DE235094C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

It has been found that by condensation of the anthraquinone mercaptans with Oxyanthraquinones get to new bodies with the help of sulfuric acid, which very valuable vat dyes and readily available raw materials for representing others Are dyes.

The reaction probably takes place with the formation of dianthraquinonyl sulfides (Thioethers), whereby the hydroxyl group is retained or a new ethereal one in turn Binding enters into, so that probably z. B. Body by constitution:

develop.

^a 5 You can replace the anthraquinone mercaptans, as they are initially oxidized to the disulfides by concentrated sulfuric acid, by these, and of course also by those mercaptan derivatives which are cleaved by the acid, such as. B. the rhodanides, xanthates, acyl compounds or ethers. The same is true of the oxyanthraquinones, also in their place

Ethers or acyl derivatives can be used.

The following examples serve to explain the process.

Example i.

3 parts of anthraquinone-i-mercaptan (or the mixture of mercaptan and disulfide formed in the treatment of anthraquinone-a-sulfonic acid with polysulfides) are heated ^{to 160 to 170 0 with 4 parts of i-oxyanthraquinone in 60 parts of 98 percent sulfuric acid} the initially yellow melt has taken on a dark green color and shows no increase in color intensity on further heating. It is now diluted with 600 parts of water, the precipitated dye is filtered off with suction and boiled with dilute sodium hydroxide solution to remove the excess oxyanthraquinone. It is obtained pure by treatment with dilute sodium hypochlorite solution or by recrystallization from high-boiling solvents. It is sparingly soluble even in boiling quinoline and crystallizes from it in brown-red needles, which dissolve in concentrated sulfuric acid with an emerald-green color. With alkaline hydrosulfite an orange colored vat is obtained, from which unheated cotton is colored brown. After rinsing and soaking, vivid yellow-red dyeings of great fastness are obtained.

The same dye is obtained if one

the anthraquinone mercaptan through the i-rhodananthraquinone or the oxyanthraquinone is replaced by its methyl ether.

'/ Example 2.

3 parts of anthraquinone-i. X 5 dimercaptan and '8 parts of i-Oxyanthrachinon are heated with 10 parts of concentrated sulfuric acid (66 ° Be.) ⁰ to 170 until the melt no longer green. As indicated in Example 1, the dye is isolated and purified. It forms a brown-red powder, the solution of which in concentrated sulfuric acid is green. When

thin with water you get red flakes. The colors on cotton are burgundy. .

A very similar dye is obtained from anthrarufin and anthraquinone-imercaptan.

If one replaces the a-oxyanthraquinone in the example the same amount of ß-compound produces a slightly yellowish product.

Analogous dyes are made from other oxyanthraquinones and anthraquinone mercaptan and their derivatives.

Lfde.
No. Dye off solution
in boiling
Naphthalene solution
in more concentrated
sulfuric acid coloring
on unheated
cotton I. Anthraquinone-1-mercaptan + 1-oxy
anthraquinone orange emerald green yellow Red 2. Anthraquinone-1 · 5-dimercaptan + 1-
Oxyanthraquinone (2 mol.) brown orange bottle green burgundy 3 · Anthraquinone-1-mercaptan (2 mol.)
'+ Anthrarunn brown orange bottle green burgundy 4 · Anthraquinone-1 ■ 5-dimercaptan + 2-
Oxyanthraquinone (2 mol.) orange bottle green brownish red 5 · Anthraquinone-1-mercaptan + 2-oxy-
anthraquinone orange yellow yellow-green orange 6th Anthraquinone-1-mercaptan (2 mol.)
+ Anthraflavic acid orange grass green red-brown 7- 5-aminoanthraquinone-1 mercaptan
■ + 5-amino-i-oxyanthraquinone brownish
(very difficult to dissolve) olive brown purple brown 8th. Anthraquinone-2-mercaptan + 2-oxy-
anthraquinone orange emerald green Red 9 · Anthraquinone-2-mercaptan (2 mol.)
+ Anthraflavic acid Orange red dull green burgundy 10. Anthraquinone-1-mercaptan + Xan-
thopurpurin cherry red green Blue burgundy.

Claims (1)

Patent claim: Process for the preparation of vat-coloring anthracene derivatives, consisting therein that one anthraquinone mercaptans or disulfides or their derivatives with oxy- anthraquinones or their derivatives, or under the influence of the condensing agent in the compounds mentioned passing substances condensed with one another with the help of sulfuric acid.