CH649568A5 - 1:2 Chromium complex dyes - Google Patents

Description

The invention relates to compounds in the form of the free acids of the formula I.

N = N - D

(I)

■ <S03H »3

correspond in the

A is the residue of an aliphatic or carbocyclic

Amine component;

D the rest of a diazo component;

Z is an aliphatic radical, a carbocyclic or heterocyclic radical which is optionally substituted by a phenyl group substituted by R2;

R

R2

-O- or -COO-;

Jr

X or -N-L;

-O- or -ti-L;

Hydrogen or optionally substituted alkyl, cycloalkyl, aralkyl or aryl;

Hydrogen, chlorine, bromine, alkyl, alkoxy, nitro, acylamino, carboxyl or optionally N-substituted carbamoyl or sulfamoyl; and hydrogen, chlorine, bromine, alkyl or nitro or R 1 and R 2 together mean a fused-on benz ring or where R 1 or R 2 each represent one of the required three hydroxysulfonyl groups.

The SCbH groups of the compounds of the formula (I) can be in the radicals D, A, Z and in the ring substituted by R 1 and R 2.

65

The residues of the diazo components D mainly come from the benzene or naphthalene series; however, heterocycles such as 3-amino-1, 2,4-triazole-5-carboxylic acid, 8-amino-2-methylquinoline and 2- (4'-aminophenyl) -6-methyl-benzothiazole are also suitable.

As substituents for the radicals D in the benzene and naphthalene series, those mentioned for Ri and R2 should be mentioned.

The amines of the formula H2N-A-BH originate as cabocyclic amines from the benzene and naphthalene series and can be substituted by R 1 and R 2; as aliphatic amines they represent 1,2- or 1,3-diamines, -hydroxyamines or aminocarboxylic acids.

Individual compounds of the formula H2N-A-BH are, for example: 2-aminophenol, 4-chloro-2-aminophenol, 4- or 5-nitro-2-aminophenol, 4,6-dichloro-2-aminophenol, 4-methyl-6 -nitro-2-aminophenol, 4-chloro-5-nitro-2-aminophenol, 2-aminobenzoic acid, 4-nitro-2-aminobenzoic acid, 2-aminobenzoic acid-5-sulfonic acid, 2-aminophenol-4-sulphonic acid , -Aminophenol-4-sulfonic acid amide, 2-aminophenol-4-sulfonic acid phenylamide, 2-aminophenol-5-sulfonic acid di-methylamide, 2-aminophenol-4-sulfonic acid-y-methoxypropy-

649 568

lamide, 4-chloro-2-aminophenol-6-sulfonic acid, 4-nitro-2-aminophenol-6-sulfonic acid, 5- or 6-nitro-2-aminophenol-4-sulfonic acid, l-amino-2-naphthol -4-sulfonic acid, 2-amino-1-naphthol-5-sulfonic acid, 1-amino-6-nitro-2-naphthol-4-sulfonic acid; 1-aminoethanol-2,1-aminopropanol-2,

1-aminopropanol-3,3-amino-3-methylbutanoI-l, 2-amino-acetic acid, 2-aminopropionic acid, 3-aminopropionic acid,

2-amino-3-hydroxypropionic acid, 2-amino-3-phenylpropionic acid, 2-aminobutyric acid, amino succinic acid or 2-aminoglutaric acid as well as ethylenediamine, 1,2- or 1,3-propylenediamine, N-phenylethylenediamine, N-phenylpropylenedi -amine-1,2 or N-methylethylenediamine.

Residues Z are residues of azo coupling component (H-Z-EH) with a complex-forming hydroxyl or amino group in the vicinity of the coupling point and originate e.g. the acetoacetarylide, pyrazole, benzene, naphthalene, pyridine, pyrimidine or quinoline series; they can carry customary substituents for these components, such as alkyl, aryl, halogen, optionally substituted amino,

Hydroxy, alkoxy or nitro.

