DE743677C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the production of vat dyes It was found that vat dyes with valuable properties can be produced if on compounds of the general formula R, -NH-Rr-NH-R3, in which R is a naphthalene radical represents which contains at least one imide group bonded in the ß-position, wherein furthermore R1 and R3 represent organic radicals which can be linked to sulfonic acid groups Contain groups, and in which finally in the radicals R1 and R3 at least one of the substitutable carbon atoms adjacent to the imide groups are bonded to hydrogen contains, allows condensing agents to act.

The compounds of the above general formula which are used as starting materials can be obtained, for example, if at least two halogen atoms are present. a naphthalenes in the β-position is reacted with amino compounds which are free from sulfonic acid groups and which have at least one unsubstituted ortho position to the amino group and groups that can be linked. The manufacture of such products is described in French patent 847,525 , for example. In these products, the groups R, NH - and R3; VH - can be identical or different from one another. Radicals R1 containing linkable groups are, for. B. those that contain ring-shaped carbonyl groups are considered. They can be anthraquinone radicals or higher fused ring systems; such connections are e.g. B. Aminoanthraquinones, such as the r-aminoanthraquinone and the r-aminoarylaminoanthraquinones, also in particular aminoacylaminoanthraquinones, in which the acyl radical can be the radical of an aliphatic, aromatic, aliphatic-aromatic or heterocyclic acid, such as i Ainino-4-benzoylainino- 5-lienzoyla.minoanthrachinorie, 1-Amino-5 -benzoy lamino-8-methoxyantl3rachinone, i Alnino-5, 8-dibenzoylalninoantlirachinone, i-Ainino-5-acetylaininoantlirachinone, i-Atnino-5-cinnatnoyl - i-Atnino-5-cinnatnoyl -pyridoylaminoanthraquinones and i -aminoantlirachinonylaminoanthracliilione, further aminodibenzanthrones and -isodibenzantlirones as well as aminopyranthrones, «-more Aminoanthraquinone.derivate whose i- and 9-positions are, the i- and 9-positions, 9-amino-anthrino, 9-iyrapyridone members of a lieterocyclic ring, 9-iyrapyrine, 9-iyrapyridone, like alil-anthrino-anthrinoyr, 9-iyrapyridone, 9-anthrino-pyrimidone, 9-aminodibenzanthrones and -isodibenzantlirones, , Amino-i, 9-isothiazolanthrone and Amino- i, 9-pyrazolantlirone, finally also those Aminoantliracliinon.derivate in which two are i N o-position to each other carbon atoms are members of a heterocyclic ring system, as z. B. is the case with the aminoanthraquinone acridones. All of these compounds can contain further substituents.

In particular, the products listed above give good results Formula in which R, and R3 represent anthraquinone radicals which are represented by at least one Acylaininogrttppe, for example a beiizoylamino group in the 4- 'or 5-position are substituted.

At least one of the groups mentioned must be in the ß-position be bound to the naphthalene residue R. Otherwise there are any binding sites into consideration, e.g. B. the 2, (- and i, 6-positions of naphthalene, with the naphthalene radical may contain even more substituents, such as alkoxy groups.

As a condensing agent, the preference - have as acidic nature and can be used combined with each other or together with indifferent "#` erdünnungsmitteln itself, are: aluminum chloride, acetyl chloride, Chlorstilfonsäure and particularly high-percentage sulfuric The action of the condensing agent can. carried out at low, medium or, if necessary, greatly increased temperature.

In some cases it is possible to use the present method in such a way to carry out in several procedural stages that for the time being \ -bindungen of the general Formula R, -NH-R2- Hal, tvorin Hal represents a halogen atom and R1 and R2 the above have mentioned meaning, treated with condensing agents, the obtained Products reacted with amines containing linkable groups and optionally treated again with condensing agents. The products obtained can if necessary purified by recrystallization, reprecipitation or in vats a form that is favorable for practical use can be carried over. In most Cases is e: advantageous, following treatment with condensing agents a treatment with oxidizing agents, optionally in an aqueous acidic medium to connect z. B. using nitrites, hypochlorites or perborates, or by passing full air through.

