DE498065C - Process for the preparation of Kuepen dyes - Google Patents

Description

Method of preparing vat dyes In the main patent 489 957 is a process for the production of valuable black vat dyes described in which i'-anthraquinonyl-6-aminabenzanthrone is treated with caustic alkalis. The i'-anthraquinonyl-6-aminobenzanthrone is z. B. by condensation of 6-halogembenzanthrone. available with i-aminoanthraquinone.

According to the additional patent 493.8i2, instead of the in the main patent applied i'-anthraquinobyl-6-aminoben, zanthrons other anthraquinonylamine; ob, enzanthrone treated with free peristaltions in the manner indicated above.

In the additional patent 495 974 the process is applied to the condensation products from halogen-2 - 2'-dibenzanthronylene with i-aminoanthraquinone and its derivatives extended.

It has now been found that the condensation products from the Halogen-Bz r - Bz i'-dibenzanthronylene, which can be used for. B. according to patent 431 774 from halobenzanthrones or can be obtained by direct halogenation of Bz i - Bz i'-dibenzanthronylene, with i-aminoanthraquinone or its derivatives when treating with alkaline agents pass into valuable vat dyes with excellent fastness properties.

Example io parts of condensation product from 6-6'-dichloro-Bz i -Bz i'-dibenzanthronyl with 2 mol. i-Aminoanthraquinone are converted into the 6- up to 10 times the amount of molten caustic potash iin: worn and so long at 24o to 25o ° merged until no more unchanged starting material can be detected. the cooled melt is taken up in water, filtered hot and washed. Of the The dye produced in very good yield is a black paste that dyes the vegetable fiber in very real black tones from a violet vat. Its properties are similar to those described in example i of additional patent 495,974 Dye.

If you replace the caustic potash with alcoholic potash and merge with Temperatures between 130 and i40 °, a dye is obtained that has a slightly bluish cast colors as the one described earlier.

Similar dyes are obtained by using the condensation product from 6 - 6 'dichloro-Bz i - Bz i'-dibenzanthronyl with i mol. i-Aminoanthraquinone der Potash meltdown subjects. Example 10 parts of condensation product, obtained from 8.8'-dichloro-Bz i # Bz i'-dibenzanthronyl and 2 mol. i-aminoanthraquinone with 4.o to 50 parts of caustic potash and 3o to 4o parts of alcohol at around 13o fused to 150 ° until the dye formation is complete. The melt is in worked up in the usual way. The dye obtained is black. Dough, dried represents a black powder that is dissolved in concentrated sulfuric acid with blue-violet color that dissolves into bottle green upon the addition of a few drops of nitric acid transforms. With caustic soda and hydrosulfite, the dye gives a violet-tinged blue Vat from which the fiber is dyed in very real black tones.

Example 3 If in Example 2 the condensation product of 8 # 8'-dichloro-Bz i # Bz i'-dibenzanthronyl and 2 mol. I-Aminoanthraquinone by that of 7.7'-dichloro-Bz i # Bz i'-dibenzanthronyl and .2 . mol replaced i-aminoanthraquinone and the rest, as cs ESpecify there HS, procedure, so Mian receives a dye in the form of a black dough dried represents a vio.lettschwarzes powder and dissolves in concentrated sulfuric acid with a violet color; with the addition of a few drops of nitric acid, the color changes to a dark brown. The dye, which is very similar to that described in Examples 3 of the additional patents 493812 and 495 974, dyes the vegetable fiber from a blue vat in a very genuine, dark blue that does not turn red with water. Tones on. Example 4 5 parts of the condensation product of 6 # 6'-dichloro-Bz i # Bz i'-dibenzanthronyl and 2 mol. I-Amino-4-methoxyanthraquinone are mixed with 150 parts of aniline and 15 parts of finely ground caustic potash while stirring Heated to reflux until the dye formation has ended. The melt, cooled to about 80 °, is filtered off with suction, washed with hot alcohol and water and, if necessary, the dye is boiled with aniline for cleaning. The dye obtained in pure form is a black powder that dissolves in concentrated sulfuric acid with a purely bluish-violet color. By pouring the sulfuric acid solution into water, the dye is obtained in the form of a black dough which, with sodium hydroxide solution and hydrosulfate, gives a red-violet vat from which the vegetable fibers are colored in very real and beautiful blue-tinged black tones. Very similar dyes are obtained if the condensation product is fused with alcoholic potash or with caustic potash in the manner indicated in Examples i to 3 instead of caustic potash in boiling aniline, or if, instead of the above condensation product, one uses one which only contains i mol i-Amino-4-methoxyanthraquinone is shown. Example s io parts of the condensation product from 6. 6'-dichloro Bzi. Bzi'-dibenzanthronyl and 2 mol. 1-Amino-4-oxyanthraquinone are fused with alcoholic potash in the manner indicated in Example 2 at temperatures which can be between 130 ° and 180 °. After working up the melt, dyes are obtained in the usual way in the form of blue-black to black doughs which, from the red-violet vat, color the vegetable fibers in shades which vary with the temperature of the melt from dark blue to blue-black. So z. B.. The dye that was shown at 13o to 135 ° melting temperature, in dark blue, the one at a higher temperature, z. B. i 7o to i 8o ', obtained in blue-black, very real nuances that do not change color when moistened with water or dilute acids. When dried, the dyes are black powders that dissolve in concentrated sulfuric acid with a bluish violet color. EXAMPLE 6 3 parts of metallic sodium are dissolved in zoo parts of anhydrous aniline in a stream of nitrogen, 5 parts of the condensation product of 6 # 6 'are added to the solution or suspension of aniline sodium in aniline produced in this way at about 10 to 1:25' Dichloro-Bz i # Bz i'-dibenzanthronyl and 2nd mol. I-Ami.noanthraquinone and heated at 100 ° to 125 ° in a stream of nitrogen until dye formation no longer increases. The violet melt is suctioned off at about 80 °, the aniline-containing residue is poured into dilute sulfuric acid and the dye which has separated out is filtered, washed and dried. The dye can be cleaned by boiling it with aniline or other high-boiling organic solvents. Example 7 parts of a condensation product which is obtained by condensation of brominated Bz i. Bz i'-dib, enzanthronyl (prepared by brominating Bz i # Bz i'-dibenzanthronyl in nitrobenzene) with i-aminoanthraquinone are fused with alcoholic potash, as indicated in Example 2. The dye, worked up in the usual way, is a black dough which, with caustic soda and hydrosulphite, gives a violet vat from which the vegetable fibers are colored in beautiful bluish black tones. When dried, the dye is a black powder that dissolves in concentrated sulfuric acid with a purple color; with the addition of a few drops of nitric acid, the color changes to a dark brown.

