DE853321C - Process for the preparation of disazo dyes - Google Patents

Description

Process for the preparation of disazo dyes It has been found that disazo dyes can be prepared by using diazotized aminoazo dyes of the general formula in which N is a nitrogen-containing link different from the azo group, R1 and R2 each represent an aryl radical, couples with 8-oxyquinolines and the dyes obtained are optionally treated with metal donating agents.

The starting materials of the above formula are preferably obtained when a diazotized amine of the formula R1-NH2, where R1 has the meaning given above, with compounds of the general formula couples in an alkaline medium. Particularly suitable diazotized amines (the remainder of which therefore corresponds to R1 of the first formula) are those of the benzene and naphthalene series. These amines can contain water-soluble groups, such as sulfonic acid or carboxyl groups, and other substituents. In some cases it is advantageous to use those amines which have a metal complex-forming group, in particular a hydroxyl, carboxyl, alkoxy group, or a group -O-alkyl-COOH, in particular -0-C H2-COOH, e.g. . B. in the ortho position to the diazotizable amino group. Such amines include 2-amino-i-methoxybenzene-4-sulfonic acid, 2-amino-i-oxybenzene-4-sulfamide, anthranilic acid, 2-aminonaphthalene-3-carboxylic acid and 3-atndno-4-methylp'hmoxyesgigsäure. Further examples of such amines can be found in the table below.

Link X of the above formula preferably consists of at least 2 atoms, at least one of which is nitrogen and the other z. B. is carbon, and 'in the simplest case can be an acid amide group; z. B. -NH-CO-, be. This Link can also be part of a ring that z. B. in the ortho-standing a-Stellurtg of the naphthalene core intervenes, as is the case with the corresponding imidazoles, Thiazoles or Triazinon is the case.

The aryl radical R2 of the above formulas can, for example, be from the benzene series belong and carries the diazotizable amino group preferably in para- or also in meta position to link X.

The diazotization of this corresponding to the formula given at the beginning In many cases, aminoazo dyes are advantageously made indirectly, by z. B. a neutral to weak containing the necessary amount of sodium nitrite alkaline solution or suspension of the aminoazo dye at a suitable temperature with acid, e.g. B. hydrochloric acid, added or enters in acid.

According to the present process, these diazotized aminoazo dyes now become of the formula given at the beginning coupled with 8-oxyquinolines. Among these comes primarily 8-oxyquinoline itself, but then also substituted 8-oxyquinoline, such as 5-chloro-8-oxyquinoline, 8-oxyquinoline-5- and -7-sulfonic acid and 8-oxyquinoline-7-carboxylic acid. The coupling takes place in an alkaline medium, which is used as alkalis z. B. alkali hydroxides, such as caustic soda, and optionally alkali metal carbonates.

It is advantageous to choose the components so that the finished dye contains no more than 2 sulfonic acid groups.

The dyes obtained by the present process can be used in usual way for dyeing and printing a wide variety of animal and in particular Cellulosic fibers are used, such as wool, silk, and leather in particular Cotton, linen, rayon and rayon made from regenerated cellulose. You get predominantly blue-red to red to yellow-red tones.

You get particularly valuable products when you use these dyes in substance, in the dyebath or on the fiber with metal donating, mainly treated copper-releasing agents. Depending on the composition of the dyes obtained complex metal compounds, especially copper compounds that are water-soluble and can be used for dyeing according to the type of substantive dyes, or in many cases sparingly to insoluble copper compounds, their production better done on the fiber.

The aftertreatment of the dyes mixes metal, mainly copper-releasing agents on the fiber can be carried out after the usual copper-plating process in a fresh bath or advantageously after the dyeing in the dyebath, whereby it is advisable to use alkaline-resistant copper agents such as complex copper tartrates (cf. French Patent 8o9 893). EXAMPLE i The aminoazo dye which has been separated off with common salt, filtered and pressed out and which is obtained from 20.3 parts of i-amino-2-methoxybenzene-5-sulfonic acid by diazotization and coupling with 35.8 parts of 2- (4-aminobenzoyl) -amino-5- oxynaphthalene-7-sulfonic acid in sodium carbonate alkali medium is available in a known manner, is suspended in 40o parts of water. Then 7 parts of sodium nitrite are added and the mixture is cooled to 6 ° by adding ice. This is followed by 3o parts of conc. Hydrochloric acid and stir for about 2 hours. The diazoazo compound obtained is then added to a solution, cooled to 4 °, of 14.5 parts of 8-oxyquinoline, 15 parts of caustic soda and 20 parts of calc. Soda. @in 500 parts of water. After a few hours, the mixture is warmed to 65 ", 100 to 100 parts of table salt are added in order to obtain a readily filterable form of the disazo dye, the precipitate is filtered and dried. A dark brown powder is obtained that dissolves in water and dilute alkalis with red, in concentrated sulfuric acid dissolves with a violet color.