The constitution of those obtainable by your present method Products has not yet been clearly identified; however, it is very likely that in the action of condensing agents on the starting materials mentioned carbazole-like Rings arise.

The nitrogen-containing ones obtainable by the present process Naphthalene condensation products are valuable vat dyes. You own for dyeing and printing a wide variety of fibers, such as wool or silk, but especially cellulosic fibers such as cotton and other vegetable fibers Fibers., Then synthetic silk, e.g. B. regenerated cellulose, as well as rayon and others Man-made staple fibers. They can be prepared using the methods known for vat dyes z. B. from medium or strongly alkaline bath, with or without addition of salt, also in the form of their conventionally preparable Lenkoestersalze according to the for this class of dye derivatives is known -, misfires, and produces tones of good to very good fastness properties.

When using sulfur-containing condensing agents, such as. B. Sulfuric acid, products can be obtained that have a low sulfur content without the water solubility of these dyes being determined can.

It is known, from 2,6-di- (2'-broln-i'-anthraquinonyl-amino) -naphthalene a vat dye containing two carbazole rings with elimination of hydrogen bromide to manufacture. However, this known method leads to a poor yield practically worthless product.

Example i 15 parts of anhydrous sodium carbonate and 15 parts of dehydrated Sodium acetate is boiled in 500 parts of nitrobenzene until 50 parts of nitrobenzene have been distilled off. After cooling to 2oo °, 14.3 Parts of 2,6-dibromonaphthalene, 35.2 parts of i-amino-4-benzoylaminoanthraquinone and 1,3 Parts of copper chloride are added and the reaction mixture is heated to 195 for 24 hours Stirred to 2o5 °. It is then filtered hot, with nitrobenzene and with benzene and alcohol washed and the product obtained for further purification Boiled with dilute hydrochloric acid, filtered off, washed and dried. Man receives a brownish black, crystalline powder in good yield, the conc. Sulfuric acid turns olive green over. _ 3 50 ° melts and does not condense.

3. Parts of the di- (4 'benzoylamina - i' - anthraquinonyl obtained in this way - (2, 6 - Diiaminonaphthalins are at a temperature of 0 to 6 ° in 54 parts 96% sulfuric acid entered and stirred for 18 hours at this temperature. To terminate the formation of the dye, atrium nitrite is added in ice to which a little N-atrium nitrite is added has been entered, stirred vigorously for 1 1/2 hours and then filtered and washed and dried. The dye forms a dark powder that is concentrated in Sulfuric acid with a green color dissolves and cotton from a pure blue-red vat in strong, colors pure and very real violet tones. Example ': 4,3 part 2, 6-dibromonaphtbalin, io, 5 T @ -ile i - amino - 5 - benzoylaminoanthraquinone, 4.5 parts calc. Soda, 4.5 Parts of dehydrated sodium acetate and 0.4 parts of copper chloride are used in 90 parts Distributed dry nitrobenzene and for 16 hours .at a temperature of igo held up to 2oo °. The reaction mixture is filtered hot, the residue with Washed nitrobenzene, benzene and alcohol; and for cleaning with dilute hydrochloric acid Boiled: A brown, crystalline powder is obtained in good yield, which Dissolves in concentrated sulfuric acid with a grass green color and has a melting point over 35o °.

3 parts of the di- (5'benzoylamino- i'-anthraquinonyl) -2, 6-diaminonaphthaIins obtained in this way are introduced into 54 parts of 96% sulfuric acid at from 0 to 6 ° and stirred for 8 hours at this temperature. Now you enter in ice, give about 0.8 parts. Sodium nitrite is added and the mixture is stirred vigorously for 2 hours. The reaction is now complete and the dye obtained in excellent yield can be filtered off, washed and dried. It forms a red-brown. Powder that dissolves in concentrated sulfuric acid with an olive green color and: dyes cotton from a pure blue-red vat in very real, pure, red-brown tones. -Example 3 14.3 parts of 2, 6-Dibromnaphth, alin, 24.5 parts of i-aminoanthraquinone, 15 parts of dehydrated sodium acetate, 15 parts of anhydrous sodium carbonate and i, 3 parts of cuprous chloride are distributed in 45oTeilen dry nitrobenzene and at 24 hours a temperature of igo to 2oo ° stirred. The reaction mixture is filtered hot, the residue is washed out with nitrobenzene and benzene and alcohol and, for cleaning, first boiled with dilute hydrochloric acid and then with alcohol. A violet-black, crystalline powder is obtained in good yield, the conc. Sulfuric acid olive green, colors, has a melting point of 370 to 38o ° and does not vat.

