DE742765C - Process for the preparation of tris and polyazo dyes - Google Patents

Description

Process for the preparation of tris and polyazo dyes It was found that valuable new tris and polyazo dyes according to the known Arbeitsweisien He r, @ estellt can be, if you build up such dyes at least once Components used which contain the binuclear 8-oxyquinoline residue with unoccupied Contain 2-position, and optionally metal complexing agents on the dyes can act.

To produce the 'dyes can, for. B. the procedures applied be, in which an initial component is diazotized, with a middle component combined, the obtained aminoazo dye further diazo @ tiert, again with a Middle component. united and the resulting amino, dis.azofarb substance after renewed Diazo ation is combined with an end component.

But you don't have to rely on it as the beginning or end component 8-oxyquinoline to use. If the trisazo dye still has diazotizable groups or into such convertible groups, which, if necessary, include conversion in amino groups, can be diazotized, so can such a diazotrisazo compound combined with the compounds containing the above-mentioned 8-Oxychnolingru! ppierun, g will.

Polyazo dyes can also be prepared by Tetrazoverbindungen are first krmpon_ente -Seamlessly with i or 2 mole of a suitable agent and the so .'- @ ER - maintained dye after the diazotisation or tetrazotizing, is combined with 2 Moleiner azo component, wherein at least i mole of a coupling oxyquinoline compound is used as the final component.

In the production of urea derivatives, two amines can be linked to form urea by means of phosgene after the coupling has taken place. In general, it is also possible to introduce the oxyquinoline residue into the new dye with the aid of a linking reaction that is not an azo coupling. In addition to the phosgenation mentioned, such reactions are generally acylations, condensation with V&rbünden.e@n containing mobile halogen atoms, for example with triazine derivatives, reduction of nitro groups to azo or azo_iy groups, for example according to the method of French Patentscliri.ft: en 823 054 and 823 137. In many cases it is advantageous to use components which give the dyes increased affinity for vegetable fibers, such as 4th, 4th'-diamiinodiphenyl derivatives, di, amidostilbenedisu, ifonic acid, dehydroth, iotoluidine, derivatives of the 2 -Amino-5-oxynaphthal, insulphonic acid, components from more highly condensed ring systems, z. B. Carbazolderiva.-te, components that arise, n.cl, pn are by concatenation through -NH -NH or -NH-CO groups, such as q., ['-Diam.inodiphenylureas, q.-aminobenzoylaniline.

The available dyes form due to the presence of Oxycliinolinre.stes Metal complex compounds with metal-releasing agents. This property can be: increased are used, if one uses in addition to the 8-Oxych.inolinen components in which OH-, N H2, NH and OH groups as a result of their position with one another or in connection meet with the azo group to form particularly valuable, lacquer-forming groups, z. B. to the o., O'-oxyazo, o-oxy-o'-amino, azo, o-oxy-o'-carboxyazo and salicylic acid groups.

These groups can also arise from the fact that in the finished azo dye Halogen atoms, O-alkyl, O acyl or COO-alkyl groups in OH or C O O H groups be transferred, what ge, if necessary during the treatment of the dyes with can track the m-metal bonded agents.

The dyes obtainable by the present process stand out compared to the known disazo dyes, which are in the end position 8-oxyquinoline: or a derivative that contains 8-oxyquinoline as the azo component, partly through increased Affinity for cotton, partly due to less change in shades when washing partly due to the improved license fastness of the dyeings obtainable with it.

