DE4403395A1 - Reactive heterocyclic azo dyes useful for dyeing, e.g. cotton or polyamide - Google Patents

Abstract

Heterocyclic azo cpds. contg. SO3H gp(s). are of formula (I): Het-N=N-(-E-N=N-)v-K-(N(R')-Z)n (I); Het = a gp. of formula (II); G = -NH-CO-NH-, -NH-CO-O-, -CO-NH-CO-, -SO2-NH-CO-, -NH-CO-CO-NH-, -CO-NH-NH-CO-, -CO-NH-CO-NH- or -NH-CO-(CH2)a-; a = 1 or 2; R = H, 1-4C alkyl, 1-4C alkoxy or SO3H; R' = H; 1-4C alkyl, opt. substd. by OH, CN, 1-4C alkoxy, COOH, SO3H, OSO3H or phosphate; or a phenyl or naphthyl gp., opt. with 1, 2 or 3 halogen, OH, CN, 1-4C alkoxy, 1-4C alkyl, 2-5C alkoxycarbonyl, COOH, sulphamoyl, SO3H or 1-4C alkylsulphonyl substits.; E = the divalent gp., free form the amino gp., derived from a cpd. of the aniline or naphthylamine series, which is capable of coupling and diazotisation; v = 0, 1 or 2; K = the divalent gp., free from the amino gp., derived from a coupling component of the aniline or naphthylamine series or a heterocyclic coupling component; n = 1, 2, 3 or 4; Z = a fibre-reactive gp.

Description

The invention is in the technical field of fiber-reactive dyes.

The object of the present invention was to develop new fiber-reactive Find dyes that meet the increased requirements of technology and Quality is enough and coloring with brilliant shades and very good ones Deliver fastness to use with a high degree of fixation.

With the present invention new azo compounds with such good fiber-reactive dye properties found. The new Azo compounds correspond to the general formula (1)

in which mean:
G is a group of formula (2), (2b), (2c), (2d), (2e), (2f), (2g) or (2h)

where in formula (2h) the index a is the number 1 or 2, and preferably a radical of the formula (2a), (2b) and (2e);
R is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, or sulfo, preferably hydrogen;
R¹ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, or alkyl of 1 to 4 carbon atoms, such as in particular ethyl, by hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, such as ethoxy and methoxy, carboxy, sulfo, sulfato or phosphato is substituted, or is phenyl or naphthyl, both by 1, 2 or 3 substituents from the group halogen, such as chlorine and bromine, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms , such as ethoxy and especially methoxy, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxycarbonyl of 2 to 5 carbon atoms, such as ethoxycarbonyl and methoxycarbonyl, carboxy, sulfamoyl, sulfo and alkylsulfonyl with an alkyl radical of 1 to 4 C atoms, such as methylsulfonyl and ethylsulfonyl, of which preferably alkoxy of 1 to 4 C atoms, alkyl of 1 to 4 C atoms, carboxy and sulfo can be substituted;
E is the bivalent residue of a coupling-capable and diazotizable compound from the aniline or naphthylamine series, free of the amino group;
v stands for the number zero, 1 or 2, preferably zero or 1 and particularly preferably zero;
K is the divalent residue of a coupling component of the aniline or naphthylamine series free of the amino group or the divalent residue of a coupling component of the heterocyclic series;
n is the number 1, 2, 3 or 4, preferably 1 or 2 and particularly preferably 1;
Z is the fiber-reactive radical of a fiber-reactive group or group -N (R¹) -Z, where in the case of n greater than 1 the radicals -N (R¹) -Z can have different meanings from one another;
the compounds of formula (1) have at least one, preferably several, such as two, three, four or five, sulfo groups.

Z is preferably a radical of the general formula (3)

in which mean:
X is halogen, such as chlorine and fluorine, or a group of the general formula (4)

in which
R² is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, or alkyl of 1 to 4 carbon atoms, such as ethyl in particular, which can be substituted by hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, such as Ethoxy and methoxy, carboxy, sulfo, sulfato or phosphato, or phenyl or naphthyl, both of which are substituted by 1, 2 or 3 substituents from the group halogen, such as chlorine and bromine, hydroxy, cyano, alkoxy from 1 to 4 C- Atoms such as ethoxy and especially methoxy, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxycarbonyl of 2 to 5 carbon atoms, such as ethoxycarbonyl and methoxycarbonyl, carboxy, sulfamoyl, sulfo and alkylsulfonyl with an alkyl radical of 1 to 4 carbon atoms, such as methylsulfonyl and ethylsulfonyl, of which preferably alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, carboxy and sulfo, can be substituted,
W is alkylene of 2 to 4 carbon atoms, preferably of 2 or 3 carbon atoms, such as 1,2-ethylene and 1,3-propylene, or phenylene or naphthylene, both of which are substituted by 1, 2 or 3 substituents Halogen group, such as chlorine and bromine, hydroxy, cyano, nitro, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxycarbonyl of 2 to 5 carbon atoms -Atoms, such as ethoxycarbonyl and methoxycarbonyl, carboxy, sulfamoyl and sulfo, preferably thereof alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, carboxy and sulfo, or phenylenealkylene or alkylenephenylene with an alkylene radical of is in each case 1 to 4 carbon atoms, in particular ethylene, and
A is vinyl or is ethyl which is substituted in the β-position by a substituent which can be split off by means of alkali to form the vinyl group;
Y is chlorine, cyanoamino or a group of the general formula (5)

in which
R³ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and methyl, or alkyl of 1 to 4 carbon atoms, such as especially ethyl, which is replaced by halogen, such as chlorine and bromine, hydroxy, cyano, alkoxy from 1 to 4 carbon atoms such as ethoxy and methoxy, alkoxycarbonyl of 2 to 5 carbon atoms, such as ethoxycarbonyl and methoxycarbonyl, carboxy, sulfo, sulfato or phosphato, or a group of the formula -W-SO₂-A with W and A one of the above meanings is and
R⁴ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and methyl, or alkyl of 1 to 4 carbon atoms, such as in particular ethyl, which is replaced by halogen such as chlorine and bromine, hydroxy, cyano, alkoxy from 1 to 4 C atoms, such as ethoxy and methoxy, alkoxycarbonyl of 2 to 5 C atoms, such as ethoxycarbonyl and methoxycarbonyl, carboxy, sulfo, sulfato or phosphato, or cycloalkyl of 5 to 8 C atoms, such as cyclohexyl, or a group of Formula -W-SO₂-A with W and A is one of the meanings mentioned above or is phenyl or naphthyl, both of 1 to 4 by 1, 2 or 3 substituents from the group halogen, such as chlorine and bromine, hydroxyl, cyano, alkoxy C atoms, such as ethoxy and in particular methoxy, alkyl of 1 to 4 C atoms, such as ethyl and in particular methyl, alkoxycarbonyl of 2 to 5 C atoms, such as ethoxycarbonyl and methoxycarbonyl, carboxy, sulfamoyl, sulfo and alkylsulfonyl with an alkyl radical of 1 to 4 carbon atoms, such as ethylsulfonyl and methylsulfonyl, may be substituted k can, or
R³ and R⁴ together represent an alkylene radical of 3 to 6 carbon atoms or a through a group -NH-, -O-, -CO-, -S-, -SO₂- or -N (R⁵) - (wherein R⁵ by sulfato or Sulfato substituted alkyl of 1 to 4 carbon atoms, such as ethyl) is an interrupted alkylene radical of 3 to 6 carbon atoms, which together with the nitrogen atom form a heterocyclic radical, such as the pyrrolidino, morpholino, piperidino or Piperazino residue.