i part of the di- (i'anthraquinonyl) -2, 6 - diaminonaphthalene obtained in this way is mixed with 1d parts of anhydrous aluminum chloride and 3 parts of dry sodium chloride and heated to 150 to 160 ° with stirring until the dye formation: g is finished. Now it is poured into ice, boiled up with dilute hydrochloric acid, filtered, washed with water, slurried the dye in plenty of water, added 0.3 part of sodium nitrite, acidified a little and stirred for 24 hours at ordinary temperature. Then it is filtered off, washed thoroughly with water and pasted with water. The dye obtained in this way is a brown powder which dyes cotton from a brown-red vat in red-brown, real shades.

In place of sodium nitrite, Sodium Bichrom.at or Sodium Chlorate can also be used. Example 4 i part - di- (5'-benzoylamino-r'-anthraquinonyl) -2, 6-diaminonaphthalene (see Example 2, i: paragraph) is added at 18 to 22 ° in 45 parts of 96% sulfuric acid and 30 hours, stirred at 18 to 22 °. Now it is put into ice, 0.3 parts of sodium nitrite are added and the mixture is stirred vigorously at 0 to 5 ° for 24 hours. The dye obtained in excellent yield can be filtered off, washed and dried. It forms a black, greenish shimmering powder that dissolves in sulfuric acid with an olive-brown color and dyes cotton from a ruby-red vat in chlorine-, wash-, beech- and lightfast red-brown tones.

The condensation can also be carried out with a smaller amount of sulfuric acid. - The analysis shows that the product contains about 0.60 / 0 sulfur. Example sz Part di- (5'-benzoylamino-i'-anthraquinonyl) -2, 6-diaminonaphthalene (see Example 2, 1st paragraph) is added at 0 ° to 5 ° in 45 ° to 100% sulfuric acid and 22 Stirred at 0 to 5 ° for hours. Now it is poured into ice, 0.3 parts of sodium dichromate are added and the mixture is stirred vigorously for 24 hours. The dye obtained in good yield is probably identical to the red-brown dye shown in Example 4.

Example 6 2.5 parts of 2,6-dibromonaphthlialin, 5.4 parts-1,4mino-5-acetylaininoanthraquinone, 2.3 parts of anhydrous sodium carbonate, 2.3 parts of dehydrated sodium acetate and o, 2 parts of copper chloride are distributed in 72 parts of dry nitrobenzene and under Stir to the boil. When the reaction has ended, the mixture is filtered hot and the residue washed with nitrobenzene, benzene and alcohol, boiled with dilute acid, filtered, washed and dried. A brown-black color is obtained in good yield Powder, which is in conc. Sulfuric acid with an olive-brown color dissolves, but not at 46o ° melts and does not clump.

i part of the thus obtained di- (5'-acetyl - «. inino-i'-anthraquinonyl) -2, 6-diamittonaphthalene is added at 18 to 22 ° in a 25 "file of 96% sulfuric acid and stirred for 24 hours at 18 to 22 °. Now it is entered in ice, with 0.3 parts Added sodium nitrite and stirred for 24 hours at 0 to 18 '. The dye obtained is a black powder that dissolves in sulfuric acid with a blue-green color and Cotton from a burgundy vat dyes in real red-brown tones. Example ; 14., 3 parts: 2,6-Dibroinnaplitlialin, 35,2'Ceile 4 - Aminoantlirachinon - 2, 1 - (N) - benzolacridone, 15 parts anhydrous sodium, carbonate, 15 parts dehydrated Sodium acetate and 1.5 parts of copper chloride are dissolved in 450 parts of dry nitrobenzene distributed and stirred for 24 hours at the zoo up to 2o6 °. When the reaction is complete filtered hot, washed with nitrobenzene, benzene and alcohol, with dilute acid boiled, filtered, washed and dried.

