DE2704333A1 - DISPERSE MONOAZO DYES - Google Patents

Description

The invention relates to disperse monoazo dyes which are particularly suitable for dyeing synthetic textile materials.

According to the invention, disperse monoazo dyes of the formula

suggested where

W represents hydrogen, chlorine, bromine, nitro or cyano;

Y is acylamino;

Z is hydrogen, lower alkyl, or lower alkoxy;

R is lower alkyl; and

X represents hydrogen or acyl.

Throughout the specification, the terms "lower alkyl" and "lower alkoxy" refer to alkyl and alkoxy groups, respectively, of 1 to 4 carbon atoms.

The acylamino groups Y preferably have the formula -NHCOT [high] 1 or -NHSO [low] 2 T [high] 2, where T [high] 1 is hydrogen, phenyl, amino, lower alkylamino or, preferably, lower alkyl and T [high] 2 represents lower alkyl.

The acyl group X preferably has the formula -COT [high] 3, where T [high] 3 is phenyl or, preferably, lower alkyl.

Examples of lower alkyl groups Z, R, T [high] 1, T [high] 2 and T [high] 3 are n-butyl, n-propyl, ethyl and especially methyl. Examples of lower alkoxy groups Z are ethoxy and especially methoxy. Examples of lower alkylamino groups T [high] 1 are methylamino and ethylamino.

A preferred class of dyes according to the invention comprises those of the formula:

where W and T [high] 2 have the meanings given above, Z [high] 1 stands for lower alkoxy and X [high] 1 stands for hydrogen or in particular -COT [high] 2. W is preferably chlorine or bromine.

According to the invention, a process for the preparation of the above dyes is also proposed, which is carried out by using an amine of the formula diazotized and the resulting diazo compound with a coupling component of the formula couples, where W, R, X, Y and Z have the meanings given above.

The process according to the invention can expediently be carried out, for example, by adding the amine to a solution of nitrosylsulfuric acid, if necessary destroying any remaining nitrous acid present by adding sulfamic acid, adding the resulting solution or suspension of the diazo compound to a solution of the coupling component in water, which is an acid and / or a water-soluble organic liquid, such as, for example, acetone, contains, adds, if necessary readjusts the pH of the mixture to facilitate the coupling and isolates the dye obtained in the customary manner.

The amines mentioned are 2,4-dinitroaniline and 2,4-dinitro-6- (chloro-, bromo-, cyano- or nitro-) - aniline.

The coupling components mentioned can in turn be obtained, for example, by reacting an alkylene oxide with the corresponding compound of the formula condensed to give the corresponding coupling component in which X is a hydrogen atom. These coupling components can be converted into coupling components in which X is an acyl group by treatment with an acylating agent.

Specific examples of these coupling components are 2-methoxy-5-acetylamino-N- (small beta-hydroxy-n-propyl) -aniline, 3-propionylamino-N- (small beta-hydroxy-n-propyl) -aniline and 2- Methoxy-5-acetylamino-N- (small beta-acetoxy-n-propyl) aniline.

Those disperse monoazo dyes according to the invention in which X stands for an acyl group can also be obtained by treating the corresponding dyes in which X stands for a hydrogen atom with an acylating agent. The reaction is preferably carried out in the presence of a basic organic liquid such as pyridine, the resulting acylated dye being isolated by pouring the reaction mixture into water and filtering off the precipitated solid.

Examples of acylating agents are acetyl chloride, acetic anhydride and propionic anhydride.

The disperse monoazo dyes according to the invention are particularly suitable in the form of aqueous dispersions for dyeing synthetic textile materials, such as those made of cellulose acetate, nylon and especially polyesters, being applied by a dyeing, padding or printing process using such conditions and other additives which are commonly used for dyeing such synthetic textile materials. At the end of this process, the dyed textile material is rinsed in water and preferably also subjected to a cleaning treatment in order to remove loosely adhering dye from the surface of the textile material. This cleaning treatment can be carried out in the usual way by immersing the dyed textile material in a warm aqueous alkaline solution of sodium hydrosulfite.