Further preferred fiber-reactive radicals Z are those from the halogen-substituted pyrimidine series, such as a difluorochloropyrimidino, Trichloropyrimidino-, methylsulfonyl-chloro-pyrimidino- and methyl-fluoro-chloro-py rimidino residue, and further the rest of the dichloroquinoxaline.

In the general formulas (1) to (5) and in the following general ones  Formulas can be the individual formula elements, both different and same name within a general formula, in the context of their Meaning mutually identical or different meanings to have.

Alkaline eliminable substituents which are in the β-position of the ethyl group of A are, for example halogen atoms such as bromine and chlorine, ester groups organic carboxylic and sulfonic acids, such as alkyl carboxylic acids, optionally substituted benzene carboxylic acids and optionally substituted benzenesulfonic acids, such as the alkanoyloxy groups from 2 to 5 Carbon atoms, of which in particular acetyloxy, benzoyloxy, sulfobenzoyloxy, Phenylsulfonyloxy and Toluylsulfonyloxy, further acidic ester groups inorganic acids such as phosphoric acid, sulfuric acid and Thiosulfuric acid (phosphato, sulfato and thiosulfato groups) as well Dialkylamino groups with alkyl groups of 1 to 4 carbon atoms each, such as Dimethylamino and diethylamino. A is preferred β-chloroethyl or vinyl and particularly preferably β-sulfatoethyl.

The groups "sulfo", "carboxy", "thiosulfato", "phosphato" and "sulfato" include both their acid form and their salt form. Accordingly, sulfo groups are groups corresponding to the general formula -SO₃M, carboxy groups are groups corresponding to the general formula -COOM, thiosulfato groups are groups corresponding to the general formula -S-SO₃M, phosphato groups are groups corresponding to the general formula -OPO₃M₂ and sulfato groups are groups according to the general formula -OSO₃M, in which
M is a hydrogen atom or an alkali metal such as sodium, potassium or lithium, or another salt-forming metal.

R1 is preferably hydrogen, methyl or ethyl, especially hydrogen. R² is preferably hydrogen, methyl, ethyl or phenyl. Residues of formula (5) are preferred phenylamino, which is represented by 1, 2 or 3, preferably 1 or 2,  Substituents from the group halogen, such as chlorine and bromine, hydroxy, cyano, Ethoxy, methoxy, methyl, ethyl, carboxy and sulfo, preferably sulfo, may be substituted, or naphthylamino, preferably naphth-2-yl-amino, the is substituted by 1, 2 or 3 sulfo groups, or is preferably morpholino or a group of the general formula (4) given above or one Group of the general formula (4a)

in which W and A the above-mentioned, particularly preferred, Have meanings.

Aromatic residues E of a couplable and diazotizable compound of general formula H-E-NH₂ are, for example, those of the general Formulas (6a), (6b) and (6c)

in which
M has the meanings given above,
m is the number zero, 1 or 2 (this group being hydrogen if m is zero),
P¹ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and methoxy, cyano, sulfo, carboxy, hydroxy, fluorine, chlorine, bromine or trifluoromethyl and
P² is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, chlorine, alkanoylamino of 2 to 5 carbon atoms, such as acetylamino and propionylamino, amino, benzoylamino , Ureido, phenylureido, alkylureido having 1 to 4 carbon atoms in the alkyl radical, phenylsulfonyl or alkylsulfonyl having 1 to 4 carbon atoms.

Residues -K-N (R¹) -Z of coupling components of the general formula H-K-N (R¹) -Z (or radicals derived therefrom of the general formula H-K-N (R¹) H, into which the fiber-reactive radical Z is subsequently introduced must) are, for example, residues of the general formulas (7a) to (7f)

in which mean:
P¹, P², M, m, R¹ and Z have the above-mentioned, particularly preferred, meanings;
in formula (7a) the free bond which leads to the azo group is bonded to the aromatic nucleus in the ortho position to the hydroxyl group;
P³ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, chlorine, bromine, fluorine, sulfo, carboxy or trifluoromethyl;
P⁴ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, chlorine or sulfo;
P⁵ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, cyano, carboxy, carbalkoxy of 2 to 5 carbon atoms, such as carbomethoxy and carbethoxy, carbamoyl or phenyl, preferably methyl, carboxy, methoxycarbonyl, ethoxycarbonyl or phenyl and in particular Methyl or carboxy;
T is a benzene or naphthalene ring, preferably a benzene ring;
P⁶ is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl, or alkyl of 1 to 4 carbon atoms, such as methoxy, or cyano-substituted alkyl of 1 to 4 carbon atoms or phenyl, preferably alkyl of 1 to 4, by alkoxy Carbon atoms or phenyl;
P⁷ is hydrogen, chlorine, bromine, sulfo, carbamoyl, methylsulfonyl, phenylsulfonyl, cyano or sulfoalkyl of 1 to 4 carbon atoms, preferably hydrogen, sulfo, sulfoalkyl with an alkyl radical of 1 to 4 carbon atoms, such as sulfomethyl, cyano or carbamoyl ;
V is phenylene, preferably meta- or para-phenylene, which can be substituted by a sulfo group.

