DE4314787A1 - N-Benzylated triazoleazo dyes and preparation thereof - Google Patents

Abstract

Known N-benzylated triazoleazo dyes are mixtures which consist of dyes which differ in their degree of benzylation, which is disadvantageous for the purity. Also, the reaction conditions lead to the formation of brown decomposition products which impair the use properties of the dye. The novel N-benzylated triazoleazo dyes are to have a high purity and good dyeing power. The invention provides N-benzylated triazoleazo dyes of the general formula <IMAGE> where R1 = hydrogen, methyl or phenyl, R2 = benzyl, p-methylbenzyl or p-methoxybenzyl, and An- = chloride, tetrachlorozincate or a p-toluenesulphonate anion, and a process for their preparation. The novel dyes can be used to produce red to bluish red dyeings. They are used for dyeing polyacrylonitrile fibres, paper and plastic materials.

Description

The invention relates to new N-benzylated triazoleazo dyes, their use and a Process for their preparation and a process for the preparation of known N-benzy lated triazole azo dyes.

It has long been known that cationic dyes based on 3-amino-1,2,4-tria zol are highly lightfast and resistant to moisture, sweat and friction.

DE-AS 19 25 475 describes a process for the production of quaternized monoazo dyes by diazotization and coupling of 3-amino-1,2,4-triazole with azo components ten and subsequent quaternization described in the dyes of the general formula

in the R₁ is a methyl, ethyl, butyl group, the benzyl or phenyl group, R₂ is an H or a CH₃, C₂H₅ or C₄H₉ group, the benzyl or phenyl group, and B one Hydrogen atom reduced group of the formula

in which A can be an optionally substituted phenyl or naphthyl group and R₃ and R₄, in addition to hydrogen, are especially optionally substituted alkyl groups, arise.

This general formula also includes cationic benzyltriazole dyes of the formula

in the
R = CH₃ or C₆H₅CH₂ and
An⁻ = Cl⁻, CH₃SO₄⁻ or ZnCl₄ ^2-
mean.

For their preparation, a 3-amino- substituted on the N₁ atom by the benzyl radical 1,2,4-triazole diazotized, coupled with an N, N-dialkylaniline and then quaternized. So is formed with dimethyl sulfate methylated on the N₂ atom, dibenzylated with benzyl chloride Dye.

The N₁-benzylated 3-aminotriazoles serving as the starting material are prepared in a 3-step reaction. Starting from benzene aminoguanidine becomes benzylamino guanidine hydrogenated and this with a carboxylic acid or its acid chloride to N₁-Ben zyl-3-aminotriazole and converted to the corresponding 5-substitution products. Of the Disadvantage of this process is the expense involved in the production of the N 1 benzylated 3-aminotriazoles are connected.

From US Pat. No. 3,291,788 biscationic triazoleazo dyes of the formula

known. Alkylation and quaternization take place in two steps, the Ben is the first step.

The disazo dye obtained by coupling 2 moles of diazotized 3-aminotriazole with 1 Mol 1,4-bis- [N-phenyl-N-alkylaminomethyl -] - 2,5-dimethylbenzene, is in dimethylformamide dissolved and ge with 1.3 moles of benzyl chloride per mole of disazo dye for 6 hours at 110 ° C. cooks. This is followed by the second reaction step, the quaternization Addition of dimethyl sulfate; after heating for a further two hours at 110 ° C. the Reaction ended.  

However, this procedure has the disadvantage that mixtures are obtained which are made from Dyes with different degrees of benzylation exist.

Dyes of high purity, in which the benzyl radicals symmetrically each on the N₂ atom Trialzol-1,2,4-rings are not available in this way. In addition, the reaction used for benzylation and methylation conditions brown decomposition products of the dye formed. This is an elevation Liche reduction in the performance properties of the cationic dye. It is extremely difficult to separate the contaminants. The percentage of decomposition products takes with increasing excess of benzyl chloride and longer reaction time significantly. This is particularly disadvantageous when triazoleazo dyes are complete to be quaternized to dibenzyitriazolium salts.

