DE924524C - Process for the preparation of symmetrical disazo dyes - Google Patents

Description

Process for the preparation of symmetrical disazo dyes In British patent 523 035 it is proposed to prepare symmetrical disazo dyes by a process in which tetrazotized diaminoalkyl or benzylanilides of dicarboxylic acids, e.g. B. adipic acid, with 2 moles of a sulfoarylpyrazolone, a naphtholsulfonic acid, an aminonaphtholsulfonic acid or a derivative of an aminonaphtholsulfonic acid substituted on the nitrogen atom. It has also been proposed to use these dyes for dyeing animal fibers, for example wool and silk, in yellow or red tones, using a neutral or acidic dye bath and thereby achieving colorations which are generally good fastness to washing, Walk and sweat.

It has now been found, according to the invention, that new symmetrical disazo dyes can be prepared by using a symmetrical diamine of the general formula in which the symbols R phenyl radicals, which can optionally be substituted by alkyl (C 1 to C 6), cycloalkyl or halogen and the nuclei X and Y can have further substituents, denote tetrazotized and i mol of the tetrazo compound with 2 mol of an i- ( Sulfophenyl) -3-methyl-5-pyrazolones is coupled. These new disazo dyes dye animal fibers, for example wool and silk, from a neutral or weakly acidic dye bath in yellow shades with very good fastness properties to washing, fulling, the action of sweat and light. These new dyes are known from British Patent Specification 523,035 dyes in the drawability of a neutral dye bath using the procedure described in British Patent 645,594 substantially superior.

As examples of diamines, which are used to produce the dyes can be used according to the invention, the following may be mentioned adipic acid bis (4-amino-N-ß-phenoxyethylanilide) (Melting point 158 to 159 °), adipic acid -bis - (4 - amino - N - ß- 4'-chlorophenoxyethylanilide) (Melting point 164o), adipic acid-bis- (4-amino-N-ß-2 ', 4'-dichlorophenoxyethylanilide) (Melting point 144 to 145 °), adipic acid bis - (4-amino-N-ß-4'-methylphenoxyethylanilide) (Melting point 166 °), adipic acid bis (4-amino-N-ß-cyclohexylphenoxyethylanilide) (Melting point 179 to 181 °), adipic acid bis (4-amino-N-ß-3 ', 5'-dimethylphenoxyethylanilide) (Melting point 100 to 1040), adipic acid bis (4-amino-2-methoxy-N-ß-phenoxyethylanilide) (Melting point 166 to 170 °), adipic acid bis - (4 - amino-2-methyl-N-β-phenoxyethylanilide) (Melting point 168 to 170 °).

As examples of i - (sulfophenyl) -3 -methyl-5-pyrazolones, which can be used according to the invention, the following may be mentioned: i- (2'-S ulfophenyl) -3-methyl-5-pyrazolone, i- (3'-sulfophenyl:) -3-methyl.-5-pyr! Azolone, 1- (4'-sulfophenyl) -3-methyl @ 5-pyrazolone, i- (2-chloro-5'-s.ulfophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 4 '- dichloro-5'-sulfophenyl) - 3 - methyl - 5-pyrazolone, 1- (2', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone, i- (4'-chloro-2'-sulfophenyl) -3-methyl-5-pyrazolone, i- (4'-chloro-3'-sulfophenyl) -3 -methyl-5-pyrazolone, 1- (2'-chloro -4'-methyl-5'-sulfophenyl) -3-methyl-5-pyrazolone, i - (6 '- chlorine -: 2- methyl -4'-sulfophenyl) - 3 -methyl-5-pyrazolone, i- (2'-methyl-5'-sulfophenyl) -3-methyl-5-pyrazolone, 1- W- methoxy-2'-sulfophenyl) - 3 - methyl - 5 -pyrazolone, i- (4'-Ethoxy-2'-sulfophenyl) -3-methyl-5-pyrazolone. The diamines that are used to manufacture the dyes according to the invention can be prepared by that a corresponding 4-nitro-N-ß-phenoxyethylaniline with Adipinsäurechlori-d in dry toluene is reacted to the corresponding adipic acid - bis - (4 - nitro-N-ß-phenoxyäthylanilide) to give their nitro groups to amino groups with the help of iron and hydrochloric acid be reduced in ethanol or in aqueous butanol.

The invention is illustrated in the following examples. The parts are parts by weight. Example i 56.6 parts of adipic acid bis (4-amino-N-ß-phenoxyethylanilide) are dissolved in 700 parts of water and 50 parts of 36% aqueous hydrochloric acid becomes a solution of 13.8 parts at 15 to 20 °. Sodium nitrite in 100 parts of water admitted. The solution thus obtained is then stirred over the course of 20 minutes a solution of 56.4 parts of the sodium salt of i- (4'-S: ulfophenyl) -3-methyl-5-pyrazolone in 1500 parts of water at 15 to 20 ° added, the 54 parts of sodium acetate crystals and contains i2o parts sodium chloride. When the coupling is complete, the mixture will warmed to 50 ° and filtered. The residue is then dried at 50 to 60 °. The new dye thus obtained is a yellow powder that dissolves in warm water soluble with reddish yellow and in concentrated sulfuric acid with greenish yellow color is. The dye dyes wool from an ammonium acetate (2 percent by weight of the material to be colored) containing dyebath in reddish yellow tones, and the colorations have very good fastness properties to repeated washing and fulling and exposure to sweat and light.