1 part of this product is stirred with 12 parts of anhydrous aluminum chloride and 3 parts of dry atrium chloride and 2 stauids at 150 ° to 160 °. Now it is poured into ice, boiled up with dilute hydrochloric acid, filtered off, washed, slurried in plenty of water, 0.3 part of sodium mitrite is added, a little acidified and stirred: 24 hours vigorously at 0 to 18 °. The dye thus obtained dissolves in conc. Sulfuric acid with blue color and dyes cotton in gray tones.

Example 8 Part of the condensation product from 1 mol 2, 6-Dibroninaphthlialin and 2 moles of 5-aminoantlirachinori = 2, i- (N) -benzolacridorC, analogous to that in, Example 7, 1st paragraph described, can be obtained, is at 18 to 22 ° in 45 parts Entered 960% sulfuric acid and stirred for 24 hours at 18 to 22 °. Well wears inan in ice, 0.3 part of sodium dichromate is added and the mixture is stirred for 16 hours at 18 up to 22 °. The dye thus obtained is filtered off, washed and made into a paste with water. It dissolves blood red in conc. Sulfuric acid and dyes cotton from red-violet Vat purple.

Example 9. 2.86 parts of 2,6-dibromonaphthalene, 5.43 parts of 5-aniino-i, 9-antlirapyrimidine, 3 parts of dehydrated sodium acetate, 3 parts of anhydrous sodium carbonate and 0.26 part of copper chloride are boiled for 24 hours with stirring in 90 parts of dry nitrobenzene heated. It is then filtered hot and the residue is purified as usual.

Part of the resulting unisposition product from 1 'N101 2, 6-bibroninaphthlialin and 2 mol of 5-anrino-1, 9-anthrapyrimidine is introduced into 45 parts of 96% strength sulfuric acid at 18 to 22 ° and stirred for 24 hours at 18 to 22 ° . = It is poured onto ice, 0.3 part of sodium nitrite is added and the mixture is stirred at 0 ° to 5 ° for 16 hours. The dye thus obtained is filtered off, washed neutral and pasted with water. It dissolves dirty green in conc. Sulfuric acid and dyes cotton from a yellow-brown vat in brown-violet tones.

The condensation can also be carried out using a smaller amount of sulfuric acid. Example 10 12 parts of anhydrous aluminum chloride are mixed with 3 parts of dry sodium chloride and melted at 120 ° with stirring. Now i part of the reaction product from i moles of 2,6-diliromonaphthalene and 2 11o1 5 aminoantlirachinon-2, i- (N) -ben: zolacridone (see Example 8) is added and the mixture is stirred for 2 hours at 150-155 °. Finally, the melt is poured into ice, boiled with dilute hydrochloric acid and the dye obtained is filtered off. It dissolves brown-violet in conc. Sulfuric acid and dyes cotton from a purple vat in purple, real tones. Example ii 5.8 parts of 2,6-dibroinnaplitlialin, 7 parts of i-amino-5-benzoylaniinoanthracliinone, 3 parts of anhydrous sodium carbonate, 3 parts of dehydrated sodium acetate and 0.25 parts of copper chloride are distributed in i45 parts of dry nitrobenz oil and stirred for 16 hours heated to 155 to 160 °. It is then filtered hot. A dark powder separates from the filtrate when it cools down, completely only after the addition of alcohol. Sulfuric acid dissolves green and does not condense.

9.5 parts of this reaction product -from 1 mol of 2,6-dibromonnaphthalene and i 1 \ 1.o1 i-amino-5-b, enzoylambioanthanoquinone become. in 360 parts of 96% sulfuric acid on; getxagen .. and stirred for 24 hours at room temperature. Now you pour on Ice, * add 3 parts of sodium nitrite and stir for 24 hours at 0 to 18 °. Then it will be the dye formed is filtered off, washed and dried. He puts a black one Powder that does not yet melt at 46o °, in conc. Sulfuric acid dissolves green and dyes cotton from a red vat in brown tones.

