrobenzene, with 21 parts of i-amino-5-benzoylaminoanthraquinone, 12 parts of soda, 2 parts of copper acetate and ι part of copper oxide for about 24 hours 205 to 208 ° and worked up as in Example 1. .

A dye is obtained which from a reddish-brown vat is strong, somewhat bluish: gray tones with good ones Dyes fastness properties. The solution color in. , concentrated sulfuric acid is reddish purple.

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

If you replace the i-amino-5-benzoylaminoanthraquinone in the above example: by the i-amino> 4-benzoyla.minoa, nthrachino'n, so> you get. out

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the nitrobenzene melt has a greenish-gray color Nuance.

Example 3

19 parts of the aedianthrone dye, den. according to patent 915 604, example 2, last section, and which, according to the analysis, contains 1 atom of bromine and 2 atoms of chlorine, 700 parts of naphthalene, together with 30 parts of i-aminoanthraquinone, are 15 parts. Soda, 3 parts of copper acetate and 2 parts of copper 24 hour, stirred at 205-230 ⁰ and the melt, after dilution with o-dichlorobenzene aspirated.

A black dye powder is obtained which dissolves in concentrated sulfuric acid in a cloudy purple color and can shrink with red-brown color. It dyes and prints the vegetable fiber in, real, neutral grays.

Example 4

10 parts of the starting material used in Example 3 be, in 700 parts of nitrobenzene together with 30 parts of i-Amino'-5-benzoylaminoa, nthra, -quinone, 10 parts, soda, 2 parts, copper acetate and ι part copper oxide for about 24 hours to 205 Heated 208 ° and worked up as in Example 1. A dye is obtained that contains cotton and related fibers from red-brown vat dyes in, olive-gray, real tones.

A very similar dye can be found in the Use of i-amino-4-benzoylaminoanthraquinone obtained.

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

If, in paragraph 1 of this example, the dichlocbromacedianthrone is replaced by the acedianthrone derivative obtainable in an analogous manner from ß, ß, ß ', / r-tetraehlordianthrone derivative, the reaction with i-amino-5-benzoylaminoanthraquinone gives a vat dye, the neutral one , very strong gray tones.

Example 5

25 parts of the starting material used in Example 1, p-3oTeile Toluolsulfaniid, 15 parts of sodium carbonate and 3 parts of copper acetate and copper are ι part in 600 parts of nitrobenzene, approximately heated 24 hours at 200-205 ^0th The isolated in a conventional manner Reaktionsiprodukt illustrating a Toluolsulfaminoverbindung is saponified by treatment with warm yo ° concentrated sulfuric acid to Aminoverbiindung which colors a violettstidhiges Dunkieilbraun from red-brown vat.

If aniline is used instead of toluenesulfamide (although it is advisable not to use nitrobenzene, but, works in an excess of aniline), SO 'you get a blue-gray body, which is very difficult to dissolve in the vat,

Claims (1)

PATENT CLAIM: Process for the preparation of vat dyes, characterized in that bromine-containing Dyes of the acedianthrone series, which are brominated from those obtainable according to patent 915,604 Derived from dianthronethylene by heating in solvents or treatment with acidic condensation agents, reacted with compounds that contain at least one exchangeable, to, nitrogen contain bound hydrogen atom, Referred publications:
German patent specification No. 589 639.