DE269800C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

- M 269800 - CLASS 22 b. GROUP

Dr. ALFRED SCHAARSCHMIDT in BERLIN.

Patented in the German Empire on October 5, 1912.

It has been found that the o-nitriles of Dianthraquinonylamines and the dianthraquinonylthioether, which z. B. by heating the o-cyano-halogenanthraquinones with aminoanthraquinones or anthraquinone mercaptans obtained in high-boiling solvents in the presence of acid-binding agents in the treatment with condensing agents, such as. B. concentrated sulfuric acid, smoothly into the dianthraquinonylacridones and thioxanthones, which are important as vat dyes pass over.

That the action of condensing agents such as sulfuric acid, those described above Would take course was not to be expected, since with the occurrence of conversions what was to be expected was the one described in patent specification 126444 of class 12 Reaction, all the more so as this takes place at far lower temperatures than the saponification of the anthraquinone nitriles, but especially the smooth feasibility the formation of acridone with regard to the information in the dissertation by van der Schalk, About anthraquinone-a-carboxylic acid, Darmstadt ΐο, ΐί, p. 29, surprise, after which the attempts to prepare the dianthraquinone acronyms from i-cyano-2-bromoanthraquinone on the inclination of the bromanthrachi-ηοη-α-carboxylic acid failed to split off carbon dioxide.

The reaction has very general applicability, and works on this Way, also to acridones and thioxanthones of a previously unknown kind, which in place of anthraquinone nuclei anthrapyridone benzanthrone nuclei etc. included to arrive.

Example 1.

a) 9.4 g of i-cyano-a-bromoanthraquinone, 6.7 g of i-aminoanthraquinone, 150 g of nitrobenzene and 3 g of sodium acetate are refluxed for ^x / ₄ to ¹ Z ₂ hours. After cooling, it is filtered, washed with ether, alcohol, water, alcohol and ether and dried. The nitrile of dianthraquinonimide obtained, which crystallizes in splendid, brownish-orange needles, dissolves in concentrated sulfuric acid with an intensely blue color. The yield is quantitative.

If the i-aminoanthraquinone is replaced by the 2-derivative and the rest of the procedure is the same stated above, the brownish-yellow colored i-cyano-2 · 2-dianthraquinonyl- amine, which dissolves in sulfuric acid with a green color.

b) Cond. to the Akridon. 10 parts of nitrile are heated with 100 parts of sulfuric acid of 96 percent ¹ Z ₄ hours at 140 to 160 °, wherein the blue color of the solution changes to brown. After cooling, it is poured into water, washed and dried. The yield of akridon is quantitative. Vat violet-red, bright red-orange color. In the same way, the imide obtained from 2-aminoanthraquinone and i-cyano-2-bromoanthraquinone is condensed with concentrated sulfuric acid to give acridone. The latter produces orange-yellow colorations from the vat.

Example 2.

a) 6.2 g of i-cyano ^ -bromoanthraquinone, 24g ι · 5-diamindanthraquinone, 120 g of nitrobenzene and 2 g of sodium acetate are boiled for 1 to 2 hours. Isolation of the dinitrile as in Example 1. Brown-red powder, solution in concentrated sulfuric acid, intensely blue. yield quantitatively. The same procedure is used for the condensation of i-cyano-2-bromoanthraquinone with 1 · 8-diamino- or with ι · 4-diaminoanthraquinone.

.b) Cond. to the trianthraquinonyl diacridon. 10 parts of the dinitrile are heated with 100 parts of 96 percent sulfuric acid at 150 to 170 ° ¹ Z for ₄ hours. It is poured into water, washed and dried. Vat violet-blue, coloring real brown-red. The dinitriles of trianthraquinonyl diimide obtained from the ι · 8- or ι · 4-diaminoanthraquinone are condensed in the same way to give the diacridones. The 1 x 8 derivative produces real brown-red shades from the vat, the 1 x 4 derivative real blue-gray nuances.

Example 3.