When the dyes according to the invention are applied to synthetic textile materials in this way, navy blue dyeings are obtained which have very good to excellent fastness to the tests which are usually applied to dyed synthetic textile materials. The dyes mentioned are particularly suitable for dyeing textile materials made of aromatic polyesters, since they have a very good affinity for these textile materials and very good build-up properties, so that deep shades can easily be obtained. The dyeings obtained have very good to excellent fastness to light, wet treatments (including sweating) and dry heat treatments.

The dyes according to the invention can also be used for dyeing aromatic polyesters in bulk or applied to synthetic textile materials by the transfer printing process, optionally under vacuum or under wet or working in damp conditions.

The invention is illustrated in more detail by the following examples, in which the parts and percentages are expressed by weight.

EXAMPLE 1

26.2 parts of 2,4-dinitro-6-bromoaniline are added to a solution of nitrosylsulfuric acid (which has been prepared by dissolving 7.0 parts of sodium nitrite in 130 parts of sulfuric acid monohydrate and 4 parts of water at 70 ° C.) at 25 ° C is added and the resulting mixture is stirred for 1 hour. The resulting solution of the diazo compound is then made into a solution of 23.8 parts of 2-methoxy-5-acetylamino-N- (small beta-hydroxy-n-propyl) aniline in a mixture of 200 parts of water and 5 parts of concentrated aqueous hydrochloric acid , which has been cooled to 0 ° C by the addition of ice, is added. Sodium acetate is added until the pH of the mixture is 5 and the mixture is stirred at 5 ° C for 30 minutes. The precipitated dye is then filtered off, washed with water and dried.

The dye is dispersed in an aqueous medium and the resulting dispersion is incorporated into a printing paste which is applied to a polyethylene terephthalate textile material in a conventional manner. A blue print is obtained which has excellent fastness to light, wet treatments, sweating and dry heat treatments.

The 2-methoxy-5-acetylamino-N- (small beta-hydroxy-n-propyl) aniline used in the above example was obtained by adding a mixture of 18 parts of 2-methoxy-5-acetylaminoaniline and 10.4 parts of propylene oxide and 250 parts of methanol 8 st was heated to boiling and then all of the methanol by vaping has been removed.

EXAMPLE 2

Instead of the 23.8 parts of 2-methoxy-5-acetylamino-N- (small beta-hydroxy-n-propyl) aniline from Example 1, equivalent amounts of the following compounds are used:

a) 2-methoxy-5-acetylamino-N- (small beta-acetoxy-n-propyl) -aniline,

b) 2-methoxy-5-acetylamino-N- (small beta-propionyloxy-n-propyl) aniline, and

c) 2-methoxy-5-acetylamino-N- (small beta-n-butyryloxy-n-propyl) aniline,

whereby similar dyes are obtained which dye polyester from an aqueous dye bath in navy blue shades.

The coupling components used in this example were obtained by treating 2-methoxy-5-acetylamino-N- (small beta-hydroxy-n-propyl) aniline with acetic anhydride, propionic anhydride or n-butyric anhydride in the presence of hydrogen chloride.

EXAMPLE 3

A mixture of 5.6 parts of the dye from Example 1, 1.4 parts of propionic anhydride and 120 parts of pyridine is stirred at 45 +/- 2 ° C. for 2 hours. The mixture is then poured into 600 parts of water, and the precipitated dye is filtered off, washed with water and dried.

The resulting dye consists of 2-acetylamino-4- [N- (small beta-propionyloxy-n-propyl) -amino] -5-methoxy-2´-bromo-4´, 6´-dinitroazobenzene.

When dispersed in an aqueous medium, it stains this dye textile materials made from aromatic polyesters in navy blue shades with excellent fastness properties.

Further examples of dyes of the formula in which W, Y, Z, R and X have the meanings given, can be seen from the following table I. The last column shows the color shades that result when dyeing on polyesters. These dyes were all prepared by the procedure described in Examples 1 and 2.

TABLE I.