2 parts of the dye obtained in the 2nd paragraph are 1.4 parts i-Amino-5-benzoylarninoantraclinone in boiling nitrobenzene in the presence of i Part dehydrated sodium acetate, i part anhydrous sodium carbonate and o, i part Copper chloride implemented. A black powder is obtained, which is concentrated in Sulfuric acid dissolves green and stains cotton from a violet vat brown.

Part of the dye obtained in paragraph 3 is treated in the usual way with concentrated sulfuric acid and post-oxidized with sodium nitrite. Practically the same dye is obtained as in Example 2., Example 12 i part of the reaction product from i mole of 2- (5'-benzoylamino-i'-antlzrachinonyl) -amino-6-bromonaphthalene (see example ii, i. Paragraph) and 1 mol of i-amino-4-benzoylaminoanthraquinone is introduced into 45 parts of 96% sulfuric acid and stirred for 24 hours at 18 to 22 °. It is then poured onto ice, 0.3 part of sodium nitrite is added and the mixture is stirred for 24 hours at 0 to z8 °. The dye formed forms a black powder that is soluble in concentrated sulfuric acid with a green color and dyes cotton from a red vat in very real Bordeaux tones.

Similar dyes are obtained if either the reaction product of 1 mol of 2- (4'-benzoylamino-i'-anthraquinonyl) -amino-6-bromonaphthalene and 1 mol of i-amino-5-benzoylaminoanthraquinone for the treatment with high percentage sulfuric acid or that Product is used which is obtained by simultaneous reaction of 1 mole of 2,6-dibromonaphthalene with 1 mole of i-amino-5-benzoylaminoanthraquinone and 1 mole of i-amino-4-benzoylaminoanthracliinone. EXAMPLE 13 3.8 parts of the reaction product of 1 mole of 2,6-dibromonaphthalene and 1 mole of i-amino-5-benzoylaininoanthraquinone, obtained according to example ii, paragraph i, line 4-amino-i, 9-anthrapyrimidine, 20 parts of anhydrous sodium carbonate , 2o parts of dehydrated sodium acetate and 2 parts of copper chloride are distributed in 65o parts of dry nitrobenzene and heated with stirring for 24 hours at a temperature of 2o6 °. Now it is filtered hot. When the filtrate cools, a dark brown powder separates out, which dissolves in concentrated sulfuric acid with a brown color and which is difficult to vat.

0.5 part of this reaction product from 2 - (5'-benzoylamino-i'-anthraquinonyl) -amino-6-bromonaphthalene and 4-amino-i, g-anthrapyrimidine are added in 22 parts of 6% strength sulfuric acid and stirred for 24 hours at 18 to 22 °. Then it is poured onto ice, 0.15 parts of sodium nitrite are added and stir for 24 hours at o to 18 °. The dye thus obtained dyes cotton from a brown vat in brown tones.

Example 14 2.86 parts of 2,6-dibromonaphthalene, 3.4 parts of 5-amino-anthraquinone-2, i- (N) -benzolacridone, 2 parts of anhydrous sodium carbonate, 2 parts of dehydrated Sodium acetate and 0.25 inches of copper chloride are mixed in two parts with dry nitrobenzene distributed and heated with stirring to 150 ° for 24 hours, then to 170 ° for 5 hours. It is then filtered hot. After cooling, the reaction product separates from the filtrate away. It is filtered, washed with nitrobenzene, benzene and alcohol and obtained a blue-black powder when dry. This is done in the usual way with 1 mole of i-aminoan: thrachinon brought to reaction.

0.5 part of this product is mixed with 6 parts of anhydrous aluminum chloride and 45 parts of dry sodium chloride and stirred at 150 ° for 2 hours. It is then poured onto ice, filtered off, washed, slurried in water, 0.15 parts of sodium nitrite added, acidified with a little sulfuric acid and stirred at 0 ° to 18 ° for 2q hours. The resulting dye forms a black powder that dyes cotton from a purple vat in purple tones. EXAMPLE 15 18 parts of dehydrated sodium acetate and 18 parts of anhydrous sodium carbonate are kept at the boil with 48o parts of nitrobenzene until 48 parts of nitrobenzene have distilled off. After cooling to igo to 200 ° (bath temperature) "-erden r9.1 parts r, 6-dibromo-2-methoxynaphthalene, 43.5 parts r-amino-5-benzoylaminoanthraquinone and rx6 parts copper chloride are added and qo hours at 193 to 23 ° stirred, Now is filtered hot, the residue washed with -nitrobenzene and benzel and alcohol and boiled for cleaning with dilute hydrochloric acid, filtered, the residue washed out and dried. A dark brown powder is obtained in very good yield, which is in conc. Sulfuric acid dissolves with an olive-green color that changes to reddish-brown, has a melting point above 300 ° and has a brown color.

