DE2634497A1 - REACTIVE COLORS - Google Patents

Description

Bayer Aktiengesellschaft

Central area of patents, trademarks and licenses

5090 Leverkusen, Bayerwerk My-kl

June 30, 1976

Reactive dyes

The present invention relates to the copper, cobalt and chromium complexes of disazo dyes of the formula

N = N-K

^{S0 3 ^H) m

• X.

(D

D = phenylene, naphthylene, optionally substituted by halogen, methyl, methoxy, carboxylic acid, nitro, Acetylamino and sulfonic acid groups

m = 1 or 2

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K = remainder of a coupling component X = -B-N-Z

R.
B = direct bond or divalent bridge link

R = hydrogen or

Z = remainder of a heterocyclic reactive component ρ = 1 or 2

means, where X is bonded to K and / or D and the OH group in D is in the o-position to the azo bridge.

Divalent bridge members B are, for example, -CH ₂ -, -N-CH ₂ -CH ₂ -, -NC-CH ₂ - and -NC- ^ \ ^

TI Il

^H 0

H £ W

Preferred dyes are the copper, cobalt and chromium complexes of the dyes of the formula

OH OH
I. A. Y-N = N-K D-N = N- ( X
HO ₃ S 0

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where D, K, X and ρ have the meaning given above and A represents hydrogen or a sulfonic acid group, particularly preferred are those in which A represents a sulfonic acid group stands. Further preferred dyes are those of the formula I or II in which X is a halopyrimidinyl, in particular 2,4-difluoro-5-chloro-pyrimidinyl-6 radical, a halotriazinyl, in particular chlorine or. Fluorotriazinyl radical or a 2,3-dichloroquinoxaline-6-carbonyl radical stands.

Further preferred dyes are those of the formulas I or II in which D is optionally represented by chlorine sulfophenylene, one disulfophenylene or one optionally substituted by nitro groups substituted sulfonaphthylene, a disulfonaphthylene or Trisulfonaphthylenrest and -K-X stands for

OH

stands,

(SO ₃ H) _n

in which X has the meaning given and η is 0 or 1.

Further preferred dyes are those of the formulas I or II in which K optionally represents the remainder of a by acetyl or benzoylamino group substituted hydroxynaphthalene mono-, di- or trisulfonic acid and

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OH OH OH

D- for H0 ₃ S _>i;; k _/ J or

^S0 3 ^H , in which X has the meaning given.

Other preferred dyes are the copper complexes.

Reactive groups Z are understood as meaning those groups which have one or more reactive groups or which can be split off Have substituents which when the dyes are applied on cellulose materials in the presence of acid-binding agents and optionally under the action of temperature the hydroxyl groups or cellulose or when applied to wool with the amide groups of the wool with formation of covalent The ability to react. Such reactive groups are known in large numbers from the literature. The following The groupings indicated therefore represent only a selection of the possible reactive groups in the new dyes. Suitable ones Reactive groups include those that have at least one reactive substituent on a 5- or 6-membered heterocyclic Ring tied included, like on a

Monazine, diazine, triazine, e.g. pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asym. Or sym. Triazine ring, or such a ring system which has one or more fused aromatic rings, such as a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system;

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the 5- or 6-membered heterocyclic rings which have at least one reactive substituent are therefore preferably those which contain one or more nitrogen atoms and can contain 5- or preferably 6-membered carbocyclic rings fused on. Among the reactive substituents on the heterocycle, halogen (Cl, Br or F), ammonium, including hydrazinium, sulfonium, sulfonyl, azido (N ₃ ), cyano, rhodanide thio, thioether, oxyether, sulfinic acid and sulfonic acid and dialkylphosphonic acid should be mentioned, for example 0

Il

residues ((RO) ₂ P-)) and benzthiazolyl- (2) mercapto residues.

Mono- or dihalogen-sym.-triazinyl radicals may be mentioned in detail, for example, in particular the mono- or dichloro and the monofluoro-sym.-triazinyl radicals, e.g. 2,4-dichlorotriazinyl-6, 2,4-dibromotriazinyl-6, 2-amino-4-chlorotriazinyl-6, 2-alkylamino-4-chlorotriazinyl-6, such as 2-methylamino-4-chlorotriazinyl-6, 2-methylamino-4-fluorotriazinyl-6, 2-ethylamino or 2-propylamino-4-chlorotriazinyl-6, 2-ß-0xethylamino-4-chlorotriazinyl-6, 2-di-ß-oxethylamino-4-chlorotriazinyl-6 and the corresponding sulfuric acid half esters, 2-diethylamino-4-chlorotriazinyl-6, 2-morpholino- or 2-piperidino-4-chlorotriazinyl-6, 2-Cyclohexylamino-4-chlorotriazinyl-6, 2-arylamino and subst. Arylamino-4-chlorotriazinyl-6, such as 2-phenylamino-4-chlorotriazinyl-6, 2-phenylamino-4-fluorotriazinyl-6, 2- (ο-, m- or p-sulfophenyl) -amino-4-chlorotriaziny1-6, 2- (2 ', S'-Disulfophenyl) -amino-4-chlorotriazinyl-6, 2-alkoxy-4-chlorotriazinyl-6, such as 2-methoxy, ethoxy or methoxyethoxy-4-chlorotriazinyl-6, 2- (phenylsulfonylmethoxy) -4-chlorotriazinyl-6, 2-aryloxy and subst. Aryloxy-4-chlorotriazinyl-6, such as 2-phenoxy-4-chlorotriazinyl-6, 2- (p-sulfophenyl) -oxy-4-chlorotriazinyl-6, 2- (o-, m- or p-

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Methyl- or methoxyphenyl) -oxy-4-chlorotriazinyl-6, 2-alkyl mercapto or 2-aryl mercapto or 2- (substituted aryl) mercapto-4-chlorotriazinyl-6, such as 2- (β-hydroxyethyl) mercapto -4-chlorotriazinyl-6, 2-phenylmercapto-4-chlorotriazinyl-6, 2- (4'-methylphenyl) -mercapto-4-chlorotriazinyl-6, 2- (2 ', 4'-dinitro) -phenylmercapto-4- chlorotriazinyl-6, 2-amino-4-sulfotriazinyl-6, 2- (o-, m-, p-methylphenyl) -amino-4-fluorotriazine _f 2- (o-, m- _f p-sulfophenyl) -amino- 4-fluorotriazine.