Groups corresponding to the general formulas (4) and (4a) are, for example:
N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N- [γ- (β'-sulfatoethylsulfonyl) propyl] amino, N- [γ- (vinylsulfonyl) propyl] amino, N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N- [β- (β'-sulfatoethylsulfonyl) ethyl] amino, N- [β- (vinylsulfonyl) ethyl] amino, N-methyl N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-ethyl-N- [β- (β'-chloroethylsulfonyl) propyl] amino, Nn-propyl-N- [β- (β '-Chloroethylsulfonyl) -ethyl] -amino, Nn-butyl-N- [β- (β'-chloroethylsulfonyl) -ethyl] -amino, N-carboxymethyl-N- [β- (β'-bromethylsulfonyl) -ethyl] - amino, N-sulfatomethyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N- (β-carboxyethyl) -N- [β '- (β''- chloroethylsulfonyl) ethyl] amino, N- (β-sulfatoethyl) -N- [β ′ - (β ′ ′ - chloroethylsulfonyl) ethyl] amino, N- (β-ethoxyethyl) -N- [β ′ - (β ′ ′ - chloroethylsulfonyl) ethyl ] -amino, N- phenyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N- (4-chlorophenyl) -N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N- (2-methylphenyl) -N-lβ- (β'-chlo rethylsulfonyl) ethyl] amino, N- (4-methoxyphenyl) -N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N- (3-sulfophenyl) -N- [β- (β'- chloroethylsulfonyl) ethyl] amino, N- (4-sulfophenyl) -N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N- (β-cyanoethyl) -N- [β '- (β''- chloroethylsulfonyl) ethyl] amino, N-phenyl-N- (β-vinylsulfonyl-ethyl) -amino, N- (4-chlorophenyl) -N- (β-vinylsulfonyl-ethyl) -amino, N- (2 -Methylphenyl) -N- (β-vinylsulfonyl-ethyl) -amino, N- (4-methoxyphenyl) -N- (β-vinylsulfonyl-ethyl) -amino, N- (3-sulfophenyl) -N- (β-vinylsulfonyl -ethyl) -amino, N- (4-sulfophenyl) -N- (β-vinylsulfonyl-ethyl) -amino, N-phenyl-N- [β- (β'-sulfatoethylsulfonyl) -ethyl] -amino, N- ( 4-chlorophenyl) -N- [β- (β'-sulfatoethylsulfonyl) ethyl] amino, N- (2-methylphenyl) -N- [β- (β'-sulfatoethylsulfonyl) ethyl] amino, N- ( 4-methoxyphenyl) - N- [β- (β′-sulfatoethylsulfonyl) ethyl] amino, N- (3-sulfophenyl) -N- [p- (β′-sulfatoethylsulfonyl) ethyl] amino, N- ( 4-sulfophenyl) -N- [β- (β'-sulfatoethylsulfonyl) -ethy l] -amino, N-methyl-N- [γ- (β'-chloroethylsulfonyl) propyl] - amino, N-ethyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amino, Nn-propyl -N- [γ- (β'-chloroethylsulfonyl) propyl] amino, Nn-butyl-N- [γ- (β'-chloroethylsulfonyl) propyl] - amino, N-carboxymethyl-N- [γ- (β '-Bromethylsulfonyl) propyl] amino, N- sulfatomethyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N- (β-carboxyethyl) -N- [γ' - (β '' - chloroethylsulfonyl) propyl] amino, N- (β-sulfatoethyl) -N- [γ '- (β''- chloroethylsulfonyl) propyl] amino, N- (β-sulfatoethyl) -N- [γ' - ( β ′ ′ - chloroethylsulfonyl) butyl] amino, N- (β-ethoxyethyl) -N- [6 ′ - (β ′ ′ - chloroethylsulfonyl) butyl] amino, N- (β-ethoxyethyl) -N- [ y ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amino, N-phenyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N- (4-chlorophenyl) -N- [γ- (β'- chloroethylsulfonyl) propyl] amino, N- (2-methylphenyl) -N- [γ- (β'- chloroethylsulfonyl) propyl] amino, N- (4-methoxyphenyl) -N- [γ- (β'- chloroethylsulfonyl) propyl] amino, N- (3-sulfophenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N- (4-sulfophenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N- (β-Cyanoethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amino, N-phenyl-N- (γ- vinylsulfonyl-propyl) amino, N- (4-chlorophenyl) -N - (γ-vinylsulfonylpropyl) amino, N- (2-methylphenyl) -N- (γ-vinylsulfonylpropyl) amino, N- (4-methoxyphenyl) -N- (γ- vinylsulfonylpropyl) amino , N- (3-sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amino, N- (4-sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amino, N-phenyl-N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N- (4-chlorophenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N- (2-methylphenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N- (4-methoxyphenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N- (3-sulfophenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N- (4-sulfophenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N-phenyl-N- [α-carboxy-γ- (β'-chloroethylsulfonyl) propyl] amino, N-phen yl-N- [α-ethoxycarbonyl-γ- (β'-chloroethylsulfonyl) propyl] amino, N-phenyl-N- [α-methoxycarbonyl-γ- (β'- chloroethylsulfonyl) propyl] amino, N- Phenyl-N- [β-methyl-γ- (β'-chloroethylsulfonyl) propyl] amino, N-phenyl-N- [β-ethyl-γ- (β'-chloroethylsulfonyl) propyl] amino, N- Phenyl-N- [δ- (β'-chloroethylsulfonyl) butyl] amino, N-phenyl-N- [ε- (β'-chloroethylsulfonyl) pentyl] amino and N-phenyl-N- [β- ( β'-chloroethylsulfonyl) hexyl] amino, bis-N, N- [γ- (β'-chloroethylsulfonyl) propyl] amino, bis-N, N- [γ- (β'- sulfatoethylsulfonyl) propyl] - amino, bis-N, N- [γ- (vinylsulfonyl) propyl] amino, bis-N, N- [β- (β'-chloroethylsulfonyl) ethyl] amino, bis-N, N- [β- (β′-sulfatoethylsulfonyl) ethyl] amino, bis-N, N- [β- (vinylsulfonyl) ethyl] amino, 4- (β-sulfatoethylsulfonyl) phenylamino, 3- (β-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5- (β-sulfatoethylsulfonyl) phenylamino, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phe nylamino, 2-sulfo-4- (β-sulfatoethylsulfonyl) phenylamino, 2-hydroxy-5- (β-sulfatoethylsulfonyl) phenylamino, 2-bromo-5- (β-sulfatoethylsulfonyl) phenylamino, 4- [β- ( β'-sulfatoethylsulfonyl) ethyl] phenylamino, 1-sulfo-6- (β-sulfatoethylsulfonyl) naphth-2-ylamino, 8-sulfo-6- (β-sulfatoethylsulfonyl) naphth-2-ylamino, 6-sulfo -8- (β-sulfatoethylsulfonyl) -naphth-2-ylamino, 6- (β-sulfatoethylsulfonyl) -naphth-2-ylamino and 8- (β-sulfatoethylsulfonyl) -naphth-2-ylamino.

Further fiber-reactive radicals Z are, for example: 2,4-dichloro-1,3,5-triazin-6-yl, 2,4-difluoro-5-chloropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 2- Methylsulfonyl-5-chloro-4-methyl-pyrimidin-6-yl, 4-methyl-2-fluoro-5-chloro pyrimidin-6-yl, 2,3-dichloro-quinoxalin-6-carbonyl and 2,4-difluoropyrimidin-6-yl, furthermore residues corresponding to the general formula (8a)

in which X is chlorine, fluorine or cyanoamino, A has one of the above-mentioned particularly preferred meanings, R² is hydrogen, ethyl, methyl, β-hydroxyethyl, β-sulfatoethyl, phenyl, 3-sulfophenyl or 4-sulfophenyl and W¹ 1, 2-ethylene, 1,3-propylene, 2-methyl-1,2-ethylene, 2-methyl-1,3-propylene, 2-ethoxy-ethyl, 1,4-phenylene, 1,3-phenylene, 2- Methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene, 2-sulfo-1,4-phenylene, 2-hydroxy-1, 5-phenylene, 2-bromo-1,5-phenylene or 4- (2'-eth) -phen-1,1'-ylene, the 1-position in these groups being connected to the N atom, or 1-Sulfo-naphth-2,6-ylene, 6-sulfo-naphth-2,8-ylene, naphth-2,6-ylene and naphth-2,8-ylene, with the 2-position in these groups with connected to the N atom,
further residues corresponding to the general formula (8b)

in which X and A have one of the above-mentioned, particularly preferred meanings and W 1 has one of the above-mentioned meanings, preferably 1,3-propylene or 1,2-ethylene,
furthermore groups corresponding to the general formula (8c)