From the work of Korinek, Adamek and Poskocil (Journal of the chemical industry CSSR, 1982, pp. 250-254) it is known for the benzylation of triazole monoazo color substances of the formula

to dissolve them in formamide or dimethylformamide and with 4 moles of benzyl chloride per mole Heat dye at 110 ° C for several hours. The separation and isolation of the quaternized dyes are technologically complex. The dimethylformamide in Va distilled off in a vacuum and excess benzyl chloride by means of steam distillation be removed from the reaction mixture. Even those made by this process Dyes are contaminated by by-products of benzylation.

It was therefore the task of new N-benzylated triazoleazo dyes which are characterized by a Characterize high purity and show good coloring ability, a process for their Production and an improved process for the production of already known N-benzy developed triazole azo dyes.

The invention relates to new N-benzylated triazoleazo dyes of the general formula

According to the invention, the new N-benzylated triazole azo dyes are obtained by that in a manner known per se, 2 moles of an optionally substituted in the 5-position ten 3-amino- (1,2,4) -triazole diazotized, with 1 mol of N, N'-diphenyl-N, N'-diethylenediamine cup pelt and the resulting disazo dye of the general formula

in which R is hydrogen, methyl or phenyl, benzylated by using the disazo dye dissolved in dimethylformamide and in the presence of zinc oxide with p-toluenesulfonic acid rebenzylester, p-methylbenzyl chloride or reacted with p-methoxybenzyl chloride, where for 1 mole of triazole azo dye per benzyl group to be introduced 1.2 to 1.5 moles of benzyly be used.

The new N-benzylated triazole azo dyes in particular become bluish red Coloring of polyacrylonitrile fibers, paper and plastic masses used.

According to the invention, known N-benzylated triazole azo dyes can be prepared by dissolving the triazoleazo dyes in dimethylformamide for benzylation and dissolving them in Presence of zinc oxide with benzyl p-toluenesulfonate, p-methylbenzyl chloride or reacted with p-methoxybenzyl chloride, introducing 1 mol of triazole azo per Rende benzyl group 1.2 to 1.5 mol of the benzylating agent can be used. The inventive procedures make it possible to use N-benzylated triazolazo to produce dyes free of decomposition products and without further cleaning options rations for dyeing. These dyes turn bluish red exercises with good general fastness.

Compared to the N-benzyl-triazoleazo dyes known from DE-AS 19 25 475 show the new dyes have a higher winding speed on polyacrylonitrile fibers; at the Dyeing process is also a complete exhaustion of the dye bath.  

The invention is illustrated by the following examples.

In Examples 1 to 5, the new N-benzylated triazole azo dyes and their Manufacturing described. Examples 6 to 8 relate to the new production process for known N-benzylated triazoleazo dyes. in example 9 the Use of a new N-benzylated triazole azo dye in a dyeing process explained in more detail.

Examples 1 to 5

These examples have N-benzylated triazole azo dyes of the general formula

to the subject. The substituents given in the examples relate on this general formula.

example 1 R₁ = H; R₂ = CH₂C₆H₅; An⁻ = p-CH₃-C₆H₄SO₃-

8.4 g (0.1 mol) of 3-aminotriazole (1,2,4) and 5 g of α-naphthalene sulfonic acid are dissolved in 130 ml of water and 15 ml of hydrochloric acid and dissolved in 6.9 g of sodium nitrite 40 ml of water at -2 to 0 ° C diazotized. For coupling, the solution of 13.4 g (0.05 mol) of N, N'-diphenyl-N, N'-diethylenediamine in 150 ml of water and 20 ml of hydrochloric acid at 0 ° C becomes the above diazo solution in about 2 hours added. When coupling is complete, the pH is adjusted to 7 to 7.5 using dilute sodium hydroxide solution and the dye is filtered off with suction. The press cake obtained is then resuspended in water, suction filtered and dried again after prolonged stirring.
9.2 g (0.02 mol) of the disazo dye obtained in this way are dissolved in 100 ml of dimethylformamide and 2.2 g of zinc oxide and 32 g of benzyl p-toluenesulfonate are added; the reaction mixture is stirred at 90 ° C for 8 hours. Then it is introduced into 800 ml of water and the dye is separated off with sodium chloride.
After drying at 60 ° C 22 g of the dye are obtained. The dye dyes polyacrylonitrile in a bluish red shade (λ _max = 535 nm)