The dyes obtained by the present process give more washfastness Colorings as the known dyes 4.-Aminoi, i'-azob, enzene-4'-sulfonic acid> - i-Amino-2,5-dimethylbenzene> 2, q.-Dioxyquinoline and 2-Am: inonaphthalin-q., 8-disulfonic acid -> i aminonaphthalene -> i amino-2-methoxy-5-methylbenzene -> i-oxycarbazole-3, 6-disulfonic acid. Example I 15.3 parts of I-Ami: no.-q.-oxybenzene-3-carboxylic acid are used in 500 parts Dissolved water with 25 parts of hydrochloric acid and by adding 7 parts of sodium nitrite converted into the diazo compound at 15 °. 22.3 parts of I-aminoiraphthalene-7-sulfonic acid are added to this in the form of their ammonium salt, dissolved in 200 parts of water, flow in. Within The aminoazo compound precipitated out as a blackish precipitate for about 10 hours and is filtered off. It is now in 500 parts of water with 2o parts of sodium hydroxide solution of 40 'Be dissolved, with' 50 parts of concentrated hydrochloric acid and with 7 parts of sodium nitrite converted into the diazonium compound. 22.3 parts of 1-aminonaphthalene-7-sulfonic acid are then again added or the corresponding amount of I-aminonaphthalene-6-sulfonic acid or the technical Mixture of the two acids, dissolved in the form of their alkali salts in zoo parts of water, to. Any excess of free mineral acid that may still be present is removed by means of Sodium acetate blunted. The coupling is complete after 10 hours. The blackish one The dye is filtered off and washed with 500 parts of water and 20 parts of sodium hydroxide solution solved by 40'B6. 7 parts of sodium nitrite and enough ice are added to this solution that the temperature is on q. falls to 6 °. Then 50 parts of hydrochloric acid are poured in and stir for a while until the diazotization is over. This diazonium compound gives to a solution v011 1q., 5 parts of 8-oxyquinoline in 500 parts of water, the 2o Contains parts of sodium hydroxide solution of 40 'B6 and 3o parts of anhydrous sodium carbonate. The blue trisazo dye is formed quickly as a black precipitate fails. It is filtered off and dried. He puts a black one. Powder, which dissolves in water and dilute alkalis with a blue color. When dyeing in a bath containing sodium carbonate and sodium sulphate is obtained on vegetable Fibers and fibers made of regenerated cellulose blue to navy blue tones, by treatment with metal donating agents, in particular Copper salts, are extremely washable and lightfast.

B-eis.pi@el 2 I 8.2 parts of 4,4'-diaminodiphenyl are tetrazated The usual way and couples the tetrazo compound in sodium carbide, onate alkali solution with 1.3.8 parts of i-oxyb; enzene-2-carboic acid. After the tetrazo compound disappeared is, a solution of 22.3 parts of i-aminonaphthalene-6-sulfonic acid neutralized with sodium carbonate is added added and acidified the reaction mass with 50% acetic acid. You couple for now 6 hours maintenance 2o ° and terminates the reaction by stirring for 12 hours hot 25 to 3o °. The disazo dye is filtered off and purified by dissolving it from water.

The dis, azo dye is then dissolved in 2,000 parts of water and 10, 6 parts anhydrous - sodium carbate, uses 6.9 parts of sodium nitrite, 25 parts of water dissolved, added and acidified at 5 ° by means of 50 parts of concentric hydrochloric acid. The diazotization takes about 12 hours. Then you couple with io to 15 ° 16 parts of 8-Oxychinoa in sodium carbonate alkaline solution. After the The coupling is heated to 60 ° and the dye is separated off by adding sodium chloride and cleanses it by dissolving it from Wiassar.

The new Trisazo @ farbsto @ ff provides getro: ckniet a gray-black Powder, which is in water with brown orange orange, in i o% soda solution and in 10% sodium hydroxide solution, it mixes brown-orange color and in concentrated sulfuric acid with blue paint dissolves. He dyes cotton in brown tones, which is the case with re-coppering can be washed and lightfast. Example 3.

27.2 parts of 4,4'-diamino-diphenyl-3, 3'-dicarboxylic seams are known Way tetrazated and in acetic acid solution with 47 parts of i-amimomaphthaliin-6-sulfons; äume coupled. After coupling has ended, the dye is filtered off and purified by dissolving from water.

The cleaned dye pas: be in dilute sodium carbonate solution solved. The solution is mixed with 13.8 parts of sodium nitrate and at io ° with i 5% hydrochloric acid acidified. It is tetrazotized for 8 to 12 hours at io up to 15 °. In it you add as much concentrated N, atrium acetate, at solution until the maleic acid reaction, has disappeared, and combines at 15 to 35 'with one solution of 47 parts of i-aminonaphthalene-7-sulfOn: acidic neutralized with sodium carbonate in 40o parts of water clearly shows acetic acid reaction. The clutch takes 2 to 3 days. The dye formed is filtered off and purified by dissolving it from water.

The purified dye is again, as described above, indirect tetrazotized. A hydrochloric acid solution of 30 parts of 8-oxyquinoline is then added and makes the reaction mass alkaline by adding 20% sodium carbonate solution. The coupling is carried out for 20 to 60 hours at 10 to 15 °. The new dye is filtered off, if necessary cleaned and dried.

