DE238981C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

CLASS 22 δ. GROUP

Method for the representation of anthraquinone cells. Patented in the German Empire on July 27, 1910.

It has been found that acyl compounds of the o-diaminoanthraquinones or theirs Derivatives can be converted into new anthraquinone derivatives by the fact that they are mentioned Body treated with water-releasing agents. You can also get the same result achieve by heating the products mentioned or the more than one acyl group containing o-diamines treated with acid-releasing agents.

The same body can also be used in one operation, starting from the o-diaminoanthraquinones themselves, can be obtained if these bodies are heated directly with the acylating agents until ring closure has occurred is.

The new bodies thus obtained are probably imidazoles, which are made according to the following Scheme arise: '

+ H.0

or z. B.

t /

N-COR ¹ ^ NH-COR ¹

= A < »C -R ¹ + R ¹ • COOH

(A = anthraquinone residue or substituted anthraquinone residue; R = H, alkyl or aryl; R ¹ ^ H, alkyl, aryl, OC ₂ H ₆ , etc.).

As water or acid-releasing agents, for. B. concentrated sulfuric acid, chlorophosphorus, Zinc chloride, organic acids and their chlorides or anhydrides can be used.

Some of the new compounds can be used directly as dyes, the rest valuable starting materials for the preparation of such.

Example 1.

5 parts benzoylated 1 · 2-diaminoanthraquinone (prepared by heating 1 ♦ 2-

Diaminoanthraquinone and benzoyl chloride in nitrobenzo solution) are dissolved in 50 parts of sulfuric acid of 66 ° Be. ¹ Z ₂ hours heated to 150 ⁰ , the initially red colored solution gradually turns brownish yellow. The reaction mixture is poured into ice water, filtered, washed with hot water and dried. The substance obtained is easily soluble in nitrobenzene, aniline or pyridine, from which it crystallizes in beautiful brass-yellow needles. In concentrated sulfuric acid it dissolves with yellow, in oleum of 40 percent SO ₃ with red color. It provides a red-brown vat with which yellow dyeings can be obtained on cotton.

Example 2.

5 parts of benzoylated 1 · 2 · 4-triaminoanthraquinone (prepared by heating 1 · 2 · 4-triaminoanthraquinone with benzoyl chloride in nitrobenzo solution) are dissolved in 50 parts of sulfuric acid at 66 ° Be. V heated for ₂ hour at 150 ^0, where the initially red-colored solution is gradually green yellow. It is poured into ice water, filtered, washed with hot water and dried. The material so obtained crystallized · of aniline in shiny metal needles in a bluish red, soluble in pyridine, in 60 percent oleum with blue in concentrated sulfuric acid green-yellow color. If formaldehyde is added to this solution, a green color occurs. It provides a red-brown vat from which greenish blue-gray dyeings are obtained on cotton.

The obtained substance, 4-amino-1 · 2-phenylanthrimidazole gives acyl compounds, which are also vat dyes; so z. B. the bezoyl compound, which in concentrated sulfuric acid with yellow-red, in oleum of 60 percent with blue-red Color dissolves, on cotton vivid orange colorations of particular clarity and lightfastness.

The corresponding with o-chlorobenzoyl chloride Aminoanthrimidazole produced dissolves in concentrated sulfuric acid with green-yellow, in oleum (60 percent) with a blue color, in pyridine with a bluish-tinted red color. It delivers a red-brown vat, from which greenish blue-gray dyeings are obtained on cotton. The benzoyl compound of the product dissolves in concentrated sulfuric acid with yellow-red color, in oleum with blue-red color and helium make a red-brown vat, from which you can get very real orange dyeings on cotton receives.

Example 3.

ι part ι · 2-diaminoanthraquinone is with 10 parts of benzoyl chloride refluxed for 2 hours. After cooling down a yellow colored substance crystallizes out, which is identical to that described in Example ι Product.

If 1 · 2-Diaminoanthraquinone is heated with a solution of excess phosgene in nitrobenzene, the yellow colored one is obtained ι · 2-oxyanthrimidazole

NH-C OH

j
\ -C0- \ "

-CO-

which is sparingly soluble in organic solvents and made of quinoline in fine needles crystallizes, which is in aqueous alkali with orange-red, in concentrated sulfuric acid with yellow, in 60 percent oleum with red color.

Example 4.

ι Part 2 · 3 - Diaminoanthraquinone is with 10 parts of concentrated formic acid refluxed until the starting material disappeared. After cooling, the precipitated product is filtered. It crystallizes in the form of pale colored Needles, which turn yellow in concentrated sulfuric acid, in oleum of 20 percent Dissolve the SOg content in orange.

Example 5.

Part of 2-diaminoanthraquinone is introduced into a mixture of 5 parts of sulfuric acid (66%) and 5 parts of acetic anhydride at ^{0 °.} The temperature is allowed to rise gradually to 60 ° with stirring and is kept at this temperature for 15 minutes. It is then poured into hot water, filtered and the base is precipitated from the filtrate with ammonia. After filtering and drying, they are recrystallized from pyridine and are obtained as fine, pale needles. The product dissolves in concentrated sulfuric acid and in pyridine yellow, in oleum (60 percent) orange.

Example 6. _no

ι part of dinitro - β - aminoanthraquinone urethane (see patent specification 171588 ¹² ) is heated to 100 ° with 6 parts of p-toluidine for 3 hours. The melt first takes on a red-brown color, which gradually turns yellow. From the melt diluted with alcohol, a yellow body separates out when it cools, which crystallizes from nitrobenzene in greenish yellow flakes. Its solutions in organic solvents as well as in concentrated or fuming sulfuric acid are yellow, in alcoholic alkali orange-red. He

is to be understood as an imidazole derivative of the following constitution:

C ₁ E,

-CO

- CO- ¹

OC ₀ H.

OH

created by replacing the α-nitro group with the toluidine residue, the ß-nitro group with hydroxyl and subsequent elimination of water between the toluidine and urethane residue; By gently warming it with oleum of 5 percent 5O ₃ content, a sulfonic acid is obtained from it, which in an acidic bath dyes wool a clear yellow.

Analogous products are made from acyl derivatives of other o-diaminoanthraquinone compounds or their derivatives.

Claims (2)

Patent Claims: 1. Process for the preparation of anthraquinone derivatives, consisting in that 'one acylated o-diaminoanthraquinones or their derivatives for themselves or with Diluents in the presence or absence of water b, zw. acid-releasing Means heated. 2. Embodiment of the under 1. marked Process for the preparation of anthraquinone derivatives, consisting of that one treats o-diaminoanthraquinones or their derivatives with acylating agents, until the ring has closed.