CH498181A - Process for the production of copper-containing azo reactive dyes - Google Patents

Description

  

  
 



  Process for the production of copper-containing azo reactive dyes
The present invention relates to a process for the preparation of new, valuable copper-containing azo reactive dyes of the formula
EMI1.1

Here, R denotes a hydroxyl group or an acylamino group, A denotes an aromatic-heterocyclic or aromatic-carbocyclic radical in which the - (CO) mO- group is located adjacent to the azo group, m the number 0 or 1, R1 and R'1 Hydrogen or an alkyl radical, B a bridge member, p the number 0 or 1 and X a reactive group.



   The dyes I can also have any substituents customary in azo dyes, such as sulfonic acid, carboxylic acid, carboxylic acid ester, sulfonamide, carbonamide, alkyl, alkoxy, nitro, halogen, such as chlorine or bromine, cyano or aryl -, amino, substituted amino, such as alkylamino, aralkylamino, arylamino, acylamino and other azo groups.



  The left-hand naphthalene nucleus of the general formula contains one or more sulfonic acid groups as preferred substituents.



   As is customary in the chemistry of reactive dyes, a reactive group X is understood to mean a group which has a labile substituent or a reactive group which is able to react with hydroxyl or amide groups of fiber materials to form a covalent bond.

  From the large number of possible reactive groups X, the following may be mentioned, for example: 2,4-dichlorotriazinyl-6-, 2-methyl-4-chlorotriazinyl-6-, 2-amino-4-chlorotriazinyl-6-, 2-methoxy -4-chlorotriazinyl-6-, 2-sulfophenylamino-4-chlorotriazinyl-6-, 2-phenoxy-4-chlorotriazinyl-6-, 2,4-dichloropyrimidyl6-, 2,4,5-trichloropyrimidyl-6-, 2-methylsulfonyl6 -methylpyrimidyl-4-, 2,3-dichloroquinoxaline-6-carbonyl-, 2,3-dichloroquinoxaline-6-sulfonyl-, 2-monochloroquinoxaline-6-carbonyl-, 2-chlorobenzothiazole 5-carbonyl- or -6-carbonyl- , 2-methylsulfonylbenzthiazole-5-carbonyl- or -6-carbonyl-, 2-phenylsulfonylbenzthiazole-5-carbonyl- or -6-carbonyl-, 2-methylsulfonylbenzthiazole-5-sulfonyl- or -6-sulfonyl-, 2-chlorobenzoxazole- 5-carbonyl- or -6-carbonyl-, 2-chloro-1-methyl-benzimidazole-5- or -6-carbonyl-,

   2,4-dichloropyrimidine-5- or -6-carbonyl, 2,4-bismethylsulfonylpyrimidine-5 or -6carbonyl groups, the bromine derivatives of the chlorine compounds mentioned, also the acryloyl, ss-chloropropionyl, BPhenyl and ss -Methylsulfonyl-propionyl-, s-bromopropionyl-, the vinylsulfonyl group, the ß-sulfatopropionyl and ß-oxethylsulfon-sulfuric acid half-ester grouping or a 1,4-dihalophthalazine-6-carbonyl or 6-sulfonyl radical
Suitable acylamino groups R include Acetylamino, chloroacetylamino, benzoylamine>, benzenesulfonylamino and alkylsulfonylamino groups.



   Particularly suitable alkyl radicals R1 and R'1 are those with 11 carbon atoms, such as CH3-, C2H5-, C3H7-.



   Bridge members B, which are between the aminomethylene group and the reactive radical X in the event that p = 1, are those of an aliphatic nature that can be interrupted by further heteroatoms, as well as those of an aromatic nature; for example:
EMI2.1
 and
EMI2.2
 In the dye I the grouping
EMI2.3
 both in the left-hand naphthalene radical of the formula I and in the radical A of this formula.



   According to the invention, the new dyes are prepared by adding dyes of the formula
EMI2.4
 oxidizing copper.



   Oxidative copper plating is usually carried out in a known manner.



   Depending on the method of preparation, the dyes III can have one or more groupings of the formula II. These groupings can be introduced into the preformed dyes III or also into the diazo or coupling components used for this purpose.



   The dyes available according to the process are new. They are particularly suitable as reactive dyes for dyeing and printing hydroxyl or amide group-containing materials, such as textile fibers, threads and fabrics made from wool, silk, synthetic superpolyamide and polyurethane fibers, in particular from native and regenerated cellulose. The dyes are applied to these materials by the techniques known for reactive dyes in the presence of acid-binding agents and, if appropriate, with the action of heat.

 

   example
0.1 mol of the reactive dye of the formula
EMI3.1
 are dissolved in 1000 ml of water. 28 g of water-containing copper sulfate and 42 g of water-containing sodium acetate are added. 100 ml of the above hydrogen peroxide solution are added dropwise at room temperature, the color of the solution changing from deep red to blue. After the oxidative coppering has ended, the dye is isolated by adding 25% by volume of sodium chloride. After drying at 70 ° C. and grinding, a blue dye powder which is readily soluble in water is obtained.

 

Claims (1)

PATENT CLAIM Process for the preparation of azo reactive dyes of the formula EMI3.2 where R is a hydroxyl or acylamino group, A is an aromatic-heterocyclic or aromatic carbocyclic radical in which the group (CO) ES is adjacent to the azo group, m is the number 0 or 1, R1 and R'1 are hydrogen or alkyl radicals mean, B stands for a bridge member, p stands for the number 0 or 1 and X stands for a reactive group, and which may have further substituents, characterized in that reactive azo dyes of the formula EMI3.3 SUBClaim Process according to claim, characterized in that reactive dyes are prepared in which R1 is hydrogen, R'1 is a lower alkyl radical, preferably -CH3, R is a hydroxyl group, m list and X for a halodiazinyl, halotriazinyl, 2,3-dihaloquinoxaline-6-carbonyl-, 2-methylsulfonylbenzthiazole-5- or -6-sulfonyl- or -carbonyl- or a methylsulfonyldiazine or a 1,4 -Dihalophthalazine-6-carbonyl radical, where halogen is Br or preferably Cl.