It represents: a gray-black powder, which is in water, in io% iger Soda solution and in 10% sodium hydroxide solution with blackish violet and in 'concentrated Dissolves sulfuric acid with a black-green color. The new dye delivers on cotton gray tones that become visible when re-coppering. Example 4 15.4 parts of 5-nitro, -2-amino-i-oxyben "ol are diazoLert and in solo alkaline solution with 24 parts of 2-amino-5-oxynaphthalene-7-sulfonic acid united. After the coupling has ended, the dye is filtered off, with a little more dilute Natidurchloridlösttn @ g; washed and then with the addition of 20 parts of 3o% Sodium hydroxide solution dissolved in 1,000 parts of lukewarm water. After adding an aqueous solution 6 parts of sodium nitrite are poured into a mixture of ice with thorough stirring. and run in 58 parts of 30% hydrochloric acid. After the Diazosus: pension einisge Has stirred for hours, this is coupled with a suspension in s: odaal'kalischer solution in front 13 parts of 8-oxyquinoline. When the coupling is complete, a little sodium chloride is added and filter off the dye. This is now according to the procedure of the French Patent 823 054 treated in alkaline solution with grapes, shrug. You get ! a dye which, when dyed on cotton, has a very good light- and delivers real blue-gray. Example 5 15.4 parts of 5-nitro @ -2-amino-i-oxybenzene will. in the usual way diazotized and in the presence of sodium bicarbonate with 24 parts, 2-amino-5-oxynaphthalene-7-sulfonic acid coupled. The monoazo dye is filtered off and used to remove excess coupling homp @ onienite Washed 50% sodium chloride solution. The dye paste is added of 20 parts of 30% sodium hydroxide solution in 100 parts of water from. : about 4o ° solved that Solution with an aqueous solution of 6.9 parts of sodium intravenous offset and pour the mixture onto a mixture of ice and 46 parts 3oo (o @ ige @ r Hydrochloric acid discharged. After the D'iazo suspension a few hours under ice cooling was stirred, you put a solution of 22.5 parts of 8-oxyquinoline-7-s: sulfonic acid in 400 parts, water and 30 parts of anhydrous sodium carbonate, initially stirred Cooling and then at room temperature. The disazo dye formed is through Addition of some sodium chloride deposited and then filtered off.

The dye paste is slurried in 2400 parts of water, the suspension heated to 6o ° and after the addition of 135 parts of 3o0j'oiger sodium hydroxide solution with a io @ 'oigcli solution of 8 parts of glucose added. The mixture is stirred for about 1.1 hours at 55 to 60 ', 100 parts of sodium chloride are added, filtered after cooling off and dry.

The dye is a blackish powder that dissolves in water and diluted alkalis with blue, in concentrated sulfuric acid with reddish blue Dye dissolves and dyes cotton from believers' salty bath in gray tones, which after treatment with copper sulphate become very real. Example 6 27.2 parts, l 4'-Diaminodipliellyl-3,3'-dicarboxylic acid are tctrazotie -t in the usual way and with 1: 1.5 parts of i-oxybenzene-2-carboxylic acid in natriumcarboro.ata.lkalischer Solution coupled. As soon as the tetrazo compound has disappeared, one is given with it Sodium carbonate-neutralized solution of 25.6 parts of 2-amino-5-oxynaphthalene-7-hydrofolic acid and couples with io to 15J. The disazo dye is made by adding sodium clohide deposited and washed with dilute saline solution.

The disazo dye is dissolved in 7,000 parts of water at 6o to 70 ", add a solution full of 7.2 parts of sodium nitrite in 36 parts of water and acidify at 0 to 5 ° with 50 concentrated hydrochloric acid, that with the same ratimmelige water The diazotization takes 12 to 16 hours. Then couple one with # 5 parts of 8-oxyquinoline in soda-alkali solution. The trisazo dye is deposited by adding high salt and, if necessary, by dissolving it in water and salting out cleaned.

The new trisazo dye is a gray-black powder when dried which is in water with violet, in 10% soda solution with reddish blue, in 100% sodium hydroxide solution with red-violet and in concentrated sulfuric acid with blue color dissolves. It dyes cotton in a one- or two-bath process with copper salts treated in real violet-blue tones.

Example. ; 18, .4 part e 4, 4'-diami-nodiphenyl. on usual Way tetrazotized and in sodium carbonate alkaline solution with 14.5 parts of I-oxybenzene-2-carbon, acid coupled at 6 to '. As soon as the tetrazo compound has disappeared, one gives a solution of 26 parts of t-alnino-2-methoxynaphthalene-6-sulfonic acid neutralized with sodium carbonate in addition, the reaction mass is acidified with acetic acid and coupled for 16 to 20 Hours at 15 to 30-. The disazo dye is filtered off without adding salt and washed with water.