Akridon from i-cyano-2-bromoanthraquinone and 4-amino-i- (N) methylanthrapyridone.

a) 2.1 g of i-cyano-2-bromoanthraquinone, 1.8 g 4-Amino-i- (N) methylanthrapyridone, 50g nitrobenzene and ι g sodium acetate are under Boiled under reflux for 2 hours. After cooling, it is filtered, with alcohol, washed with hot water, alcohol and ether and dried. A brownish-red, nicely crystallized product is obtained, which dissolves in concentrated sulfuric acid with an intense red color and from this solution precipitates again in red flakes on addition of water.

b) Cond. to the Akridon. The imide obtained according to a) is heated with 10 parts of sulfuric acid to 170 ° to 190 ° for about ^x / ₂ hours, the cooled melt is poured into water, filtered and washed. The red dye obtained produces real red nuances from a red vat on cotton.

Example 4.

Akridone from i-cyano-2-bromoanthraquinone and aminobenzanthrone, obtained by reduction des Mon on isobenzanthrone of French patent 349531, 8th addition no. 6435, example ι:

a) i, g g aminobenzanthrone, 2.4 g i-cyano-2-bromoanthraquinone, 0.7 g of sodium acetate and 50 g of nitrobenzene are used for 2 to 3 hours Boiling heated. After cooling, the crystal slurry obtained is worked up as in Example 3 a). A brown powder is obtained which dissolves in concentrated sulfuric acid with a violet color.

b) Cond. to the Akridon. 10 parts of the imide obtained in a) are heated in 100 parts of concentrated sulfuric acid for ₂ Z ¹ hour at 140 to 170 ^0th The purple color of the solution changes to red. After cooling, it is poured into water, filtered and washed. The dye formed is a brownish-yellow powder, which turns a brown vat onto cotton and creates real orange-yellow nuances.

Example 5.

Representation of the i-nitrile of 2 i'-dianthraquinonyl thioether:

a) 5 g of i-thioanthraquinone, 6.3 g of i-cyano-2-bromoanthraquinone, 1.5 g of potash and 120 g of amyl alcohol are _{refluxed for about V 2} hours. The condensation takes place very quickly, the thioether formed separating out as a yellow precipitate. It is allowed to cool, filtered, washed with alcohol, hot water, alcohol and ether and dried. Quantitative yield. The yellow powder obtained dissolves in sulfuric acid with an orange-red color. The 2 '· 2-thioether obtained in the same way from 2-thioanthraquinone and i-cyano-2-bromoanthraquinone is pale yellow in color.

b) Preparation of 1 · 2 · 1'2'-dianthraquinone thioxanthone:

10 parts of the thioether obtained according to a) are heated to 170 ° to 190 ° ^{with 10 parts of sulfuric acid for about 1} Z _{2 hours.} The cold melt is then introduced into water, the thioxanthone formed separating out in orange flakes. Vat bluish green, initially the same color, orange when oxidized.

That from the i-cyano-2 · 2'-dianthraquinone thioether The thioxanthone obtained is greenish-yellow in color and delivers greenish-yellow from the vat Colorations.

105 Example 6.

a) 3.1 g of i-cyano-2-bromoanthraquinone, 1.4 g ι · 5-Dithioanthraquinone and ι g potash are in 70 g of amyl alcohol for two hours Heated to reflux. The excreted yellow-orange product is, as indicated in Example 5 a, isolated. It dissolves in sulfuric acid with an intense purple-blue color.

b) ι part of Trianthrachinondithioäthers obtained according to a) is heated with 10 parts of concentrated sulfuric acid ¹ Z ₂ hours at 170 to 190 °. After cooling, the melt is poured into water, washed neutral and dried. The obtained dithioxanthone

is brownish-orange in color and creates real orange-red nuances from a violet vat.

Claims (1)

Patent claim: Process for the preparation of vat dyes of the anthraquinone series, therein consisting that one of the ortho-halonitriles of anthraquinone or its derivatives by condensation with amino or thio derivatives of anthraquinone and its derivatives obtainable ortho-cyanimides or -thioethers with condensing Means treated.