DE91150C - METHOD OF INTRODUCING AMINE RESIDUES INTO OXYANTHRACHINONE - Google Patents

Description

IMPERIAL

PATENTAM

I.

In the patent specification No. 86150 a green dye ("quinizarin green") is described which formed by condensation of 1 mol. quinizarine and 2 mol. p-toluidine. In the patent specification No. 91149 it was also shown that this "chinizarin green" is much smoother, when the leuco derivative of quinizarin, known in the literature as quinizarine (Leucoquinizarin II of patent specification No. 89027) heated with p-toluidine and boric acid will.

Further investigations into this last process have now shown that the Procefs this takes place in two phases, in that first a leuco derivative of quinizarin green is created, which very easily changes into the chinizarin green itself through oxidation. This oxidation already takes place through the action of atmospheric oxygen in the course of the melt itself, so that one can use the method of Patent specification No. 91149 only with access to the air Chinizarin green receives. The information given there must therefore be specified respectively to expand that, for the purpose of representing chinizarin green, the melt upon access must be carried out in the air.

But you can too. add any suitable oxidizing agent directly to the melt, and it has proven to be very expedient to simply choose quinizarine as such, that is, to fuse a mixture of quinizarine and quinizarine with p-toluidine and boric acid. The formation of the quinizarin green then proceeds extremely easily and smoothly, and the experiment has further shown that the quantity of quinizarin in relation to that of the quinizarin hydride can be measured very high without the smooth course of the reaction being impaired by under these conditions the quinizarin itself turns smoothly into quinizarin green. The process has to be explained in such a way that the leucoquinizarin green initially formed from the quinizarin hydride is oxidized by the quinizarin to quinizarin green, the quinizarin itself being reduced to its leuco compound, which then reacts further with p-toluidine to form a new amount of leucoquinizarin green. This process is repeated as long as there is still uncontaminated Chinizarin. For the practical implementation of the method z. B. 10 kg quinizarine, 20 kg quinizarine, 300 kg p-toluidine and 20 kg boric acid ^{heated to 110 to 130 0} for a few hours with Luftabschlufs until the quinizarine has disappeared. That which is then still present in the melt

Claims (2)

Leukochinizarin green is transformed into the chinizarin green itself by being admitted heated in the air for some time. The condensation can also be brought about with a much smaller amount of p-toluidine by using an inert solvent, such as alcohol or glacial acetic acid, clogs. In this process, the p-toluidine can be replaced by other primary aromatic mono- and diamines are replaced. ', II. In addition to the quinizarin hydrochloride used above, certain are also suitable Leuco derivatives of other oxyanthraquinones to represent similar green dyes, by condensing them with primary aromatic amines, especially the leukopentacyanine described in patent specification No. 89027, and the leuco derivative of alizarin bordeaux described in patent specification No. 90722. The conditions here are quite analogous to those shown above for the quinizarin series. By condensation With primary aromatic amines, leuco derivatives are also initially formed, which, however, do not need to be isolated, but directly in the same operation by the action of atmospheric oxygen or by addition a suitable oxidizing agent can be converted into the dyes themselves. Even here it is expedient to mix a mixture of Alizarinbordeaux respectively. Alizarin pentacyanine with to use the corresponding leuco derivative for the melt. Example: ι ο kg leucoalizarin bordeaux, 20 kg alizarin bordeaux, 300 kg of p-toluidine and 20 kg of boric acid are heated on the water bath with the admission of air until the green color of the melt no longer changes. The work-up takes place in the well-known way; the pure dye is obtained by recrystallizing from glacial acetic acid in the form of long needles. The dyes thus obtained by means of the various amines are the corresponding ones derived from the quinizarin quite analogously. Some of the same, e.g. B. the condensation product from ι Mol. Alizarinbordeaux and 2 Mol. a-Naphtylamine, are already described in the main patents, but according to whose process they are sometimes only in small yield and accompanied by other substances. she all have a great ability to crystallize. Their nuance is in general greener than the corresponding dyes of the quinizarin series. Are the most yellowish the derivatives of alizarin pentacyanine. The properties of some of these are summarized in the following table: Dye off solution
in aniline Solution in
more concentrated
sulfur
acid ι Mol. Leucoalizarine
burgundy and
2 - aniline green green ι Mol. Leucoalizarine
burgundy and
2 - ρ-toluidine green, something
more yellowish
as the
previous dull
greenish
blue ι Mol. Leucoalizarine
burgundy and
2 - a-naphthylamine green pure blue ι Mol. Leukopenta
cyanine and
2 - ρ-toluidine yellow-green dirty
brownish red. The sulfonic acids of these dyes dye unheated wool in an acid bath in green-blue to yellow-green shades of extraordinary Clarity and great authenticity. It should also be mentioned that in the above-described condensations there are not two Amine residues enter the nucleus, but rather that the monosubstitution products are temporarily removed form. So it succeeds z. B. by carefully fusing Quinizarinhydrür with p-toluidine and a suitable condensing agent in the presence of air or a suitable one Oxidizing agent, the condensation product of 1 mole described in the main patents. Quinizarin with 1 mole of p-toluidine. Pa τ ε ν τ-A ν s ρ R 0 c η ε: ι. Innovation in the method of claim 1 of Patent No. 86150, which consists of that the oxyanthraquinones used there are replaced by leuco derivatives of them replaced with the simultaneous addition of an oxidizing agent. 2. The special embodiments of the method claimed under 1. under Use: a) the following leucooxyanthraquinones:
. Quinizarine hydrate (leucoquinizarine II of patent specification No. 89027), leucoalizarine bordeaux (Patent No. 90722), leukopentacyanine (Patent No. 89027); b) the following amines: Aniline, o-toluidine, p-toluidine, a-naphthylamine, ß-naphthylamine, ρ - phenylenediamine, benzidine; c) the following condensation agents: boric acid, hydrochloric acid, hydrobromic acid, Sulfuric acid, zinc chloride, acetic acid, benzoic acid; d) the following oxidizing agents: free oxygen, oxyanthraquinones.