in which X is chlorine or fluorine and Y¹ is amino, methylamino, Ethylamino, dimethylamino, diethylamino, bis (β-hydroxyethyl) amino, β- Hydroxyethylamino, phenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 2-sulfophenylamino, 2,5-disulfophenylamino, 2,4-disulfophenylamino, 2- Carboxy-phenylamino, 4-carboxy-phenylamino, 2-sulfo-4-methoxy-phenylamino, 2-sulfo-4-methylphenylamino, 3-sulfo-4-methylphenylamino, 2-methyl phenylamino, 3-methylphenylamino, 4-methylphenylamino, 2,5-dimethyl phenylamino, 2,4-dimethylphenylamino, 2-methoxyphenylamino, 3-methoxy phenylamino, 4-methoxy-phenylamino, 2- or 3- or 4-ethoxy-phenylamino, N-ethylphenylamino, N-methylphenylamino, N- (β-hydroxyethyl) phenylamino, 2-chlorophenylamino, 3- or 4-chlorophenylamino, 2,5-dichlorophenylamino, Naphth-2-yl-amino, 1-sulfonaphth-2-yl-amino, 3,6,8-trisulfonaphth-2-yl-amino, 4,6,8-trisulfonaphth-2-yl-amino, 4,8-disulfonaphth-2-yl-amino, 1,5-disulfon naphth-2-yl-amino, N-morpholino, N-piperidino, N-piperazino, N-pyrrolidino, N'- (β-Sulfatoethyl) -N-piperazino or N ′ - (β-hydroxyethyl) -N-piperazino.

Of the azo compounds of the general formula (1) according to the invention in particular those of the general formulas (1A), (1B) and (1C)

preferred, in which E, v, K, R¹, Z and n one of the above, have particularly preferred meanings, R is hydrogen, methyl or Is methoxy and B is -NH- or -O-.

Of these, in particular those azo compounds are to be emphasized that the general formulas (9a), (9b), (9c) and (9d)

correspond in which mean:
D is the benzoimidazolidin-2-one-4-yl or -5-yl radical;
M has one of the meanings given above;
R⁶ is hydrogen or sulfo;
the group -NH-Z¹ is in formula (9a) in the meta or para position to the group -NH-Z¹ and in formula (9b) in the ortho or meta position to R⁶;
E¹ is 1,4-phenylene, which may be substituted by 1 or 2 substituents from the group sulfo, methyl, methoxy, ureido and acetylamino, or is 1,4-naphthylene, which is substituted by a sulfo group in 6-, 7- or 8 Position, preferably 6- or 7-position, may be substituted;
E² is 1,4-phenylene, which can be substituted by 1 or 2 substituents from the group sulfo, methyl, methoxy, ureido and acetylamino, or is 1,4-naphthylene, which is substituted by a sulfo group in 6-, 7- or 8 Position, preferably 6- or 7-position, may be substituted;
Z 1 is a radical of the general formula (10A) and defined and defined below
Z² is a radical of the general formula (10B) given and defined below

in which
X is chlorine or fluorine,
Y² is phenylamino which may be substituted by 1 or 2 sulfo groups or a group of the general formula -SO₂-A with A of the abovementioned meaning or by 1 or 2 sulfo groups and one of these groups -SO₂-A, or naphthylamino, preferably naphth- 2-yl-amino, which can be substituted by 1, 2 or 3 sulfo groups or by a group of the general formula -SO₂-A with A of the abovementioned meaning or by 1 or 2 sulfo groups and this group -SO₂-A, or a group of the general formula (11a) or (11b)

is in which
U represents -O-, -S-, -SO₂- or -NH- or a group of the formula

is where R ^{A is} hydrogen, β-hydroxyethyl or β-sulfatoethyl,
n represents the number 2 or 3,
A has one of the meanings given above and
R ° is hydrogen, methyl, ethyl, phenyl or a radical of the formula - (CH₂) _n -SO₂-A with n and A of the meanings given above, and
Q is phenyl which can be substituted by 1, 2 or 3 sulfo groups or by a group of the general formula -SO₂-A with A of the abovementioned meaning or by 1 or 2 sulfo groups, preferably 1 sulfo group, and this group -SO₂-A , or naphthyl, preferably 2-naphthyl, which can be substituted by 1, 2 or 3 sulfo groups or by 1 group of the general formula -SO₂-A with A of the abovementioned meaning or by 1 or 2 sulfo groups and this group -SO₂-A can.

The present invention further relates to methods for producing the Azo compounds of general formula (1) according to the invention, which thereby are characterized in that a compound of the general formula (12)  

in which R and G are one of the above, particularly preferred, Have meanings, diazotized and with a compound of general Formula (13)

in which E, v, K, R¹, Z and n are one of the above, in particular preferred, have meanings, couples, or that a compound of the general formula (14)

with G, R, E and v one of the above-mentioned, particularly preferred, Meanings diazotized and with a compound of the general formula H-K-Z couples with K and Z of the meaning given above, or that one Compound of the general formula (15)

in which G, R, v, K, R¹ and n are one of the above, in particular  preferred, have meanings with a compound of the general formula X ° -Z, in which X ° represents chlorine, bromine or fluorine and Z the above Has meaning, preferably thereof with a radical of the general Formula (16)

in which X and Y are the above-mentioned, particularly preferred, Have meanings and Hal stands for chlorine or fluorine.

The diazotization reactions take place in a manner known per se Procedure in aqueous medium at a pH less than 2 and at a temperature between -5 ° C and + 15 ° C. The coupling reactions are also carried out in a manner known per se in aqueous Solution or in an aqueous organic medium at a pH between 4 and 9, preferably between 5 and 7, and at a temperature between 0 ° C and 40 ° C, preferably between 5 ° C and 25 ° C.

The condensation reactions between the compounds of the general Formula (15) and the fiber-reactive starting compound of the general formula X ° -Z with X ° and Z of the abovementioned meaning, such as that preferably above defined general formula (16), are also carried out in aqueous or aqueous-organic medium in suspension or solution. If you run this Reactions in an aqueous-organic medium, so is the organic Medium, for example acetone, dimethylformamide, dimethyl sulfoxide or N- Methyl pyrrolidone. The one that becomes free during implementation becomes advantageous Hydrogen halide continuously by adding aqueous alkali or Alkaline earth metal hydroxides, carbonates or bicarbonates neutralized. Usually the reaction takes place at a temperature between -5 ° C and + 95 ° C and at a pH between 3 and 11, preferably between 4 and 6, in the case of  X ° or Hal is fluorine, preferably at a temperature between 20 and 40 ° C and at a pH between 4 and 10, particularly preferably between 4 and 7.

The starting compounds of the general formula (12) are known from the literature (See, e.g., Dyes and Pigments 21 (1993), 123, and Ann. Chim. 49 (1959), 1809). Furthermore, the other starting compounds are like Compounds of the general formulas H-E-NH₂ and H-K-N (R¹) H and the numerous fiber-reactive starting compounds of the general formula X ° -Z described in the literature and often for the production of fiber-reactive Dyes used (see, for example, the European patent application Publications no. 0 541 057, 0 542 214 and 0 548 795) or leave analogous to the procedures specified there with corresponding Establish output connections.