Mono-, di- or trihalopyrimidyl radicals, such as 2,4-dichloropyrimidyl-6, 2,4,5-trichloropyrimidyl-6, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-mono-, -di- or - trichloromethyl- or -S-carboalkoxy-pyrimidyl-6, 2 , 6-dichloropyrimidine-4-carbonyl, 2,4-dichloropyrimidine-5-carbonyl, 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio-4-fluoropyrimidine -5-carbonyl, 6-methyl-2,4-dichloropyrimidine-5-carbonyl, 2,4,6-trichloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl _/ 2-fluoro-4-pyrimidinyl, 2 , 6-difluoro-4-pyrimidinyl, 2,6-difluoro-S-chloro - ^ - pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl , 2,5-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo -2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6 -chlo rmethyl-2-fluoro-4-pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimidinyl, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 2-fluoro-5-bromo-6- chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, · 2-fluoro -5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4 -

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pyrimidinyl, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl _f 2-fluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-phenyl-4-pyrimidinyl, 2-fluoro-5-carbonamido-4-pyrimidinyl _/ 2-fluoro-5-carbomethoxy-4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl-4- pyrimidinyl, 2-fluoro-6-carbonamido-4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl _/ 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl _/ 2, 6-difluoro-5- trifluoromethyl-4-pyrimidinyl.

2-chloroquinoxaline-3-carbonyl _/ 2- or 3-monochloroquinoxaline-6-carbbnyl, 2- or S-monochloroquinoxaline-G-sulfonyl, 2 _f 3-dichloroquinoxaline-6-carbonyl, 2,3-dichloroquinoxaline-6-sulfonyl, 1,4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-sulfonyl or -carbonyl, 2- or 3- or 4- (4 ', 5'-dichloropyridazon-6 '-yl-1') - phenylsulfonyl or -carbonyl, β- (4 ', 5'-dichloropyridazon-6'-yl-1') - ethylcarbonyl, N-methyl-N- (2,4-dichlorotriazinyl-6) -carbamyl, N-methyl-N- (2-methylamino-4-chlorotriazinyl-6) -carbamyl, N-methyl-N- (2-dimethylamino-4-chlorotriazinyl-6) -carbamyl, N-methyl- or N- Ethyl-N- (2,4-dichlorotriazinyl-6) -aminoacetyl, N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) -aminoacetyl, N-methyl-N- (2,3-dichloroquinoxaline-6 -carbonyl) -aminoacetyl,

as well as the corresponding bromine and fluorine derivatives of the aforementioned chlorine-substituted heterocyclic radicals;

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triazine radicals containing sulfonyl groups, such as 2,4-bis- (phenylsulfonyl) -triazinyl-6, 2- (3'-Carboxyphenyl) -sulfony1-4-chlorotriazinyl-6, 2- (3'-sulfophenyl) -sulfonyl-4-chlorotriazinyl-6, 2,4-bis (3'-carboxyphenylsulfonyl-1 ') - triazinyl-6;

pyrimidine rings containing sulfonyl groups, such as 2-carboxymethylsulfonyl-pyrimidinyl-4, 2-methylsulfony1-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-6-ethyl-pyrimidinyl-4, 2-phenylsulfonyl-5-chloro-6-methyl-pyrimidinyl -4, 2,6-Bis-methylsulfonyl-pyrimidinyl-4, 2 , 6-bis-methylsulfonyl-5-chloro-pyrimidinyl-4, 2,4-bis-methylsulfonyl-pyrimidine-5-sulfonyl / 2-methylsulfonyl-pyrimidinyl -4, 2-Phenylsulfonyl-pyrimidinyl-4, 2-trichloromethylsulfonyl-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-S-chloro-δ-methyl-pyrimidinyl-4 , 2-methylsulfonyl-5-bromo-6 -methyl-pyrimidinyl-4, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidinyl-4, 2-methylsulfonyl-5-chloro-6-chloromethyl-pyrimidinyl-4, 2-methylsulfony1-4-chloro-6 -methylpyrimidine-5-sulfonyl, 2-methylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4, 2,5,6-tris-methylsulfonyl-pyrimidinyl-4, 2-methylsulfony1-5,6-dimethyl-pyrimidinyl-4 , 2-Ethylsulfonyl-5-chlo-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-6-chloropyriinidinyl-4, 2,6-bis-methylsulfonyl-5-chloro-pyrimidiny1-4, 2-methylsulfony l-6-carboxy-pyrimidinyl-4 , 2-methylsulfonyl-5-sulfo-pyrimidinyl-4, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl-4, 2-methylsulfony1-5-carboxy-pyrimidiny1-4, 2-methylsulfonyl 5-cyano-6-methoxy-pyrimidinyl-4, 2-methylsulfony1-5-chloropyrimidinyl-4, 2-sulfoethylsulfonyl-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-5-bromo-pyrimidinyl-4, 2-phenylsulfonyl 5-chloro-pyrimidinyl-4, 2-carboxymethylsulfonyl-S-chloro-e-methylpyrimidinyl-4, 2-methylsulfonyl-6-chloropyrimidine-4- and -5-carbonyl, 2,6-bis- (methylsulfonyl) -pyrimidine- 4- or -5-carbonyl, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl, 2,4-bis (methylsulfonyl) -pyrimidine-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methylprimidine-5- sulfonyl or carbonyl.

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triazine rings containing ammonium groups, such as 2-trimethylammonium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6, 2- (N, N-dimethylhydrazinium) -4-phenylamino- or - 4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6, 2- (N ¹ -Isopropylidene-N ^ N-dimethyl) -hydrazinium-4-pheny! Amino- or -4- (o- , m- or p-sulfophenyl) -amino-triazinyl- 6, 2-N-aminopyrrolidinium- or 2-N-aminopiperidinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino- triazinyl-6,

also 4-phenylamino or 4- (SuIfopheny! amino) -triazinyl-6 radicals, which in the 2-position via a nitrogen bond are 1,4-bis-aza-bicyclo - /> f, 2 _/ 27-octane or the Contain 1,2-bis-aza-bicyclo-ZPf3,37-octane bonded quaternary, 2-pyridinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triaziny1-6- and corresponding 2-onium-triazinyl-6 radicals, which are in the 4-position by alkylamino, such as methylamino, ethylamino or ß-hydroxyethylamino, or alkoxy, such as methoxy or ethoxy, or aroxy, such as phenoxy or sulfophenoxy groups are substituted;

