DE280712C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

- Yes 280712 CLASS 22 b. GROUP

Patented in the German Empire on July 10, 1913.

Acridons of the naphtoanthraquinone series have so far only been obtained from those that are difficult to access ο - halocarboxylic acids of anthraquinones by condensation with naphthylamines and subsequent ring closure produced. It introduced a new method of representation of these compounds found. It consists in the easily accessible ß-naphthoquinone-3-carboxylic acid (described in Reports 37, 3094) condensed with aminoanthraquinones to form quinonanilide-like bodies and these latter compounds by treatment with suitable condensing agents be converted into acridone derivatives.

The new method has a great applicability and diversity, which the well-known acridone syntheses is missing; for every amine of the anthraquinone series with free one Orthodistribution to the amino group is to that

ao reaction enabled; It can therefore be a large number of Technically win acridone derivatives of the naphtoanthraquinone series, which according to the previously known methods were difficult or impossible to produce.

The almost quantitative course of both phases of the reaction is surprising.

The ß-naphthoquinone-3-carboxylic acid condenses easily with the aminoanthraquinones without the formation of by-products and without splitting off the CO ₂ group, and the homologues of the anthrachmone series of ß-anilinonaphthoquinone obtained in this way go smoothly into acridone derivatives under the influence of concentrated mineral acids, without suffering a cleavage into β-oxynaphthoquinone and amine, like their parent substance (see Ber. 14, 1496). The products obtained in this way are in part already vat dyes themselves, in part valuable starting materials for the production of such; they combine the properties of an akridone complex and a true aromatic orthoquinone and are therefore able to react with orthodiamines to form azines, whereby dyes are formed which contain both the akridone and azine ring in their molecule.

The process is illustrated by the following examples: 20.5 kg of β-naphthoquinone-3-carboxylic acid are suspended in 200 kg of glacial acetic acid and 22.3 kg of ß-aminoanthraquinone are added to this.

The mixture is stirred for a few hours at water bath temperature; the condensation product precipitates in yellow crystal needles when it cools. They are insoluble in water in hot alcohol, glacial acetic acid, toluene and especially in nitrobenzene with ease yellow color soluble. In dilute alkalis, the condensation product dissolves with cherry red Colour.

10 kg of the dry condensation product are used to transfer to the akridon dissolved in about ten times the amount of concentrated sulfuric acid and heated to 80 to 100 ° C for a few hours. The originally towards the end of the reaction, the deep yellow color of the solution changes to a dirty bottle green. One pours the cold one

Solution on ice and filtered off the akridon which has separated out in orange-brown flakes and dry it.

The formation of acridone is even easier if chlorosulfonic acid is used instead of concentrated sulfuric acid. One proceeds z. B. as follows:

The condensation product of β-naphthoquinone-3-carboxylic acid obtained according to the example and ß-aminoanthraquinone is at 0 to 10 ° C slowly in 5 to 10 times the amount - Entered chlorosulfonic acid and then stirred the whole thing at this temperature for so long until a sample has become insoluble in alkali. It is then poured onto ice and filtered the excreted Akridon and washes ι neutral.

When dry, the akridon is a red-brown powder that is insoluble in alkalis and dilute acids. In alcohol, it is very difficult to deal with, even in the heat yellow color soluble. From hot toluene it crystallizes in red needles on cooling, in the same crystal form from hot nitrobenzene; concentrated sulfuric acid dissolves it with yellow-green color. The alkaline hydrosulfite vat is colored red-brown, cotton is stained from the same in orange-red tones. If you use in place of ß-Aminoanthraquinone the same amount of α-aminoanthraquinone is obtained initially a cherry-red colored condensation product, which in dilute cold alkalis with is soluble in the same color; when this solution is heated, decomposition occurs immediately Separation of a flaky, red-brown precipitate.

The conversion into the Akridon takes place as described in the example; it runs just as smoothly as with the isomeric ß-compound.

In the dry state it is a brownish red, in the usual organic solvents poorly soluble powder; from hot nitrobenzene it separates as red crystalline Powder off, in concentrated sulfuric acid it is soluble with a yellow-brown color. Cotton is colored from the brown-red colored alkaline hydrosulfite vat in yellow-brown tones.

In the same way, 1 .5 and 2 · 6-diaminoanthraquinone the condensation products and the corresponding acridones win, the properties of which are summarized here:

'■ ■.

Condensation product from color of the alkaline
aqueous solution

Solution in hot nitrobenzene

β-naphthoquinone-3-carboxylic acid.
+ 2 x 6-diaminoanthraquinone cherry red;
resistant to heat

easily soluble with a yellow color

+ ι · 5-diaminoanthraquinone red-brown solution,
decomposes when heated

soluble with red color

Akridon out

Solution in

more concentrated: sulfuric acid hot
Nitrobenzene

colour
the vat

Staining on cotton

β-naphthoquinone-3-carboxylic acid
+ 2 · 6-diaminoanthraquinone yellow-brown

Red

dark brown

red-brown

+ ι • 5-diaminoanthraquinone

green yellow red

brownish red

Brown

Claims (1)

Patent claim: Process for the preparation of akridon-like condensation products of the anthraquinone series, consisting in that the ß-naphthoquinone-3-carboxylic acid initially with aminoanthraquinones with free o-position to the amino group is condensed and the bodies thus obtained are then split off with water Condensation agents are treated further.