DE1061462B - Process for the production of metal-containing azo dyes - Google Patents

Description

Process for the production of metal-containing azo dyes It has been found that valuable azo dyes are obtained if a diazotized 2-amino-6-nitronaphthalenesulfonic acid is used couples with an azo component containing amino groups in the o-position to the amino group, converted the aminoazo dye into the corresponding triazole compound, in this converting the nitro group to an amino group, diazotized, with an amino compound the benzene or naphthalene series, which in the o-position to the amino group forms a metal complex Group or a radical which, under the conditions of metallization, forms a metal complex Group is transferred, contains, combined in such a way that the clutch is in p-position takes place to the amino group, after further diazotization with one in the o-position to one Hydroxyl group coupling azo component combined and the dye thus obtainable converted into its metal complex compound by the action of metal-releasing agents.

The same dyes are obtained if one uses of 2-acetylamino-6-aminonaphthalenesulfonic acid goes out, diazotizes and couples, splitting off the acetyl group after the triazolation and otherwise proceed in the same way - as stated above.

Further embodiments of the method consist in that the The order of the various necessary reaction steps has been reversed. So can for example, starting from 2-amino-6-nitronäphthalinsulfonic acids, by coupling with the aforementioned amino compound of the benzene or naphthalene series, Further diazotization, association with one in o-position to a hydroxyl group coupling azo component and metallization containing the metal complex compound Build up part of the molecule, then after converting the nitro group into an amino group, Diazotization and coupling with a compound containing amino groups in the o-position carry out the triazolation to the amino group.

A variant of the last-mentioned method is that one the conversion into the metal complex compound as the last stage of the triazolation connects.

The conversion of the o-aminoazo dyes into the corresponding triazole compounds takes place according to methods known per se, for example by the action of ammoniacal Küpfer (II) salt solution or with chlorine lye.

The conversion of the nitro group into an amino group can, for example with sodium sulfide or - in the first-mentioned embodiment of the process - also be made with iron and acetic acid.

As a metal complex-forming group in the middle components of the benzene or naphthalene series used, for example, the hydroxyl group or the carboxyl group come into question. Substituents which are converted into a metal complex-forming group under the conditions of the metallization are, for example, the alkoxy group or a half-ring substituent. In the case of an alkoxy group, the metalization, for example coppering, is carried out in a known manner, replacing alkoxy with hydroxyl and, in the case of halogen substitution, by methods that are likewise known, by replacing the halogen substituent with hydroxyl. The residue in question can also mean a hydrogen atom or a sulfonic acid group, which can be converted into hydroxyl groups by the process of oxidative copper engineering (German patents 807 289, 889196, 893 699 and German Auslegeschrift 1006 098e.

2-Amino-6-nitronaphthalenesulfonic acids suitable for the present process are for example 2-amino-6-nitronaphthalene-8-sulfonic acid and 2-amino-6-nitronaphthalene-4,8-disulfonic acid. As amino compounds, which are capable of triacolation after the coupling, come for example in question: 2-aminonaphthalene, 2-aminonaphthalene-5-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 2-aminonaphthaline-3,6-disulfonic acid and 1-aminonaphthalene-4-sulfonic acid.

Suitable middle components of the benzene or naphthalene series, the couple in the p-position to the amino group and those in the o-position to the amino group carry substituents required for metallization z. B. aminobenzene, 2-methoxyaminobenzene, 5-methyl-2-methoxyaminobenzene, 1-aminonaphthalene, 1-aminonaphthalene-6-sulfonic acid, 2-chloro-1-aminonaphthalene-6-sulfonic acid and 2-ethoxy-1-aminonaphthalene-6-sulfonic acid.

As azo components that couple in the o-position to a hydroxyl group, may be mentioned: 1-oxy-4-methylbenzene, 1-oxynaphthalene-4-sulfonic acid, 2-oxynaphthalene-4-sulfonic acid, 2-oxynaphthalene-3,6-disulfonic acid, 1-acetylamino-8-oxynaphthalene-4-sulfonic acid and phenylmethylpyrazolone.

The dyes dye fibers made from natural or regenerated cellulose in predominantly green tones with excellent lightfastness.