The disazo dye is distributed in 800 parts of water and at 70 Dissolved up to 80 'with 1o.6 parts of anhydrous sodium carbonate. Then you give one Add a solution of 7.2 parts of sodium nitrite and acidify it at 0 to 5 ° with a mixture of 5o parts by volume of concentrated hydrochloric acid and 3o parts of water. The diazotization takes 12 to 16 hours. Then you couple at to up to 15 ° with 15 parts of 8-oxychiliolin in soda-alkaline solution. After the coupling has ended, the mixture is heated to 6o and separates the dye by adding table salt.

The new trisazo dye is a brown powder when dried that is in water with braufiolit-er, in ioobiger soda solution and in Io% iger Sodium hydroxide solution with brown and in concentrated sulfuric acid with black-violet Color dissolves. It dyes cotton, treated with copper salts in a one or two bath process, in real black- 1 brown tones. Example 8 18,: 1 part of 4- 4'-diaininodipheliyl are tetrazotized in the usual way and at 6 to i o 'in sodium carbonate alkaline Solution coupled with 14.5 parts of 1-oxybenzene-2-carboxylic acid. After the tetrazo compound Has disappeared, it is coupled with 22.5 parts i Amiiionaphthalin-6-sulfonic acid in acetic acid solution at 15 to 3o '. The disazo dye is made without adding salt filtered off and washed with water.

The dis, azofa dye is dissolved in 80o parts of water and 1.6 parts of anhydrous sodium carbonate at 70 to 80, a solution of 2 parts of sodium nitrite in 36 parts of water is added and acidified at 0 to 5 "with a mixture of 50% Parts by volume of concentrated hydrochloric acid and 50 parts of water.The diazotization lasts from 6 to 20 hours.Then the mixture is coupled hot to 15 with 23.6 parts of 8-oxyquinoline-7-sulfonic acid: an alkaline sodium carbonate solution remove the dye by adding table salt.

The new trisazo dye is a gray-black powder when dried that is in water, in 10% solo solution and in 10% sodium hydroxide solution with brown-orange and dissolves in concentrated sulfur fringes with a blackish-blue-violet color. He dyes cotton, treated with copper salts in a one or two bath process, in real red-brown tones. Example 9 18.4 parts of 4,4 @ -di'amino, -diphenyl are tetrazated in the usual way and couples the Tetrazoverbindumg at 6 to 10 ° with 14.5 parts i-Oxyb, enzol-2-carb, o @ n acid in sodium caxbonate solution. As soon as the tetrazole solution has disappeared, a mixes sodium carbonate-neutralized solution of 22.5 is added Share i-Amitionaph @ thalin-6-sulfonic acid and acidify the reaction mass 5o% E, aesigsäuTe. The coupling takes about 60 hours at 15 to 30 degrees Disazo dye is filtered off without the addition of salt and washed with water.

The disazo dye is dissolved by adding 6 parts sodium carbonate in 8oo parts of water from 7o to 8o °, gives a sewing solution, corresponding to 7.2 parts Sodium nitrite, and acidify at 0 to 5 ° with a mixture of 50 parts by volume concentrated hydrochloric acid and 50 parts of water. The diazotization lasts in the Usually 16 to 20 hours. It is then coupled at 10 ° to 15 ° with 23.6 parts of 8-oxyquinolin-5-sulfonic acid in a solo alkaline solution. After the coupling has ended, the dye is separated by adding table salt.

The new trisazo dye is a gray-black powder when dried that is in water and in 10% soda solution with brown, 10% sodium hydroxide solution dissolves with reddish-brown and in concentrated sulfuric acid with a black-blue color. It dyes cotton, treated with copper salts in an egg or two-bath process, in red-brown shades with good fastness properties. Example 10 8.3 parts of the sodium salt of the dye prepared according to Example 3 are in 500 parts of hot water solved. The solution is mixed with 2 parts of crystallized sodium acetate and after adding 3o parts of 10% copper sulphate solution for about ½ hour at 9o to 95 ° touched. The precipitated dye is filtered off and dried. Created a dark one. Powder, which is in dilute sodium carbonate solution with gray Dye dissolves and dyes cotton from a bath containing Glauber's salt in gray tones.

Claims (1)

Claim: A process for the production of tris and polyazo dyes, characterized in that at least one component is used to build up the dyes which contain the binuclear 8-oxyquinoline radical with an unoccupied 2-position, and the dyes obtained are optionally treated with metal complexing agents. The following publications have been taken into account in the granting procedure: German patents .. No. 355 534, 59 0 190, 243 124e USA-Pat: enitschrift 1975411-