DE274357C - - Google Patents

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PATENT LETTERING

- JV * 274357 CLASS 226th GROUP

Anthraquinone mercaptan anthraquinonyl ether have not yet become known. The for the representation of the anthraquinone mercaptanaryl or alkyl ethers leading methods, which in the patents 116951, class 12 and 224589, cl. 22 and in the heating of negatively substituted anthraquinone derivatives pass with aromatic or aliphatic mercaptans, fail when using anthraquinone mercaptans, apparently because the temperature required for the reaction is different Action of the alcoholic or aqueous alkali takes place on the haloanthraquinones.

It has now been found that the Dianthraquinonylthioäther in pure form and good yield is obtained if halogenanthraquinones with the alkali salts of the anthraquinone mercaptans in a high-boiling inert solvent with or without the addition of a catalyst, such as. B. Copper or its salts, heated. Instead of the ready-made mercaptan alkali salts, one can also use the free mercaptans together with acid-binding agents such as alkali carbonates, acetates etc., apply.

The dianthraquinonyl thioethers form valuable vat dyes and can also be used as Starting materials for the preparation of other dyes are used.

Example 1.

11 parts of anthraquinone-2-mercaptan sodium and 10 parts of i-chloroanthraquinone are in Entered 100 parts of molten naphthalene and after adding 0.2 parts of copper chloride cooked until there is an increase in the formation of the condensation product in the melt is imperceptible. From the melt cooled to about 100 °, it separates out Addition of pyridine of the 1 ^ '- dianthraquinonyl thioether as yellow crystal powder. Its solution in organic solvents is yellow, in fuming sulfuric acid (20 percent) green, in sulfuric acid monohydrate blue and in Sulfuric acid of 66 ° Be. gray-blue. When diluted with water, the latter becomes first brown-red and then separates the dye in yellow flakes, which are in alkaline Dissolve hydrosulphite to an orange-red vat, with which you can smear sulfur-yellow on cotton Receives colorations.

If you replace the anthraquinone-2-mercaptan sodium with the sodium salt of the anthraquinone-i-mercaptan, the ΐ, ΐ'-dianthroquinonyl thioether is obtained as an orange-brown one crystalline powder whose solutions are orange in pyridine, in oleum of 20 percent emerald green, olive green in concentrated sulfuric acid. Its made in the vat The colors are reddish yellow.

Example 2.

10 parts of anthraquinone-2-mercaptan, 15 parts ι - Benzoylamino - 4 - chloranthraquinone, 10 parts Powdered potassium carbonate, 0.1 parts of copper bronze, 100 parts of naphthalene are 8 hours cooked. The i-benzoylamino-4-2'-dianthraquinonylthioether is obtained from the melt worked up as in Example 1 in the form of scarlet needles, which are yellow-red in pyridine and yellow-red in concentrated sulfuric acid give green solution. In the vat one receives bright yellow-red colorations of great size Authenticity.

Example 3.

10 parts of anthraquinone-2-mercaptan, 15 parts 4 - bromo -1 - methylanthrapyridone, 10 parts dehydrated Sodium acetate, 100 parts nitrobenzene

are heated to the boiling point of the latter for about 6 hours. The condensation product separates out of the melt as orange-colored needles. Its solution in concentrated sulfuric acid has a bluish tinge 65 red, the staining on cotton is orange-yellow.

The anthraquinone dimercaptans and the substitution products of the anthraquinone mercaptans or the haloanthraquinones behave in a completely analogous manner. So you get z. B. from anthraquinone · 5-dimerkaptan - \ - 2 mol. I-chloro-4-oxyanthraquinone a brown-red vat dye, from ι - chloranthraquinone sulfonic acid + anthraquinone -1 - mercaptan an orange-yellow wool dye. The properties of some of the dyes represented in this way are given in the following table:

Thioether from

Appearance

Solution in conc. H ₂ SO ₁

Staining on cotton

Anthraquinone-2-mercaptan-j-i-chloranthraquinone

yellow square leaves

gray-blue

sulfur yellow

Anthraquinone-2-mercaptan + 2-chloroanthraquinone

orange-yellow needles

red purple

golden yellow

Anthraquinone-i-mercaptan - | - i-Chloranthraquinone

orange-brown crystals

olive green

reddish yellow

Anthraquinone-2-mercaptan + i-benzoylamino-4-chloro-A scarlet needles

green

Anthraquinone-2-mercaptan-f- 4-bromi-N-methylanthrapyridone orange needles

bluish red

scarlet

orange yellow

Anthraquinone-i · 5-dimerkaptan -f 2 mol. i-chloro-4-oxyanthraquinone dark blue

Powder (alkali salt)

green

brownish red

Anthraquinone-2-mercaptan (2 mol.) -J- ι · 5-dichloroanthraquinone orange-yellow needles

very poorly soluble, blue

golden yellow

Anthraquinone-2-mercaptan (2 mol.) + Ι · 8-dichloroanthraquinone orange needles

gray-blue

orange yellow

Anthraquinone-2-mercaptan (2 mol.) + Ι · 4-dichloroanthraquinone scarlet prisms

dull green

orange

Anthraquinone-2-mercaptan (2 mol.) + 2 · 7-dichloroanthraquinone yellow powder

blue-violet

golden yellow

Anthraquinone-2-mercaptan (4 mol.) -F ι · 4 · 5 · S-tetrachloroanthraquinone red needles

gray-blue

Anthraquinone-i-mercaptan + i-chloranthraquinone-5-sulfonic acid orange powder

olive green

yellow " ⁵

mad at wool

colored, orange-yellow

Claims (1)

Sponsorship τ claim: Process for the preparation of dianthraquinonyl thioethers, consisting therein that you halogen thraquinones in inert, high-boiling solvents with or without the addition of a catalyst heated free anthraquinone mercaptans in the presence of acid-binding agents or with anthraquinone mercaptan salts.