Vegetable fibers and those made from regenerated cellulose are made from neutral or alkaline Glauber's salt bath colored in vivid red tones, those with Copper salts after treatment become more lightfast and washfast.

Example e The precipitated with common salt, filtered and squeezed Aminoazo dye obtained from 2o.5 parts of 3-amino-4-methylphenoxyacetic acid by diazotization and coupling with 35.8 parts of 2- (4-aminobenzdyl) -amino-5-oxynaphthalene-7-sulfonic acid in sodium carbonate-alkaline medium in a known manner is available in Suspended 400 parts of water. Then 7 parts of sodium nitrite are added and the mixture is cooled with ice at 6 ° '. Then 3o parts of conc. Hydrochloric acid and stir about 2 hours. The diazo compound obtained is then added to a cooled to 4 ° Solution of 14.5 parts of 8-oxyquinoline, 15 parts of caustic soda and 2o parts of calc. soda in 500 parts of water. After a few hours you warm up to 65 °, give 100 to the zoo Add table salt to obtain a readily filterable form of the disazo dye, filtered and dried the precipitate. A dark brown powder is obtained which in water and diluted Alkalis with red, in conc. sulfuric acid dissolves with purple color.

Vegetable fibers and those made from regenerated cellulose are made from neutral or alkaline Glauber's salt bath colored in bright yellowish-red tones, which are treated with copper salts and are more lightfast and washfast.

Example 3 The precipitated with common salt, filtered and squeezed Aminoazofarbstöff, which from i3.7 parts of i-amino-2-metlioxy-5-methyll> enzol by Diazotization and coupling with 35.8 parts of 2- (4'-amino-1) enzoyl) -amitio-5-oxynaphthalene-7-sulfonic acid in sodium carbonate-alkaline medium in a known manner is available in 400 parts of water distributed. Then 7 parts of sodium nitrite are added and the mixture is cooled Ice at 6 °. This is followed by 3o parts of conc. Hydrochloric acid and stir about 2 Hours. The diazo compound obtained is then added to a solution cooled to 4 ° of 14.5 parts of 8-oxyquinoline, 15 parts of caustic soda and 2o parts of calc. Soda in 5oo Share water. After a few hours it is warmed to 65 ° and gives 100 to Zoo parts Table salt to obtain a readily filterable form of the disazo dye, filtered and dries the precipitate. A dark brown powder is obtained, which is in Water and dilute alkalis with red, in conc. Sulfuric acid of purple color solves.

Vegetable fibers and those made from regenerated cellulose are made from neutral or alkaline Glauber's salt bath colored in vivid red tones, those with Copper salts after treatment become more lightfast and washfast.