The starting compounds correspond to the general formula (17)

with R², W and A of the meanings given above, which as amino residues in the Starting compounds of the general formulas (13) and (16) are included and serve to synthesize them are known in some cases, for example from European Patent Application Publications No. 0 070 806. 0 070 807, 0 374 758, 0 499 588, 0 541 057 and 0 568 860 as well as from the U.S. Patents 4,908,436 and 5,138,041 and the British Patent 1,576,237. The amino compounds of the general formula (17) in which R² represents an optionally substituted phenyl radical and W is 1,3-propylene The rest, however, have not yet been described per se. You let yourself for example, in such a way that N-allyl-N-acetyl-aniline (see J. Org. Chem. 14, 1099 (1949)) analogous to that in German Offenlegungsschrift No. 41 06 106 described procedure with 2-mercapto-ethanol in  In the presence of a radical initiator, the N- [γ- (β′- Hydroxyethylthio) propyl] -N-acetyl-aniline compound to the sulfonyl compound oxidized, for example by means of hydrogen peroxide in the presence of a catalytic amount of a transition metal compound such as Tungsten oxide. The sulfonyl compound thus obtained becomes the acetyl group in the alkaline or acidic range, preferably in hydrochloric acid aqueous solution, such as in 5 to 30% aqueous hydrochloric acid, at one temperature split off hydrolytically between 80 and 100 ° C.

The N-phenyl-N- [γ- (β'-hydroxyethylsulfonyl) propyl] amine thus obtained can be from the neutral aqueous synthesis solution from the aqueous phase be separated. Its β-hydroxyethylsulfonyl group can be removed esterify usual methods, for example by means of concentrated Sulfuric acid at a temperature between 10 and 30 ° C in the β-sulfatoethylsulfonyl compound or with thionyl chloride or gaseous Transfer hydrogen chloride to the β-chloroethylsulfonyl compound.

Starting compounds of the general formula (17) are, for example N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- [γ- (β'-sulfatoethylsulfonyl) propyl] - amine, N- [γ- (vinylsulfonyl) propyl] amine, N- [β- (β'-chloroethylsulfonyl) ethyl] amine, N- [β- (β'-sulfatoethylsulfonyl) ethyl] amine, N- [β- (vinylsulfonyl) ethyl] amine, N-methyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amine, N-ethyl-N- [β- (β'- chloroethylsulfonyl) propyl] amine, N-n-propyl-N-β- (β'-chloroethylsulfonyl) ethyl] - amine, N-n-butyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amine, N-carboxymethyl-N- [β- (β'-bromethylsulfonyl) ethyl] amine, N-sulfatomethyl-N- [β- (β'-chloroethylsulfonyl) - ethyl] amine, N- (β-carboxyethyl) -N- [β ′ - (β ′ ′ - chloroethylsulfonyl) ethyl] amine, N- (β- Sulfatoethyl) -N- [β ′ - (β ′ ′ - chloroethylsulfonyl) ethyl] amine, N- (β-ethoxyethyl) -N- [β′- (β ′ ′ - chloroethylsulfonyl) ethyl] amine, N-phenyl-N- [β- (β′-chloroethylsulfonyl) ethyl] - amine, N- (4-chlorophenyl) -N-lβ- (β'-chloroethylsulfonyl) ethyl] amine, N- (2- Methylphenyl) -N- [β- (β'-chloroethylsulfonyl) ethyl] amine, N- (4-methoxyphenyl) -N- [β- (β'-chloroethylsulfonyl) ethyl] amine, N- (3-sulfophenyl) -N- [β- (β'- chloroethylsulfonyl) ethyl] amine, N- (4-sulfophenyl) -N- [β- (β'-chloroethylsulfonyl) - ethyl] amine, N- (β-cyanoethyl) -N- [β ′ - (β ′ ′ - chloroethylsulfonyl) ethyl] amine, N-phenyl-  N- (β-vinylsulfonyl-ethyl) amine, N- (4-chlorophenyl) -N- (β-vinylsulfonyl-ethyl) amine, N- (2-methylphenyl) -N- (β-vinylsulfonyl-ethyl) amine, N- (4-methoxyphenyl) -N- (β vinylsulfonyl-ethyl) amine, N- (3-sulfophenyl) -N- (β-vinylsulfonyl-ethyl) amine, N- (4- Sulfophenyl) -N- (β-vinylsulfonyl-ethyl) -amine, N-phenyl-N- [β- (β′- sulfatoethylsulfonyl) ethyl] amine, N- (4-chlorophenyl) -N- [β- (β′- sulfatoethylsulfonyl) ethyl] amine, N- (2-methylphenyl) -N- [β- (β'- sulfatoethylsulfonyl) ethyl] amine, N- (4-methoxyphenyl) -N- [β- (β′- sulfatoethylsulfonyl) ethyl] amine, N- (3-sulfophenyl) -N- [β- (β′- sulfatoethylsulfonyl) ethyl] amine, N- (4-sulfophenyl) -N- [β- (β′- sulfatoethylsulfonyl) ethyl] amine, N-methyl-N- [γ- (β'-chloroethylsulfonyl) propyl] - amine, N-ethyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N-n-propyl-N- [γ- (β'- chloroethylsulfonyl) propyl] amine, N-n-butyl-N- [γ- (β'-chloroethylsulfonyl) propyl] - amine, N-carboxymethyl-N- [γ- (β'-bromethylsulfonyl) propyl] amine, N- Sulfatomethyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (β-carboxyethyl) -N- [γ′- (β ′ ′ - chloroethylsulfonyl) propyl] amine, N- (β-sulfatoethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amine, N- (β-sulfatoethyl) -N- [δ ′ - (β ′ ′ - chloroethylsulfonyl) - butyl] amine, N- (β-ethoxyethyl) -N- [δ ′ - (β ′ ′ - chloroethylsulfonyl) butyl] amine, N- (β- Ethoxyethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amine, N-phenyl-N- [γ- (β′- chloroethylsulfonyl) propyl] amine, N- (4-chlorophenyl) -N- [γ- (β'-chloroethylsulfonyl) - propyl] amine, N- (2-methylphenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (4- Methoxyphenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (3-sulfophenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (4-sulfophenyl) -N- [γ- (β'- chloroethylsulfonyl) propyl] amine, N- (β-cyanoethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) - propyl] amine, N-phenyl-N- (γ-vinylsulfonyl-propyl) amine, N- (4-chlorophenyl) -N- (γ- vinylsulfonyl-propyl) amine, N- (2-methylphenyl) -N- (γ-vinylsulfonyl-propyl) amine, N- (4-methoxyphenyl) -N- (γ-vinylsulfonyl-propyl) -amine, N- (3-sulfophenyl) -N- (γ vinylsulfonyl-propyl) -amine, N- (4-sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amine, N- Phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine, N- (4-chlorophenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amine, N- (2-methylphenyl) -N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine, N- (4-methoxyphenyl) -N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine, N- (3-sulfophenyl) -N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine, N- (4-sulfophenyl) -N- [γ- (β′-  sulfatoethylsulfonyl) propyl] amine, N-phenyl-N- [α-carboxy-γ- (β′- chloroethylsulfonyl) propyl] amine, N-phenyl-N- [α-ethoxycarbonyl-γ- (β'- chloroethylsulfonyl) propyl] amine, N-phenyl-N- [α-methoxycarbonyl-γ- (β'- chloroethylsulfonyl) propyl] amine, N-phenyl-N- [β-methyl-γ- (β'-chloroethylsulfonyl) - propyl] amine, N-phenyl-N- [β-ethyl-γ- (β'-chloroethylsulfonyl) propyl] amine, N-phenyl-N- [δ- (β'-chloroethylsulfonyl) butyl] amine, N-phenyl-N- [ε- (β'- chloroethylsulfonyl) pentyl] amine, N-phenyl-N- [β- (β'-chloroethylsulfonyl) hexyl] - amine, 3- and 4- (β-sulfatoethylsulfonyl) aniline, 2-methoxy-5- (β- sulfatoethylsulfonyl) aniline, 2-, 5-dimethoxy-4- (β-sulfatoethylsulfonyl) aniline, 2- Methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) aniline, 2-sulfo-4- (β- sulfatoethylsulfonyl) aniline, 2-hydroxy- and 2-bromo-5- (β-sulfatoethylsulfonyl) - aniline, 4- [β- (β'-sulfatoethylsulfonyl) ethyl] aniline, 1-sulfo-6- (β- sulfatoethylsulfonyl) -2-naphthylamine, 8-sulfo-6- (β-sulfatoethylsulfonyl) -2- naphthylamine, 6-sulfo-8- (β-sulfatoethylsulfonylamine) and 8- and 6- (β- Sulfatoethylsulfonyl) -2-naphthylamine.