If one takes instead of the brominated Bz i # Bz i'-dibenzantlironyl used above other brominated Bz i # Bz i'-Dibenzanthrony 1e, as z. B. by brominating in Chlorosulfonic acid can be obtained, and if one submits the obtained therefrom Condensation products with i -: @ ininoaiitlirachinon an alkali melt, so obtained similar black-staining vats can be dyed.

Example 8 i, -) Parts of a condensation product which is obtained by condensation of 6 # 6'-dichloro-Bz i # Bz i'-dibenzanthronyl with @ -, Mol. i # 6-Diaminoanthraquinone, as indicated in example e, with alcoholic Potash fused at around 130 to 14o °. The dye thus obtained is a black one Dough, dried a black powder that is in concentrated sulfuric acid dissolves with purple paint. With sodium hydroxide solution and hydrosulfite, the dye gives a violet vat from which cotton is dyed in gray-black tones.

Similar dyes are obtained by fusing a condensation product in which the i # 6-diaminoanthraquinone is replaced by other diaminoanthraquinones. The most important properties of the starting materials used in the examples are given below '"Mp. Solution color Designation Representation 'Appearance o C in conc. sulfuric acid i i'-dianthraquinonyl- from 6. 6'-dichloro-Bz i # Bz i'-crystall. purple over carmine 6th 6'-diamino-Bz i # Bz i'-dibenzanthronyl with 2 mol. Brown powder 30 ° dibenzanthronyl i-aminoanthraquinone 2 i'-dianthraquinonyl from 8. 8'-dichloro-Bz i # Bz i'-crystall. brown over bluish 8. 8'-diamino-Bz i. Bz i'-dibenzanthronyl with 2 mol. Powder 300 ° violet dibenzanthronyl i-aminoanthraquinone i'-Dianthraquinonyl- from 7 # 7'-dichloro-Bz i # Bz i'- in purified at wine red 7th 7'-diamino-Bz i. Bz i'-dibenzantlironyl with 2 mol. State: crystall. approximately dibenzantbronyl i-aminoanthraquinone dark brown 300 ° powder 4'-Dimethoxy-i'-di- from 6 # 6'-Diehlor-Bz i # Bz i'- in raw zu- over blue anthraquinonyl-6. 6'-di-dibenzanthronyl with 2 mol. Status: dark-30o ° amino-Bz i # Bz i'-dibenz-i-amino-q.-methoxyanthra brown powder anthronyl quinone .; '- Dioxy-i'-dianthra- from 6 # 6'-dichloro-Bz i # Bz i'- in raw zu- over violet-tinged- quinonyl-6,6'-diamino- dibenzanthronyl -! - 2 mol. Stand: violet- 3oo ° blue with red- Bz i. Bz i'-dibenz- i -amino-q.-oxyanthraquinone brown powder brown fluo- anthronyl rescence 6 Condensation product of brominated red-brown in nitrobenzene over carmine red tem Bz i # Bz i'-Dibenz powder 300 ° with red-brown anthronyl with 2 mol. fluorescence i-aminoanthraquinone 7 Condensation product of dark brown over wine red in chlorosulfonic acid brominated Bz i - Bz i'-Di powder 30o ° benzanthronyl with 2 moles. i-aminoanthraquinone 8 6'-diamino-i'-dianthra from 6.6'-dichloro-Bz i # Bz i'- violet-brown over red Quinonyl-6,6'-diamino-dibenzanthronyl with 2 mol. Powder 300 ° Bzi # Bzi'-dibenzanthronyl i # 6-diaminoanthraquinone

Claims (1)

PATENT CLAIM: Further development of the process of patent 489957 for the preparation of vat dyes, characterized in that the condensation products of halogen-Bz i # Bz i'-dibenzanthronylene with i-aminoanthraquinone or its derivatives are treated with alkaline agents.