Example 2 R₁ = CH₃; R₂ = CH₂C₆H₅; An⁻ = p-CH₃-C₆H₄SO₃-

9.8 g (0.1 mol) of 5-methyl-3-aminotriazole are diazotized analogously to Example I and coupled with 13.4 g (0.05 mol) of N, N'-diphenyl-N, N'-diethylethylene diamine.
9.7 g (0.02 mol) of the disazo dye obtained are dissolved in 100 ml of dimethylformamide, 2.2 g of zinc oxide are added and the mixture is stirred at 90 ° C. for about 8 hours with 32 g of benzyl p-toluenesulfonate. The reaction mixture is then carried into 800 ml of water and the dye is separated with common salt. 18 g of the dyestuff are obtained.
The dye stains polyacrylonitrile in a bluish red shade (λ _max = 536 nm).

Example 3 R₁ = C₆H₅; R₂ = CH₂C₆H₅; An⁻ = p-CH₃-C₆H₄SO₃-

16 g (0.1 mol) of 5-phenyl-3-aminotriazole are diazotized in a known manner and coupled analogously to Example 1 with 13.4 g (0.05 mol) of N, N'-diphenyl-N, N'-diethylethylene diamine. 12.2 g (0.02 mol) of the disazo dye obtained are dissolved in 120 ml of dimethylformamide, 2.2 g of zinc oxide and 32 g of benzyl p-toluenesulfonate are added. After a reaction of about 6 hours at 90 to 95 ° C., the reaction mixture is introduced into 1200 ml of water and the dye is completely precipitated with common salt. 23 g of the dyestuff are obtained. The dye dyes polyacrylonitrile in a red shade (λ _max = 527 nm).

Example 4 R₁ = H; R₂ = p-CH₃O-C₆H₄CH₂; An⁻ = Cl⁻

To the solution of 9.2 g of the disazo dye from diazotized 3-aminotriazole and N, N'- Diphenyl-N, N'-diethylethylenediamine, obtained according to Example 1, in 100 ml of dimethylformamide 2.2, g of zinc oxide and 18.8 g of p-′ methoxybenzyl chloride are added and 10 hours stirred at 90 to 95 ° C. Then it is mixed with 1000 ml of water and the dye with Salt separated. 24 g of the dye are obtained.

The dye stains polyacrylonitrile in a bluish red shade (λ _max = 538 nm).

Example 5 R₁ = CH₃; R₂ = p-CH₃-C₆H₄CH₂; An⁻ = Cl⁻

9.7 g (0.02 mol) of the disazo dye obtained in Example 2 from 5-methyl-3-aminotria zol and N, N'-diphenyl-N, N-diethylethylenediamine are in 100 ml of dimethylformamide dissolved, 2.2 g of zinc oxide and 14 g of 4-methylbenzyl chloride added and 8 hours at 90 stirred up to 95 ° C. The reaction mixture is then mixed with 1000 ml of water and the dye is completely separated by the addition of table salt. There will be 21 g of the dye obtained.

The dye stains polyacrylonitrile in a bluish red shade (λ _max = 535 nm).

Examples 6 to 8

These examples have N-benzylated triazole azo dyes of the general formula

to the subject.

The substituents given in the examples refer to these general my formula.  