Beispie12 56.6 parts of adipic acid bis (4-amino-N-ß-phenoxyethylanilide) are tetrazotized in the manner described in Example i. The solution of the tetrazo compound is then in the course of 10 minutes at 10 to 15 ° while stirring a solution of 69 parts of the sodium salt of i- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone added in 1,000 parts of water to which 54 parts of sodium acetate have been added. Stirring is continued until the coupling is complete. The mixture is then filtered, and the residue consisting of the new dye is dried at 6o °. The new dye is a yellow powder that dissolves in warm water with dissolves greenish-yellow in color and in concentrated sulfuric acid with a greenish-yellow color. The dye dyes wool from a dyebath containing 2% ammonium acetate in greenish-yellow tones, and these colorations have very good fastness properties against repeated washing, fulling, exposure to sweat and light. Of the Dye also pulls out very well from a neutral dye bath. after that in the British Patent 645 594 described method on the fiber.

Example 3 63.5 parts of adipic acid bis (4-amino-N-ß-4'-chlorophenoxyethylanilide) are in a mixture of 100 parts of water and 63 parts of 36% hydrochloric acid dissolved by heating to 90 °. After cooling the solution to 15 'your will a solution of 14 parts of sodium nitrite in 100 parts of water was added. The solution the tetrazo compound thus obtained is then at 15 to 20 ° im course from 10 to 15 minutes while stirring a solution of 69 parts of the sodium salt of 1- (2 ', 5'-dichloro -. @' - sulfophenyl) -3-methyl-5-pyrazolone in 750 parts of water added containing 72 parts of sodium acetate crystals. The mixture will last so long stirred until the coupling is complete, and opposed by adding sodium carbonate Litmus neutralized, warmed to 50 ° and filtered. The one representing the dye The residue is then dried at 5o to 6o °. The new dye represents a yellow one Powder that is in warm water and in concentrated sulfuric acid with greenish yellow Color dissolves. The dye dyes wool from a 21 / o ammonium acetate containing Dyebath in yellow tones. The colorations have excellent fastness properties against washing, fulling and perspiration and very good fastness properties against exposure to light. The dye is also very well absorbed. The fiber, if he from a neutral dye bath by the method described in British patent specification 645 594 described method is applied.

Beispie14 In example i, the 56.4 parts of the sodium salt of i- (4'-sulfophenyl) -3-methyl-5-pyrazolone by the same amount by weight of the sodium salt replaced by 1- (3'-sulfophenyl) -3-methyl-5-pyrazolone. The new dye thus obtained has similar properties to the dye according to example i.

Example s In Example 2, the 69 parts of the sodium salt of i- (2 ', 5'-dichloro-q .'- s, ulfophenyl) -3-methyl-5-pyrazolone by the same amount by weight of the sodium salt of i- (2 ', q .'-dichloro-5'-sulfophenyl) -3-methyl-5-pyrazolone replaced. The new dye thus obtained has properties similar to those of the dye according to example 2.

Beispie16 62.6 parts of adipic acid bis (4-amino-2-methoxy-N-ß-phenoxyethylanilide) are in a mixture of 14oo parts of water and 50 parts. 36% hydrochloric acid dissolved, and the solution thus obtained becomes a solution at a temperature of 15 ° of 13.8 parts of sodium nitrite in 100 parts of water were added. After 1/2 hour Stirring the solution becomes the tetrazo compound thus obtained by adding animal charcoal clarified and then filtered. The resulting solution is then taken at 15 to 2o ° Stirring a solution of 62 parts of the sodium salt of i- (2'-chloro-5'-sulfophenyl) -3-methyl-5-pyrazolone added in 70o parts of water containing 54 parts of sodium acetate crystals. To 18 hours of stirring at 15 to 20 ° is the coupling by heating to 30 ° and 3 hours Maintaining this temperature stops. The precipitated dye is then filtered off and dried at 60 °.

The new dye forms a reddish-yellow: b colored powder, which Dissolves in poor water and in concentrated sulfuric acid with a reddish yellow color. The dye dyes wool from a dyebath containing ammonium acetate in yellow Tones, and the colorations have very good fastness properties Wet treatments and good lightfastness properties.

Beispie17 73 parts of finely powdered adipic acid bis (4-amino-N-ß-4'-cyclohexylphenoxyethylanilide) are added to a mixture of 1200 parts of water and 50 parts of 36% hydrochloric acid, and the suspension is heated to 5o to 6o °. After cooling to 15 to 20 ° a solution of 13.8 parts of sodium nitrite in 100 parts of water is added, and the mixture is stirred for 1/2 hour. The solution of the tetrazo compound thus obtained is at 15 to 20 ° while stirring a solution of 69 parts of the sodium salt of 1- (2; 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone in 700 parts of water was added, Sodium acetate has been added to the 54 line. When the clutch is finished, the mixture is made alkaline to litmus by adding sodium carbonate, and 240 parts of sodium chloride are added. The solution will then. heated to 40 °. The precipitated dye is then filtered off and dried.

The new dye is a reddish yellow powder that turns into hot water with reddish yellow color and in concentrated sulfuric acid with yellowish green Color dissolves. He dyes wool from a dyebath containing ammonium acetate in yellow Tones. These dyeings have very good fastness properties to washing, exposure to sweat and light.

Claims (1)

PATENT CLAIM: Process for the production of symmetrical disazo dyes, characterized in that a. symmetrical diamine of the formula in which the symbols R denote phenyl radicals which - if appropriate, can be substituted by alkyl (Cl to C6), cycloalkyl or halogen and the nuclei X and Y can have further substituents, tetrazotized and 1 mol of the tetrazo compound with 2 mol of one. i- (sulfophenyl) -3-methyl-5-pyrazolones is coupled. References: British Patent No. 523 o35.