DE1060521B - Process for the production of metalizable monoazo dyes free of sulfonic acid groups and their metal complex compounds - Google Patents

Description

Process for the production of metallisable materials free from sulfonic acid groups Monoazo dyes and their metal complex compounds It has been found that valuable dyes are obtained if diazo compounds free of sulfonic acid groups are used aromatic amines which contain an alkoxy group in the o-position to the diazonium group, with 4-oxydiphenyl and optionally the resulting monoazo dyes for or in a mixture with sulfonic acid group-free `o, o'-dioxy-, o-alkoxy-o'-oxy- or o-carboxy-ö -oxyazo- or -azomethine dyes in their one per metal atom to two metal complex compounds containing dye residues.

The above-mentioned diazo compounds are amines of the benzene or naphthalene series, which is an -alkoxy group in the o-position to the amino group contain. You can add other substituents such as halogen atoms, nitro, acylamino, Carboxylic acid, carboxamide or sulfonic acid amide groups contain.

The dyes thus obtained can, for. B. by the process of patents 479 373, 715 082, 715 948, French patent 836 257 or by the process of patent 1016 866 in metal complex compounds containing at least one dye molecule per metal atom. Particularly suitable metal-releasing agents are compounds of metals with atomic numbers 24 to 29, in particular chromium and cobalt.

For the preparation of 1: 2 metal complex compounds, it is also possible to use mixtures of different dyes, at least one of which corresponds to the constitution indicated at the outset. The new dyes are ideal for dyeing wool, silk, casein wool and leather as well as polyamide or polyurethane fibers. They can also be used for the production of colored organic solutions or colored plastic masses, e.g. B. of colored zapon varnishes, varnishes, objects made of cellulose esters and cellulose ethers or plastics as well as for spin dyeing of acetate rayon or other spun synthetic fibers. If the dyes contain 1 mole of dye per metal atom, they are also suitable for further reaction with colorless complex-forming compounds, e.g. B. by the method of patent 846 142, or with dyes containing complexing groups.

Compared to the metal-containing dyes, which instead of 4-oxydiphenyl The new dyes are characterized by containing 1-oxy-4-alkylbenzenes as the azo component through better wet fastness and better absorption. Compared to dyes, which contain 2-oxynaphthalene as the azo component, the new dyes have better ones Wet fastness properties and better leveling properties.

From sulfonic acid group-containing, with the help of 4-oxydiphenyl as azo component produced dyes differ in that they have better leveling properties and, as a result, a considerably calmer surface appearance of their colorations.

The parts given in the examples are parts by weight.

Example 1 10.1 parts of 1-amino-2-methoxybenzene-5-sulfonic acid amide are used stirred with 65 parts of 8% hydrochloric acid and then mixed with 50 parts of ice. A solution of 3.8 parts of sodium nitrite in 50 parts of water is added and the mixture is stirred 1 hour at 0 ° C. The solution obtained is left at 0 ° C. within half a period Drip the 9 parts of 4-oxydiphenyl, 4 parts into a solution, with stirring, for an hour Sodium hydroxide and 10 parts of sodium carbonate in 150 parts of water and 100 parts Contains ice. After stirring for 5 hours, the dye is filtered off with suction, dried and ground.

The dye is then heated with a solution of 11 parts of cobalt acetate in 200 parts of acetamide for 5 hours at 130 ° C, the reaction mixture contributes 2000 parts of water, mixed with 200 parts of sodium chloride, stirred for 3 hours, sucks off, washes with water and dries at 80 ° C.

The dye dyes wool from a weakly acidic bath in bordeaux red tones of very good authenticity.

The cobalt-containing dyes can be mixed with the diazo compounds in the same way make the following amines; the hue of the dyeing on wool is in each case Brackets: 1-Amino-2,4- dimethoxybenzene- 5 - sulfonic acid phenylamide (Bordo red), 1-Amino-2-methoxybenzene-5-sulfonic acid-3'-methoxyiropylamide (Bordo red), 1-amino -2,5-dimethoxybenzene -4 - sulfonic acid methyl-lmid (violet), 1- Amino - 2 - methoxy - 5 - chlorobenzene - 4 - sulfonic acid diethanolamide (violet), 1-amino-2-methoxy-5-nitrobenzene (brown), 1-amino-2,4-dimethoxybenzene (Bordo). example 2 7.7 parts of 1-amino-2,5-dimethoxybenzene are in the manner indicated in Example 1 diazotized; the diazoiium compound is coupled with 9 parts of 4-oxydiphenyl.

The dried dye is dissolved in 150 parts of β, β'-dioxy-ethyl ether entered, the mixture heated to 120 ° C ind then within 1 hour with constant stirring with 5 parts of finely powdered, crystallized sodium dichromate offset.