2-chlorobenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonyl- or -alkylsulfonylbenzthiazole-5- or -6-carbonyl or -5- or -6- sulfonyl, such as 2-methylsulfonyl- or 2-ethylsulfonyl-benzothiazole-5- or -6-sulfonyl or -carbonyl, 2-phenylsulfonyl-benzthiazole-5- or -6-sulfonyl or -carbonyl and the corresponding 2-sulfonyl-benzothiazole-5- or -6-carbonyl- containing sulfo groups in the fused benzene ring or sulfonyl derivatives, 2-chloro-benzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-benzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-1-methyl-benzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-4-methyl-thiazole- (1,3) -5-carbonyl or -4- or -5-sulfonyl, N-oxide of 4-chloro- or 4-nitro-quinoline-5-carbonyl, 3,5-dichloro-isothiazole- (1,2) -4-carbonyl, 3,5-bismethylsulfonyl-isothiazole- (1,2) -4-carbonyl, Benzthiophene-S-dioxide-5- or -6-sulfonyl,

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The present invention also relates to processes for the production of copper, cobalt and chromium complexes of disazo dyes of the formula

N = N-K

(SO ₃ H)

(D

wherein

D = phenylene naphthylene, optionally substituted

by halogen, methyl, methoxy, carboxylic acid, nitro, acetylamino and sulfonic acid groups

m = 1 or 2

K = remainder of a coupling component

X = -B-N-Z

R B = direct bond or divalent bridge member

R = hydrogen or C.-C ₄ -AlkVl Z - radical of a heterocyclic reactive component

ρ «1 or 2

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denotes, where X is bonded to K and / or D and where the OH group in D is in the o-position to the azo bridge.

The following processes may be mentioned in detail: 1. The metal-free dyes of the formula

N = N-K

(D

where D, m, K, X and ρ have the meaning given above to have,

are treated in the usual way with copper, cobalt or chromium donating agents.

2. The copper, cobalt, or chromium complexes of disazo dyes the formula

N = N-K

- (B-N-H) ι Ρ R

(III)

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where D, m, K _/ B, R and ρ have the meaning given above,

are with ρ mol of a reactive component Y-Z according to conventional Process implemented with elimination of ρ mol H-Y.

3. The copper, chromium or metal complexes of aminoazo dyes the formula

in which X, D and m have the meaning given above and q = 0 or 1 / are diazotized and with coupling components of the formula H-K- (X), in which K and X have the meaning given, r = 0 or 1 and q + r = 1 or 2.

The metal-free dyes I can be prepared by first adding diazo compounds of the amines

OH
D-NH ₂

with coupling components

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OH

combined, diazotized the aminoazo and on coupling components the formula H-K-X couples.

Metal-free dyes I can also be obtained if diazo compounds of the amines are first used

OH
D-NH ₉

on coupling components

< ^S0 3 ^H) m

coupled, diazotized the aminoazo dye and with coupling components H-K united.

Metal-free dyes of the formula I can also be obtained by using diazo compounds of the amines

OH

D-NH ₂

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with coupling components of the formula

N = N-K-X

implements.

The disazo dyes III can be prepared in such a way that the diazo compounds of amines

OH
D-NH ₂

with coupling components

combined, diazotized the aminoazo and on coupling components

H-K-B-N-acetyl or H-K-B-N-H

I I

R R

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couples and, in the case of using H-K-B-N-acetyl, then saponify the amino

group exposes and treats the amino-disazo dye converted into the metal complex with metal-releasing copper, cobalt or chromium salts.

III is also reached when one of compounds of the formula

OH D-NH ₀ ,

which are substituted by nitro or acetylamino groups, goes out, these are diazotized and on compounds

(SO ₃ H) _1n

couples, the aminoazo dye on coupling components H-K, then with sulfides the nitro group reduced to the amino group or the acetylamino group converted into an amino group by saponification and the amino disazo dye by treating with metal-releasing copper,

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Cobalt or chromium salts transferred into the metal complex

III can also be obtained by using diazo compounds of the amines

OH

D-NH ₂

B-N-H

starts, where B stands for an aliphatic bridge member, this with coupling components

(SO ₃ H)

combined, diazotized the aminoazo dye obtained, coupled to H-K and treated the aminodisiazo dye converted into the metal complex with metal-releasing copper, cobalt or chromium salts.

Compounds of the formula IV are obtained by the Diazo compounds of amines

OH

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with coupling components

^(S0 3 ^H > m

combined and the aminoazo dye by treatment with a metal donating copper, cobalt or chromium salt transferred to the metal complex.

OH

Suitable diazo components D-NH ₂ are, for example: 2-amino-1-oxy-4-sulfobenzene, 2-amino-1-oxy-4,6-disulfobenzene, 2-amino-1-oxy-5-sulfobenzene , 2-amino-1-oxy-4-nitro-6-sulfo-benzene, 2-amino-1-oxy-4-sulfo-6-nitro-benzene, 2-amino-1-oxy-4-chloro-6 -sulfo-benzene, 2-amino-1-oxy-4-sulfo-6-chlorobenzene, 2-amino-1-oxy-4-chloro-5-sulfo-benzene _/ 2-amino-1-oxy-4 -methyl-6-sulfo-benzene, 1-amino-2-oxy-4-sulfonaphthalene, 1-amino-2-oxy-4,6-disulfo-naphthalene and 1-amino-2-oxy-4-sulfo-6 -nitro-naphthalene.

Suitable coupling component 3H

(SO ₃ H) ^NH
jm

are for example:

1-oxy-6-amino-3-sulfonaphthalene 1-oxy-6-amino-3,5-disulfonaphthalene 1 -oxy ^ -6-amino-4,8-disulfonaphthalene i-oxy-o-amino-ß-sulfo-S-chloronaphthalene

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Suitable coupling components H-K-B-N-Z are example

R the condensation products of the following compounds H-K-B-N-H

R with the corresponding reactive components X-Z:

1-amino-8-oxy-3,6-disulfonaphthalene, 1-amino-8-oxy-4,6-disulfonaphthalene, 6-amino-1-oxy-3-sulfonaphthalene, 6-amino-1-oxy-3,5-disulfonaphthalene, 7-amino-1-oxy-3-sulfonaphthalene, 7-amino-1-oxy-3,6-disulfonaphthalene, 6-amino-1-oxy-4,8-disulfonaphthalene, 1- (3'- or 4'-aminophenyl) -S-carboxy-pyrazolone-S,

1- (2'-Methy-3'-amino-5'-sulfophenyl) -3-methyl-pyrazolone-S,

1- (3'- or 4'-aminophenyl) -3-methyl-pyrazolone-S,

1-N-methylaminoacetylamino-e-oxy-S, 6-disulfonaphthalene, 1-N-methylaminoacetylamino-8-oxy-4,6-disulfonaphthalene, 6_N_Methylaminoacetylamino-1-oxy-3-sulfonaphthalene

OH

Suitable diazo components D-NH ₂ are, for example

X reaction products of the following compounds

OH

D-NH ₂

B-N-H

with the corresponding reactive components Y-Z: 2-amino-1-oxy-4-N-methylamino-acetylamino-6-sulfo-benzene, 2-Amino-1-oxy-4-N-methylamino-methyl-benzene, 2,4-diamino-1-oxy-6-sulfo-benzene.