5 parts of the thus obtained di - (5 '- benzoylamino - i' -antlirachinonyl) . 1.6 - @ diamino-2-methoxynaphthalene are introduced into 90 parts of 96% strength sulfuric acid and stirred for 16 hours at 2o to 25 °. Now you enter in ice, give 5 parts of N atrium dichromate and stir first: 2 hours at 0 to 20 °, then 6 hours at 5o °. The reaction is now complete and the dye obtained in good yield can be filtered off, washed out and made into a paste. He dyes cotton from purple-brown Vat in strong, red-brown tones.

The condensation product of one mole of i, 6-dibromo-2-nietlioxynaphthalene and 2 11o1 i-amino-.I-benzoylaminoanthraquinone gives when stirred with conc. sulfuric acid at 0 to 5 ° and post-oxidizing with sodium nitrite a dye, cotton dyes from blue-red vat in blackish-olive tones.

If the condensation product of i mol r r, 6-dibromo-2-metlioxynaphthaliii and 2 moles of i-aminoantlirachinon with a mixture of aluminum chloride and common salt stirred at iqo to 15o °, then poured into ice; filtered and sulfuric acid with If sodium nitrite is post-oxidized, a dye is obtained, the cotton from red-brown Küpe colors in blackish brown tones. Example 16 14.3 Tele 2,6-Dibromonaphthalene be, with 5i parts of aminodibenzanthrone in the presence of 43 parts of copper chloride, 15 parts of anhydrous sodium carbonate and 15 parts of dehydrated sodium acetate implemented in q.8o parts of boiling, dry nitrobenzene. That 'in the usual way Reconditioned product is a black powder.

"One part of the product is mixed with two parts of anhydrous aluminum chloride and 3 parts of dry sodium chloride and stirred for 2 hours at 150 to 160 °. Then it is poured onto ice, boiled up with dilute hydrochloric acid, filtered off, washed well, and added in a lot of water and, after adding 0.3 parts of sodium nitrite and 2 parts of concentrated sulfuric acid, stirred for 2q hours at 0 ° to 18 ° The dye thus obtained dissolves in purple in concentrated sulfuric acid and dyes cotton from a blue vat in blue-gray tones .

In a corresponding manner one can from i part of the condensation product from 1 mole of 2,6-dibromonaphthalene and 2 moles of Aminoantha.nthron, 12 parts of anhydrous Aluminum chloride and 3 parts of dry sodium chloride obtained a dye, which is grass green in conc. Sulfuric acid dissolves and cotton from red-violet vat colors in violet-gray tones.

Claims (2)

PATENT CLAIMS: i. Process for the production of vat dyes, characterized in that compounds of the general formula Rl-NH-R2-NH-R3, where R2 is a naphthalene radical which contains at least one of the iniid groups in contains bonded ß-position, in which also R, and R3 su.lfonsäuregruppe-free organic Represent residues which contain linkable groups, and in which finite in the residues R1 and R3 at least one of the substitutable carbon atoms adjacent to the imide groups 'Contains hydrogen bonded, allows condensing agents to act. 2nd embodiment of the method according to claim i, characterized in that compounds of the general formula R.-NH-R2-Hal, 'in which Hal stands for a halogen atom and R1 and R2 have the meaning given above, treated with condensing agents, the products obtained are reacted further with amines containing linkable groups and optionally the products obtained again with condensing agents treated. To distinguish the subject of the application from the state of the art are The following publications were considered in the granting procedure: German Patents ..... No. 263. [24 and 653 67, I.