Example 6 Alkyl₁ = CH₃; Alkyl₂ = CH₃; An⁻ = p-CH₃-C₆H₄SO₃-

22.6 g (0.1 mol) of triazole (1,2,4) -3-azo-4 '- (1'-dimethylamino) benzene are dissolved in 250 ml of dimethylformamide, 5.2 g of zinc oxide and 68 g of benzyl p-toluenesulfonate are added and the mixture is stirred at 90 to 95 ° C. for about 8 hours. The reaction solution is then introduced into 2000 ml of water and the dye is completely precipitated with sodium chloride. 48 g of the dye are obtained.
The dye dyes polyacrylonitrile in a bluish red shade (λ _max = 541 nm).

Example 7 Alkyl₁ = C₂H₅; Alkyl₂ = C₂H₅; An⁻ = p-H₃-C₆H₄SO₃-

24.4 g (0.1 mol) of triazole (1,2,4) -3-azo-4 '- (1'-diethylamino) benzene are in 250 ml of dimethyl dissolved formamide, 5.2 g of zinc oxide and 68 g of benzyl toluenesulfonate were added and stirred for about 10 hours at 90 to 95 ° C.

Then the reaction mixture is introduced into 2500 ml of water and the precipitation of the dye is completed by adding saline. 57 g of the dye are obtained.
The dye stains polyacrylonitrile in a bluish red shade (λ _max = 543 nm).

Example 8 Alkyl₁ = CH₃; Alkyl₂ = CH₂C₆H₅; An⁻ = p-CH₃-C₆H₄SO₃

29.2 g (0.1 mol) of triazole (1,2,4) -3-azo-4 ′ - [1 ′ - (N-methyl-, N-benzyl) amino] -benzene are dissolved in 250 ml of dimethylformamide solved. After adding 5.2 g of zinc oxide and 68 g of benzyl p-toluenesulfonic acid, the mixture is heated at 90 to 95 ° C. with stirring for 8 hours. The reaction mixture is then introduced into 2500 ml of water and the dye is precipitated by adding saline. 64 g of the dye are obtained.
The dye dyes polyacrylonitrile in a red shade (λ _max = 536 nm).

Example 9

5 g of polyacrylic fibers are introduced at 40 ° C in 200 ml of dye liquor, the 0.05 g of dye prepared according to Example 1, 3 ml of acetic acid and 0.5 ml of a 10% sodium hydroxide umacetatlösung contains. The mixture is heated to boiling within 20 to 30 minutes and held the bath at this temperature for 1 hour. After rinsing and drying you get one bluish-red coloration with good general fastness properties.

The dyes from Examples 2 to 5 can also be used in an analogous manner the.

Claims (4)

1. N-benzylated triazole azo dyes of the general formula in which R₁ = hydrogen, methyl or phenyl
R₂ = benzyl, p-methylbenzyl or p-methoxybenzyl and
An⁻ = a chloride, tetrachlorozincate - or a p-toluenesulfonate anion. 2. Use of N-benzylated triazoleazo dyes according to claim I for the bluish red Coloring of polyacrylonitrile fibers, paper and plastic masses. 3. A process for the preparation of N-benzylated triazoleazo dyestuffs according to Claim 1, characterized in that 2 moles of a 3-amino (1,2,4) -triazole optionally substituted in the 5-position are diazotized with 1 mole of N in a manner known per se , N'-Diphenyl-N, N'-diethylenediamine couples and the resulting disazo dye of the general formula in which R is hydrogen, methyl or phenyl, benzylated by dissolving the disazo dye in dimethylformamide and reacting in the presence of zinc oxide with benzyl p-toluenesulfonate, p-methylbenzyl chloride or with p-methoxybenzyl chloride, with 1,2 mol per triazoleazo dye to be introduced per benzyl group to be introduced up to 1.5 mol of the benzylating agent are used. 4. Process for the preparation of N-benzylated triazoleazo dyes, thereby characterized in that the triazole azo dyes in Dimethylformamide dissolves and in the presence of zinc oxide with p- Benzyl toluenesulfonate, p-methylbenzyl chloride or with p-methoxybenzyl chloride is implemented, for 1 mol of triazole azo dye per benzyl group to be introduced from 1.2 to 1.5 mol of the benzylating agent can be used.