DE931830C - Process for the preparation of derivatives of anthracene - Google Patents

Description

Issued on the basis of the First Transitional Act of July 8, 1949

(WiGBl. P. 175)

FEDERAL REPUBLIC OF GERMANY

ISSUED AUGUST 18, 1955

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 12 q GROUP 37

F 67 86 IVc 112 q

Dr. Heinz-Werner Schwechten, Leverkusen-Bayerwerk and Dr. Dr. H. c. Otto Bayer, Leverkusen-Bayerwerk

have been named as inventors

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Process for the preparation of derivatives of anthracene Patented in the territory of the Federal Republic of Germany from July 20, 1951

Patent application published February 24, 1955

Patent issued July 21, 1955

In the patent specification 268 592 is a reaction product of sulfur trioxide and 1,4-diaminoantbrachinon described to whom the constitution

= SO ₉

ON = SO ₂

should come. It has now been found that this compound is highly unsaturated in character and behaves in many ways like benzoquinone or a-naphthoquinone. Consequently it is very likely that those in the above

The compound described in the patent specification has the constitutional formula

and thus a derivative of 1,4-anthra-35 represents chinons.

It has now been found that this reaction product consists of sulfur trioxide and i, 4-diaminoanthorachinone ■ and its core substitution products are easily found as derivatives of 1,4-anthraquinones with the most varied of compounds, such as hydrogen, alkalis, ammonia, amines, mercaptans, Let phenols, bisulfite, alkali metal cyanide or dienes react. Because of this unexpected Reactivity and the easy accessibility of the starting materials opens up thus a multitude of possibilities for the production of new anthracene derivatives and an abundance new intermediate products for the production of vat, acetate silk and acidic wool dyes.

example 1

5 g of the product of action of oleum on 1,4-diamino-2,3-dichloro-anthraquinone are dissolved in 100 ecm of water -) - 3 ecm of concentrated sodium hydroxide solution and the solution is acidified. An orange-red body precipitates out, which is suctioned off, washed with water and dried. In contrast to the starting material, which dissolves violet in concentrated sulfuric acid, it dissolves in concentrated sulfuric acid with a bluish-red color. When the solution is heated in concentrated sulfuric acid for several hours to 90 ^0, enters saponification. A sulphate is then deposited by dilution with water, which upon decomposition with water yields a substance which crystallizes excellently from nitrobenzene, dissolves in pyridine in a bluish-tinted red color and is not precipitated from this solution by water. With concentrated sulfuric acid she gives an orange-red solution, which is colored red-violet by formaldehyde.

Example 2

5 g of the product of action of oleum on _{1,4-diamino-2I>} 3-dichloro-anthraquinone are briefly heated on a water bath with 50 ecm ammonia solution. The orange-red starting material turns into brown crystals, which are filtered off with suction, washed with water and methanol and dried. When exposed to acid, the substance turns orange-red. It also dissolves in concentrated sulfuric acid with orange-red fairbe. By saponifying with concentrated sulfuric acid, a product is obtained in the manner indicated above, which crystallizes excellently from nitrobenzene, dissolves in cherry red pyridine, is precipitated from this solution with water and redissolves with the addition of lye. With concentrated sulfuric acid, a yellowish solution is obtained, which is colored red-violet by formaldehyde. The reaction proceeds in a similar way if, instead of ammonia, an approximately ι ο 0/0 methylamine solution is used. With aromatic amines, the reactions are best carried out in glacial acetic acid at a low temperature.

Example 3

10 g of the product of the action of oleum i, 4-diamino-2,3-dichloro-anthraquinone and 10 g of i-amino-anthraquinone are heated in 100 cc of dry nitrobenzene 6 hours at 140 ^0th With evolution of HCl, the aranger-red starting product changes into a brown, well-crystallized body which, after cooling, is filtered off with suction, washed with nitrobenzene and methanol and dried. Saponification with concentrated sulfuric acid (see above) gives a product that is converted into a substance by vat which is apparently a derivative of indanthrene and which dyes cotton from the vat navy blue.

Example 4

log of the product of action of oleum 1.4-Diaminoanthraquinone are in 250 ecm glacial acetic acid suspended and slowly mixed with log zinc dust at room temperature, with less than Increase in temperature Reduction occurs. When the orange-red starting material in the green-yellow Reduction product is transformed, is diluted with water and sucked off. The sucked off Product is dissolved with methanol to a brownish yellow solution, the solution filtered and diluted with Hydrochloric acid added. The reaction product deposited in green-yellow leaflets is suctioned off, washed with water and dried. It dissolves in glacial acetic acid with a yellow color and green fluorescence difficult, but easy in acetone, from which it turns into yellow leaflets by adding water is deposited again.

