DE2020479A1 - Basic azo dyes - Google Patents

Abstract

Basic azo dyes where R is H, Cl or Br or NO2, R1 is Me or Et, R2 is opt. substd alkyl, cycloalkyl, aralkyl, aryl, R3 is opt. substd alkyl or aralkyl, X is H, MeO, or EtO, Y is H or Cl, or Me or MeO and A- is an anion. Dyes can be used for dyeing or printing textiles, leather or synthetic materials.

Description

Basic azo dyes The invention relates to basic azo dyes of the general formula I. in which R is a hydrogen, chlorine or bromine atom or a nitro group, R1 is a methyl or ethyl group, R2 is an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical, R3 is an optionally substituted alkyl or aralkyl radical, X is a hydrogen atom or a Methoxy or ethoxy group, Y denotes a hydrogen or chlorine atom or a methyl or methoxy group and AG denotes an anion.

R1 is preferably methyl.

The alkyl radicals R2 and R3 can, for. B. by hydroxy, cyano, chlorine, Methoxy, ethoxy, acetoxy, carbomethoxy or carboethoxy, the aralkyl and aryl radicals z. B. substituted by chlorine, methyl, methoxy or ethoxy.

Specifically, as radicals R2 and R3 z. B. called: methyl, ethyl, n- or i-propyl, n- or i-butyl, hydroxyethyl, hydroxypropyl, dihydroxypropyl, Methoxy or ethoxyethyl, mettioxy or ethoxypropyl, cyanoethyl, chloroethyl, Acetoxyethyl, Carbomethoxyäthyl, GarboEthoxyäthyl, Benzyl, Phenyläthyl as well as in the benzene ring through Benzyl or phenylethyl substituted with chlorine, methyl, methoxy or ethoxy. riir R2 are also z. B. still cyclohexyl, phenyl or chlorine, methyl, methoxy or ethoxyphenyl.

The anions Ao are simple or complex, inorganic or organic Anions into consideration. In detail, for example, chloride, bromide, sulfate, nitrate, Methosulfate, formate, acetate, toluenesulfonate or tetrachlorozincate should be mentioned.

Technically particularly suitable dyes correspond to the general formula in which Z is a hydrogen or bromine atom and Y is a hydrogen atom or a methyl group and R2p R3 and A have the meaning given0 To prepare the new dyes, diazo compounds of amines of the general formula II with coupling components of the general formula III convert and alkylate the coupling products.

As diazo components, for example: 4-Amino-7-nitro-1.2-benzisothiazole 4-Amino-5-chloro-7-nitro-1.2-benzisothiazole 4-Amino-5-bromo-7-nitro-1.2-benzisothiazole 4- Amino-5.7-dinitro-1.2-benzisothiazole coupling components of the formula III are, for example: The preparation of the dyes by diazotization and coupling is carried out as usual. The coupling reaction can be carried out in aqueous or organic media or in mixtures of the two, optionally with the addition of acid-binding agents. The alkylation of the coupling products can be carried out solvent-free or in the presence of solvents or diluents, preferably at temperatures between 20 and 150,000, optionally with the addition of acid-binding agents, such as magnesium oxide, sodium methylate, dimethylformamide.

Examples of alkylating agents are diethyl sulfate, toluenesulfonic acid methyl or ethyl ester, methyl iodide, but especially dimethyl sulfate.

The dyes according to the invention are readily soluble in water as quaternary salts. From an aqueous solution, they can be used for dyeing or printing textiles stained cotton, leather and structures such as fibers, flakes, threads, foils or webs made of synthetic materials such as cellulose esters or ethers, Use polyamides, polyurethanes or polyesters. Especially on formations Acrylonitrile polymers and copolymers give them dyeings and prints in pure purple to greenish blue tones. Draw the new dyes is characterized by a very high lightfastness on polyacrylonitrile.

The parts and percentages given in the following examples are units of weight, unless otherwise stated. Parts of the room behave to parts by weight like liter to kilogram under normal conditions.

Example 1 A solution of 39.0 parts of 4-amino-7-nitro-1,2-benzisothiazole in 280 parts of concentrated hydrochloric acid is stirred for 30 minutes while cooling with ice and after adding 400 parts of ice, diazotized with 42 parts of 23 pointer sodium nitrite solution.

The mixture is subsequently stirred for 1 hour while cooling with ice, and the small amount is removed Excess nitrite with sulfamic acid and combined the filtered diazo solution with a solution of 24.2.

Parts of dimethylaniline, 100 parts of water, 24 parts of concentrated Hydrochloric acid and 400 parts of ice. The dye precipitates in crystalline form. One completes the coupling by adding 1400 parts of 30% sodium acetate solution, stirs 2 Hours after, sucks off the dye, washes it neutral with water and dries him at 50 Oc under reduced pressure.

A blue-black product is obtained which has a red-violet color dissolves in dimethylformamide.

The total amount of dry dye is taken along with 500 parts Toluene, 3 parts of magnesium oxide and 60 parts of dimethyl sulfate for 3 to 4 hours the boiling point of toluene stirred until no more starting dye can be detected is. Most of the toluene is then distilled off and the toluene distilled off through Replaced water and distilled until all of the toluene is removed. the aqueous solution of the quaternary dye is filtered hot and the dye through Saturated sodium chloride solution was added. One sucks the product off and washed with diluted atrium chloride solution. After drying, a black gloss powder that dissolves in hot water with blue color and polyacrylonitrile fabric colors in very real blue tones.

