CS247026B1 - Brown reactive bisazopigments and method of their preparation - Google Patents

Description

The invention relates to brown reactive triazine bisazo dyes of the formula I

where the dashed circle means an optional benzene core,

Me denotes hydrogen or a cation, η = 1 to 3, m = 0,1 or 2,

Z = 1 or 2

X is chloro, amino, C 1 -C 4 alkylamino, phenylamino optionally substituted with methyl, carboxy or 1 to 2 sulfo, C 1 -C 4 alkoxy or phenoxy, optionally substituted sulfo, and processes for their preparation.

Said dyes are suitable for dyeing cellulose fibers from both natural and regenerated cellulose. Hitherto known dyes have been used for this purpose, e.g. U. S. Patent No. 1,483,235, brit. No. 973,114, Belg. No. 624,403 and U.S. Pat. AO No 184 468.

It has now been found that the novel dyes according to the invention are well suited for dyeing said materials.

The dyes of the formula I can be prepared by diazotizing the selected active azo component of the benzenic or naphthalenic series and treating the 2,3-dimethyl-1-aminobenzene with a diazonium compound, then diazotizing the resulting aminomonoazo dye with diazotizing agents and treating the diazonium compound with to a passive azo component of formula II

where

Me and m are as defined above, whereupon the aminobisazo dye is condensed with cyanuric chloride optionally previously substituted with group X or the substituent X is introduced after coupling with XH or X Me, where Me is cationic.

The primary active azo component to be coupled with 2,3-dimethyl-1-aminobenzene is, for example, one of the anilino- or -disulfonic acids or naphthylamino-mono-, di- or tri-sultanoic acids.

Substituted aminobenzene sulfonic acids, such as 2,6-dimethylaniline-3,5 disulfonic acid, protected by AO No. 177,293, can also be used. 2,3-Dimethyl-1-aminohenzene (vicinal o-xylidine) can be used either in the form of a base, or one of its salts, for example hydrochloride, sulfate and the like.

As final passive azo components of naphthylamine type are suitable:

1-naphthylamine, 1-naphthylamine-6-sulfoacid,

1-naphthylamine-7-sulfoacid, 1-naphthylamine-8-sulfoacid or a mixture of two or more of these compounds.

While the monoazo dyes need not be isolated from the reaction mixtures after coupling, it is preferred to isolate the aminobisazo dyes, for example, by adding sodium chloride, potassium chloride, potassium acetate in solid form and mechanically separating them from the mother liquors.

From the reaction mixture after the second coupling, optionally salted and isolated and redissolved disazo dyes are added with the addition of alkaline agents such as carbonate or sodium hydroxide at a temperature of 0 to 10 ° C and a pH of 5 to 7 maintained by the addition of the above alkaline reagents. the presence of organic solvents (such as acetone) or surfactants condenses with cyanuric chloride.

The resulting dichlorotriazine dyes are either isolated and used for dyeing as such, or the other triazine reactive chlorine is replaced by reaction with ammonia, aliphatic or aromatic amines or phenols. The substitution of the second reactive chlorine is carried out at an elevated temperature of 20 to 50 ° C with the addition of acid binders.

The dyes of the formula I can also be obtained by condensing the bisazo dyes prepared as described above with dichlorotriazine derivatives of the formula IV

Ci (IV) in which X is as defined above and obtained by conventional and well-known methods of reacting cyanuric chloride with ammonia, with aliphatic or aromatic amines, with alcohols or with phenols.

The final mono- or dichlorotriazine bisazo dyes are isolated from the reaction mixtures by conventional means, for example by salting out of the solutions by addition of salts (sodium chloride, potassium chloride or potassium acetate J) or by evaporating the whole reaction mixture to dryness, for example in a spray drier or other similar apparatus.

The dyes obtained according to the invention are suitable for dyeing, in particular, cellulose fibers, both natural (cotton, flax, hemp) and regenerated (viscose staple). They are applied to said materials by conventional methods, such as, for example, pull-out dyeing, so-called flaking processes, or preferably printing in the presence of acid binders.

The new dyes provide brown coloring with very good color stability on the above materials.

Example 1

0.1 mole of aniline-2,5-disulfonic acid is stirred in 150 ml of water, acidified with 55 ml of 10% hydrochloric acid and 6.9 g of sodium nitrite are precipitated at 5 DEG C. in the form of a 40% aqueous solution over 30 minutes. The mixture was stirred for an additional 30 minutes.

To the obtained mixture was added 0.1 mol of 2,3, -dimethyl-1-aminobenzene, after which the system was stirred for 5 hours at 10 ° C and the pH of the reaction mixture was maintained at 3-4 during the coupling by adding 10% sodium carbonate solution. .

After coupling, the monoazo dye solution is neutralized with 10% sodium carbonate solution to pH 7.5, 6.9 g of sodium nitrite is added thereto and added dropwise over a period of 30 to 40 minutes to a mixture of 250 g of ice and 75 g of 10% hydrochloric acid. The diazotization mixture is stirred for a further 15 minutes.

