CS260631B1 - Unsymmetrical 1: 2 metal complex dyes and method of their preparation - Google Patents

Abstract

Unsymmetrical 1:2 metallocomplex dyes with two sulfo groups based on chromium complexes of constitution I, where the substituents At and Až are different and denote —NOž, —Cl, —SOs" and A3 is —H or —Cl, with one of the substituents Ai or Až being —SO3-, and M+ being Na+ and/or NH4+, and a method of their preparation.

Description

SUMMARY OF THE INVENTION The present invention provides an unsymmetrical meth complex of Formula I: 2 chromium-based metal-complex dyes.

(I) wherein the substituents A1 and A2 are different and denote —NO2, —Cl, —SO3 ”and A3 is —H, or —Cl, wherein each of the substituents A1 or A2 is —CO3 -, and M represents Na ⁺ and or NHr.

These dyes are new and usable for dyeing wool and polyamide textile materials, which dye with highly stable olive to brown shades.

Hitherto known metal-complex dyes are prepared as 1: 1 chromium complexes and 1: 2 symmetric chromium or cobalt complexes, or asymmetric 1: 2 chromium 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 baths.

A disadvantage of the 1: 2 symmetrical metal-complex dyes is that it is relatively difficult to achieve the high lightfast dyes of the desired shades applicable to said textile materials. The disadvantage of 1: 2 unsymmetrical metal-complex dyes with one sulfo group is their lack of solubility and leveling in conventional dyeing processes.

It has now been found that said drawbacks do not exhibit a 1: 2 two-sulfo metal complex complex dye according to the invention which is based on an asymmetric chromium complex of formula I, wherein the substituents A 1, A 2, A 2 are as previously defined.

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

where

A 1, A 2, A 3 are as defined above, at 1; 1 a chromium complex of azo dye of the formula Π1

26Θ631

or by treatment with an azo compound of formula IV

to 1: 1 chromium complexes of formula V

where

A 1, A 2, A 3 are as defined above in an alkaline neutral or weakly acidic environment at temperatures usually 80 to 100 ° C.

The process for the preparation of unsymmetrical 1: 2 chromium complexes of the formula I according to the invention can be carried out advantageously in a reaction medium containing ammonium 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, since the currently used methods of synthesis of unsymmetrical 1: 2 metallocomplex dyes. : 2 metal complex dyes. In addition to the high solubility of the dye, the dyes of the formula I are distinguished by excellent coloristic properties and high photostability.

An advantage of the process of preparing 1: 2 chromium asymmetric complexes according to the invention is furthermore the achievement of high production on a simple production equipment and the control of the production process so that it can be operated by waste-free technologies. A further advantage of producing 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. Example 1

To a suspension of 0.02 moles of the 1: 1 chromium complex of formula II in 400 ml of water was added 0.02 moles of azo compound of formula II, where A 1 = -NO 2, Up = -SO 2, and A3 = H. The pH was adjusted to 9.8 and 0.01 mol of sodium hydrogen carbonate was added and the reaction mixture was heated at 95 DEG C. for 1 h. The dye solution obtained was dried and 19.5 g of a dye of formula I were obtained, where Al = NO2, A2 - SO3 - and A3 = H dyeing wool and polyamide textile materials to a high shade olive shade.

Example 2

To a suspension of 0.02 moles of 1: 1 chromium complex V, where A 1 = -SO 3 ', Aa = -NO 2, and A 3 = H, 0.02 moles of dye IV were added and the pH of the mixture was adjusted to 10 by adding sodium hydroxide solution. c (NaOH) 10 mol / L. The reaction mixture was heated at 90-95 ° C for 4 hours. After sclering the dye, 21 g of a dye of formula I were obtained, where A 1 = -SO 2 ^- , Aa = -NOa and As-1H, dyeing wool and polyamide materials with a high shade brown color.

Example 3

Following the procedure of Example 1, reaction of a 1: 1 chromium complex III with an azo compound of formula II wherein A 1 = -SO 3, Aa-Cl and A3 = -H yielded a 1: 2 metal complex dye of formula I wherein At, Aa and A3 have as defined above, and, staining wool, polyamide fibers and textile materials of ¹ m and olive shade of high light fastness.

Claims (3)

OBJECT OF THE INVENTION 1. Non-symmetrical 1: 2 metallocamplex dyes with two sulfo groups based on chromium complexes of constitution I 3M + wherein A 1 and A 2 are different and denote -NO 2, -Cl, -SO 3 - and A 3 is -H, or -Cl, wherein each of A 1 or Aa is -SO 3 -, M ⁺ is Na ⁺ and / or NH 4 ⁺ . (I) 2. A process for the preparation of asymmetric chromite dye complexes according to claim 1, which comprises reacting an azo dye of the formula II. A ^ (II) HO ~ C ~ CH II N ~ h - C- CONH- 1B where A 1, A 2, A 3 are as defined above, with a 1: 1 chromium complex of azo dye of formula III optionally reacting an azo compound of formula IV with a 1: 1 chromium complex of azo dye of general formula V Cr A, n = n - c - con H ^A 1 V) wherein the dye complexes of dyes according to items 1 and 2 are characterized by. The method according to claim 1, wherein the synthesis of dyes is carried out A 1 is NO 2, —Cl, —SO 3 ^- , A 1> is —NO 2, Cl, in alkaline, neutral or weakly acidic --SO 3 - and As is -H or Cl. environment. 3. Method for the preparation of unsymmetrical chromium