Metal complex dyes based on Bucherer naphthols

Organic compounds -- part of the class 532-570 series – Organic compounds – Azo

Reexamination Certificate

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Details

C534S624000, C534S629000, C534S634000, C534S638000, C534S642000, C008S549000

Reexamination Certificate

active

06809187

ABSTRACT:

RELATED APPLICATIONS
This application is a Rule 1.137 application of PCT application No. PCT/EP01/11542 filed Oct. 6, 2001 which claims benefit to German application no. 100 51 018.3 filed Oct. 14, 2000.
DESCRIPTION
The present invention relates to novel reactive dyes, processes for their preparation and their use for dyeing or printing textile fiber materials.
Reactive dyes for dyeing or printing hydroxyl- and/or carboxamido-containing materials these days must combine good general fastness properties with good washoff of the unfixed portions. Given the dyes available at present, there is accordingly room for improvement.
It is an object of the present invention to provide novel, improved reactive dyes for the dyeing and printing of hydroxyl- and/or carboxamido-containing materials, especially fiber materials, that combine good general fastness properties, especially a high lightfastness, with good washoff of the unfixed portions.
This object is surprisingly achieved by the hereinbelow described dyes according to the invention.
The present invention accordingly provides reactive copper, cobalt or chromium complex compounds of the general formula (1)
where
B is a direct bond or a bridge member;
X is a fiber-reactive structural element;
W
1
is vinyl or a group of the formula —CH
2
—CH
2
—V, where V is an alkali-eliminable radical;
R
1
, R
2
are independently hydrogen, chlorine, alkyl of 1-4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, alkoxy of 1-4 carbon atoms, such as methoxy, ethoxy, n-propyloxy, i-propyloxy, carboxyl or sulfamoyl, hydrogen, hydroxyl or sulfo, preferably hydrogen;
R
3
is hydrogen, hydroxyl, carboxyl or sulfo;
R
4
is hydrogen or sulfo;
R
5
is hydrogen, alkyl of 1 to 4 carbon atoms which can be substituted by halogen, hydroxyl, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxyl, sulfo or sulfato;
h, k, l, m are independently 0 or 1;
Me is copper, cobalt or chromium, preferably copper and cobalt and particularly preferably copper;
M is hydrogen or an alkali metal, such as sodium, potassium or lithium, or the mole equivalent of an alkaline earth metal, such as calcium, and preferably is hydrogen or an alkali metal.
Suitable fiber-reactive radicals X, i.e., those which react with the OH or NH groups of the fiber under dyeing conditions to form covalent bonds, are for example —SO
2
Ch═CH
2
or —SO
2
CH
2
CH
2
V, where a V grouping, which can be eliminated through the action of alkali, represents in particular radicals of the formula —OSO
3
M, thiosulfato of the formula —SSO
3
M, acetyloxy of the formula —OCOCH
3
, phosphato of the formula —OPO(OM)
2
and chloro, bromo, benzyloxy of the formula —OCOC
6
H
5
, phenylsulfonyloxy of the formula —SO
2
—C
6
H
5
or pyridinium, which may be substituted, for example by alkyl of 1-4 carbon atoms, carboxyl, sulfo, cyano or carbamoyl, where M is as defined above, or are fiber-reactive radicals X, especially those which contain at least one reactive substituent attached to a 5- or 6-membered aromatic heterocyclic ring, for example to a monoazine, diazine or triazine ring, especially a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or to such a ring system that comprises one or more fused-on aromatic carbocyclic rings, for example a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring system.
Fiber-reactive radicals selected from the pyrimidines or triazines are particularly suitable.