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Suitable coupling components H-K are, for example:

1-oxy-3,6-disulfonaphthalene, 1-oxy-3,8-disulfonaphthalene, 1-oxy-4,7-disulfonaphthalene, 1-oxy-4,8-disulfonaphthalene, 1-oxy-5-sulfonaphthalene, 1-oxy-e-acetylamino-S, 6-disulfonaphthalene, 1-Oxy-e-acetylamino-S, 5-disulfo-naphthalene, i-Oxy-S-benzoylamino-3,6-disulfonaphthalene, 1-oxy-7-acetylamino-3-sulfonaphthalene, 1-oxy-6-acetylamino-3-sulfonaphthalene, 1-oxy-7-acetylamino-3,6-disulfonaphthalene, 1-oxy-6-acetylamino-3,5-disulfonaphthalene, 2-oxy-3,6-disulfonaphthalene, 2-oxy-3,7-disulfonaphthalene, 1 - (3 'or 4'-sulfophenyl) -3-methyl-pyrazolon-S, 1- (2'-chloro-5'-sulfophenyl) -3-methyl-pyrazolone-S, 1- (2'-methyl-4-sulfophenyl) -3-carboxy-pyrazolone-5, 1 - (3'-sulfophenyl) -S-methyl-S-amino-pyrazole.

Suitable reactive components Y-Z are, for example, those on which the aforementioned reactive groups Z are based, i.e. generally the halides or sulfonyl compounds of the aforementioned Acy! Components Z. From the large number of available standing compounds are mentioned here in extracts: Trihalogen-sym.triazines, such as cyanuric chloride and cyanuric bromide, Dihalo-monoamino- and mono-substituted-amino-sym.-triazines, such as 2,6-dichloro-4-amino-triazine, 2, e-dichloro ^ -methylamino-triazine, 2,6-difluoro-4- (o-, m-, p-sulfophenyl) -amino-triazine, 2,6-difluoro-4- (o-, m-, p-methylphenyl) aminotriazine, 2,6-difluoro-4-phenylaminotriazine, 2,6-difluoro-4-methylamino-triazine, 2,6-dichloro-4-ethylamino-

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triazine, 2 _/ 6-dichloro-4-oxäthylamino-triazine, 2,6-dichloro-4-phenylamino-triazine, 2,6-difluoro-4-phenylamino-triazine, 2,6-dichloro-4- (o-, m- or p-sulfophenyl) -amino-triazine, 2,6-dichloro-4- (2, '3 · -, -2', 4 · -, -2 ', S ¹ -, -3', 4 · - or -3 ¹ , 5'-disulfophenyl) aminotriazine, dihalo-alkoxy- and -aryloxy-sym.-triazines, such as 2 _/ 6-dichloro-4-methoxy- or ethoxy-triazine, 2,6-dichloro 4-ethoxy-triazine, 2,6-dichloro-4-phenoxy-triazine, 2,6-dichloro-4- (o-, m- or p-sulfophenyl) -oxy-triazine, dihaloalkylmercapto- and -arylmercapto-sym. -triazines, such as 2,6-dichloro-4-ethylmercaptotriazine, 2,6-dichloro-4-phenylmercaptotriazine, 2,6-dichloro-4- (p-methylphenyl) mercapto-triazine, 2-amino-4-sulfo- 6-chloro-triazine;

Tetrahalogen-pyrimidines, such as tetrachloro-, tetrabromo- or tetraf luorr-pyrimidine, 2,4,6-trihalogen-pyrimidines, such as 2,4,6-trichloro-, -Tribromo- or -trifluoropyrimidine, dihalopyrimidines, such as 2,4-dichloro-, -dibromo- or difluoropyrimidine, 2,4,6-trichloro-5-nitro- or -5-methyl- or -5-carbomethoxy- or -5-carboethoxy- or -5-carboxymethyl- or -5-mono-, -di- or -trichloromethyl- or -5-carboxy- or -5-sulfo- or -5-cyano- or -5-vinyl-pyrimidine, 2,4-dichloro-pyrimidine-5-carboxylic acid chloride, 2,4,6-trichloropyrimidine-5-carboxylic acid chloride, 2-methyl-4-chloropyrimidine-5-carboxylic acid chloride, 2-chloro-4-methyl-pyrimidine-5-carboxylic acid chloride, 2,6-dichloro-pyrimidine-4-carboxylic acid chloride;

2,4-difluoro-6-methyl-pyrimidine, 2,6-difluoro-4-methyl-5-chloropyrimidine, 2,4-difluoro-pyrimidine-5-ethylsulfone, 2,6-difluoro-4-chloropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 2,6-difluoro-4-methyl-5-bromo-pyrimidine, 2,4-difluoro-5,6-dichloro or -di

