DE964974C - Process for the preparation of mono- and disazo dyes - Google Patents

Description

Process for the preparation of mono- and disazo dyes It has been found that valuable mono- and disazo dyes are obtained if the diazo or tetrazo compounds of amines of the general formula are used where R is an aromatic or heterocyclic radical, X and Y are hydrogen and / or a non-water-solubilizing substituent and n is the number = or 2, with compounds of the general formula where R1 is hydrogen, a sulfonic acid, sulfonic acid amide or hydroxyl group, RE is hydrogen or a sulfonic acid group and R3 is hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, couples in an acidic medium.

The aminoaryldisulfimides of the formula given above which are used as diazo or tetrazo components can be obtained, for example, by referring to sulfonamides of the general formula R (-SOZNH2) n o-nitrobenzenesulfochlorides of the general formula where R, X, Y and n have the meaning given above, allowed to act in aqueous solution and, after the reaction is complete, the nitro group is reduced by known processes. The same diazo or tetrazo components are obtained if sulfamides of the general formulas are used with sulfochlorides of the general formula R (- SO, Cl), where R, X, Y and n have the meanings given above, and the reaction products are converted into the corresponding amines by reduction of the nitro group or by saponification of the acylamino group.

For example, Z aminobenzene-2-sulfonic acid (phenylsulfonyl) amide is obtained by the action of o-nitrobenzenesulfonyl chloride on benzenesulfamide in phenolphthalein alkaline Solution and subsequent reduction of the nitro group with hydrogen in the presence by Raneynickel.

Suitable amines are, for example: i-aminobenzene-2-sulfonic acid- (4'-chloro-, 3 ', 4'-dichloro or 2' or. 4'-methylphenylsulfonyl) amide, r-aminobenzene-2-sulfonic acid - (4'-acetylaminophenylsulfonyl) amide, i-aminobenzene-2-sulfonic acid (2'-aminophenylsulfonyl) - amide, i - amino - 4 - nitrobenzene - 2 - sulfonic acid (phenylsulfonyl) amide, i-amino-5-chlorobenzene-2-sulfonic acid (phenylsulfonyl) or 4'-methylphenylsulfonyl) amide, i-aminobenzene-2-sulfonic acid- (2'-amino-4 '- chlorophenylsulfonyl) - amide, benzene -1, 3 - disulphonic acid (2'-aminophenylsulphonyl) amide, benzene-1, 3-disulphonic acid - (--'- amino - 4 ', 6'-dicblorphenylsulfonyl) -amide, diphenyl ether - 4, 4'-disulfonic acid - (2 "- aminophenylsulfonyl) -amid, Diphenylsulfon-3, 3'-disulfonic acid - (2" - aminophenylsulfonyl) - amide, diphenylene oxide - 3, 6 - disulfonic acid - (?, '- aminophenylsulfonyl) amide, Naphthalene -1, 5 - or 2,6 - disulfonic acid (2'-aminophenylsulfonyl) amide.

The following 2-aminonaphthalene sulfonic acids, for example, can be used as azo components 2-Amino-8-oxynaphthalene-6-sulfonic acid, 2-methylamino-8-oxynaphthalene-6-sulfonic acid are used, 2-amino-8-oxynaphthalene-3, 6 - disulfonic acid, 2 - cyclohexylamino-8-oxynaphthalene-6-sulfonic acid, 2-Benzylamino-8-oxynaphthalene - 6 - sulfonic acid, 2 - aminonaphthalene -3, 6-disulfonic acid, 2-aminonaphthalene-6-sulfonic acid-8-sulfonic acid amide, 2-aminonaphthalene-6-sulfonic acid and 2-methylaminonaphthane-3,6-disulfonic acid.

The coupling is carried out in a known manner in aqueous solution or suspension in the presence of mineral acids or weak organic acids, e.g. B. acetic acid, carried out.

The new azo dyes dye wool and fibers in similar dyeing ways Behavior, such as polyamide or polyurethane fibers from weakly acidic bath in clear Tones. The wool dyeings are characterized by very good wet and light fastness properties the end.

The azo dyes of a similar composition known from German Patent 821 977 are superior to the azo dyes obtainable according to the invention in the lightfastness of their wool dyeings. Example 1 31.22 g of i-aminobenzene-2-sulfonic acid (phenylsulfonyl) amide are diazotized indirectly with 619 g of sodium nitrite. After the excess nitrite has been removed, the suspension of the diazo compound is mixed with a suspension of 23.9 g of 2-amino-8-oxynaphthalene-6-sulfonic acid. mixed, the pH was adjusted to 4 by adding sodium acetate and the mixture was stirred at 0 ° to 5 ° for 16 hours. The mixture is blunted, left to stir for a few hours, the batch is heated to 60 ° to 70 ° and the dye is isolated by adding sodium chloride. The dye thus obtained dyes wool in clear red shades of very good light and wet fastness.