In particular, the residues of the coupling components correspond to the formulas, for example

CH.

rÇ = Ç-C0-NH- ^ 2 ^ * R2 '

$ î "

M 0H

YV

OH

or where

R3 is hydrogen, methyl, phenyl, carboxyl or carbamoyl, R4 is hydrogen or phenyl which is optionally substituted by methyl, carboxyl or chlorine,

R5 is methyl, methoxy, acetylamino, propionylamino, benzoylamino, N-phenylamino, dimethylamino or diethylamino,

Re is hydrogen or methyl and

R? Are hydrogen or, together with R & a optionally benzyl ring fused by hydroxysulfonyl. Individual compounds of the formula HZ-EH are, for example: 4-methylphenol, 3,4-dimethylphenol, 4-acetylaminophenol, 4-methyl-3-acetylaminophenol, 4-methoxyphenol, 3-diethylaminophenol, 4-methyl-3- ethylaminophenol, 3- (o-tolylamino) phenol, 2-naphthylamine, 2-naphthol, 6-bromo-2-naphthol, 8-acetylamino-2-naphthol, 5,8-dichloro-1-naphthol, l- Naphthol-5-sulfonic acid, 2-naphthol-6-sulfonic acid, l-naphthylamine-4- or-5-sulfonic acid, 2-naphthyl-amine-5- or -6-sulfonic acid, 8-acetylamino-l-naphthol- 5-sulphonic acid, 6-phenylamino-l-naphthol-3-sulfonic acid, 7-amino-l-naphthol-3-sulfonic acid, 3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone, l-phenyl-5-aminopyrazole, 1,3-diphenyl-5-pyrazolone, l-phenyl-5-pyrazolone-3-carboxylic acid, 1 - (2'-methylphenyl) -3-methyl-5-pyrazolone, 1 - (4'-chlorophore-

nyl) -3-methyl-5-pyrazolone, l- (2 ', 5'-dichlorophenyl) -3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone-4'-carboxylic acid, l- Phenyl-3-methyl-5-pyrazolon-3'- or -4'-sulfonic acid,

1,3-diphenyl-5-pyrazolone-2'-sulfonic acid, 1 - (2'-chlorophenyl) -5 -3-methyl-5-pyrazolone-5'-sulfonic acid, l- (2 ',

5'-dichlorophenyl) -3-methyl-5-pyrazolone-4'-sulfonic acid,

2,4-dihydroxyquinoline, N-acetoacetylphenylamide, N-acetoacetylcyclohexylamide, N-acetoacetyl- (4-methylphenyl) -2-sulfonic acid.

10 The benzene ring contained in the formula I, substituted by R 1 and R 2 -The benzene ring contained in the formula I, substituted by R 1 and R 2, is the remainder of an aniline derivative which, in the o-position to the diazotizable amino group, carries a complex-forming hydroxyl or carboxy group ; these aniline derivatives 15 thus correspond to the carbocyclic compounds H2N-A-BH and can be the same or different from them.

Individual compounds of the diazo components containing the rest D include Aniline, 2-, 3- or 4-methylaniline, 20 2,5-dimethylaniline, 2-, 3- or 4-chloroaniline, 4-bromoaniline,

2,5-dichloroaniline, 5-chloro-2-methoxyaniline, 4-chloro-2,5-dimethoxyaniline, 4-acetylaminoaniline, 4-benzoylamino-aniline, N- (4-aminophenyl) oxamic acid, 2-, 3- or 4- Nitro-aniline, 2-chloro-4-nitroaniline, 4-methyl-2-nitroaniline,

25 2-methoxy-5-nitroaniline, aniline-4-sulfonic acid amide, aniline-3-sulfonic acid-N-phenylamide, 2-aminobenzoic acid, aniline-Soder -4-sulfonic acid, 4-methylaniline-2-sulfonic acid, 4-ethoxy-aniline -2-sulfonic acid, 2-methoxyaniline-5-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid, 4-chloro-5-methylaniline-30 2-sulfonic acid, 4-nitroaniline-2-sulfonic acid, 1-aminonaphthalene, l-aminonaphthalene-4- or -5-sulfonic acid, 2-aminonaphthalene-5- or -6-sulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid.

