DE728301C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the production of vat dyes It has been found @ That new valuable vat dyes are obtained if you q.-Aminoanthraquinone-2, 1-N-1 ', 2'-N-acridones in which a hydrogen atom of the amino group is replaced by an aryl radical is replaced, which contains a carboxylic acid halide group, with viable amines of the anthraquinone series. A special embodiment of the new invention consists in using aminoanthraquinones which are in the o-position to the amino group still contain an OH, S H or N HR group (R = H, alkyl or aryl). In the the latter. In some cases, an oxazole, thiazole or imidazole ring is formed a. The conversion of the acid halides with the amines takes place. in the presence of a additional inert solvent, such as o-dichlorobenzene, trichlorobenzene, Nitrobenzene, chloronaphthalene. or ethyl carbazole, instead of. The vat dyes obtained generally dye in green tones and are similar to green vat dyeing dyes superior to the anthraquinone acridone series in terms of lightfastness. In organic solvents they are generally sparingly soluble and can be recrystallized from quinoline will. They dissolve in sulfuric acid with a brown color. The vat color is red-violet to reddish brown.

The q.-arylaminoanthraquinone-2, iN-i ', 2'-N-acridonecarboxylic acids serving as starting compounds are obtained by reacting q.-aminoanthraquinone-2, iN-i', 2'-N-acridones with halobenzoic acid esters. The esters are then saponified to carboxylic acids and z. B. converted into the acid halides with thionyl chloride. The starting compounds can also be obtained by reacting 1,4-dihaloanthraquinone-2-carboxylic acids with 1 mol of an aminobenzoic acid ester to give the acridone and then replacing the halogen in the 4-position by an arylamine radical. The ester is then saponified in the customary manner and heats the carboxyl group in the chloride converted (see. Also the patent specification 444 984 and 495 975) Example i ii parts by weight of a-Aminoanthracbinonwerden in 8oo parts by weight of nitrobenzene to 1200. At this temperature 24 parts by weight of 3 ', 5-dichloroanthraquinone-2, 1-N-1', 2'-N-benzolaeridone-4 (anilido-p-carboxylic acid chloride) are added and the mixture is stirred at 130 'until the evolution of hydrogen chloride has ended. The dye is filtered off with suction at 90 °, washed with nitrobenzene and dried. The green dye powder combines with burgundy color and dyes cotton in green tones.

If i - amino - 5 - benzoylaminoanthraquinone is used instead of the a-aminoanthraohinone, a yellowish olive green dyeing dye is obtained in this way; 4-amino-i, 9-anthrapyrimidine also provides an olive green dye. Against it arises by reacting the acid chloride with 4-amino-5'-chloroanthraquinone-2, 2'-N-benzolacridone a dye that turns the vegetable fiber from a dull purple vat into a greenish blue colors.

The carboxylic acid chloride used for the reaction is obtained by condensation of 4-amino-3 ', 5'-dichloroanthraquinone-2, iN-1'-, 2'-N-benzolacridebns (cf. Example i of patent 5310.3) methyl bromobenzoate in nitrobenzene solution in the presence of potassium acetate and copper. The ester, which crystallizes in blue-black needles, is then saponified under alkaline conditions and the carboxylic acid is converted into the chloride with thionyl chloride in triclorobenzene at up to 95 °.

. Example 2 5 parts by weight of the 3 'shown in Example i, 5'-dichloroanthraquinone-2, i-N-i'- 2'-N -benzolacridon-4 (anilido-m-carbonate chloride) Earth together with 5 parts by weight of a aminoantlirachinon in 16o parts by weight of anhydrous trichlorobenzene slowly heated to the boil. After conversion of the carboxylic acid chlorine: it becomes difficult soluble dye. sucked off about 12o °, washed with pyridine and dried. The dye, which crystallizes in green needles, dyes cotton from violet-brown Vat green.

Example 3 26 parts by weight of that obtainable in the manner described above 5'-chloroanthraquinone-2, i-N-i'.a'-N-benzolacridone-4- (anilido-p-carboxylic acid chloride) and 12 parts by weight of 2-amino-3-oxyanthraquinone are heated in parts by weight Nitrobenzene to the boil for a few hours. The green dye is sucked off warm, washed with nitrobenzene and dry.

The still alkali-sensitive compound is then briefly heated to boiling in ethyl carbazole and, after dilution with pyridine, filtered off at 100 °. The dye has the following composition Obtained in the form of beautiful, green crystals, which dissolve in sulfuric acid to a yellow-brown color and, from the red-brown vat, turn cotton into a yellow-tinged green after hanging. If the 2-amino-3-oxyanthraquinone is replaced by the i-amino-2-oxyanthraquinone, the isomeric 2, i-oxazole is formed, which gives cotton from a dull red-brown vat a strong greenish olive color.

A higher-boiling solvent is used instead of nitrobenzene used in the implementation, the pure osazole is obtained immediately. example A mixture consisting of 13 parts by weight. 5'-chloranthraquinone-2, 1-N-1 ', 2'-N-benzolacridone-4.- (anilido-p-carboxylic acid chloride), obtainable according to the example 2 of patent 531 013, and 7 parts by weight of 2-amino-3-mercaptoanthraquinone is entered at 120 to 130 ° in ¢ 0o parts by weight of α-chloronaphthalene and gradually heated to 26o °. From the originally green. Solution separate at boiling point green needles off. Heat to the boil for about 30 minutes and filter the green one Dye at 10 °. After drying, it represents a green dye powder, that after crystallization from quinoline cotton from a black-brown vat yellow-green colors.

That from 4-chloroanthraquinone-2, i-N-1 ', 2'-N-benzolacridone-4 .- (anilido-p-carboxylic acid chloride) thiazole obtainable with 2-amino-3-mercaptoanthraquinone has a slightly more bluish tint green..

The dye of the following composition which can be represented in the same way dyes cotton a bluish green.

The thiazoles obtainable from i-mercapto-2-aminöanthraquinone provide olive green dyes.

Example 5 By heating to 26o ° for about one hour 26 parts by weight of 5'-chloroanthraquinone-2, iN-i ', 2'-N-benzolacridone-q .- (anilidop-carboxylic acid chloride) and 18 parts by weight of i-anilido-2-aminoanthraquinone in 4.o_ parts by weight of a-chloronaphthalene gives the dye of the following composition which is sucked off at room temperature. It can be recrystallized from nitrobenzene and dyes cotton from a red-brown vat green.

Claims (1)

Claim: Process for the production of vat dyes, characterized in that 4-aminoanthraquinone-2, iN-i ', a'-N-acridones, in which one hydrogen atom of the amino group is replaced by an aryl radical containing a carboxylic acid halide group, with connectable amines the anthraquinone series are implemented.