Examples of reactive substituents on the heterocycle include halogen (Cl, Br or F), ammonium including hydrazinium, pyridinium, picolinium, carboxypyridinium, sulfonium, sulfonyl, azido(N3), thiocyanato, sulfinic acid and sulfonic acid.
X can accordingly be in particular
where
Hal=Cl, F and
A is the radical of an amine AH which may be unsubstituted or substituted by one or two C
1
-C
6
alkyl groups, which may independently be substituted by hydroxyl, C
1
-C
2
alkoxy groups, sulfato, phenyl or hydroxycarbonyl, or by a phenyl radical which is unsubstituted or substituted by one or two substituents selected from the group consisting of C
1
-C
2
-alkyl, C
1
-C
2
-alkoxy, C
1
-C
2
-alkoxyalkyl, C
1
-C
2
-alkoxyalkoxy, amino, hydroxyl, chlorine, sulfo, sulfomethyl, sulfonamide, carboxyl, carboxamide, carboxylic ester, nitrile, aminocarboxamide and oxalamino or by a naphthyl radical which is unsubstituted or substituted by one, two or three sulfo groups or is taurine, N-methyltaurine, methylaminomethanesulfonic acid, pyrrolidine, piperidine, 1-methylpiperazine, morpholine.
Preferred compounds AH include for example ammonia, methylamine, ethylamine, n-propanolamine, isopropanolamine, n-butylamine, isobutylamine, tert-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, methylethylamine, ethanolamine, diethanolamine, 2-methoxyethylamine, 2-ethoxyethylamine, sulfatoethylamine, aminoacetic acid, N-methylaminoacetic acid, taurine, N-methyltaurine, methylaminomethanesulfonic acid, pyrrolidine, piperidine, 1-methylpiperazine, cyanamide, morpholin, benzylamine, &bgr;-phenylethylamine, N-methylbenzylamine, dibenzylamine, aniline, 1-amino-2-, 3- or 4-methylbenzene, 1-amino-3,4- or 3,5-dimethylbenzene, 1-amino-2-, 3- or 4-ethylbenzene, 1-amino-2-, 3- or 4-methoxybenzene, 1-amino-4-ethoxybenzene, 1-amino-2-, 3- or 4-(2-hydroxyethoxy)benzene, 1-amino-2-, 3- or 4-(2-methoxyethoxy)benzene, 1-amino-2-, 3- or 4-chlorobenzene, 2-, 3- or 4-aminophenylmethanesulfonic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene-sulfonic acid, 5-aminobenzene-1,3- or 1,4-disulfonic acid, 4-aminobenzene-1,2- or 1,3-disulfonic acid, 2-, 3- or 4-aminobenzenesulfonamide, 2-, 3- or 4-aminobenzene-N-methylsulfonamide, 2-, 3- or 4-aminobenzene-N-dimethylsulfonamide, 2-, 3- or 4-aminobenzene-N-(2-hydroxyethyl)sulfonamide, 5-aminobenzene-1,3-dicarboxylic acid, 2-, 3- or 4-aminobenzoic acid, 2-, 3- or 4-aminobenzamide, methyl or ethyl 2-, 3- or 4-aminobenzoate, 2-, 3- or 4-aminobenzonitrile, 3-amino-(N-phenylsulfonyl)benzenesulfonamide, 2-, 3- or 4-aminophenol, 5-amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxy-benzenesulfonic acid, 5-amino-2-ethoxybenzenesulfonic acid, 1-acetylamino-2- or 4-aminobenzene, 1-amino-3- or 4-(hydroxyacetyl)aminobenzene, 1-amino-4-(sulfoacetyl)aminobenzene, 3- or 4-aminophenylurea, N-(3-aminophenyl)-N′-(2-hydroxyethyl)urea, 3- or 4-aminophenyloxamic acid, 1-methylamino-3- or -4-methylbenzene, 1-ethylamino-4-chlorobenzene, 2-amino-5-methoxybenzenesulfonic acid, 3-amino-4-methoxy-benzenesulfonic acid, 1-ethylamino-3- or -4-methylbenzene, N-(2-hydroxyethyl)-aniline, 1-(2-hydroxyethyl)amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 4-methylaminobenzenesulfonic acid, 5-amino-2-oxalaminobenzenesulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfonic acid, 7-butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-1,3-disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 8-aminonaphthalene-1,3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,6-disulfonic acid, 8-aminonaphthalene-1,6-disulfonic acid, 4-aminonaphthalene-1,7-disulfonic acid, 3-aminonaphthalene-2,6-disulfonic acid, 4-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 4-aminonaphthalene-2,7-disulfonic acid, 6-amin

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