22.3 g of 1-naphthylamine-6-sulfoacid are dissolved in 250 ml of water by addition of sodium carbonate to a neutral solution, which is poured onto the diazotized monoazo dye described above, 16.4 g of anhydrous sodium acetate are added and the mixture is stirred at 10 degrees C 12 hours. The resulting bisazo dye is precipitated from the solution by the addition of 220 g of potassium chloride and filtered off.

The isolated bisazo dye paste is dissolved in 750 ml of water by addition of sodium carbonate to a neutral solution, after cooling to 0-3 ° C, 18.4 g of cyanuric chloride are added and the mixture is stirred for 4 hours while maintaining a pH of 6-7 with 10% sodium carbonate solution. After completion of the condensation, excess cyanuric chloride is removed by filtration. The dichlortriazine dye is precipitated by the addition of 200 grams of potassium chloride, filtered off and dried at 40 ° C. The dried dye is mixed with 12 g of anhydrous primary sodium phosphate.

A dye is obtained which is a brown powder, soluble in water, to a reddish-brown solution. When applied to cellulosic material in the presence of alkali and electrolytes, it gives a brown coloration with very good wash and light fastnesses.

Example 2

To the dichlorotriazine dye solution prepared according to Example 1 was added 27 grams of a 25% aqueous ammonia solution and the mixture was heated to 45 ° C for 3 hours. The dye is precipitated from the solution by the addition of potassium chloride, filtered and dried at 80 ° C.

A dye is obtained which is a brown powder which is soluble in water. When applied to cellulosic materials, it provides a very stable brown coloration.

Example 3

0.1 mol of 1-naphthylamine-2,5,7-trisulfonic acid, as a 40.2% strong acid paste, is mixed with 650 ml of water and at 10 DEG C. is diazesified by the successive addition of a solution of 6.9 g of sodium nitrite in 30 ml. ml of water. Then, 0.1 mol of 2,3-dimethyl-1-aminobenzene is added and the mixture is stirred for 5 hours at 10-15 ° C.

After coupling, the resulting aminoazo dye solution is diazotized as in Example 1, followed by the addition of a solution prepared from 22.3 g of a 1: 1 250 mixture of 1-naphthylamine-6-and-7-sulfoacids (Cléve acid) at 10 ° C. ml of water and the addition of sodium carbonate, followed by 16.4 g of anhydrous sodium acetate, and the mixture was stirred at 10 ° C for 12 hours. The resulting dye was salted out by the addition of potassium chloride and filtered.

Condensation with cyanuric chloride is carried out analogously to Example 1. After evaporation of the reaction mixture and homogenization of the phosphate stabilizer residue, a dark brown powder is readily soluble in water to a reddish brown solution.

Example 4

22.3 g of 1-naphthylamine-8-sulfoacid are stirred in 250 ml of water with the addition of sodium carbonate to a neutral suspension. This was added to the diazotized aminomonoazo dye prepared according to Example 3, and the coupling mixture was stirred at 10-15 ° C for 12 hours while maintaining a pH of 4-5 by adding 10% sodium carbonate solution.

The resulting bisazo dye is separated from a solution of 500 g of potassium acetate, filtered off and washed with 750 ml of ethanol. The bisazo dye paste is mixed with 750 ml of water and made neutral by the addition of sodium carbonate, then a solution of 18.4 g of cyanuric chloride in 100 ml of acetone is added dropwise and stirred at 10 ° C for 6 hours while maintaining a pH of 6-7 10%. sodium carbonate solution. After completion of the condensation, excess cyanuric chloride is removed by filtration.

To the reaction mixture was added 27 g of a 25% aqueous ammonia solution and heated to 45 degrees C for 2 hours. The final dyestuff is precipitated from a solution of 250 g of potassium chloride, filtered off and dried at 70 ^C.

The colorant obtained is a dark brown powder, soluble in water to a reddish brown solution. On cellulosic materials it provides a reddish brown color with high wash and light fastness in the presence of alkali.

Example 5

0.1 mol of 1-naphthylamine-4,6-disulfonic acid was diazotized in an analogous manner to the aniline disulfo acid of Example 1.

12.1 g of 2,3-dimethylaniline is dissolved in 39 ml of 10% hydrochloric acid, the solution is added to the above diazonium salt, and the mixture is stirred at 10 ° C for 4 hours while maintaining the pH 4 to 5 with 10% sodium carbonate solution. After completion of the coupling, the pH is adjusted to 7.5.

To the solution of the monoazo dye described above was added 6.9 g of sodium nitrite, the mixture was added dropwise to 250 g of ice and 75 ml of 10% hydrochloric acid over 20 minutes and stirred for a further 30 minutes. 22.3 g of 1-naphthylamine-6-sulfoacid are mixed with 250 ml of water and rendered neutral by the addition of sodium carbonate, which is added to the diazotized monoazo dye; 16.4 g of anhydrous sodium acetate are added and the mixture is stirred at 15 ° C for 12 hours. The resulting bisazo dye is isolated by precipitation from the solution with sodium chloride and filtration.