Example 5 _Q5

log of the product of action of oleum 1.4-Diaminoanthraquinone are in 100 ecm glacial acetic acid heated to boiling with 8 g of mercaptoacetic acid until there is no more starting material. The solution is then quickly freed of impurities by suction. Crystallized from the filtrate the reaction product in yellow needles, which are suctioned off, washed with glacial acetic acid and water and be dried. The new connection dissolves, in contrast to the hydroproduct (Example 4) slightly in dilute sodium acetate solution and only with difficulty in acetone.

Example 6

log of the product of action of oleum on 1,4-diaminoanthraquinone are in 100 ecm of methanol Stirred with iog p-thiocresol at room temperature until no more starting material can be detected is. The yellow reaction product is then filtered off with suction and washed with methanol and acetone and dried. Based on the analysis (found S = 21.1 o / o, reported S = 21.50 / 0) there are 2 moles of thiocresol has been added. The compound is sparingly soluble in acetone, but dissolves in hotter dilute Soda solution and separates from it as a poorly soluble sodium salt in long orange-yellow needles when it cools.

Like p-thiocresol, other thiophenols also react, such as thiophenol, trichlorothiophenol, etc.

The thiophenols can also be used as alkali metal salts in an aqueous medium

receives the same result with appropriate processing.

Example 7

A solution of iog / J-naphthol in 50 ecm glacial acetic acid 10 g of the product of action of oleum on 1,4-diammoanthraquinone are added and stirred at room temperature, the corresponding quinhydrone in the form of deeper colors Forms small crystals. After adding 0.5 g of p-toluenesulphonic acid is heated to the boil until a sample does not have a sparingly soluble quinhydrone when it cools down separates more. The reaction product crystallizes very slowly in yellowish form from the cooled solution Crystals from which sucked off, washed with a little glacial acetic acid and with water and dried will. The condensation product is very easily soluble in acetone, it also dissolves easily at first in ether, but then spontaneously separates out of the ethereal solution in yellow crystals.

In the same way, other phenols can also be absorbed with the product of the action of oleum Condense i, 4-diaminoanthraquinone, so z. B. Resorcinol a product that works against ether similar to the condensation product with / S-naphthol behaves.

Example 8

iog of the product of action of oleum 1, 4-diaminoanthraquinone are mixed with 100 ecm sodium bisulfite solution warmed on the water bath. The orange-red starting material turns into a crystalline paste of a yellow-brown sodium salt over, which is suctioned off after cooling and washed with saline solution. It dissolves with a yellow-brown color in water, acidification gives a greenish-yellow acid, which in the case of the Oxidation with a bichromate solution gives a deep red sulfonic acid.

Example 9

iog of the product of action of oleum on 1,4-diaminoanthraquinone are ^{heated to 30 to 40 0} with iog potassium yanide and 40 ecm of water on a water bath, then the temperature rises by itself. Solution occurs and an orange-colored potassium salt crystallizes out immediately Is suctioned off immediately after cooling and washed with saline solution. Recrystallization from four times the amount of saturated sodium chloride solution gives a salt which crystallizes in long, yellow-brown needles. This easily dissolves in water with a yellow-brown color. In glacial acetic acid, a green fluorescent solution is obtained which, after diluting with water and adding dilute hydrochloric acid, separates out yellow needles. If the glacial acetic acid solution of this substance is oxidized with a solution of sodium dichromate in glacial acetic acid, brown-red crystals separate out, which dissolve violet in concentrated sulfuric acid. When the sulfuric acid solution is heated to 90 ^° , saponification occurs slowly, which leads to a blue product, probably 1,4-diaminoanthraquinone-2-carboxamide.

Example 10

20 g of the product of action of oleum on 1,4-diaminoanthraquinone are placed in an autoclave with 200 ecm of chlorobenzene, 20 ecm of butadiene are added and the mixture is first heated ^{to 80 to 90 0} for a few hours, then to 150 ^0. After cooling, the contents of the autoclave are suctioned off on a suction filter and the residue is dried. The product thus obtained is crystallized but not pure. The chlorobenzene filtrate gives yellow-brown crystals on strong concentration, which are filtered off with suction, washed with methanol and dried. The product can be recrystallized from nitrobenzene, in which it is soluble with a brownish yellow color. The solution in concentrated sulfuric acid is orange-red with orange-red fluorescence.

Claims (1)

PATENT CLAIM: Process for the preparation of derivatives of anthracene, characterized in that one the quinone-like reaction products of sulfur trioxide on 1,4-diaminoanthraquinone and its core substitution products with hydrogen, alkalis, ammonia, amines, mercaptans, phenols, bisulfite, alkali cyanide or serving. Referred publications:
German patent specification No. 268 592. © 509 534 8.55