DE534933C - Process for the preparation of Kuepen dyes - Google Patents

Description

Method for the representation of pebble color substances According to patent 5z8 335 vat dyes of the benzanthrone pyrazole anthrone series are obtained by negative 'Substituted benzanthrone pyrazole anthrones with nitrogen-containing compounds, the contain at least one exchangeable hydrogen atom bound to nitrogen, implemented. The starting products for this process are primarily used the halogen and nitro derivatives of Benzanthronpyrazolanthrons into consideration, either by synthetic construction or according to the procedures of patents 492,274 and 492 275 can be obtained.

It has now been found that vat dyes are particularly valuable Properties can be obtained by following the procedures of patents 516,313 and 531 red halobenzanthrone pyrazole anthrones are reacted with compounds, the at least one replaceable one bound to nitrogen, oxygen or sulfur Contain hydrogen or metal atom.

The reaction is expediently carried out in high-boiling diluents in Carried out in the presence of acid-binding agents and catalysts. The yields are mostly approximately quantitative, the reaction products are almost always in obtained crystalline form. The procedure can be varied within the broadest limits will.

You can optionally during the reaction or afterwards substituting, z. B. alkylating, acylating, etc., or condensing agents act leave, whereby new dyes of mostly different shades also arise.

The dyes obtained can be used for the customary methods their leuco compounds, e.g. B. represent their leucoesters.

The new dyes available in this way differ of the corresponding compounds obtained by the method of patent 518,335. For example, shows that shown in Example r of the present invention Condensation product of dibromobenzanthrone pyrazole anthrone and 2 moles of z-aminoanthraquinone, which, according to the gross formula, could be identical to the product of example 4 of the patent 518 335. in sulfuric acid a green solution color and yields from dark green Küpe neutral gray dyeings on cotton, while the comparative product according to patent 518 335 dissolves in sulfuric acid with a gray-violet color and turns reddish blue-gray from the blue vat Dye supplies.

Example s o 62 parts of that obtainable according to Example 2 of patent 516313 Dibromobenzanthronpyrazolanthrons are in 10000 parts of naphthalene after the addition of 50 parts of sodium acetate, 12 parts of copper oxide and 46 parts of i-aminoanthraquinone Cooked with stirring until a sample taken is practically bromine-free. Then allowed to cool, diluted with a low-melting diluent, e.g. B. with 100 parts of monochlorobenzene, and sucks off the reaction product. One can also distill off the suspending agent, if necessary under reduced pressure, or with steam or with steam and under reduced pressure. . The received Dye, a crystalline blue-black powder, dissolves in concentrated sulfuric acid with green color and delivers strong gray on cotton from a dark green vat * Dyeings of excellent fastness, in particular excellent fastness to lye boiling.

If the equivalent amount is used instead of i-aminoanthraquinone i-Amino-q.-benzoylaminoanthraquinone, a greenish gray color is obtained Reaction product; the same dye is obtained by condensation of the Brombenzanthronpyrazolanthrons with i # 4. diaminoanthraquinone mentioned at the outset and subsequent benzoylation.

2-Aminoanthxaquinone ', n position of i-aminoanthraquinone provides one bluish gray coloring dye.

By condensation of that obtainable according to example i of patent 5311o2 Brombenzanthronpyrazolanthrons with i-Anünoanthraquinone give a similar one Condensation product. If 2 moles of i-aminoanthraquinone-2-aldehyde are used a greenish gray coloring dye.