i-aminobenzene-2-sulfonic acid (phenylsulfonyl) -anüd can be obtained by adding partially gi g of o-nitrobenzenesulfonyl chloride to 65 g of benzenesulfonamide in 400 ml of water at 70 °, the pH of the solution being kept constant by adding sodium hydroxide solution phenolphthalein is kept alkaline. When the solution is complete, the batch is rendered neutral, optionally clarified, and the solution is reduced with hydrogen in the presence of Raney nickel. The amine is then precipitated by acidification. III g (g3% of theory) of i-aminobenzene-2-sulfonic acid (phenylsulfonyl) amide (mp 193 to 1 g4 °) are obtained. Example 2 37.1 g of aminobenzene-2-sulfonic acid (4'-acetylaminophenylsulfonyl) amide are diazotized indirectly with 6.9 g of sodium nitrite and with 23.9 g of 2-amino-8-oxynaphthalene-6-sulfonic acid at a p $ coupled from 4 to 5 24 hours. The mixture is heated to 60 ° and the dye is isolated by adding sodium chloride. The dye thus obtained is a red powder with very good leveling power; he dyes wool in lightfast red tones. Example 3 35.7 g of i-Anüno-4-mtrobenzene-2-sulfonic acid (phenylsulfonyl) amide are dianotized indirectly with 6.9 g of sodium nitrite and, at a p $ of 4 to 5, with 23.9 g of 2-amino 8-oxynaphthalene-6-sulfonic acid coupled at 0 to 5 ° for 24 hours. The isolated dye dyes wool in reddish shades of blue.

Example 4 35.7 g of i-amino-4-nitrobenzene-2-sulfonic acid (phenylsulfonyl) amide are dianotized with 6.9 g of sodium nitrite and, at a pu of 4 to 5, with 25.3 g of 2-methylamino-8 - oxynaphthalene-6-sulfonic acid coupled for 24 hours. The isolated dye dyes wool from an acid bath in blue shades with good wet fastness properties. Example 5 34.9 g of the sodium salt of i-aminobenzene-2-sulfonic acid (2'-aminophenylsulfonyl) amide are indirectly tetrazotized with 13.8 g of sodium nitrite and, if the PR is 4 to 5, with 47.8 g of 2-amino -8-oxynaphthalene-6-sulfonic acid coupled for 24 hours. The disazo dye dyes wool in real red tones. Example 6 54.6 g of benzene-i, 3-disulphonic acid (2'-aminophenylsulphonyl) amide are indirectly tetrazotized with 13.8 g of sodium nitrite, and the precipitated tetrazo compound is at a pa of 4 to 5 with 47.8 g of 2 -Amino-8-oxynaphthalene-6-sulfonic acid coupled for 48 hours. The disazo dye, which is isolated with the addition of sodium chloride, dyes wool in very lightfast and washfast clear red tones. Example 7 63.8 g of diphenyl ether-4,4'-disulfonic acid (2 "-aminophenylsulfonyl) amide are tetrazotized with 13.8 g of sodium nitrite and 47.8 g of 2-amino-8-oxynaphthalene-6-sulfonic acid for 48 hours The isolated disazo dye dyes wool from an acid bath in clear red tones of very good light and wet fastness Sodium nitrite tetrazotized and at a pH of. 4 to 6 coupled with 47.8 g of 2-amino-8-oxynaphthalene-3, 6-disulfonic acid. The isolated disazo dye dyes wool in lightfast red tones. Example 9 34.9 g of - aminobenzene - 2 - sulfonic acid - (2 '- aminophenylsulfonyl) amide are tetrazotized with 13.8 g of sodium nitrite and at a pH of 4 to 6 with 30.3 g of 2-aminonaphthalene-3, 6- disulfonic acid coupled. The disazo dye dyes wool in yellowish red tones with good lightfastness and washfastness.

Example 1o 63.8 g of diphenylene oxide-3,6-disulfonic acid (2 "-aminophenylsulfonyl) amide are indirectly tetrazotized with 13.8 g of sodium nitrite; the tetrazo compound obtained is filtered off with suction and for 48 hours first in Congo acid and finally in acetate acid medium with 47 , 8 g of 2-amino-8-oxynaphthalene-6-sulfonic acid coupled. The isolated disazo dye dyes wool from an acid bath in very light and wet-fast red tones. Example ii 37.1 g of i-aminobenzene-2-sulfonic acid- (4'- Acetylaminophenylsulfonyl) amide is dianotized indirectly with 6.9 g of sodium nitrite and coupled with 345 g of 2-phenylamino-8-oxynaphthalene-6-sulfonic acid for PR 4 to 5. The isolated dye dyes wool in reddish Bordo shades of very good light and wet fastness Example 12 37.1 g of aminobenzene-2-sulfonic acid (4'-acetylaminophenylsulfonyl) -amide are dianotized indirectly with 6.9 g of sodium nitrite and, for Pu 4 to 5, with 32.9 g of 2- (4'-methylphenylamino) -8-oxynaphthalene-6-sulfonic acid coupled. The isolated dye ff dyes wool from an acidic bath in lightfast and wetfast reddish-red shades.

Claims (1)

Claim: Process for the preparation of mono- and disazo dyes, characterized in that the diazo compounds of amines of the general formula where R is an aromatic or heterocyclic radical, X and Y are hydrogen and / or a non-solubilizing substituent and n is the number i or 2, with compounds of the general formula where R1 is hydrogen, a sulfonic acid, sulfonic acid amide or hydroxyl group, R, hydrogen or a sulfonic acid group and R3 is hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, couples in an acidic medium. Publications considered: German Patent No. 82: 1977.