Starting compounds which are used to prepare dis- and Trisazo compounds of the general formula (1) initially as Coupling component and then, in the form of the amino Azo compound serve as the diazo component and the general formula H-E-NH₂ correspond, for example, aniline, 3-methyl-aniline, 2-methoxy-5- methyl aniline, 2,5-dimethyl aniline, 3-ureido aniline, 3-acetylamino aniline, 3-propionylamino-aniline, 3-butyrylamino-aniline, 3-methoxy-aniline, 2-methyl-5- acetylamino-aniline, 2-methoxy-5-acetylamino-aniline, 2-methoxy-5-methyl-aniline, 3- (hydroxyacetylamino) aniline, 1,3-diaminobenzene, 1,3-diaminobenzene-4- sulfonic acid, 2- and 3-sulfo-aniline, 3-hydroxy-aniline, 1-amino-naphthalene-6-, -7- or -8-sulfonic acid, 1-amino-2-methoxy-naphthalene-6-sulfonic acid, 2-amino-5- hydroxy-naphthalene-7-sulfonic acid, 2-amino-5-hydroxy-naphthalene-1,7- disulfonic acid, 2-amino-8-hydroxy-naphthalene-6-sulfonic acid, 2- (4'-amino-benzoylamino) -5-naphthol-7-sulfonic acid, 1- (4'-amino-2'-sulfo phenyl) -3-methyl-5-pyrazolone, 1- (4'-amino-2'-sulfo-phenyl) -3-carboxy-5- pyrazolone and N- (acetoacetyl) -3-sulfo-4-amino-anilide.  

Coupling components according to the general formula H-K-N (R¹) H, the can serve to build up the azo compounds according to the invention and in whose amino groups the rest of the fiber-reactive group are introduced aniline, 3-methyl-aniline, 2,5-dimethyl-aniline, 2,5- Dimethoxy aniline, 3-methoxy aniline, 3-acetylamino aniline, 3-propionylamino aniline, 3-butyrylamino-aniline, 3-benzoylamino-aniline, 3- (hydroxyacetylamino) - aniline, 3-ureido-aniline, 2-methyl-5-acetylamino-aniline, 2-methoxy-5-acetylamino aniline, 2-methoxy-5-methyl-aniline, 1-amino-naphthalene-6-sulfonic acid, 1-amino naphthalene-7-sulfonic acid, 4-sulfo-1,3-diamino-benzene, 6-sulfo-2-methoxy-1- amino-naphthalene, 5,7-disulfo-2-aminonaphthalene, 1-amino-8-hydroxy- naphthalene-4-sulfonic acid, 1-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino 8-hydroxynaphthalene-2,4-disulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-hydroxy-4,6-disulfonic acid, 1-amino-8-hydroxy-naphthalene-2,4,6- trisulfonic acid, 2- (methylamino) - and 2- (ethylamino) -5-hydroxynaphthalene-7- sulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2- (methylamino) - and 2- (ethylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8- hydroxynaphthalene-3,6-disulfonic acid, 2- (4'-amino-3'-sulfophenylamino) -5- hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxy-2- (phenylazo) naphthalene 3,6-disulfonic acid, 1-amilno-8-hydroxy-2- (4'-sulfophenylazo) -naphthalene-3,6- disulfonic acid, 1-amino-8-hydroxy-2- (2 ′, 5′-disulfophenylazo) -naphthalene-3,6- disulfonic acid, 1- (β-aminoethyl) -3-cyano-4-methyl-6-hydroxy-pyrid-2-one, 1- (γ-aminopropyl) -3-sulfomethyl-4-methyl-6-hydroxy-pyrid-2-one, 1,3-diaminobenzene, 3- [N, N-di- (β-hydroxyethyl)] - amino-aniline, 3- [N, N-di- (β- sulfatoethyl)] - amino-4-methoxy-aniline, 3- (sulfobenzylamino) aniline, 3- (sulfobenzoylamino) -4-chloro-aniline and 3- [N, N-di- (sulfobenzyl)] - amino-aniline, 2-sulfo-5-acetylamino-aniline, 2-amino-5-naphthol-7-sulfonic acid, 2-amino-8- naphthol-6-sulfonic acid, 1- (4'-aminobenzoyl) amino-8-hydroxynaphthalene-3,6- disulfonic acid, 1- (4'-aminobenzoyl) amino-8-hydroxynaphthalene-4,6- disulfonic acid, 1- (3'-aminobenzyl) amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1- (3'-aminobenzoyl) amino-8-hydroxy-naphthalene-4,6-disulfonic acid, 1- (2'-aminobenzoyl) amino-8-hydroxy-naphthalene-3-6-disulfonic acid, 1- (2'-aminobenzoyl) amino-8-hydroxyphaphthalene-4,6-disulfonic acid,  2- (3'-aminobenzoyl) amino-5-hydroxy-naphthalene-7-sulfonic acid, 2- (2'-aminobenzoyl) amino-5-hydroxy-naphthalene-7-sulfonic acid, 2- (4'-aminobenzoyl) amino-8-hydroxynaphthalene-6-sulfonic acid, 2- (3'-aminobenzoyl) amino-8-hydroxynaphthalene-6-sulfonic acid, 2- (2′-aminobenzoyl) amino-8-hydroxynaphthalene-6-sulfonic acid, 2- (4'-aminobenzoyl) amino-5-naphthol-7-sulfonic acid, 1- (4'-amino- or 1- (4'-acetylamino-2-sulfophenyl) -3-methyl- or -3-carboxy-5-pyrazolone, N- (3-sulfo-4-amino) -acetoacetyl-anilide, (1- (3'-aminobenzoyl) - or 1- (4'-aminobenzoyl) amino-8-naphthol-3,6- or -4,6-disulfonic acid, 1- Acetylamino-8-naphthol-3,6- or -4,6-disulfonic acid, 2-acetylamino-5-naphthol- 7-sulfonic acid, 2-acetylamino-8-naphthol-6-sulfonic acid, 3-acetylamino-8- naphthol-6-sulfonic acid, 3- (N-methylamino) -8-naphthol-6-sulfonic acid, 1- (3′- Amino- or 1- (3'-acetylamino-6'-sulfophenyl) -3-methyl- or -3-carboxy-5- pyrazolone, 2- (N-methyl-N-acetylamino) - or 2-methylamino-5-naphthol-7- sulfonic acid, N-methyl-aniline and N-propyl-m-toluidine.

