DE204411C - - Google Patents

Description

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PATENT OFFICE.

PATENT LETTERING

- Ju 204411 CLASS 22 δ. GROUP

Patented in the German Empire on August 9, 1907.

Patent 91149 states that all primary aromatic mono- and Diamines on leucoquinizarin with the formation of blue-green to yellow-green dyes react.

It has now been found that when treating leucoquinizarin with arylhydrazines new bodies arise, which are just as much in the form of their leuco compounds as in that the corresponding oxidation products are yellow and their sulfonic acids are yellow-brown or represent red-brown wool dyes. These sulfonic acids are made directly from leucoquinizarine and arylhydrazine sulfonic acids obtain.

Also the aryl hydrazine derivatives of substituted quinizarines obtainable in the same way are yellow.

The only known arylhydrazine derivative of the anthraquinone series is that in Patent specification 99078 described condensation product of phenylhydrazine with dichloroanthrachrysondisulfonic acid. It is said to be a wool in an acidic bath red, chrome-stained wool which dyes red-violet.

No normal condensation product could be obtained from quinizarine and phenylhydrazine will; only if the exposure is prolonged, small amounts of the leuco-i · 4-diphenylhydrazinoanthraquinone described below arise, by apparently reducing part of the quinizarine and subsequently reducing the leucoquinizarine thus formed with phenylhydrazine reacted.

The new aryl hydrazine derivatives, which are not dyes themselves, can easily be converted into convict such.

Example I.

10 parts of leucoquinizarin are heated with 10 parts of phenylhydrazine diluted with twice the amount of alcohol for about 1 hour or so long on the water bath on the reflux condenser until there is no longer any unchanged leucoquinizarine. The reaction product separates out as a crystalline mass when it is hot. Recrystallization from nitrobenzene gives it in the form of small, metallic, shiny yellow crystals which ^{melt at 256 °} with decomposition.

Analysis:

Calculated for C ₂₆ H ₂₂ O ₂ N ^.

C 73.93, H 5.2i, N 13.27.

Found: G 73.46, H 5.25, Ni3.45 ·

The leuco-i · 4-diphenylhydrazinoanthraquinone is in alkalis and dilute acids insoluble, very sparingly soluble in inert solvents. In concentrated sulfuric acid it dissolves with a green color, which turns into a reddish yellow-brown due to boric acid. Both solutions turn reddish-brown when heated more strongly.

Treatment with cold methyl alcoholic sodium hydroxide solution turns the leuco derivative converted into a well-characterized oxidation product.

55

This is much more soluble in inert solvents as the starting material and crystallized from benzene in shiny, melting at about 240 ⁰ red-brown needles. The solution in concentrated sulfuric acid is cherry red. According to the analysis, it is probably not a hydrazo compound, but an azo compound. This is supported by the resistance of the body, which is probably to be designated as 1 · 4-disbenzolazoanthraquinone, to oxidizing agents, e.g. B. when boiling the benzene solution with mercury oxide.

Analysis:

Calculated for

C 74.29,
Calculated for

C 75.00,
Found: C 75.01,

H ₂₀ O ₉ .

26 ^ 16 '

H 4.76, N 13.33.

, 2V ₄ :
H 3.84,
H 3.95,

2V 13.46.
2V ΐλ, 5ΐ.

The other leuco-i · 4-diarylhydrazinoanthra-

. quinones shown.

In the same way, z. B that Condensation products of leuco-i · 4 · 5-trioxyanthraquinone and leuco-i · 4 · 5 · 8-tetraoxyanthraquinone obtain. They are due to the presence of at least one Hydroxyl group soluble in alkali.

The direct representation of the sulfonic acids is done using suitable Diluents such as phenol, glycerin, etc.

Example II. ^ ₅

5 parts of leucoquinizarin are z. B. with 15 parts of phenylhydrazine-p-sulfonic acid, 10 parts of sodium acetate and 40 parts of glycerol heated ^{to 130 to 140 0 for about 10 hours with stirring.} After the reaction has ended, the mass is poured into water and the reaction product is precipitated from the filtered solution using common salt. It dyes wool in yellow-brown shades that are not changed by acids and ammonia, but has no pronounced dye character.

Used in the aqueous solution of this product after the addition of caustic alkalis If air is introduced, the color of the solution changes from yellow to green and blue to red-brown by forming a red-brown dye. Both products differ They are also characterized by the color of their solution in concentrated sulfuric acid. While the leuco derivative dissolves in it with a yellow-green color, gives the oxidation product a brown-red solution.

Claims (1)

Patent claim: Method for the representation of Leuko-ι ·. 4 - diarylhydrazinoanthraquinones or their oxidation products, characterized in that one leucoquinizarin condensed with aryl hydrazines or their sulfonic acids and the products thus obtained possibly oxidized.