In addition to hydrogen, radicals L are, for example, Ci to 35 Co alkyl, C2 or C3 hydroxyalkyl, β-cyanoethyl, Ci to C4 alkoxyethyl or propyl, phenoxyethyl or propyl, C2 to C4 alkanoyloxy ethyl or propyl, benzoyloxyethyl or propyl, phenylsulfonyloxyethyl or propyl, tolylsulfonyloxyethyl or propyl, cyclohexyl, benzyl, phenylethyl 40 or phenyl optionally substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or hydroxysulfonyl.

Preferred radicals L are, for example, C 1 -C 4 -alkyl, β-hydroxyethyl or propyl, methoxyethyl, phenylsulfonyl-45oxyethyl, tolylsulfonyloxyethyl, cyclohexyl or phenyl optionally substituted by chlorine, methyl, methoxy or hydroxysulfonyl.

In addition to the already mentioned Ci - to C4-alkyl, especially methyl, methoxy, so ethoxy, Ci to Gi alkanoylamino, especially acetylamino or propionylamino, R 1 and R 2 radicals are benzoylamino or N-mono-, optionally substituted by methyl or chlorine. or N, N-di-Ci to C4-alkyl- or N-phenyl-substituted carbamoyl or sulfamoyl.

55 The 1: 2 chromium complexes are produced in stages via the 1: 1 complexes; The 1: 1 chromium complexes of the formula (II) are expediently prepared and set

65

(II)

with the arylazo-azomethine compounds of the formula (III)

5

649 568

N = N-D -,

a-n = ch-bh y ~ j

HO

correspond in which A is a radical of the formula

(III)

to the 1: 2 chromium complex compounds of the formula (I).

In formulas (II) and (III), m and n represent the numerical values 0 to 3, where m + n = 3; the other symbols io have the meanings given for the formula (I).

The 1: 1 chromium complexes are generally prepared by known processes; in the case of the o, o'-dihydroxyazo complexes, one can also start from the corresponding o-alkoxy-o'-hydroxyazo compounds.

The reaction of the 1: 1 chromium complexes of the formula (II) with the arylazo-azomethines of the formula III or their individual components is generally carried out in aqueous solution or suspension; optionally the addition of organic solvents such as alcohols, glycols, carboxylic acid amides or urea derivatives is advantageous. The 1: 2 complex formation takes place in the weakly acidic to alkaline range, preferably at pH 6 to 9 and at elevated temperature, e.g. 50 ° to the boiling temperature.

The resulting 1: 2 complexes can be isolated by acidification, 25 salting out with alkali salts, evaporation or spray drying.

If suitable solvents or mixtures are selected, the 1: 2 chromium complexes can also be prepared in the form of stable, concentrated solutions, which in this form can then be used directly for the preparation of dye baths or printing pastes. To prepare these dye solutions, the compounds of the formulas (II) and (III) are advantageously used in the form of the free dye sulfonic acids and the solvent is used to set the suitable pH with alkanoamines.

The 1: 2 chromium complex dyes of the formula (I) are suitable for dyeing and printing natural or synthetic nitrogen-containing materials, such as wool, leather, polyamide or polyurethane fibers. The dyeings 40 obtained are characterized by a high level of fastness, e.g. Lightfastness, from; in particular they show very good wet fastness properties, such as fastness to washing, milling, sweating and potting,

in which they are superior to comparable dyes with only one or two sulfonic acid groups. 45 It was surprising that the dyes according to the invention, despite their molecular size and high number of anionic charges, have good migrating properties and thus result in level dyeings. Due to their high solubility, the dyes are particularly suitable for continuous dyeing processes, e.g. suitable for carpet dyeing.