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bromopyrimidine, 4,6-difluoro-2,5-dichloro- or -dibromopyramidine, 2,6-difluoro-4-bromopyrimidine, 2, 4,6-trifluoro-5-bromopyrimidine, 2, 4,6-trifluoro-5-chloromethyl-pyrimidine, 2,4,6-trifluoro-5-nitropyrimidine, 2,4,6-trifluoro-5-cyano-pyrimidine _/ 2,4,6-trifluoro-pyrimide-n- 5-carboxylic acid alkyl esters or -5-carboxamides, 2,6-difluoro-5-methyl-4-chloro-pyrinidine, 2,6-difluoro-5-chloro-pyrimidine, 2,4,6-trifluoro-5-methyl pyrimidine, 2,4,5-trifluoro-6-methylpyrimidine, 2,4-difluoro-S-nitro-e-chloro-pyrimidine, 2,4-difluoro-5-cyano-pyrimidine, 2,4-difluoro-5 -methyl-pyrimidine, 6-trifluoromethyl-5-chloro-2,4-difluor-pyrimidine, 6-phenyl-2,4-difluoropyrimidine, 6-trifluoromethyl-2/4-difluor-pyrimidine, 5-trifluoromethyl-2,4 , 6-trifluoro-pyrimidine, 5-trifluoromethyl-2,4-difluoropyrimidine, 2,4-difluoro-5-nitro-pyrimidine, 2,4-difluoro-5-trifluoromethyl-pyrimidine, 2,4-difluoro-5-methylsulfonyl pyrimidine, 2,4-difluoro-5-phenyl-pyrimidine, 2,4-difluoro-5-carbonamidopyrimidine, 2,4-difluoro-5-carbomethoxypyrimidine, 2,4-difluoro-6-trifluoromethyl l-pyrimidine, 2,4-difluoro-5-bromo-6-trifluoromethylpyrimidine, 2,4-difluoro-6-carbonamido-pyrimidine, 2,4-difluoro-6-carbomethoxy-pyrimidine, 2,4-difluoro-6- phenyl-pyrimidine, 2,4-difluoro-6-cyano-pyrimidine, 2,4,6-trifluoro-5-methylsulfonyl-pyrimidine, 2,4-difluoro-5-sulfonamido-pyrimidine _/ 2,4-difluoro-5 -chlor-6-carbomethoxy-pyrimidine,

Pyrimidine reactive components with removable sulfonyl groups, such as 2-carboxymethylsulfonyl-4-chloropyriiaidin. 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine _f 2,4-bis-methylsulfonyl-6-methylpyrimidine, 2,4-bis-phenylsulfonyl-S-chloro-6-methyl-pyrimidine, 2,4,6- Tris-methylsulfonyl-pyrimidine, 2,6-bis-methylsulfonyl-4,5-dichloro-pyrimidine, 2,4-bis-methylsulfonyl-pyrimidine-5-sulfonic acid chloride, 2-methylsulfonyl-4-chloro-pyrimidine, 2-phenyl

Le A 17 349-21

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2Ö3A497 Jl?

sulfonyl-4-chloropyrimidine, 2,4-bis-trichloromethylsulfonyl-6-methyl-pyrimidr.n, 2,4-bis-methylsulfonyl-5-chloro-6-methyl-pyrimidine, 2,4-bis-methylsulfonyl- S-bromo-6-methyl-pyrimidine, 2-methylsulfonyl-4, S-dichloro-e-methyl-pyrimidine, 2-methylsulfonyl-4, S-dichloro-e-chloromethyl-pyrimidine, 2-methylsulfonyl-4-chloro 6-methyl-pyrimidine-5-sulfonic acid _{chloride /} 2-methylsulfonyl-4-chloro-5-nitro-6-methyl-pyrimidine, 2,4,5,6-tetramethylsulfonyl-pyrimidine, 2-methylsulfonyl-4-chloro-5 , 6-dimethylpyrimidine, 2-ethylsulfonyl-4, S-dichloro-G-methyl-pyrimidine, 2-methylsulfonyl-4,6-dichloro-pyrimidine, 2,4,6-tris-methylsulfonyl-5-chloro-pyrimidine, 2 -Methylsulphonyl-4-chloro-6-carboxypyrimidine, 2-methylsulphonyl-4-chloro-pyrimidine-5-sulphonic acid, 2-methylsulphonyl-4-chloro-6-carbomethoxy-pyrimidine _/ 2-methylsulphonyl-4-chloro-pyrimidine-5 carboxylic acid, 2-methylsulphony1-4-chloro-S-cyano-δ-methoxy-pyrimidine, 2-methylsulphonyl-4,5-dichloropyrimidine, 4,6-bis-methylsulphonyl-pyrimidine, 4-methylsulphonyl-6-chloro-pyrimidine , 2-sulfoethyl sulf onyl-4-chloro-6-methylpyrimidine, 2-methylsulfonyl-4-chloro-5-bromo-pyrimidine, 2-methylsulfonyl-4-chloro-5-bromo-6-methyl-pyrimidine, 2,4-bis-methylsulfonyl -5-chloro-pyrimidine, 2-phenylsulfonyl-4,5-dichloropyrimidine, 2-phenylsulfonyl-4, S-dichloro-e-methyl-pyrimidine, 2-carboxymethylsulfonyl-4, S-dichloro-e-methyl-pyrimidine, 2 -Methylsulfonyl-e-chloropyrimidine ^ - or -S-carboxylic acid chloride, 2-ethylsulfonyl-6-chloro-pyrimidine-4- or -S-carboxylic acid chloride, 2,6-bis (methylsulfonyl) -pyrimidine-4-carboxylic acid chloride, 2-methylsulfonyl-6-methyl-4-chloro- or -4-bromo-pyrimidine-S-carboxylic acid chloride or bromide, 2,6-bis (methylsulfonyl) -4-chloro-pyrimidine-5-carboxylic acid chloride;

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other reactive components of the heterocyclic series with reactive sulfonyl substituents are, for example, 3,6-bisphenylsulfonyl-pyridazine, 3-methylsulfonyl-6-chloropyridazine, 3,6-bis-trichloromethylsulfonyl-pyridazine, 3,6-bis-methylsulfonyl-4-methyl- pyridazine, 2,5,6-tris-methylsulfonyl-pyrazine, 2,4-Bismethylsulfonyl-1,3,5-triazine, 2,4-Bismethylsulfonyl-6- (3-sulfophenylamino) -1,3, 5 triazine, 2,4-bis-methylsulfonyl-6-N-methylanilino-1,3, 5-triazine / 2,4-bis-methylsulfonyl-6-phenoxy-1,3,5-triazine, 2,4-bis -methylsulfonyl-6-trichloroethoxy-l, 3,5-triazine, 2,4,6-tris-phenylsulfonyl-1,3,5-triazine, 2,4-bismethylsulfonyl-quinazoline, 2,4-bis-trichloromethylsulfonylquinoline, 2,4-bis-carboxymethylsulfonyl-quinoline, 2,6-bis- (methylsulfonyl) -pyridine-4-carboxylic acid chloride and 1- (4'-chlorocarbonylphenyl- or 2'-chlorocarbonylethyl) -4,5-bis-methylsulfonyl -pyridazon- (6);

other heterocyclic reactive components with mobile halogen include 2- or S-monochloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2- or 3-dibromo-quinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 2,3-dichloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3-dibromo-quinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 1 ^ -Dichlorophthalazine-e-carboxylic acid chloride or -6-sulfonic acid chloride and the corresponding bromine compounds, 2-chloroquinoxaline-3-carboxylic acid chloride and the corresponding Bromine compound, 2,4-dichloroquinazoline-6- or -7-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine compounds,

