DE678556C - Process for the production of anthraquinone dyes - Google Patents

Description

Process for the preparation of anthraquinone vat dyes. Subject of patent 675,818 is the preparation of anthraquinone derivatives by heating of 2-cyananthraquinone-3-carboxylic acids or the esters or amides thereof with benzyl cyanides. The constitution of the new products available has not been determined.

It has now been found that the anthraquinone derivatives obtainable by the process of patent 675818 can be converted into new, valuable vat dyes if they are first converted into their chlorides and then reacted with primary or secondary amines which contain a vettable ring system of the anthraquinone series . The compounds obtainable by the process of the earlier patent presumably contain a hydroxyl group which can be converted into the chloride in the same way as with carboxylic acids. Accordingly, the first stage of the new process can e.g. B. by reacting with phosphorus pentachloride, expediently in an inert high-s: edenden solvent such as nitrobenzene or Tric'hlorbenzol can be carried out. In most cases the chloride formed separates out in crystalline form. The chloride obtained in this way is distinguished by its high reactivity and easily reacts with amines with the escape of hydrochloric acid. The reaction with the amines is also expediently carried out in a high-boiling inert solvent such as r-chloro-d.-methylbenzene or trichlorobenzene. In most cases the dye obtained separates out in crystalline form, while hydrogen chloride escapes. A wide variety of primary or secondary amines, which contain a linkable ring system: the anthraquinone series, can be used for this reaction. Aminoanthraquinones, which may contain other reactive groups, are preferred.

The new vat dyes obtainable in this way are colored in red, orange or brown tones from the vat, depending on the type of components used. Example i 40 parts by weight of the anthraquinone compound obtainable according to patent 675818, example i, are added to 600 parts by weight of dry trichlorobenz oil and at i So °. C mixed with 60 parts by weight of phosphorus pentachlot @ d. After the phosphorus pentachloro has been sprinkled in, the temperature is slowly increased to 210 ° C. with simultaneous removal of the phosphorus oxychloride that forms. The difficult-to-dissolve initial compound with a yellow color dissolves. As soon as a clear solution has entered, it is allowed to cool and the chloride, which has crystallized out in large lemon-yellow prisms, is suctioned off.

a5-. Parts by weight of i-amino-5-benzoylaminoanthraquinone are in 400 Weighted @ ilen nitrobenzene to i 50 °. C, and the mixture is heated at this Temperature mixed with 18 parts by weight of the chloride described above. It kicks Immediately implement one. The dye separates well with the evolution of hydrochloric acid crystallizes. In order to bring the reaction to the end, it is heated briefly at the end to boiling: the sparingly soluble dye is suctioned off at 80 ° C; with nitrobenzene, then washed out with fuel and dried. The brown-red needles come off in Sulfuric acid with a yellow-brown color. They deliver from a grass-green vat on cotton clear orange-red colors after hanging.

Will the chloride with 5-Am @ ino-i, 9-anthrapyrimi! Din in the same way brought to implementation, one obtains a -brown needles crystallizing Dye that dissolves in sulfuric acid with a yellow-brown color and cotton The green vat has a strong brownish red color.

Example In 600 parts by weight of anhydrous nitrobenzene, 21 Parts by weight of the chloride obtainable according to Example i together with 19 parts by weight 4 - aminoanthraquinone - 2; r (N) -i ', 2' (N) -5'-chlorobenzacridone about 25 minutes to the Heated to the boil until the starting compounds can no longer be verified under the microscope are. The dye deposited in fine needles is sucked off at 100 ° C, washed and dried. The sulfuric acid solution of the black-brown crystal powder is yellow. When the sulfuric acid solution is poured into water, olive-brown ones are obtained Flakes. The dye colors the vegetable fiber from the gray-green vat in strong, real olive tones.

The 4-aminoanthraquinone-2, i (N) -1 ', 2' (N) -5'-chlorobenzacridone used can be obtained by i -amino- 4- brom@anthrach.i non - 2 - sulf ons äure reacts with the correspondingly substituted chloranthranilic acid, the sulfonic acid group splits off by reduction and causes ring closure to form acridone.

Beis piel3 28 parts by weight of finely sieved 5-amino-4'-benzoylamino- i, I'-anthrimidcarbazole (accessible according to patent specification 491428, example i) are distributed in 800 parts by weight of trichlorobenzene and at 160 to 170 ° C ao parts by weight of the a chloride described in Example i. The rapidly thickening mixture is stirred at 170 ° C. until the elimination of hydrochloric acid has ended. The 'work-up can, for. By distilling off the solvent under reduced pressure. The remaining black-brown powder dyes cotton from the yellow-brown vat red-brown.

If instead of 5-Am: no-4'-benzoylam @ ino-i, i'-anthrimide carbazole , the 4-amino-4'-benzoylamino-i, i'-anthrimidcarbazole, a dye is obtained the cotton from the brown vat dyes black-brown.

These dyes can of course also be produced in such a way that that the mentioned chloride is reacted with i-amino-4- (or -5 -) - chloranthanoquinone, the chlorine atom then in an anthrimide melt against the remainder of the i-amino-4-benzoylaminoanthraquinone exchanges and .the anthimides obtained in this way are subsequently colorazolated.

Claims (1)

PATENTARY PRUCI3: Process for the production of anthraquinone vat dyes, This indicates that the anthraquinone compounds obtainable according to patent 675 818 are in the same way as carboxylic acids are converted into chlorides and then with, primary or secondary amines that contain a linkable ring system of the anthraquinone series, implements.