SU252223A1 - METHOD OF OBTAINING MONOAZOKANE - Google Patents

Description

The invention relates to the field of production of new monoazo dyes, which can be used for dyeing cotton. Stained fabrics, wool, silk, synthetic polyamide fibers and leather.

A method for the preparation of monoazo dyes of the general formula

Y- CH

X is the anion equivalent to the dye cation;

R is a quaternary radical of esters of strong mineral acids or organic sulfonic acids.

The method consists in the fact that the corresponding azo-dye, which does not contain sulfo groups, is reacted with "n moles of a compound of the general formula

Where A is the radical of the benzo-azo-benzene, benzene-azo-naphthalene: sulfur, naphthalene-azo-naphthalene, benzene-azo-pyrazolone, benzene-azo-aminopyrazole, benzene-acetyl-acetic acid, aryl amides, dimethylsulfonate groups; -benzene, thiadiazole-azo-benzene, thiadiazole-azo-naphthalene or thiadiaz, o-azo-pyrazolone row; Y is a direct bond or a bivalent radical; for example, -O-, -S-, -NH-; n - 1 or 2, radical Shg CH-d-, followed by separation of the target product by treating it with a quaternary base of esters of strong mineral acids or organic sulfonic acids, for example, alkyl chlorides, alkyl bromides, etc. Example 1. A mixture of 23.4 h. 4 -vinylniridine, 24.2 parts of ethylaminobenzene and 12 parts of 100% acetic acid are stirred for 6 hours at 110 ° C. Then acetic acid, excess 4-vinylpyridine and, if present, ethylaminobenzene, are distilled off at 70 ° C and a pressure of 15 mm Hg. Art. The L-ethyl-M-p- (pyridyl-4) -ethyl-aminobenzene obtained in this way is sufficiently pure to make a color. Separately prepare a solution of the diazonium salt as follows.

To a mixture of 60 parts of water and 40 parts of concentrated hydrochloric acid, 17.2 parts of 1-amino-2-chloro-4-nitrobenzene are added at room temperature and stirred for 3 hours. The resulting suspension is cooled by adding 100 parts of ice and a temperature of 0 to 5 ° C is diazotized for 2 hours with a solution of 6.9 parts of sodium nitrite per 100 hours of water. The reaction mass is stirred for another 15 minutes, 10 parts of aminosulfonic acid are added to the resulting solution and filtered. To a clear solution of the diazonium salt was added a solution of 22.6 parts of H-ethyl-M-p- (pyridyl-4) -ethyl-aminobenzene in 50 parts of glacial acetic acid and the combination was completed in an acidic medium with pH 4 that is achieved by the addition of sodium acetate. The dye is sucked off, washed to remove the acid and dried.

The dry dye is dissolved in 500 parts of acetone. 14.2 parts of methyl iodide were added to the resulting solution at room temperature and allowed to stand for 3 hours, with the quaternary dye salt precipitating completely and in pure form. The resulting dye is filtered and dried, so pl. 179 ° C (from alcohol). Dye paints polyacrylonitrile fibers in ruby colors with good durability. The same dye is obtained if N-ethyl-N-p- (pyridyl-4) -ethyl-aminobenzene is first treated in benzene solution with dimethyl sulfate, and then the quaternary salt obtained is combined with the diazonium salt described above.

Example 2. A mixture of 23.4 parts of 4-vinylpyridine, 28.6 parts of 1-aminonaphthalene and 24 hours of 100% acetic acid is stirred for 6 hours at 100-105 ° C. The reaction mixture is cooled to room temperature, poured into 400 parts of ice water and neutralized with 30 parts of sodium bicarbonate. Liquid (pyridyl-4) ethyl-aminonaphthalene is separated in a separatory funnel and washed with water.

Separately, a diazo solvent was prepared as described in Example 1. A solution of 24.8 parts of (pyridyl-4) -ethyl-aminonaphthalene in 100 parts of glacial acetic acid was added to the clear solution of the diazonium salt and the combination was mixed until acidic reaction mixture for several hours. The separated dye is sucked off, washed to remove the acid and dried. The dry dye is dissolved at boiling point in 200 parts of chlorobenzene. 14.2 parts of methyl iodide are introduced into the resulting solution and allowed to stand for 1 hour at 60 ° C, while quaternary salt is quantitatively precipitated. The obtained basic dye is filtered off and dried. The crude dye melts at 220 ° C and colors the polyacrylonitrile fibers in violet hues.

The duration of the coupling reaction can be significantly shortened if the mixture to be combined is neutralized by adding sodium acetate or sodium carbonate to a pH of 4.0-4.5.

Example 3. To 120 parts of concentrated sulfuric acid was added at 60-70 ° C, well stirred, 6.9 parts of suspended sodium nitrite. The solution is stirred still in

for 10 minutes at 60 ° C .; cooling to 10 ° C and at a temperature of 10-20 ° C, 100 parts of glacial acetic acid are added, then 16.3 parts of 1-amino-2-cyano-4-nitrobenzene and 100 including glacial acetic acid. The reaction mass is additionally stirred for 2 hours and the resulting solution of the diazonium salt is poured into a mixture of 24.8 hours. (pyridyl-4) -ethyl-aminonaphthalene, 100 parts of glacial acetic acid, 10 parts of aminosulfonic acid, and 200. ice The coupling reaction is carried out until the end in an acidic medium with a pH of 3.4-4, which is achieved by adding sodium acetate. Immediately a dye is formed which precipitates. It is filtered, washed to remove the acid and dried. The dry dye is dissolved at 131 ° C in 2000 hours of chlorobenzene. The resulting solution is filtered to clarify, then 14.2 parts of methyl iodide are added to it at 60 ° C. The reaction mixture was incubated for 1 hour at

60 ° C, and there is a quantitative selection of the Quaternary salt of the dye, which is filtered and dried. Beauty-. Tel has so pl. 192 ° C and dyes polyacrylonitrile fibers in blue tones.

Example 4. To 140 parts of concentrated sulfuric acid is slowly added at 60-70 ° C, well stirred, 6.9 parts of sodium nitrite. The solution is stirred es, e for 10 minutes at 60 ° C, then cooled to 10 ° C and

download 26.2 parts of 1-amino-2-bromo-4,6-dinitrobenzene. After 3 hours, the diazotization is completed. 8 hours of urea are added to the diazo solution and stirred for another 15 minutes at 10 ° C. The resulting solution of the diazonium salt is poured into a cold mixture of 24.8 parts (pyridyl-4) -ethyl-aminonaphthalene, 50 parts of glacial acetic acid, and 200 parts of ice. The coupling reaction is brought to the end in an acidic medium, which is achieved by adding sodium acetate. Immediately a dye is formed which precipitates. It is filtered, washed to remove the acid and dried. The dry dye is dissolved in 131 ml of C in 2000 parts of chlorobenzene. The resulting solution is filtered to reflux, then 14.2 parts of methyl iodide are added to it at 60 ° C. The reaction mixture is incubated for 1 hour at 60 ° C, and there is a quantitative selection of the main dye. The resulting dye is filtered and dried, so pl. 211 ° C. K rasitel colors polyacrylonitrile fibers in, blue tones.