Example 2 9.8 parts of 4-amino-7-nitro-1,2-benzisothiazole are as in Example 1 described, diazotized and with the solution from 8.7 Parts of N-ß-cyanoethyl-N-ethylaniline, 25 parts of water, 7 parts of 37% hydrochloric acid and 100 parts of ice combined. The coupling is made by adding 300 parts of 30% Sodium acetate solution completes. The crystalline dye lies after suction, Wash and dry as a blue black powder that turns into dimethylformamide dissolves with red-violet paint.

The total amount of dry dye is dissolved in 150 parts of chloroform, 0.6 parts of magnesium oxide and 15 parts of dimethyl sulfate with stirring for several hours heated under reflux until the methylation is complete. The progress of the Methylation can be done, for. 3. follow chromatographically.

Work-up is carried out by distilling off the chloroform while at the same time Inflow of water and a few parts of 37 point hydrochloric acid. The chloroform-free dye solution is filtered hot and the quaternary salt from the solution with saturated sodium chloride solution salted out. The dried, light-colored powder dissolves in a blue color hot water and colors polyacrylonitrile from acetic acid bath in very lightfast blue tones.

Example 3 11.5 parts of 4-amino-5-chloro-7-nitro-1,2-benzisothiazole are at 10 to 15 0C in 100 parts of 96% sulfuric acid and 50 parts of a glacial acetic acid / propionic acid mixture (17: 3) entered. 16.5 parts of nitrosylsulfuric acid are then left at 0 to 5 ° C (11.5 ffi N203) run in, stir for 9 hours at 0 to 5 0C and combine the Diazo solution with the solution of 10.9 parts of N-ß-methoxyethyl-N-ß-cyanoethyl-m-toluidine, 25 parts of water, 8 parts of 37% hydrochloric acid and 1500 parts of ice / water. The reaction mixture the mixture is stirred overnight, then the crystalline dye is separated off. You get 18 parts of a blue-black powder that turns red-violet in color in dimethylformamide solves.

The total amount of the coupling product is described as in Example 2 methylated and worked up. The resulting quaternary dye dyes polyaeryl nitrile flakes from acid bath in real blue tones.

Analogously to the procedure described in the examples, dyes are obtained from the components of the following table which color acrylonitrile polymers in the specified shades: shade of the example diazo component coupling component product on number of product on polyacrylonitrile fabric blue blue blue-violet blue reddish blue reddish blue blue shade of the methylation pro-example. Diazo component coupling component ductile on polyacrylonitrile fabric red-tinged blue red-tinged blue blue blue blue blue blue blue blue blue-violet 1 green-tinged blue hue of the Me-Ex. Diazo component coupling component thylation pro no. on polyacrylonitrile fabric green-tinged blue blue blue blue blue blue green-tinged blue red-tinged blue blue blue Color of the methylation pro-example. Diazo component coupling component duktes on poly no. acrylonitrile fabric blue blue blue blue violet blue blue red pungent blue Example 39 11.5 parts of 4-amino-5-chloro-7-nitro-1,2-benzisothiazole are dissolved in 100 parts of 96% sulfuric acid at 10 to 15 ° C. with stirring 0 to 5 ° O with 50 parts of a mixture of glacial acetic acid / propionic acid (17: 3) and then gradually with 16.5 parts of nitrosylsulfuric acid (11.5% N2O3).

After stirring for 3 hours at 0 to 5 ° C., the diazo solution is combined with 9.8 parts of N, N-ß-dihydroxyethyl-m-toluidine, in 25 parts of water and 6 parts 36% hydrochloric acid are dissolved and 1 part sulfamic acid and 1500 parts ice water.

The mixture is stirred overnight, the dye is suctioned off, it is washed neutral and dry it at 60 ° C in the drying cabinet.

-The total amount of paraffin is as described in Example 2, methylated with dimethyl sulfate and worked up accordingly. A blue-black is obtained Powder that dissolves in hot water with blue color and polyacrylonitrile fabric from acetic or sulfuric acid bath dyes in lightfast blue tones.

Example 40 12.0 parts of 4-amino-5.7-dinitro-1,2-benzisothiazole become at 0 to 5 OC in 100 parts of 96% sulfuric acid entered, at this temperature 50 parts of a glacial acetic acid / propionic acid mixture (17: 3) are added and done Addition of 16.5 parts of nitrosylsulfuric acid (11.5 N205) diazotized. One stirs 3 Hours at 0 to 5 ° C and then combined the diazo solution with the solution of 8.7 parts N-ß-cyanoethyl-N-ethylaniline in 25 parts of water, 7 parts of 36% hydrochloric acid, 1 Part of sulfamic acid and 1000 parts of ice / water, stirred overnight, filtered off with suction, washed neutral with water and dries at 60 ° C. The dye thus obtained is as in Example 2 described, methylated and worked up. You get a blue black Powder that dissolves in hot water - blue in color and polyacrylonitrile fibers colors in lightfast blue tones

Claims (4)

Claims 1. Basic azo dyes of the general formula in which R is a hydrogen, chlorine or bromine atom or a nitro group, R1 is a methyl or ethyl group, R2 is an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical, R3 is an optionally substituted alkyl or aralkyl radical, X is a hydrogen atom or a methoxy - Or ethoxy group, Y is a hydrogen or chlorine atom or a methyl or methoxy group and AG is an anion. 2. Dyestuffs according to Claim 1 of the general formula in which Z is a hydrogen or bromine atom and Y is a hydrogen atom or a methyl group and R2 and R3 and e have the meanings given. 3. The use of the dyes according to claim 1 or 2 for coloring or printing of acrylonitrile polymers and copolymers. 4. A process for the preparation of dyes according to claim 1 or 2, characterized in that one diazo compounds of amines of the general formula with coupling components of the general formula converts and alkylates the coupling products.