CS265450B1 - Unsymmetrical violet 1: 2 chromocomplex dyes and method of their preparation - Google Patents

Abstract

New 1:2 unsymmetrical metallocomplex dyes with two sulfo groups of formula I, where the substituents Aj and A2 are different and denote H, NO2, Cl, SO3-, with one of the substituents always denoting SO3- and Me+ is a cation Na, NH4, K, are useful for dyeing wool and polyamide textile materials and dye highly stable violet shades and are prepared either by reacting a compound of formula II with a chromium complex of formula III, or by reacting an azo compound of formula IV with a chromium complex of azo dyes of formula V, where the symbols Aj, A2 and Me+ have the above-mentioned meaning.

Description

The invention relates to 1: 2 unsymmetrical formula I metal-complex dyes based on a tremendous complex

where the substituents and A ₂ are different and denote H, NO ₂ , Cl, SO 4, one of the substituents each being SO- and Me ⁺ denoting the cation Na ⁺ , NH 4, K ⁺

These dyes are new and usable for dyeing woolen and polyamide textile materials that dye highly stable violet shades.

Hitherto known metal-complex dyes are prepared as 1: 1 chromium, 1: 2 symmetric and 1: 2 asymmetric complexes containing one sulfo group per molecule. The disadvantage of 1: 1 metal-complex dyes is their low pull-out from neutral and weakly acid dye baths. A disadvantage of symmetrical 1: 2 metal-complex dyes is that. it is difficult to obtain highly stable dyes of the desired shades for dyeing wool and polyamide. A disadvantage of 1: 2 unsymmetrical single-sulfo metal complex dyes is their lack of solubility in conventional dyeing processes.

It has now been found that said drawbacks do not show unsymmetrical 1: 2 chromium metal-complex dyes with two sulfo groups (I), wherein the substituents A 1, A _{2 <} Me ⁺ are as previously defined. These dyes are the subject of the invention.

The unsymmetrical metal-complex dyes of the formula I according to the invention are readily obtainable by reaction of the compounds of the formula II

Me ^f (II) where A 1 and A ₂ are as previously defined, with a chromium complex of formula III ° 3 ^{S -} 4 h

(III) or by treatment with an azo compound of formula IV

OH

HO (IV) to 1: 1 chromium complexes of formula V h ₂ ° h ₂ oh ₂ o

(V) wherein A 1 and A 2 are as previously defined, in an alkaline, neutral or slightly acidic environment at temperatures usually 50 to 100 ° C.

The process for the preparation of unsymmetrical 1: 2 chromium complexes of the formula I according to the invention can advantageously be carried out in a reaction medium containing ammonium ions or alkali carbonates. The presence of these substances makes it easier to carry out the complexing reaction in a high concentration of reacting components.

The advantage of the process for the preparation of 1: 2 unsymmetrical complexes of the formula I according to the invention is the high purity of the dye, as hitherto commonly used methods for the synthesis of unsymmetrical 1: 2 metalocomplex dyes. both possible symmetrical 1: 2 metal complex dyes.

In addition to the high solubility of the dye, the product I is distinguished by excellent coloristic properties and high light fastness.

The advantage of the process of preparing 1: 2 asymmetric complexes according to the invention is furthermore to achieve high production on a simple production equipment and to guide the production process so that it is possible to work with waste-free technologies. Another advantage of 1: 2 unsymmetrical chromite complexes with two sulfo groups is that it is not necessary to isolate the dye itself before drying.

The invention is further illustrated by the following non-limiting examples.

He did

To a suspension of 0.02 mol of azo compound 1-diazo-2-naphthol-4-sulfo acid ----> 1-phenyl-3-methyl-5-pyrazolone in 400 ml of water was added 0.02 mol of a 1: 1 chromium complex of the azo compound

4-nitro-2-aminophenol-6-sulfoacid ----> 2-naphthol and the pH of the reaction mixture was adjusted to 8.

The reaction mixture was heated with stirring to 60 ° C while maintaining the pH at 8 by the addition of sodium hydroxide solution. The resulting dye solution was sclerated and dried.

21 g of a very soluble wool dye and polyamide violet shades with excellent fastnesses were obtained.

Example 2

To a suspension of 0.02 mol of azo compound 6-nitro-2-aminophenol-4-sulfo acid ---- 2-naphthol in 400 mL of water was charged 0.02 mol of 1: 1 chromium complex of azo compound 1-diazo-2-naphthol-4 -sulphonic acid ---- 1-phenyl-3-methyl-5-pyrazolone and the pH was adjusted to pH 9 by the addition of sodium hydroxide solution. 0.01 mol of sodium bicarbonate was added and the reaction mixture was heated at 90 ° C for 2 hours with stirring. Deň: 32 ° C. The resulting dye solution was sclerated and dried.

22 g of a very soluble wool dye and polyamide violet shades with excellent fastnesses were obtained.

Example3

To a suspension of 0.02 mol of azo compound 4-chloro-2-aminophenol-6-sulfo acid -----2-naphthol in 400 ml of water was added 0.02 mol of 1: 1 chromium complex of azo compound 1-diazo-2-naphthol- The pH of the 4-sulfo acid ---- 1-phenyl-3-methyl-5-pyrazolone was adjusted to 9 by the addition of ammonium hydroxide solution. The reaction mixture was heated with stirring at 60 ° C for 4 h while maintaining the pH at 9 by addition of ammonium hydroxide solution. . The resulting dye solution was sclerated and dried.

22 g of a very soluble wool dye and polyamide violet shades with excellent fastnesses were obtained.

Claims (3)

1. Unsymmetrical 1: 2 metal-complex dyes with two sulfo groups based on chromium complexes of formula I Γ Ί 3® where the substituents Α _χ and A ₂ are different and denote H, NO ₂ , Cl, SOj, one of which denotes SO " Me ⁺ denotes the cation Na ⁺ , K ⁺ , NH4. 2. A process for preparing a 1: 2 chromium complexes of claim 1, wherein the azo compound of general formula II wherein the substituents Aj, A ⁺ ₂ and Me are as defined above is applied to the 1: 1 chromium complex of the formula III (III) optionally, treating the azo compound IV to 1: 1 chromium complexes of azo dyes of formula V (IV) (V) wherein the substituents Aj A ₂ and Me are as previously defined. 3. A process for the preparation of asymmetric 1: 2 chromium complexes according to claim 1 or 2, characterized in that the synthesis of the dyes is carried out in an alkaline, neutral or slightly acidic medium.