The isolated bisazo dye paste is mixed with 800 ml of water (made neutral with addition of sodium carbonate), cooled to 0-3 ° C, 18.4 g of cyanuric chloride are added and stirred for 3 hours while maintaining a pH of 6-7 ° C. % sodium carbonate solution. After completion of the condensation, unreacted cyanuric chloride is removed by filtration.

17.3 g of aniline-3-sulfoacid are dissolved in 100 ml of water (rendered neutral by addition of sodium carbonate) and added to the above-described dichlorotriazine dye; The mixture was heated to 45 ° C for 3 hours while maintaining the pH 6-7 by the addition of alkali. The final dye was isolated from the solution with potassium chloride, filtered and dried at 70 ° C.

The colorant obtained is an orange-brown powder, readily soluble in water. On cellulosic materials, when applied in the presence of alkaline agents, it gives an orange-brown color with high light and wash fastness.

Example 0

The isolated bisazo dye prepared according to Example 3 is dissolved in 750 ml of water by adding sodium carbonate to a neutral solution, 18 g of 2,4-dichloro-6-methoxy-5-triazine are added, and the mixture is stirred at 20 ° C for 3 hours. while maintaining a pH of 6-7 by addition of alkali. After completion of the condensation, the product is precipitated from the solution with potassium chloride, filtered off and dried at 50 ° C.

A dye is obtained which is a reddish-brown powder, well soluble in water to a reddish-brown solution. When applied to the cellulosic material, it gives a color shade similar to that of the dye described in Example 3.

Dyes of similar properties are also obtained when using the same molar amount of 2,4-dichloro-6-ethoxy-s-triazine instead of 2,4-dichloro-6-methoxy-s-triazine in the procedure of Example 6, or 2,4-dichloro-6-phenoxy-s-triazine.

The following table gives examples of other dyes that are obtained by procedures similar to those described in the previous examples, by compensating Compound I and coupling it with 2,3-dimethyl-1-aminobenzene and further diazotizing the resulting aminoazo dye. and coupled with the amino compound listed in column II, whereupon the resulting bisazo dye (usually after previous isolation) is condensed with cyanuric chloride and the second reactive chlorine is then replaced by reaction with the amino compounds or hydroxylates listed in column III. Column IV shows the coloristic characteristics of the dyes obtained when applied to cotton.

Example number

Table

II

III

IV 1-, naphthylamine-4,7-disulfoic acid 1-naphthylamine-4,6-disulfoic acid 1-naphthylamine-6-sulfoic acid 1-naphthylamine-7-sulfoic acid aniline

2-aminotoluene-5-sulfoacid brown brown

9 l-naphthylamine-2,5,7- -trisulfoacid mixture 1-naphthylamine-6-sulfoacid and 1-naphthylamine-7-sulfoacid aniline-4-sulfo-acid- on brown 10 aniline-2,5-disulfo- acid 1-naphthylamine-6-sul- Foacid phenol-4-sulfo-acid- on orange. brown 11 aniline-2,5-disulfo- acid 1-naphthylamine-8-sul- Foacid aniline-3-sulfo-acid- on orange. brown 12 l-naphthylamine-2,5,7- -trisulfoacid 1-Naphthylamine-7-sulfoacid 4-Amibenzoic acid orange. brown 13 l-naphthylamine-2,4,7- -trisulfoacid 1-naphthylamine-2,6-di- sulfoacid aniline dark brown 14 l-naphthylamine-2,4,7- -trisulfoacid mixture 1-naphthylamine-6- and -7-sulfoacid aniline-4-sulfoacid- lina brown 15 Dec l-naphthylamine-2,5,7- -trisulfoacid 1-naphthylamine-6-sul- Foacid aniline-4-sulfoacid- lina brown

Claims (2)

OBJECT OF THE INVENTION A brown reactive bisazo dye of formula I wherein the dashed ring is an optional benzene ring, Me denotes the cations Na ⁺ , K ⁺ , NH 4 ⁺ or Mg ^{+ +} η = 1 to 3, m = 0.1 or 2, Z - 1 or 2, X is chloro, amino, phenylamino, optionally substituted with methyl, carboxy or sulfo, and mixtures of dyes of formula (I). 2. A process for the preparation of brown reactive bisazo dyes of the formula I according to claim 1, characterized in that the active azo component is diazotized and the diazonium compound is treated with 2,3-dimethyl-1-aminobenzene. is applied to a passive azo component of formula II wherein Me and m are as defined above, whereupon the aminobisazo dye is condensed with cyanuric chloride, optionally substituted previously X, or the X is introduced after condensation by reaction with compounds of formula XH or XMe, where X and Me are as defined in point 1.