The invention particularly relates to compounds in the form of the free acids of the formula

N = N - D

CH,

'- (CVa

1

-, -CH- (CH0). , -

2 B'

CH-3

B

a b B1

B2

the numbers 1, 2 or 3,

the numbers 0, 1 or 2,

Hydrogen, chlorine, bromine, nitro, methyl, methoxy, acetylamino, sulfamoyl, N-phenylsulfamoyl, N-dimethyl, N-diethyl- or N-methoxypropyl-sulfamoyl or hydroxysulfonyl,

Hydrogen, chlorine, nitro or hydroxysulfonyl,

B1 and B2 together a benzo ring optionally substituted by nitro, chlorine or hydroxysulfonyl, -CH2OH, -CH2NH2 or - (CH2) aCOOH,

-O- or -COO-,

-O-, -COO- or -N-L,

-O- or -N-L,

Hydrogen, optionally substituted by hydroxy or Ci to C4 alkoxy Ci to Ci5-alkyl, phenylsulfonyloxyethyl, tolylsulfonyloxyethyl, cyclohexyl, phenyl-Ci to Ci-alkyl or phenyl optionally substituted by chlorine, methyl, methoxy or ethoxy,

phenyl optionally substituted by chlorine, bromine, nitro, methyl, methoxy, ethoxy or hydroxysulfonyl, naphthyl substituted by hydroxysulfonyl or 2- (4'-aminophenyl) -6-methylbenzthiazolyl, hydrogen, chlorine, bromine, Ci to Gi alkyl, Ci - to Gi-alkoxy, nitro, Ci to Gi alkanoylamino, benzoylamino, carboxyl, optionally mono- or disubstituted by Ci-C4-alkyl or phenyl or disubstituted carbamoyl or sulfamoyl or hydroxysulfonyl, R2 hydrogen, chlorine, bromine, Ci to Gf- Alkyl, nitro or hydroxysulfonyl,

R1 and R2 together represent a benz ring optionally substituted by nitro or hydroxysulfonyl and Z represents a radical of the formulas

R "

D

R1

• to

CH "-C = C-CO

* 3> »

-NH- ^ y-2

N

R,

55

or

65 mean where

R3 is hydrogen, methyl, phenyl, carboxyl or carbamoyl, R4 is hydrogen or phenyl which is optionally substituted by methyl, carboxyl or chlorine,

649 568

6

Rs methyl, methoxy, acetylamino, propionylamino, benzoylamino, N-phenylamino, dimethylamino or diethylamino,

Rs is hydrogen or methyl, and

R7 are hydrogen or, together with Rö, a fused-on benzene ring and the molecule bears a total of three hydroxysulfonyl groups.

Of particular technical importance are 1 ^ chromium complexes, which are composed of 1: 1 chromium complexes of azo compounds of the formula (IV) XH

HE. .

(SO H) 3 p

(S03H) r

(V)

N = N Z (IV)

(

with arylazo-azomethines of the formula (V)

N = N- ^

(HO S) q-A-N = CH ^)

BH ■

• 'HO.

be preserved.

In formulas (IV) and (V) mean independently of each other

Rs and R9 are hydrogen, chlorine, bromine, nitro, acetylamino or Rs and R9 together are a fused-on benzene ring and p, q and r are the numerical values 0, 1 or 2, with the proviso that

that the total number of sulfonic acid groups in the resulting 1: 2 complexes is three.

The formulas belonging to the examples are shown on the drawing sheets. Example and formula numbers match.

example 1

A suspension of 15.3 parts of 5-phenylazo-2-hydroxy-benzaldehyde-4'-sulfonic acid in 150 parts of water is heated to 50 ° with 11.4 parts of 4-chloro-2-aminophenol-6-sulfonic acid and 12 parts of sodium acetate . After the azo-azomethine compound has been formed, the same molar amount (approx. 26 parts) of the 1: 1 chromium complex compound of the azo dye is added from diazotized 4-nitro-2-aminophenol-6-sulfonic acid and l-phenyl-3-methylpyrazolone-5 added and heated to 70-80 ° with stirring. At the same time, a pH of 7-8 is maintained by adding sodium hydroxide solution until the 1: 2 complex formation has ended; the solution is then evaporated or spray dried.