The deposition of the azo compounds produced according to the invention General formula (1) from the synthesis approaches follows in general known methods either by precipitation from the reaction medium by means of electrolytes, such as sodium chloride or potassium chloride, or by evaporating the reaction solution, for example by spray drying, a buffer substance can be added to this reaction solution.

The azo compounds of the general formula (1) - in the following dyes (1) - are suitable for dyeing and printing a wide variety Materials such as silk, leather, wool, polyamide fibers and polyurethanes, and in particular cellulose-containing fiber materials of all kinds. Such fiber materials are, for example, the natural cellulose fibers such as cotton, linen and Hemp, as well as cellulose and regenerated cellulose. The dyes (1) are too suitable for dyeing or printing fibers containing hydroxy groups, which in Blended fabrics are included, e.g. B. of mixtures of cotton with Polyester fibers or polyamide fibers.  

The dyes (1) can be applied to the fiber material in different ways apply and fix on the fiber, especially in the form of aqueous Dye solutions and printing pastes. They are suitable for both Exhaust process as well as for dyeing according to the foulard dyeing process, after which the goods with aqueous, optionally saline dye solutions impregnated and the dye after an alkali treatment or in the presence of alkali, optionally under the action of heat. Especially the dyes according to the invention are suitable for the so-called Cold residence process, after which the dye together with the alkali on the Foulard applied and then by storage for several hours Room temperature is fixed. After fixing, the stains or Print with cold and hot water, possibly with the addition of one dispersing and promoting the diffusion of the unfixed portions Medium, rinsed thoroughly. These dyeing and printing processes are numerous in the general specialist literature as well as in the patent literature, such as in the publications mentioned at the beginning.

The present invention therefore also relates to the use of Dyes (1) for dyeing (including printing) these materials or Process for dyeing (and printing) such materials in and of itself usual procedure in which a dye (1) is used as the colorant is by placing the dye (1) in an aqueous medium on the material applied and using heat or an alkaline Connection or by means of both fixed on the material.

The dyes (1) are notable for high reactivity and good fixing properties and a very good build-up ability. You can therefore after Pull-out dyeing processes are used at low dyeing temperatures and require only short steaming times with pad-steam processes. The degrees of fixation are high, and the unfixed portions can be washed out easily the difference between the degree of exhaustion and the degree of fixation is remarkably small, d. H. the soap loss is very low. The dyes (1) are also particularly suitable  for printing, especially on cotton, but also for printing on nitrogen-containing fibers, e.g. B. of wool or silk or of mixed fabrics, that contain wool or silk.

The dyes (1) are particularly suitable for low-salt extractants. Dyeing processes, which are characterized in that the dyeing liquor one or several electrolyte salts, such as sodium chloride, potassium chloride and sodium sulfate, from a total of 20 to 40 g / l (instead of the usual 50 to 80 g / l in technology) contain. Despite this low electrolyte salt concentration in the pull-out Dyeing liquor draw the dyes (1) onto the fiber material evenly and in high color strength, which is why level and strong colorations are obtained become. The high level of coloration also exists with low-salt dyeing when light shades of color are desired and the dyes (1) are only available in small amounts can be used in the dyeing liquor. By the possibility low-salt dyeing with the dyes (1) results Application technology advantage, especially from an ecological point of view.

The dyeings and prints produced with the dyes (1) have especially on cellulose fiber materials, a high color strength and a high Fiber-dye binding stability in both acidic and alkaline Area, continue to have good lightfastness and very good Wet fastness properties, such as washing, water, seawater, over-dyeing and Sweat fastness, as well as good pleating fastness, ironing fastness and Fastness to rubbing.

The following examples serve to explain the invention. The parts are Parts by weight, the percentages are percentages by weight, if not noted otherwise. Parts by weight relate to parts by volume such as kilograms to liters.

The compounds described by formula in the examples are in the form of specified free acid; generally they are in the form of their  Alkali metal salts, such as lithium, sodium or potassium salts, prepared and isolated and used in the form of their salts for coloring. Likewise, in the following examples, especially table examples, in the form of the free Starting compounds and components mentioned as such or in acid Form of their salts, preferably alkali metal salts, used in the synthesis become.

The absorption maxima (λ _max ) in the visible range specified for the dyes according to the invention were determined on the basis of their alkali metal salts in aqueous solution. In the table examples, the λ _max values are given in brackets when specifying the color; the wavelength specification refers to nm.

Example 1

a) A suspension of 37.6 parts of cyanuric chloride in 2000 parts of water are at a temperature between 0 and 3 ° C and a pH between 2 and 2.5 with about 50.6 parts of aniline-2.5- disulfonic acid added. The mixture is stirred for about 30 minutes and then gives an aqueous suspension of 50 parts of 3-amino-8-hydroxy-6-sulfo add naphthalene in 1000 parts of water, adjust the pH to 4.5, warmed to 40 ° C and stirred the batch in compliance with these conditions about two hours more.

b) 29.8 parts of 5-amino-benzoimidazolidin-2-one in 3000 parts of water at 0 ° C to 5 ° C with good stirring with 60 parts of a 31% aqueous Hydrochloric acid and 14 parts of sodium nitrite are added. The approach is still stirred 30 minutes at this temperature and then gives the thus obtained Diazonium salt solution within about 15 minutes while maintaining a pH Value between 6 and 7 to the solution prepared under a) as Coupling component serving compound 3-N- [2 ′ - (2 ′ ′, 5 ′ ′ - disulfophenyl) - amino-4'-chloro-1 ', 3', 5'-triazin-6'-yl] amino-8-hydroxy-6-sulfo-naphtha-haline. Man the mixture is stirred for about 12 hours while maintaining this pH and at a temperature between 20 and 25 ° C and then isolates the obtained azo compound according to the invention, which, in the form of the free acid written the formula

corresponds, as alkali metal salt (sodium salt) in a conventional manner, for example by salting out with sodium chloride.  

The monoazo compound according to the invention shows very good fiber-reactive Dye properties and provides after in technology for fiber reactive Dyes usual dyeing and printing processes on the in the description mentioned fiber materials, in particular on cellulose fiber materials, such as Cotton, strong red dyeing and prints with good fastness properties.

Example 2

14.9 parts of 5-amino-benzoimidazolidin-2-one are placed in 600 parts of water good stirring at a temperature between 0 and 5 ° C with 30 parts of a aqueous 31% hydrochloric acid and 6.9 parts of sodium nitrite. You stir the batch for another 30 minutes at this temperature and then gives the obtained diazonium salt solution within 15 minutes to a solution of 54.5 parts of 1-N- (2′-morpholino-4′-fluoro-1 ′, 3 ′, 5′-triazin-6′-yl) amino-8-hydroxy-- 3,6-disulfonaphthalene (manufactured according to the European patent application Publication No. 0 542 082) in 1000 parts of water and stir the mixture about 12 hours while maintaining a pH of 7 and at one Temperature between 20 and 25 ° C after.