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2634437

2- or 3- or 4- (4 ¹ , 5'-dichloropyridazon-6'-yl-1 ') -phenylsulfonic acid chloride or -carboxylic acid chloride and the corresponding bromine compounds, ß- {4', S'-dichloropyridazon-ö ' -yl-1 ') -ethylcarboxylic acid chloride, N-methyl-N- (2,4-dichlorotriazinyl-6) -carbamic acid chloride, N-methyl-N- (chloro-4-methylamino-triazinyl-6) -carbamic acid chloride, N-methyl -N- (2-chloro-4-dimethylamino-triazinyl-6) -carbamic acid chloride, N-methyl- or N-ethyl-N- (2,4-dichloro-triazinyl-6) -aminoacetyl chloride, N-methyl-, N -Ethyl- or N-hydroxyethyl-N- (2,3-dichloro-quinoxaline-6-sulfonyl- or -6-carbonyl) -aminoacetyl chloride and the corresponding bromine derivatives,

also 2-chloro-benzothiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride and the corresponding bromine compounds, 2-Arylsulfonyl- or 2-Alkylsulfonyl-benzthiazole- -5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride, like 2-methylsulfonyl- or 2-ethylsulfonyl- or 2-phenylsulfonyl-benzthiazole-5- or -6-sulfonic acid chloride or -5- or -6-carboxylic acid chloride and the corresponding im fused-on benzene ring containing 2-sulfonyl-benzothiazole derivatives, 2-chloro-benzoxazole-5- or sulfonic acid groups -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding Bromine derivatives, 2-chloro-benzimidazole-5- or -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding Bromine derivatives, 2-chloro-1-methyl-benzimidazole-5- or -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding Bromine derivatives, 2-chloro-4-methyl-thiazole- (1,3) -5-carboxylic acid chloride or -4- or -5-sulfonic acid chloride, 2-chloro-thiazole-4- or -5-sulfonic acid chloride and the corresponding bromine derivatives, 3,5-dichloro-isothiazole- (1,2) -4-carbon ~ acid chloride and the corresponding bromine compound, 3,5-bis-methylsulfonyl-isothiazole- (1,2) -4-carboxylic acid chloride, Benzthiophene-S-dioxide-5- (or -6-) sulfonic acid chloride.

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The new dyes are suitable for dyeing and printing materials containing hydroxyl or amide groups, like textile fibers. Threads and fabrics made of wool, silk, synthetic polyamide and polyurethane fibers and for washable dyeing and printing of native or regenerated Cellulose, the treatment of cellulose materials expediently in the presence of acid-binding agents Means and optionally by the action of heat according to the methods that have become known for reactive dyes.

The formulas given for the dyes are those of the corresponding ones free acids. The dyes were generally in the form of the alkali salts, especially the Na salts isolated and used for dyeing.

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example 1

22.4 g of 2-amino-1-oxy-4-sulfo-6-chlorobenzene are with
Sodium hydroxide solution dissolved in 400 ml of water until neutral. The solution is mixed with 7 g of sodium nitrite and then allowed to run into a template of 400 ml of ice water and 28 ml of concentrated hydrochloric acid. After the diazotization is complete
the resulting slurry of the diazo compound is added to a mixture of 31.9 g of 1-oxy-G-amino-SjS-disulfonaphthalene, 28 g of sodium hydrogen carbonate, 200 ml of water and 1 spatula tip of calcium oxide. To speed up
the clutch is heated to 40.degree. The dye is isolated by suction filtration at room temperature. The moist paste is dissolved in 1 l of water with sodium hydroxide solution at pH 12, mixed with 7 g of sodium nitrite and then added dropwise to a template made of ice and 40 ml of concentrated hydrochloric acid.

The mixture is stirred at 5 for 1 to 2 hours and then added
the diazotization partially in a solution of 46.75 g of 1-0xy-8- (2 ', 4'-difluoro-5'-chloropyrimidinyl-δ-amino) -3,6-disulfonaphthalene and 40 g of sodium hydrogen carbonate in 300 ml
Water. After the coupling has ended, 28 g of crystalline are added.
Add copper sulfate, adjust the pH to 5 to 6 with the help of a glass electrode and stir for some time at room temperature. The dye is isolated by salting out. Dried and ground, it represents a black one
Powder that turns blue in water slightly
solves.

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In the form of the free acid it corresponds to the following formula

C —Cn Cl> LN = N

HO ₃ S

SO ₃ H

The same product is obtained if one uses the amino monoazo dye First treated with crystalline copper sulphate, the copper complex is diazotized in an acetic acid medium and then alkaline bicarbonate with the condensation product of 1-oxy-8-amino-3,6-disulfonaphthalene and 2,4,6-trifluoro-5-chloropyrimidine united.

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2534497 33

Color examples Printing specification

If you print cotton nettle with a printing paste containing 20 g of the dye shown in Example 1 per kilogram, 100 g urea, 300 ml water, 500 g alginate thickener (60 g sodium alginate / kg thickener) and 10 g Contains soda, and which was precipitated to 1 kg with water, dries, steams 1 minute at 103 ° C, with hot water rinsed and soaped at the boil, a strong, navy blue print of good wet and light fastness is obtained.

Blocking regulation

30 parts of the dye shown in Example 1 are dissolved in 1000 parts of water. With this solution a cotton fabric is fouladed and pressed down to a weight loss of 90%. The still damp cotton is at 70 ° for 30 minutes in a tape, which in 1000 parts of water 300 parts of calcined sodium sulfate and 10 parts of calcined sodium carbonate in solution. Subsequently, the coloring finished in the usual way. A strong, navy blue dyeing with excellent wet and light fastness properties is obtained.