This gives 62 parts of the dye of the formula (see drawing sheet no. 1, example 1) which gives level, yellowish orange dyeings on wool and polyamide fibers with very good light and wet fastness values.

The dyes listed in the table (see drawing sheet No. 2, examples 2 to 6) are obtained analogously.

Example 7

15.3 parts of 5-phenylazo-2-hydroxybenzaldehyde-4'-sulfonic acid, 11.8 parts of 4-chloro-2-aminophenol-6-sulfonic acid and 35.5 parts of the 1 μl-chromium-5 complex compound are added to 200 parts of water of the azo dye from diazotized l-amino-2-naphthol-4-sulfonic acid and l-phenyl-3-methyl-5-pyrazolone. The mixture is heated to 80 ° with stirring and adjusted to pH 7.5 by adding potassium hydroxide solution. After the 1: 2 complex formation has ended, 180 parts of 10 potassium chloride are added and the precipitated dye is isolated.

79 parts of the complex compound of the formula (see drawing sheet No. 3, example 7) are obtained, which dyes wool in yellowish red tones; the dyeings have a high level of fastness, in particular very good wet fastness properties. 15 The dyes in the table (see drawing sheet Nos. 4 and 5, Examples 8 to 13) were obtained accordingly.

20th

example

hue

example

hue

example

Hue reddish orange yellowish red

4th

5

olive green, reddish yellow, yellowish orange

example

hue

example

hue

example

hue

8th

yellowish

10th

brown

12

reddish

red

11

orange

orange

9

red

13

green

25th

Example 14

30 11.2 parts of 4-chloro-2-aminophenol-6-sulfonic acid and 15.5 parts of 5-phenylazo-salicylaldehyde-4'-sulfonic acid are in 30 parts of di (2-hydroxypropyl) ether and 40 parts of water for 30 minutes heated to 50 °; 22.6 parts of the 1: 1 chromium complex compound of the azo dye from diazotized 1-amino-2-naphthol-4-sulfonic acid and 2-naphthol are added to the resulting azo-azomethine compound, and the mixture is added dropwise with stirring at 70 ° 26.2 parts of 2- (dimethylamino) ethanol. When the 1: 2 complex formation is complete, the mixture is diluted with water to a total weight of the reaction mixture of 40 165 parts.

There is an approximately 45 percent solution of the complex salt of the formula (see drawing no. 6, example 14), which is stable in storage and produces olive-colored patterns when printed on textile floor coverings made of wool and / or synthetic polyamides.

The dye solutions in the table (see drawing sheet Nos. 7 and 8, Examples 15 to 19) were obtained in a corresponding manner.

55

example

hue

example

hue

example

hue

15

green

17th

yellowish

19th

yellow

16

blue green

red

18th

red

60

Example 20

15 parts of 5-phenylazosalicylaldehyde-4 -'-sulfonic acid are suspended in 300 parts of water and stirred with 8 parts of N-phenylethylenediamine at 50 ° C. for 30 minutes. After adding 30 parts of the 1: 1 chromium complex compound of the azo dye from diazotized 1-amino-2-hydroxy-naphtha-lin-4-sulfonic acid and 1-hydroxynaphthalene-8-sulfonic acid, the mixture is heated to 80 ° and kept at pH 7 , 5 to the finished

7

649 568

Complex formation. After salting out with sodium chloride, 60 parts of the complex dye of the formula (see drawing no. 9, example 20) are obtained, which gives true green colorations on wool and synthetic polyamides.

The dyes in the table (see drawing sheets Nos. 10 and 11, Examples 21 to 28) were obtained in a corresponding manner.

