DE643608C - Process for the preparation of polyoxy compounds of the dibenzanthrone series - Google Patents

Description

Process for the preparation of polyoxy compounds of the dibenzanthrone series It has been found that polyoxy compounds of the dibenzanthrone series are obtained when one Bz-Amino-Bz 2-Bz a'-diöxydibenzanthrone or the corresponding quinones with treated with hydrolyzing agents.

The starting materials are the compounds of the following structure and called their descendants.

Hydrolyzing agents include, for example, water and solutions of acids, bases or salts in water or other diluents. The implementation is in. generally expediently effected by heating. The split the amino compounds can sometimes also advantageously be carried out in the same operation how to carry out their manufacture. So you get z. B. by about Heating a slurry of the Bz 3-Bz 3'-diamino-Bz2-Bz2'-dioxydibenzanthrone for 10 hours in dilute sulfuric acid to 22o to 230 ° in good yield the Bz 2-Bz 2 ', Bz 3-Bz 3'-tetraoxydibenzanthrone. Obtainable from your according to Example'-6 of the patent 62..637 Dibron`r7. =, Bz 3 - Bz 3'- diamino- Bz 2 - Bz 2'- dioxvdibenz- @ "anthrone arises under these conditions a dibrometraoxydibenzantlirone. To its manufacture but you can also use the solution of dibronidiaminodioxvdibenzanthrons obtainable according to the example mentioned in concentrated sulfuric acid after separation of undissolved components and after Dilute with water and heat to 220 to 23o °.

If you go from the diaminodichinone instead of the diaminodioxydibenzanthrone off, you get the corresponding dichinone.

If desired, the polyoxydibenzanthrones can be passed through Urn crystallize from or by washing with concentrated or moderately diluted Purify sulfuric acid. In some cases it is possible to manufacture the Polvoxydibenzanthrone the introduction of further atoms or residues connect. So. You can z. B. by Heating of Bz 3 - aminodil> enzanthron-Bz 2-Bz2'-ch: inone with dilute hydrochloric acid simultaneously obtained a chlorine-containing compound. Even with the implementation of Bz 3-Amino-Bz 2-Bz: '- @ dioxydibenzanthrons with dilute hydrochloric acid are sometimes formed chlorine-containing compounds.

The polyoxydibenzanthrones are partly dyes, partly they can be used for the production of dyes. Example i 25 parts of Bz 3, Nmino-Bz 2-8z 2'-dioxydibenzanthrone, obtainable according to Patent 624 6 37, Example 13, are heated with 75o parts of 10% sulfuric acid for 10 hours to 22o to 230%. After cooling, the compound obtained in almost the calculated yield is filtered off with suction and, if desired, recrystallized from concentrated or moderately dilute sulfuric acid for purification. The concentrated solution of the purified compound in pyridine is yellowish green; when diluted with more pyridine it becomes greenish blue. The compound dissolves in purple in concentrated sulfuric acid. After production, analysis and properties, the Bz 2-Bz 2'-Bz 3-Trioxy dibenzanthron is available. It provides a greenish blue vat from which cotton is dyed in strong blue-green tones.

Instead of dilute sulfuric acid, one can split off the Amino group also use dilute hydrochloric acid, acetic acid or soda solution, whereby if dilute hydrochloric acid is used, a chlorine-containing acid is used at the same time Connection received.

Example 2 25 parts of Bz3-Aniinodibenzanthron-Bz2-Bz 2'-quinone, available by oxidation of the Bz 3-amino-Bz 2-Bz 2'-dioxvdibenzanthrone used in Example i with ferric sulfate in dilute sulfuric acid, it is heated with 75o parts of iop% Sulfuric acid at 22o to 23o ° for ten hours. Blue-green needles are obtained which sucked off, washed with water and dried. The one in excellent yield The resulting dye is almost completely nitrogen-free. He dissolves in more concentrated Sulfuric acid with a cloudy, brownish-violet color; by adding hydroquinone the solution becomes purely bluish purple.

The new dye, which is to be regarded as the quinone of the Bz 2-Bz 2'-Bz 3-trioxydibenzanthrone described in Example i, can be reduced to the trioxy compound by dilute sodium bisulfite solution. Example 3 25 parts of Bz 3-Bz 3'-diaminodibenzanthrone - Bz 2 - BZ 2'-quinone, obtainable by oxidation of Bz 3-Bz 3'-D @amino-Bz 2-, which can be prepared according to Patent 624637, Example 1.4, are added Bz 2'-dioxydibenzanthrons with ferric sulphate in dilute sulfuric acid, by dissolving in concentrated sulfuric acid and precipitating with water in fine division and then heated with 750 parts of 10% sulfuric acid for 10 hours at 22o to 23o °. As good as nitrogen-free, olive-gray needles are obtained, which dissolve in concentrated sulfuric acid with a brownish-olive color; when hydroquinone is added, the solution turns blue-violet. The new compound is Bz 3-Bz 3'-dioxydibenzanthrone - Bz 2-Bz 2'-quinone, which turns into Bz 2-Bz 2 ', Bz 3-Bz 3'-tetraoxydibenzanthrone by boiling with dilute sodium bisulfite solution. The concentrated solution of the reduced compound in pyridine is green; when diluted with more pyridine, the color changes to violet-blue. It produces olive-green dyeings on cotton from a greenish blue vat.

If one uses instead of Bz 3-Bz 3'-diaminodibenzanthrone-Bz 2-Bz 2'-quinone 25 teriles Bz 3-Bz 3'-Iaiamino-Bz 2-Bz 2'-dioxydibenzanthrone, the Bz mentioned in the first paragraph is obtained immediately 2-Bz 2 ', Bz 3-Bz 3'-tetraoxydibenzanthrone. Example 4 25 parts of dibromo-Bz 3-Bz 3'-diaminodibenzanthrone-Bz 2-Bz 2'-quinone, obtainable by oxidation of the dibromo-Bz 2-Bz 2'-dioxy which can be prepared according to Patent 624637, Example z6, are treated -Bz 3-Bz 3 '-, diaminodibenzanthrons with ferric sulfate in dilute sulfuric acid, in the manner indicated in Beispie13 with 10% sulfuric acid. This gives a D.ibrom-Bz 3-Bz 3'-dioxydib; enzanthron-Bz 2 - Bz 2 '- chin, :) n. This dissolves in concentrated sulfuric acid with a slightly brownish color, which turns violet when hydroquinone is added. The concentrated solution of the compound reduced with sodium bisulfite solution in Pyrvdin is green and turns blue when diluted with more pyridine.

The same compound is obtained if the according to Example 16 of the Patent 624 637 available purple solution of Aminoverbin-Jung in concentrated Sulfuric acid diluted with water after separation of undissolved components and for a while heated to 22o, to 23o °.

If instead of Dibrom-Bz 3-Bz 3 '-. Diaminodibenzanthron-Bz 2-Bz 2'-quinone a chlorine-containing Bz3-Bz 3'-D-iam, inodibenzanthron-Bz 2-Bz 2'-quinone, how to do it B. from a chlorinated Bz 2-Bz 2'-dimethoxydibenzanthrone according to the patent 514433 by nitration, reduction and oxidation to the quinone according to Paragraph i of the present For example, a chlorine-containing Bz3-Bz3'-D, ioxydibenzanthron-Bz2-Bz is obtained 2'-quinone.

Claims (1)

PATENT CLAIM A process for the production of polyoxy compounds of the dibenzanthrone series, characterized in that Bz-amino - Bz 2 - Bz 2'-dioxydibenzanthrones or the corresponding quinones are treated with hydrolyzing agents.