Compared to the copper-containing disazo dye known from Example 2 of German Patent 737 941, the copper-plated disazo dye of the formula is distinguished due to the better lightfastness of the dyeings on cotton. Example 1 55.1 parts by weight (0.1 mole) of the aminotriazole compound of the formula (produced by coupling dianotized 2-amino-6-nitronaphthalene-4,8-disulfonic acid with 2-aminonaphthalene-6-sulfonic acid (triazole component), triazolation and reduction of the nitro group to the amino group) are dissolved in 800 parts by volume of water with a weak soda alkaline solution and after addition dianotized 69 parts by volume of 10% sodium nitrite solution by running into 35 parts by volume of hydrochloric acid (d = 1.14) and 350 parts by volume of water at about 20 ° C. When the dianotization is complete, 26.7 parts by weight of 1-amino-2-ethoxynaphthalene-6-sulfonic acid, mixed in 100 parts by volume of water, are added and the mixture is brought to a p $ value of about 4 by adding approximately 35 parts by volume of 200% sodium acetate solution . When the coupling is complete, it is suctioned off and redissolved in water using an alkaline soda solution. The paste obtained is dissolved in 1400 parts by volume of hot water and dianotized with 69 parts by volume of 10% sodium nitrite solution by running into 100 parts by volume of hydrochloric acid (d = 1.14) at about 30 ° C .; the precipitated diazonium salt is then filtered off with suction. The paste obtained is added to the soda-alkaline solution of 30.4 parts by weight of 2-oxynaphthalene-3,6-disulfonic acid in 350 parts by volume of water and 140 parts by volume of 20% soda solution and stirred at room temperature until the coupling is complete. The precipitated dye is isolated and converted into the copper complex compound by conventional methods by treatment with copper salts. The dried dye is a dark powder that dissolves in water with a green color and dyes cotton in green, lightfast shades.

100 parts by weight of cotton are placed in a dyebath at room temperature which contains, in 5000 parts by volume of water, 2 parts by weight of this dye, 1 part by weight of soda and 20 parts by weight of sodium sulfate. The dyebath is heated to 90 to 95.degree. C. in about half an hour and held at 95.degree. C. for 1/2 hour. The cotton is then rinsed and dried. A green dyeing is obtained which has very good lightfastnesses.

If the metallization is carried out with nickel salts instead of copper salts, in this way a dye is obtained which dyes cotton in bluish green tones.

If the end component 2-oxynaphthalene-3,6-disulfonic acid is replaced by the equivalent amount of 1-oxy-8-acetylaminonaphthalene-5-sulfonic acid, the Final coupling is carried out in the presence of pyridine, one obtains a Dye that dyes cotton in yellowish green tones.

If, instead of the 2-aminonaphthalene-6-sulfonic acid as the triazole component and the 2-oxynaphthalene-3,6-disulfonic acid as the endazo component, the equivalent amount of the compounds given below is used and the procedure is analogous to that described, then dyes are obtained which include cotton in the in colors given in the following table. Triazole component Endazo component Coloring of the copper-containing Dye on cotton 2-aminonaphthalene-6-sulfonic acid 2-oxynaphthalene-5-sulfonic acid bluish green Likewise. 2-oxynaphthalene-6-sulfonic acid bluish green likewise. 1-oxy-8-acetylaminonaphthalene green 3,6-disulfonic acid likewise. 1-oxynaphthalene-4-sulfonic acid green likewise. 1-oxynaphthalene-3,8-disulfonic acid green 2-aminonaphthalene-5-sulfonic acid 2-oxynaphthalene-3,6-disulfonic acid bluish green likewise. 2-oxynaphthalene-5,7-disulfonic acid green likewise. 1-oxynaphthalene-4,8-disulfonic acid green Likewise. 1-Oxy-8-acetylaminonaphthalene yellowish green 5-sulfonic acid 2-aminonaphthalene-7-sulfonic acid 2-oxynaphthalene-3,6-disulfonic acid bluish green likewise. 1-oxy-8-acetylaminonaphthalene green 5-sulfonic acid 2 aminonaphthalene-3,6-disulfonic acid 2-oxynaphthalene-5-sulfonic acid bluish green Likewise. 2-oxynaphthalene-6-sulfonic acid bluish green 1-oxy-8-acetylanonaphthalene yellowish green 5-sulfonic acid Likewise. 1-Oxy-8-benzoylaminonaphthalene yellowish green 5-sulfonic acid Likewise. 1-chloro-2-acetylamino-5-oxynaphthalene bluish green 7-sulfonic acid 1-aminonaphthalene-4-sulfonic acid 2-oxynaphthalene-3,6-disulfonic acid bluish green Likewise. 1-Oxy-8-acetylaminonaphthalene yellowish green - 5-sulfonic acid If the central component of the basic example 1-amino-2-ethoxynaphthalene-6-sulfonic acid is replaced by the equivalent amount of 1-amino-2-ethoxynaphthalene-7-sulfonic acid, a dye is obtained which dyes cotton in green shades.

If the equivalent is used instead of the aminotriazole compound (I) Amount of the aminotriazole compound prepared by coupling diazotized 2-amino-6-nitronaphthalene-8-sulfonic acid with 2-aminonaphthalene-3,6-disulfonic acid, triazolation and reduction of the nitro group, after diazotization and coupling with 1-amino-2-ethoxynaphthalene-6-sulfonic acid, Further diazotization and coupling with 1-oxy-8-acetylaminonaphthalene-5-sulfonic acid a dye whose copper complex compound is cotton in real green tones colors. Example 2 55.1 parts by weight (0.1 mol) of the aminotriazole compound (I) are as described in Example 1, diazotized and, after the reaction has ended, with 22.3 Parts by weight of 1-aminonaphthalene-6-sulfonic acid, dissolved in 350 parts by volume of water, united, decoupled from acetic acid and isolated.