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Dyeing prescription

In a staining beaker with a content of 300 ml, which is located in a heatable water bath, 168 ml of water are removed from 20 - 25 ° presented. 0.3 g of the dye obtained according to Example 1 is mixed well with 2 ml of cold water add 30 ml of hot water (70 °); the Dye on. The dye solution is added to the water added and 10 g of cotton yarn kept constantly in motion in this dye liquor. Within 10 minutes the temperature of the dye liquor is increased to 70-80 °, 10 g of anhydrous sodium sulfate are added and the dye is colored 30 minutes further. Then 4 g of anhydrous sodium carbonate are added to the dye liquor and dyeing is carried out for 60 minutes 70 - 80 °. The dyed material is then removed from the dye liquor and the liquor adhering to it is removed by wringing out or squeezing and rinsing the material first with cold water and then with hot water until the rinsing solution is no longer bled. Then the colored material is in 200 ml of a liquor containing 0.2 g of sodium alkyl sulfate contains, soaped for 20 minutes at boiling temperature, rinsed again and in dried in a drying cabinet. A strong navy blue dyeing with excellent wash and light fastness properties is obtained.

Likewise valuable dyes are obtained if one proceeds according to the information in Example 1, but the Diazo, middle and end components listed below are used.

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tr « (O

example Diazo component Middle component Final component

metal

hue

on cotton

4 5 6 7

2-amino-1-oxy-4-sulfo-benzene

1-oxy-6-amino-3,5-disulfonaphthalene

2-amino-1-oxy-4 sulfo-6-nitro-benzene

2-Amino-1-oxy-4 nitro-6-sulfo-benzene

2-amino-1-oxy-4,6-disulfobenzene

1-

sulfo-naphthalene

2-Amino-1-oxy-4- 1-Oxy-6-amino-4,8-sulfo-6-chlorobenzene disulfo-naphthalene

2-amino-1-oxy-4,6-disulfo-benzene

1-oxy-6-amino-3,5-disulfonaphthalene

2-Amino-1-oxy-4-sulfo-6-chlorobenzene 1-Oxy-8- (2 ', 4' ₇ di-

fluoro-5'-chloro-pyri-Cu

midinyl-6'-amino) -3,6-

disulfo-naphthalene

1-Oxy-6- (2 ', 4'-difluoro-5'-chloro-pyrimidinyl-6'-amino) -3-sulfonaphthalene

1-oxy-7- (2 ', 4'-difluoro- "
5'-chloro-pyrimidiny 1-6'-amino) -3-sulfo-naphthalene

1-oxy-8- (2 ', 4'-difluoro- "
5'-chloro-pyrimidiny 1-6'-N-methylamino-acetyl-amino) -3,6-disulfonaphthalene

Navy blue

greenish navy blue

grünstichi - yj? blue

violet

reddish blue

Navy blue

IjJ VO

Example diazo component

Middle component End component

metal

10 11 12

13 14 15 16

2-Amino-1-oxy-4- 1-Oxy-6-amino-3,5-sulfo-6-chloro-benzene disulfo-naphthalene

1-Amino-2-oxy-4,6-1-oxy-6-amino-3,5-disulfonaphthalene disulfo-naphthalene

2-amino-1-oxy-4,8-disulfonaphthalene

2-amino-1-oxy-5,7-disulfonaphthalene

2-amino-1-oxy-6,8-disulfonaphthalene

1 sulfo-benzene 1-oxy-8- (2 ', 4'-dichloro-Cu triazinyl-6'-amino) -3,6-disulfonaphthalene

1-0xy-8- (2'-chloro-4'-ami- " no-triazinyl-6'-amino) -3,5-disulfo-napthalene

1-Oxy-8- (2 '^' - chloro-pyrimidinyl-6'-amino) -3,5-disulfonaphthalene

sulfo-phenylamino) -triazinyl-6'-amino_7-3,6-disulfonaphthalene

Shade on cotton

Navy blue

greenish navy blue

Example 17

18.9 g of 2-amino-1-oxy-4-sulfo-benzene are dissolved in 200 ml of water with sodium hydroxide solution, then 7 g of sodium nitrite are added and the solution is poured into a template of 28 ml of concentrated hydrochloric acid and 400 ml of ice water. When the diazotization is complete, the suspension of the diazo compound is partially introduced into a mixture of 31.9 g of i-oxy-e-amino-SjS-disulfonaphthalene, 28 g of sodium hydrogen carbonate and 400 ml of water. The aminoazo dye is isolated by salting out. The paste is mixed in water, dissolved at pH 12 by adding sodium hydroxide solution and mixed with 7 g of sodium nitrite. The resulting solution is added dropwise to a mixture of 40 ml of concentrated hydrochloric acid and 400 ml of ice water and the mixture is stirred at 5 for two to three hours. The excess of sodium nitrite is removed with sulfamic acid and the suspension of the diazo compound is added to a mixture of 21.9 g of 1- (3'-aminophenyl) -3-carboxy-pyrazolone-5 and 40 g of sodium hydrogen carbonate in 200 ml of water. After the coupling is complete, 28 g of crystallized copper sulfate are added and the mixture is stirred for a few hours at room temperature while maintaining a pH of 5-6.5. The copper complex of the amino disazo dye is isolated by salting out. For acylation, it is redissolved in water at 15-20 with 17 g of 2,4,6-trifluoro-5-chloropyrimidine, a pH between 6 and 7 being maintained by simultaneous addition of 10% sodium carbonate solution. When the acylation has ended, the dye is precipitated and isolated by salting out. In the dried and ground

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2g

State represents a dark brown powder that is easily dissolves in water with purple color. After one of the color examples given in connection with Example 1 is obtained you can use it on cotton with deep, brownish violet tones Dyeings or prints.

In the form of the free acid, the dye corresponds to the following formula

P-Cn

COOH

If one proceeds according to the information in this example, but using the following diazo, middle, end and reactive components, one also obtains
valuable reactive dyes, the hues of which on cotton are listed in the last column.