Color hue color hue color hue

5 21 red 24 green 27 reddish

22 red 25 green brown

23 green 26 olive 28 brown

G

il sheet of drawings

Claims (5)

649 568 2nd PATENT CLAIMS 1.1: 2-chromium complex dyes, in the form of the free acids of formula I N = N - D N = N - Z H (I) '<SO3H) 3 correspond in the A is the residue of an aliphatic or carbocyclic Amine component; D the rest of a diazo component; Z is an aliphatic radical, a carbocyclic or heterocyclic radical which is optionally substituted by a phenyl group substituted by R2; -O- or -COO-; X or - & - L; -O- or -N-L; 30th Hydrogen or optionally substituted alkyl, cycloalkyl, aralkyl or aryl; Hydrogen, chlorine, bromine, alkyl, alkoxy, nitro, Acylamino, carboxyl or optionally N-substituted carbamoyl or sulfamoyl; and 35 Hydrogen, chlorine, bromine, alkyl or nitro or R 1 and R 2 together mean a fused-on benz ring or where R 1 or R 2 each represent one of the required three hydroxysulfonyl groups. 2. Compounds according to claim 1, which are in the form of the free 40 acids of the formula = N - D R: in which A is a remainder of the formulas B CH, -ÒH- (CH2) g, -CH-, a the numbers 1, 2 or 3, b the numbers 0, 1 or 2, B1 hydrogen, chlorine, bromine, nitro, methyl, methoxy, acethylamino, sulfamoyl, N-phenylsulfamoyl, N-dimethyl, N-diethyl or N-y-methoxypropylsulfamoyl or hydroxysulfonyl, B2 hydrogen, chlorine, nitro or hydroxysulfonyl, B1 and B2 together form a benz ring optionally substituted by nitro, B 'chlorine or hydroxysulfonyl, B3 -CH2OH, -CH2NH2 or - (CH2) aCOOH, -O- or -COO-, -O-, -COO- or -N-L, -O- or -N-L, Hydrogen, optionally substituted by hydroxy or Ci to G »alkoxy Ci to Ci5-alkyl, phenylsulfonyloxyethyl, tolylsulfonyloxyethyl, cyclohexyl, phenyl-Ci to C4-alkyl or phenyl optionally substituted by chlorine, methyl, methoxy or ethoxy, D phenyl optionally substituted by chlorine, bromine, nitro, methyl, methoxy, ethoxy or hydroxysulfonyl, naphthyl or 2- (4'-aminophenyl) -6-methylbenzthiazolyl substituted by hydroxysulfonyl, R1 hydrogen, chlorine, bromine, Ci- to Gt-alkyl , Ci to Gt-q 45 alkoxy, nitro, Ci to C4 alkanoylamino, benzoylamino, carboxyl, optionally carbamoyl or sulfamoyl or sulfamoyl or hydroxysulfonyl mono- or disubstituted by Ci to C4 alkyl or phenyl, R2 is hydrogen, chlorine, bromine, Ci - to C4-alkyl, nitro or 50 hydroxysulfonyl, R1 and R2 together represent a benz ring optionally substituted by nitro or hydroxysulfonyl and Z represents a radical of the formulas H R, CH3-C = C-CO-NH- er N. \ / - N R. 65 R, _ CH3 XX "- N OH 3rd 649 568 Claim 1, characterized in that compounds of the formula , N = N-D mean where R3 is hydrogen, methyl, phenyl, carboxyl or carbamoyl, R4 is hydrogen or phenyl which is optionally substituted by methyl, carboxyl or chlorine, Rs methyl, methoxy, acetylamino, propionylamino, benzoylamino, N-phenylamino, dimethylamino or diethylamino, Ra is hydrogen or methyl, and R7 are hydrogen or, together with R & a fused benz ring and the molecule carries a total of three hydroxysulfonyl groups. 3. Process for the preparation of compounds according to ■ (S03H) n 10th on 1: 1 chromium complexes of the formula 20 attaches, m and n have the numerical values zero, 1, 2 or 3 and m + n is 3.