DE566708C - Process for the production of Kuepen dyes of the anthraquinone series - Google Patents

Description

Process for the production of vat dyes of the anthraquinone series It is known that aluminum chloride gives rise to very different condensations can, if you do it with or without organic solvents on .gewisse derivatives of the anthraquinone can act.

So one already has condensation products from a- and p-aminoanthraquinones obtain. It is also known that the u., C '-Diantlirachinonylamin in 1,: 2, 7, B-DiphtIialoyl-Carbazole condenses through the action of aluminum chloride alone or in the presence of Pvridin.

On the other hand, it is known that aluminum chloride is deacvating Has properties and that its effect on certain o-acylated derivatives themselves may be accompanied by migration of the aroyl radical in the nucleus.

It is also known that certain α, α-dibenzo3-Iamino-di @ anthraquinoriy lamine can undergo a ring closure to carbazoles through the action of concentrated Sulfuric acid or chlorosulfonic acid. This: method has no general application, and certain i, i'-dibenzoylamino-dianthrimides are not subject to this conversion or experience other adverse reactions.

It has now been found that these substances and, in general, mono- or Paly acylarnino- (li- lind trianthrimi.de easily converted into new dyes can be made by treating them with a metal chloride, for example aluminum chloride or ferric chloride, advantageously in the presence of a solvent such as Nitrobenzene, and heated at the lowest possible temperature.

It is already known (patent specification -i51 -195, Example 2), d.-Benzoylamino-i, Suspend i'-dianthraquinonylamine in pyridine and melt it with aluminum chloride. This gives a dye which dissolves brownish-red in sulfuric acid and cotton turns brown.

Examples i and 9 given below give in contrast in addition cherry-red sulfuric acid solutions, and cotton is dyed brown-red. While according to this patent specification aromatic bases are used as solvents, the present invention does not concern the use of aromatic bases as solvents. That other organic solvents are more non-basic Allowing nature to be used in aluminum smelting contradicts the information given above Reference.

The desired transformation according to the invention can be seen as moderated Reaction conditions achieve that the deacylating effect of the metal chloride can be completely avoided in certain cases can. on the other hand this conversion can be conducted so that at the same time the partial or Complete deacylation of the acylamino groups is achieved without secondary Reactions occur as a result of the presence of free amino groups, which one does not could foresee. In the latter case one does not only get those in the French Patent 67o 7o2 described dyes, but also new dyes, their production could not be achieved so far by the ring closure mentioned above and which consists in using concentrated sulfuric acid or chlorosulfonic acid can act on certain a, a-benzoylaminated dianthraquinonylamines. Likewise can one by a more energetic action of the aluminum chloride during the condensation Obtained monoacyl diamino dyes.

The partially or completely deacylated products so obtained can serve as an intermediate in the manufacture of other dyes.

Example i In a mixture of 5 parts of aluminum chloride and 10 parts Nitrobenzene is introduced i part .I-Benzoylamino-i, i'-dianthrimide. One heats up for about an hour to sun to 60 ° until samples become more concentrated Dissolve the sulfuric acid in cherry red and the solution color no longer changes.

After completion, the nitrobenzene is removed by steam distillation removed. The dye is freed from the aluminum salts - and if necessary through cleaned with a suitable solvent.

'It dyes cotton in brown-red shades of very good fastness. The vat is brown-orange. Your sulfuric acid solution is cherry red.

The same dye is obtained if the aluminum chloride in the example is used replaced by the same weight of anhydrous ferric chloride.

EXAMPLES A mixture of 5 parts of aluminum chloride is added and io parts nitrobenzene i part d., 8'-dibenzoylamino-i. i ', dianthrimide (the example by condensation of i-amino-4-benzoylamino-anthraquinone with i-chloro-8-benzoylamino-anthraquinone is preserved).

The mixture is heated, as in Example i, to 55 to 60 °; further treatment is the same as in example i.

The brown-red dye crystallizes in lamellae. The solution in Sulfuric acid is red-orange. He dyes cotton in a brown vat. The received The dyeings are red-brown and have very good fastness.

Example 3 A mixture of i part q., 5'-Dibenzoyldiamino-i, i '= dianthrimide, 5 parts of aluminum chloride and 10 parts of nitrobenzene are kept at 100 ° for 21/2 Heated for hours.

The subsequent treatment is the same as in Example i. After recrystallization from nitrobenzene, a red-brown dye of very good fastness is obtained. It is identical to the dye of the above-mentioned French patent 670 702, example i, namely the carbazole of 5-amino-4'-benzoylamino-i, i'-dianthrimide.

Example q.

If in Example 3 the q., 5 '.- Dibenzovidiamino-i, i'-dianthrirnid replaced by the 5, 5'-dibenzoyldiamino-i, i'-dianthrimide and the mixture Heated i2o ° for i1 / 2 to 2 hours, irian takes on a brownish reddish color of very good authenticity. According to the constitution, it is probably carbazole des 5-amino-5'-benzoviaminoi, i'-dianthi # imi.ds.

Benzoylation turns it into an orange dye with very good fastness convicted.

Using, for example as described in Example i, the 5, 8'-Dibenzoylamino-i, i 'dianthrimid, but keeping this temperature to 8o to 9o ° while i to il /, hours.

Nachbenzoylation of the brownish-red dye gives a brown powder that turns bluish green in sulfuric acid after cleaning with hypochlorite dissolves and -on cotton a yellow-orange with excellent fastness properties colors.

Example 6 The procedure is as in the previous example the 5-benzoyiaminoi, i'-dianthrimide. A vat dye, which is yellow-orange, is obtained is of very good authenticity. The sulfuric acid solution is blue, the artificial one Light turns red. Example ? By treating the 4th, 8-dibeiizoylamino-i, i'-dianthrimids according to example i at 80 ° for i hour one receives one Vat dye, which is brown-olive, of very good fastness. The sulfuric acid solution is brownish red. Your vat is brown-orange. Example through ring closure des 4 ', 4'-dibenzovlamino-i', i ", i, 5-trianthrimids at 80 to 100 ° by the method Example i gives a reddish brown dye of very good fastness.

The trianthrimide, which serves as the starting material, can be obtained by condensation of a molecule of i, 5-dichloroanthraquinone with 2 moles of i-amino-4-benzoylamino-anthraquinone under the usual conditions. Example 9 In a melted blend of 3.4. Parts of sodium chloride and 16.6 parts of aluminum chloride -, 3 parts -.- Benzoylamino-i, i'-dianthraquinone vinylamine are introduced at a temperature of 1000 C. The temperature of 100 ° is maintained for about hours until the conversion is complete. It is then poured onto ice and the dye formed is isolated in the usual way and purified either by vaporizing or by crystallization from nitrobenzene.

The dye obtained is identical to that according to Example i.

Claims (1)

PATENT CLAIM: Process for the production of vat dyes and Intermediates of the anthraquinone series, consisting in that one mono- or poly-acylamino-di- and trianthrimide with a metal chloride (aluminum chloride, ferric chloride, etc.), advantageously in the presence of a suitable non-basic solvent such as for example Nitrobenzene, heated.