The reaction mixture is held for 4 hours at 130 to .35 ° C and then added to 1500 parts of water to separate the chromium complex compound, 150 parts of sodium chloride were added to the complete precipitation of the dye are. The separated and rocked dye dyes wool from a weakly acidic bath n blue-violet shades of very good fastness properties.

The chromium-containing dyes can be mixed with the diazo compounds in the same way of the following amines are 1-amino-2-methoxybenzene-5-sulfonic acid amide (violet), 1-Amino-2-methoxy-5-nitrobenzene (Braun), 1-amino-2-methoxy-5-methylbenzene-4-sulfonic acid ethylamide (Purple), 1-amino-2-methoxy-5-chlorobenzene (purple). Example 3 8.4 parts of 1-amino-2-methoxy-5-nitrobenzene are diazotized in the usual way and coupled with 9 parts of 4-oxyliphenyl.

The dried dye is added to 150 parts of β, ß'-Diixyäthyläther, which contains 14 parts of crystallized chromium chloride Cr Cl, -6 HZ O), and the mixture is stirred at 135 ° C for 3 hours. The resulting brown dye solution is introduced into 1000 files of water after cooling, 20 parts of crystallized sodium acetate and 16 parts of 2-oxybenzoic acid-5-sulfonic acid-) henylamide are added and the mixture is stirred for 1 hour at 2 to 90 ° C. After cooling, the dye ib is sucked up and dried at 70 ° C. It dyes wool from acid 3ad in brown shades.

If 1-amino-2-ethoxynaphthalene is used instead of 1-amino-2-methoxyä-nitrobenzene as a diazo component, a dye is obtained after chromation, the `solid colors in purple tones.

Example 4 12.3 parts of 1-amino-2,5-dimethoxybenzene-4-sulfonic acid ethylamide are diazotized in the usual way and coupled with 9 parts of 4-oxydiphenyl.

The dried dye is made in the same manner as in Example 3 chromed. The blue dye solution gives nan in 1000 parts of water, adds 20 parts crystallized .'iatrium acetate and 20.8 parts of the monoazo dye from diazotized 1-amino-2-oxybenzene-5-sulfonic acid amide and 1- (carbomethoxy) -amino-7-oxynaphthalene and holds for 1 hour at 80 to 90 ° C with stirring. After cooling down, you suck remove the dye and dry it at 60 to 70 ° C. It dyes wool from weakly acidic materials Bathroom in blue tones.

Is used in place of the monoazo dye from diazotized 1-amino-2-oxybenzene-5-sulfonic acid amide and 1- (carbomethoxy) -amino-7-oxynaphthalene made 16.1 parts of the monoazo dye diazotized 1-aminobenzene-2-carboxylic acid and 1-phenyl-3-methyl-5-pyrazolone or 18 parts of the azomethine dye from 1-amino-2-oxybenzene-5-sulfonic acid amide and 2-oxy-3,5-dichlorobenzaldehyde, this is how dyes are obtained that dye wool in olive green tones.

Example 5 11.9 parts of the monoazo dye from diazotized 1-amino -2,5 - dimethoxybenzene-4-sulfonic acid morpholide and 4-oxydiphenyl and 9.9 parts of des Monoazo dye from diazotized 1-amino-2-methoxybenzene-5-carboxylic acid and 1- (carbomethoxy) -amino-7-oxynaphthalene are chrome-plated in the same way as in Example 2. The dye obtained stains Wool from a weakly acidic bath in blue-gray tones.

Example 6 10 parts of the monoazo dye from diazotized 1-amino-2-methoxybenzene-5-sulfonic acid methylamide and 4-oxydiphenyl and 8.9 parts of the monoazo dye from diazotized 1-amino-2-methoxy-5-nitrobenzene and 1-phenyl-3-methyl-5-pyrazolone are chromated in the same manner as in Example 2. The dye obtained dyes wool from a weakly acidic bath in brown shades.

Example 7 9.7 parts of the monoazo dye from diazotized 1-amino-2-methoxybenzene-5-sulfonic acid amide and 4-oxydiphenyl and 8.8 parts of the monoazo dye from diazotized 1-amino-2-methoxy-5-nitrobenzene and 4-oxydiphenyl are given in the same manner as in Example 1 in the Cobalt complex compounds transferred. The dye obtained dyes wool from weak acid bath in brown tones.

Claims (1)

Claim: A process for the preparation of sulfonic acid group-free metallizable monoazo dyes and their metal complex compounds, characterized in that sulfonic acid group-free diazo compounds of aromatic amines which contain an alkoxy group in the o-position to the diazonium group are coupled with 4-oxydiphenyl and optionally the monoazo-free groups obtained with sulfonic acid groups alone or as a mixture o; ö -Dioxy-, o-alkoxy-ö -oxy- or o-carboxy-ö -oxyazo- or -azomethine dyes are converted into their metal complex compounds containing one to two dye radicals per metal atom. Documents considered: German Patent No. 541 195. When the application was published, a coloring table was laid out.