The paste obtained is stirred in 1100 parts by volume of water, 69 Parts by volume of 10o% sodium nitrite solution were added and allowed to run in at about 10 ° C in 42 parts by volume of hydrochloric acid (d = 1.14), diluted with 50 parts by volume of water, diazotized. When the diazotization has ended, the diazonium salt is filtered off with suction. The soda-alkaline Solution of 30.4 parts by weight of 2-oxynaphthalene-3,6-disulfonic acid in 350 parts by volume Water is mixed with the resulting diazonium salt paste after adding 140 parts by volume 20% soda solution combined and uncoupled at 0 ° C., then with sodium chloride salted out and isolated. The dye paste obtained is in 2100 parts by volume Stirred water, weakly acidified with acetic acid and with 140 parts by volume of 20% Sodium acetate solution and the solution of 25 parts by weight of crystallized copper sulfate added in 130 parts by volume of water. After heating to 60 ° C are in the solution about 280 parts by volume of 3o / o hydrogen peroxide added dropwise in 3 hours until the oxidizing copper plating has ended. The oxidatively coppered dye is with Salt out sodium chloride. and isolated. It represents a dark powder when dried which dissolves in water with a green color and dyes cotton in green tones.

If the equivalent is used instead of 1-aminonaphthalene-6-sulfonic acid Amount of 2-chloro-1-aminonaphthalene-7-sulfonic acid and leads to coppering by boiling with tartrate-containing copper salt solution in an alkaline medium, one obtains hue similar to green dye on cotton.

Example 3 A neutral solution of 63.1 parts by weight (0.1 mole) of the aminotriazole compound of the formula in 700 parts by volume of water is diazotized analogously to the instructions in Example 1, coupled with 13.7 parts by weight of 1-methyl-3-amino-4-methoxybenzene in acetic acid at 0 ° C. and the monoazo compound obtained is isolated. The paste obtained is dissolved in 1400 parts by volume of water and diazotized with 69 parts by volume of 10% sodium nitrite solution by running into 42 parts by volume of hydrochloric acid (d = 1.14) and 50 parts by volume of water at 25 ° C. When the diazotization is complete, the solution of 30.4 parts by weight of 2-oxynaphthalene-3,6-disulfonic acid in 350 parts by volume of water is added, the solution is decoupled using alkaline soda and isolated. The dye paste obtained is aftertreated as usual with copper salts.

The copper-plated dye is a dark powder when dried, which dissolves in water with a blue color and cotton in a greenish blue-gray Clay colors.

If the 2-oxynaphthalene-3,6-disulfonic acid is used instead equivalent amount of 1- (4'-sulfophenyl) -3-methyl-5-paryzolone, a dye is obtained which dyes cotton in violet-brown tones.

If you replace the middle component 1-methyl-3-arnino-4-methoxybenzene by the equivalent amount of 2-aminobenzoic acid, 2-oxynaphthalene-3,6-disulfonic acid is obtained as the final component on cotton a red-brown color.

If an aminotriazole compound with 2 aminonaphthalene-5-sulfonic acid is used as a triazole component and uses 2-aminobenzoic acid as a middle component, see above obtained with 2-oxynaphthalene-3,6-disulfonic acid or 1-oxy-7-acetylaminonaphthalene-3-sulfonic acid orl-oxy-7-phenylaminonaphthalene-3-sulfonic acid as endazo component dyes, which dye cotton in red to black-brown shades after coppering.

Claims (4)

PATENT CLAIMS: 1. Process for the production of metal-containing azo dyes, characterized in that one diazotized 2-amino-6-nitronaphthalenesulfonic acid couples with an azo component containing amino groups in the o-position to the amino group, converted the aminoazo dye into the corresponding triazole compound, in this converting the nitro group to an amino group, diazotized, with an amino compound the benzene or naphthalene series, which in the o-position to the amino group forms a metal complex Group or a radical of the metal complex forming under the conditions of the metallization Group is converted, contains, couples in p-position to the amino group, after further diazotization combined with an azo component coupling in the o-position to a hydroxyl group and the dyes thus obtainable by the action of metal donating agents converted into their metal complex compounds. 2. The method according to claim 1, characterized characterized in that one starts from a 2-acetylamino-6-aminonaphthalenesulfonic acid and the acetyl group is split off after the triazolation has taken place. 3. The method according to claim 1, characterized in that a diazotized 2-amino-6-nitronaphthalenesulfonic acid with an amino compound of the benzene or naphthalene series, which is in the o-position to Amino group has a metal complex-forming group or a group which can be converted into such a group, in the p-position to the amino group, after further diazotization with one in the o-position combined to form an azo component coupling a hydroxyl group, the dye thus obtained converted into its metal complex compound by the action of metal-releasing agents, in this dye converts the nitro group into an amino group, diazotized with an amino group-containing compound in o-position to the amino group and then triazolized. 4. The method according to claim 3, characterized in that that the metal complex formation only occurs after the triazolation in the final stage undertakes. Documents considered: German Patent No. 737 941. A coloring table was displayed when the application was announced.