Further dyes obtainable by the present process are compiled in the following table. Color of Diazo component: Aminoazo dye made from coppered azo component coloring 2-aminobenzene- H 03S 8-oxyquinoline brick red i-carboxylic acid @. @ - NH - CO @ N H2 OH 2-aminonaphthalene-like-like-blue-red 3-carboxylic acid 4-aminobenzene like. Like. Cloudy red i-carboxylic acid 2-Amino-i-oxybenzene like the like bordo 4-sulfamide 2-aminophenoxyacetic acid like red acid-4-sulfamide 2-amino-4-chlorine like the like red phenoxyacetic acid 2-amino-6-chloro-i-oxy- like the like bordo. benzene-4-sulfonic acid 2-Amino-i-oxybenzene like the like bordo 4-sulfonic acid Monosulfonated like: like red i-amino-5-chloro 2-methoxybenzene 2-aminobenzene like 5-chloro-8-oxy yellow red i-carboxylic acid quinoline i-Amino-2-methoxy- like 8-oxyquinoline- red g-methylbenzene 7-sulfonic acid the same. the same. 8-oxyquinoline red 7-carboxylic acid 2-amino-4-chloro-like 8-oxyquinoline-yellow-red phenoxyacetic acid 7-sulfonic acid Color of Diazo component: Aminoazo dye made from coppered azo component coloring 2-aminobenzene-H035 8-oxyquinoline yellow-red i-carboxylic acid -NH-CO-- < N 112 Oh 2-aminonaphthalene like the like bordo 3-carboxylic acid 2-amino-4-chlorine like the like yellow-red phenoxyacetic acid i-Amino-2-methoxy- like. like. yellowish-red 5-methylbenzene 2-Amino-i-oxybenzene like the like bordo 4-sulfamide 4-aminobenzene like like red orange i-carboxylic acid 2-aminobenzene like 5-chloro-8-oxy-red orange i-carboxylic acid quinoline 2-Amino-i-oxybenzene = similarly similarly blue-red 4-sulfamide, i-Amino-2-methoxy- like 8-oxyquinoline-bordo 5-methylbenzene 7-sulfonic acid i-Amino-2-methoxy- / 8-oxyquinoline bordo benzene-5-sulfonic acid N H i 7 - < N H2 H03S- @ -N \ X, OH i-Amino-2-methoxy- N - \ COOH or bordo 5-methylbenzene HNC - @@ N H2 H 03S - @@@ - N OH 2-aminobenzene- N #C @ also yellowish red i-carboxylic acid H 03S @@ \ 7 NH . N H2 0 H Color of Diazo component: Aminoazo dye made from coppered azo component coloring 2-aminophenoxy- N -TC 8-oxyquinoline brown-red acetic acid H03S ' --NH NH $ OH 2-amino-4-chlorine like the same bordo i-oxybenzene 6-sulfonic acid 4-aminobenzene like like red i-carboxylic acid 4-Amino-i-oxybenzene like the like like brown 2-carboxylic acid 2-aminonaphthalene like the like bordo 3-carboxylic acid 2-Amino-q.chlor- desg :. also blue-red phenoxyacetic acid i-Amino-2-methoxy- like. like. yellow-red benzene-5-sulfonic acid sulfonated i-amino like. like. red 2-methoxy-5-methyl- benzene sulfonated i [-amino- like. like. yellow-red 2-methylbenzene 2-aminobenzene like 5-chlorine yellow-red i-carboxylic acid 8-oxyquinoline 6-nitro-2-amino-i-oxy- like. Like bordo benzene-4-sulfonic acid 4-nitro-2-amino-i-oxy- like. Like bordo benzene-6-sulfonic acid i-Amino-2-methoxy- like 8-oxyquinoline-bordo 5-methylbenzene 7-sulfonic acid Example 4 The diazo compound from 13.7 parts of 2-aminohenzene-i-carboxylic acid is mixed with 37.2 parts of 2 '- (4'-aminol) henyl) -5-oxy-7-sulfo-i, 2 in the presence of excess sodium carbonate -naphthothiazole coupled at room temperature. After a few hours, the coupling mixture is heated and the monoazo dye is precipitated by adding sodium chloride and filtered. This dye is brought to solution in 1,000 parts of water and diazotized at 40 by adding 7 parts of sodium nitrite and 35 parts of conc. Hydrochloric acid. After the dianotation is complete, the suspension of the diazoazo compound is neutralized with soda and the solution of 14.5 parts of 8-oxyquinoline in 100 parts of 100% sodium hydroxide solution is added. A red disazo dye of the formula is formed which is separated out after a while by heating the egg and adding sodium chloride. After filtering off and drying, a dark powder is obtained that dissolves in water and dilute alkalis with a red color and dyes plant fibers and artificial fibers made of regenerated cellulose in blue-tinged red tones, which are washable and lightfast when treated with copper salt solution.

Claims (1)

PATENT CLAIM: Process for the preparation of disazo dyes, characterized in that diazotized aminoazo dyes of the general formula where X is a nitrogen-containing link other than the azo group, R1 and R2 each represent an aryl radical, couples with 8-oxyquinolines and the dyes obtained are optionally treated with metal donating agents.