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Example diazo component middle component end component Reactive components

metal

Shade on cotton

18th

19th

2-amino-1-axy-4,6-1-oxy-δ-amino-S, 5- 1- (3'-aminophenyl) -2,4,6-trifluorodisulfobenzene disulfo-naphthalene 3-carboxy-pyrazo-5-chloro-pyrimidine

lon-5

"" "2,3-dichloroquinoxa

lin-6-carboxylic acid chloride

Cn brownish violet

O CO OO

20th

21

22nd

23

sulfonaphthalene 2,4,6-trifluoro-5-chloro-pyrimidine

2,4-difluoro-6- (3'-sulfophenylamino) triazine

Red-brown

1 -Qxy-6-amino-4,8-disulfonaphthalene

1-0> ^ - 6-amino-3,5-

disulfonaphthalene 3-sulfonaphthalene

(then saponified) reddish blue

Example 24

24.6 g of 2-amino-1-oxy-4-acetylamino-6-sulfo-benzene are dissolved in 400 ml of water until neutral, then 7 g of sodium nitrite are added and the resulting solution is placed in a template of 28 ml of concentrated hydrochloric acid and 400 ml Dripped in ice water. When the diazotization is complete, the excess sodium nitrite is removed with sulfamic acid. The solution is then added to a slurry of 1-oxy-6-amino-3,5-disulfonaphthalene in 400 ml of water, a pH of 9 is adjusted with milk of lime and heated to higher temperatures in order to complete the coupling . During the coupling, the pH is continuously monitored and kept between 9 and 10 with milk of lime. After the coupling has ended, the monoazo dye is isolated by salting out. The moist paste is dissolved in ~ 800 ml of water, mixed with 7 g of sodium nitrite and added to a mixture of 28 ml of concentrated hydrochloric acid and 500 ml of ice water. During the diazotization, the temperature is maintained at 5, if necessary by throwing in ice. The finished diazotization is then introduced into a solution of 30.4 g of 1-oxydisulfonaphthalene, 28 g of sodium hydrogen carbonate in 400 ml of water. For metallization, 28 g of crystallized copper sulfate are added and the mixture is stirred for a few hours at room temperature, the pH being between 5 and 6. The Küpfer complex is isolated by salting out. For saponification, it is stirred for several hours at 95-100 ° in a solution of 80 g of sodium hydroxide in 1.5 liters of water. After the split

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the acetyl group is adjusted to a neutral medium with hydrochloric acid and the dye is salted out again. The moist paste is mixed in 1 l of water from 12-15 and 16g trifluoro-5-chloropyrimidine are added. While After the acylation, the pH is kept between 6 and 7 by the simultaneous addition of 10% sodium carbonate solution. if the acylation is complete, the dye is salted out by adding sodium chloride and isolated. In the dry and ground it is a dark powder that easily dissolves in water with purple Color dissolves. According to one of the dyeing examples given in connection with Example 1, this is obtained on cotton strong violet dyeings with a strong bluish tinge and very good fastness properties.

In the form of the free acid, the dye corresponds to the following formula

OH

If one proceeds according to the information in Example 24, but using the diazo, Middle, end and reactive components, valuable reactive dyes and their hues are also obtained are listed in the last column.

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Example diazo component middle component end battle oriente Reactive kariponente

metal

Shade on cotton

CJ CO OO

25th

26 27

28 29 30

2-amino-1-oxy-4-

acetylamino-6-sulphonulfonaphthalene

fo-benzene 1 ~ oxy-4,7-disul-2,4,6-trifluoro-5-fo-naphthalene chloro-pyrimdidine

1-oxy-3,5-disulfonaphthalene

1-Oxy-8-benzoylamino-3,6-disulfonaphthalene 2-Amino-4, 6-αL- chlorotriazine

2-phenylamino-2,4-difluorotriazine

2,3-dichlorotrinoxa-

lin-6-carboxylic acid

chloride

Cn

bluish purple

violet

bluish purple

.V

Claims (10)

Claims 1. Copper, cobalt and chromium complexes of disazo dyes the formula (SO., H) N = N-K (D wherein D = phenylene, naphthylene, optionally substituted by halogen, methyl, methoxy, carboxylic acid, nitro, acetylamino and sulfonic acid groups m = 1 or 2 K = remainder of a coupling component X = -BNZ R B = direct bond or divalent bridge member R = hydrogen or C ₁ -C alkyl Z = radical of a heterocyclic reactive component ρ = 1 or 2 Le A 17 349 - 38 - 809809/0012 fMQINAL INSPECTED 2134497 where X is bonded to K and / or D and the OH group in D is in the ortho position to the azo bridge. 2. Copper, chromium and cobalt complexes of disazo dyes of the formula OH .0H
ι A. • MB -N = N-K D-N = N- J
HO ₃ S wherein D, K, X and ρ have the meaning given in claim 1 and A = hydrogen or sulfonic acid group. 3. Dyes of claims 1 and 2, wherein D = optionally sulfophenylene substituted by chlorine, nitro or sulfo, optionally by nitro or sulfo substituted sulfonaphthylene and -K-X = (SO ₃ H) _n wherein X has the meaning given in claim 1 and η = 0 or 1. Le A 17 349 - 39 - 809809/0012 263A497 4. Dyes of claims 1 and 2, wherein OH X-D- or SO ₃ H and K = optionally by acetylamino or benzoylamino substituted sulfo- or disulfohydroxynaphthyl. 5. Dyes of claims 1 to 4, wherein X = halopyrimidinyl, in particular 2,4-difluoro-5-chloropyrimidinyl, Halotriazinyl, especially chloro- or fluorotriazinyl, or 2,3-dichloroquinoxaline-6-carbonyl. 6. Copper complexes of the disazo dyes of claims 1 until 5. 7. Use of the dyes of claims 1 to 5 for dyeing and printing of fiber materials containing hydroxyl groups or amide groups. Le A 17 349 - 40 - 809809/0012 2534497 8. A process for the preparation of the dyes of claim 1, characterized in that there are dyes of the formula OH N = N-K (SO, H) X. wherein D, K, X, ρ and m have a meaning given in claim 1 have treated in the usual way with copper, cobalt or chromium-releasing agents. 9. Process for the preparation of the dyes of claim 1, characterized in that the copper, chromium or Cobalt complexes of disazo dyes of the formula N = N-K - (B-N-H) ι Ρ R wherein D, K, B, R and ρ have the meaning given in claim 1 have, reacts with pMpl a reactive component Y-Z with elimination of H-Y, where Z = remainder of one heterocyclic reactive component and Y = removable radical. Le A 17 349 - 41 - 809809/0012 10. A method for the production of claim 1, characterized ge indicates that the copper, chromium or cobalt complexes of aminoazo dyes of the formula OH (X) -D-N = N wherein X, D and m have the meaning given in claim 1 and Is 0 or 1, diazotized and with coupling components of the formula H-K- (X) united, wherein K and X the meaning given in claim 1 to have, r Is 0 or 1 and q + r Is 1 or 2. Le A 17 349 42 - 809809/0012