Instead of naphthalene, other suspending agents, e.g. B. Use nitrobenzene. By subsequent melting with alcoholic potash or by treating with aluminum chloride (possibly with the addition of common salt and introducing an oxidizing gas, such as oxygen, air) is obtained from these reaction products the corresponding carbazole derivatives, which have similar coloring properties, however usually have a slightly different shade. Example 2 6.2 parts of dibromobenzanthrone pyrazolanthrone (Prepared from Benzanthronpyrazolanthron by bromination in chlorosulfonic acid at 8o to go ° and in the presence of manganese as a catalyst according to the method of Patent 516,313 are zoo parts naphthalene with 2.3 parts i-aminoanthraquinone and 5 parts of copper acetate cooked with stirring until the i-aminoanthraquinone is used up. Then allowed to cool) and work as described in Example i on. The obtained monobromo-a-anthraquinonylaminobenzanthronpyrazolanthron provides is a blue-black powder, dissolves green and in concentrated sulfuric acid delivers strong blue-gray to blue-black very real colors from the blue-green vat. The bromine atom present in the reaction product can still by the methods of the present Procedure can be exchanged for other remnants.

The condensation product of dibromobenzanthrone pyrazolanthrone (obtained according to patent 5311o2, example i) with 2 moles of Bz-3 # 5-dichloro-q.-aminoanthraquinone-2 - i-benzakridon turns green-gray.

Monobromobenzanthrone pyrazole anthrone (prepared according to patent 516 313 by brominating benzanthrone pyrazole anthrone with 1 atom of bromine in chlorosulfonic acid with iodine as a catalyst) gives a strong gray color when condensed with i-aminoanthraquinone. EXAMPLE 3 30 parts of the bromobenzanthrone pyrazolanthrone obtainable according to the examples of patent 516313 are dissolved in 100 parts of nitrobenz oil after the addition of 50 parts of calc. Soda, 7 parts of copper oxide and 3o parts of benzamide are boiled with stirring until the reaction product is practically bromine-free. Then you work in the usual way. on. The reaction product obtained, a dark blue-green powder, dissolves in concentrated sulfuric acid with an olive-green color, cools blue and provides very real green-blue colorations on the vegetable fibers.

Substituted benzamides or the react similarly to benzamide Amides of naphtha. Anthraquinone carboxylic acids or higher molecular acid amides.

With p-toluenesulfamide or phthalimide potassium one obtains condensation products, when treated with acids analogously to the benzoylamino derivatives in the free amino compounds pass over. Example q. 5.5 parts of monobromobenzanthrone pyrazolanthrone (shown according to patent 531: 102) are in a suspension of 50 parts phenol and 20 parts Potash entered at roo to i2o °, slowly heated to 18o ° and so long held until the reaction has ended. Then let it cool down the excess phenol is distilled off with steam and the reaction product is sucked off away. It is a blue powder that dissolves in concentrated sulfuric acid blue color and delivers real navy blue colors from the blue vat. Example 5 6z parts of dibromobenzanthrone pyrazolanthrone are added in 2.5o parts of nitrobenzene Addition of 50 parts of sodium acetate, = 0 parts of copper oxide and 82 parts of 4-amino-Bz-3 - 5-dichloroanthraquinone-2 - I-benzacridone (obtainable from i-amino-4-bromoanthraquinone by condensation with 3 "5-dichloro-2-amino-I-benzoic acid and ring closure to the acridone derivative) Boiled with stirring until the reaction product is practically bromine-free. Then you let it cool down and work up in the usual way. That in crystalline Form and excellent yield obtained condensation product dissolves in concentrated Sulfuric acid with brownish-purple color and delivers on the vegetable fiber blue vat green-gray, very real colorations.

In an analogous manner one obtains 7 #, 'from tetrabromobenzanthrone pyrazole anthrone an olive coloring reaction product.

Instead of dibromobenzanthrone pyrazole = anthrone, one can also use the Use the equivalent amount of the dichloro derivative.

Claims (1)

PATENT CLAIM: Further development of the process for the preparation of vat dyes according to patent 518 335, characterized in that the halobenzanthrone pyrazole anthrones obtainable according to the process of patents 516 313 and 531 are reacted with compounds which have at least one replaceable bonded to nitrogen, oxygen or sulfur Contain hydrogen or metal atom, and optionally can act simultaneously or subsequently substituting or condensing agents.