Table I continued

EXAMPLE 37

15.6 parts of 2-cyano-4,6-dinitroaniline become a solution of nitrosylsulfuric acid (which has been prepared by dissolving 5.7 parts of sodium nitrite in 110 parts of 98% strength sulfuric acid at 70 ° C.) at -10 to -5 ° C added, whereupon the resulting mixture is stirred for 3 hours. The resulting solution is then added to a solution of 17.25 parts of 3- (small beta-hydroxybutylamino) -4-methyl-acetanilide in a mixture of 200 parts of water and 5 parts of concentrated aqueous hydrochloric acid, which can be reduced to 0 to 5 by adding ice ° C is maintained. Sodium acetate is then added until the pH of the mixture is 4, whereupon the precipitated dye is filtered off, washed with water and dried.

The dye is dispersed in an aqueous medium and the resulting dispersion is used for dyeing polyethylene terephthalate textile materials from an aqueous dyebath at 130.degree. The greenish-blue coloration obtained has excellent fastness to light, wet treatments, sweating and dry heat.

EXAMPLE 38

A mixture of 3 parts of the dye from Example 1, 4 parts of acetic anhydride and 100 parts of pyridine is stirred at 45 ° C. for 3 hours. The mixture is then poured into 500 parts of ice-cold water, whereupon the precipitated dye is filtered off, washed with water and dried.

When the dye is dispersed in an aqueous medium, it dyes textile materials made of aromatic polyesters in blue shades with excellent fastness properties.

EXAMPLES 39 to 53

In the following Table II, the columns W, Y, Z, R and X relate to the formula immediately in front of Table I. The dye of Example 39 was prepared by the procedure described in Example 37, while the dyes of Examples 40-53 were obtained by the procedure of Example 38, i.e. by acylating the corresponding dye where X is hydrogen. The last column shows the color shades that are obtained when dyeing on polyesters.

TABLE II

Claims (16)

1. Disperse monoazo dyes of the formula wherein W represents hydrogen, chlorine, bromine, nitro or cyano; Y is acylamino; Z is hydrogen, lower alkyl, or lower alkoxy; R is lower alkyl; and Y represents hydrogen or acyl. 2. Dyestuffs according to claim 1, characterized in that the acylamino group Y has the formula -NHCOT [high] 1 or -NHSO [low] 2 T [high] 2, where T [high] 1 is hydrogen, phenyl, amino, lower alkylamino or lower alkyl and T [high] 2 is lower alkyl. 3. Dyestuffs according to Claim 2, characterized in that T [high] 1 is lower alkyl. 4. Dyestuffs according to one of claims 1 to 3, characterized in that the acyl group X has the formula -COT [high] 3, where T [high] 3 is lower alkyl or phenyl. 5. Dyestuffs according to Claim 4, characterized in that T [high] 3 is lower alkyl. 6. Dyestuffs according to Claim 2 or 3, characterized in that the lower alkyl groups Z, R, T [high] 1 and T [high] 2 are methyl. 7. Dyestuffs according to Claim 4 or 5, characterized in that the lower alkyl group T [high] 3 is methyl. 8. Dyes according to any one of claims 1 to 5 and 7, characterized in that the lower alkoxy group Z is methoxy. 9. Dyestuffs according to Claim 1, characterized in that they have the formula have, in which W has the meaning given in claim 1; T [high] 2 is lower alkyl; Z [high] 1 is lower alkoxy; and X [high] 1 is hydrogen or -COT [high] 2. 10. Dyestuffs according to Claim 9, characterized in that X [high] 1 is -COT [high] 2. 11. Dyestuffs according to claim 9 or 10, characterized in that W stands for chlorine or bromine. 12. Process for the preparation of the dyestuffs according to Claim 1, characterized in that an amine of the formula diazotized and the resulting diazo compound with a coupling component of the formula couples, where W, R, X, Y and Z have the meanings given above. 13. Process for the preparation of the dyes according to claim 1, wherein X is acyl, characterized in that the corresponding dye, wherein X is hydrogen, is treated with an acylating agent. 14. The method according to claim 13, characterized in that the reaction is carried out in the presence of a basic organic liquid. 15. Use of the dyes according to claim 1 for dyeing synthetic textile materials by means of a dyeing, padding or printing process with subsequent rinsing of the dyed textile material in water. 16. Use according to claim 15, characterized in that a cleaning treatment is also carried out in order to remove loosely adhering dye from the surface by immersing the dyed textile material in a warm aqueous alkaline solution of sodium hydrosulfite.