The azo compound according to the invention, which, in the form of the free acid written the formula

has, is from the synthesis solution in the usual manner, for example by Salting out with sodium chloride, isolated as alkali metal salt (sodium salt).  

It shows very good fiber-reactive dye properties and stains, for example Cellulose fiber materials using the usual application methods in strong, brilliant violet tones with a high degree of fixation.

Example 3

30 parts of 4-amino-benzoimidazolidin-2-one are mixed in a mixture of 3000 Parts of water and 60 parts of a 31% aqueous hydrochloric acid at one Temperature from 0 to 5 ° C diazotized by adding 14 parts of sodium nitrite. The mixture is stirred for a further 30 minutes and the resulting mixture is added Diazonium salt solution while maintaining a pH of 6 to 7 within of about 15 minutes to the solution of Example 1a) Coupling component. The coupling reaction is carried out within this pH Range with further stirring at 20 to 25 ° C for about 12 hours End and then isolate the azo compound of the formula (in Form of free acid)

as an alkali metal salt (sodium salt) in a conventional manner, for example by Spray drying the aqueous synthesis solution or by salting out the Compound from the synthesis solution with sodium chloride.

The azo compound according to the invention shows very good fiber-reactive Dye properties and colors the materials mentioned in the description,  in particular cellulose-containing fiber materials, such as cotton, according to the in the Technology for fiber-reactive dyes usual application methods in strong, reddish brown tones with good fastness properties.

Example 4

14.9 parts of 4-amino-benzoimidazolidin-2-one are diazotized in aqueous hydrochloric acid Solution (600 parts of water and 30 parts of an aqueous 31% hydrochloric acid) 0 to 5 ° C using 6.9 parts of sodium nitrite. After adding the Sodium nitrite after 30 minutes at 0 to 5 ° C and gives the obtained diazonium salt solution then to that according to the instructions of the Example 2 produced coupling component. You stir it Reaction mixture for about 12 hours while maintaining a pH of about 7 and a temperature of 20 to 25 ° C and then isolates the Azo compound according to the invention in a conventional manner.

Written in the form of free acid, it has the formula

and shows good fiber-reactive dye properties. For example, it delivers Cotton according to the dyeing and printing processes customary in technology brilliant bluish red tones with good fastness properties.

Example 5

59 parts of 2- (8′-hydroxy-3 ′, 6′-disulfonaphth-1′-yl-amino) -4-chloro-6- (3 ′ ′ - sulfophenylamino) -1,3,5-triazine are mixed with 29 parts of 4- (β-sulfatoethylsulfonyl) - aniline in 1000 parts of water at a pH between 3 and 4 and one  Temperature between 85 and 95 ° C within four hours implemented. The reaction solution is then cooled to 20 to 25 ° C. and gives a pH between 6 and 7 according to the instructions of the Example 1 prepared diazonium salt solution from 14.9 parts of 5-amino benzoimidazolidin-2-one added. You stir for a while to finish the Coupling reaction after.

The azo dye according to the invention, which, written in the form of the free acid, the formula

has, is isolated in the usual way as an alkali metal salt. He shows very good ones fiber-reactive properties and dyes cotton, for example, in brilliant colors violet shades with good fastness properties.

Example 6

31.7 parts of 3-amino-4,6-disulfo-8-hydroxy-naphthalene are added in 500 parts Water at a pH between 2 and 2.5 and at a temperature between 0 and 5 ° C within 2 to 3 hours with 19 parts of cyanuric chloride implemented. Then 36 parts of bis- (β- chloroethylsulfonyl-ethyl) amine hydrochloride and leads to the implementation a pH between 6 and 6.5 and a temperature between 40 and 50 ° C with stirring to the end. The mixture is then left to 20 to 25 ° C. cool and then give a pH between 6 and 7  a diazonium salt solution prepared according to Example 1 from 14 parts of 5-amino benzimidazolidin-2-one added. Continue stirring for about 12 hours and then isolates the azo dye of the invention, in the form of the free Acid written, the formula

has, in the usual way as an alkali metal salt. It shows very good fiber-reactive Dye properties and dyes cotton in red shades, for example with good fastness properties.

Examples 7 to 21

The following table examples show further examples according to the invention Azo compounds according to the general formula (A)

described with the help of their formula components. You let yourself in inventive manner, for example according to one of the above examples, by means of the from the respective table example in connection with the formula (A) apparent components (the diazo component D-NH₂, the Coupling component H-K ° -NH₂, cyanuric fluoride or cyanuric chloride, optionally an amino compound H-X and a compound H-Y) produce. They have very good fiber-reactive dye properties and  deliver on the materials mentioned in the description, in particular Cellulose fiber materials, such as cotton, according to the well-known dyeing and Printing process strong, true colors and prints in the in the respective table example for dyeings on cotton given shade.  

Claims (14)

1. Azo compound according to the general formula (1) in which mean:
G is a group of formula (2a), (2b), (2c), (2d), (2e), (2f), (2g) or (2h) where in formula (2h) the index a stands for the number 1 or 2;
R is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or sulfo;
R¹ is hydrogen, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms, which is substituted by hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, carboxy, sulfo, sulfato or phosphato, or is phenyl or naphthyl, both with 1, 2 or 3 substituents from the group halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, Sulfamoyl, sulfo and alkylsulfonyl can be substituted with an alkyl radical of 1 to 4 carbon atoms;
E is the bivalent residue of a coupling-capable and diazotizable compound from the aniline or naphthylamine series, free of the amino group;
v represents the number zero, 1 or 2;
K is the divalent residue of a coupling component of the aniline or naphthylamine series free of the amino group or the divalent residue of a coupling component of the heterocyclic series;
n is the number 1, 2, 3 or 4;
Z is the fiber-reactive radical of a fiber-reactive group or group -N (R¹) -Z, where in the case of n greater than 1 the radicals -N (R¹) -Z can have different meanings from one another;
the compounds of formula (1) have at least one sulfo group. 2. Azo compound according to claim 1, characterized in that Z is a radical of the general formula (3) is in which mean:
X is halogen or a group of the general formula (4) in which
R² is hydrogen or alkyl of 1 to 4 carbon atoms or is alkyl of 1 to 4 carbon atoms which is substituted by hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, carboxy, sulfo, sulfato or phosphato, or phenyl or naphthyl, both by 1, 2 or 3 substituents from the group halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy , Sulfamoyl, sulfo and alkylsulfonyl with an alkyl radical of 1 to 4 carbon atoms, may be substituted,
W is alkylene of 2 to 4 carbon atoms or phenylene or naphthylene, both of which are substituted by 1, 2 or 3 substituents from the group halogen, hydroxy, cyano, nitro, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 C atoms, alkoxycarbonyl of 2 to 5 C atoms, carboxy, sulfamoyl and sulfo can be substituted, or phenylene alkylene or alkylene phenylene with an alkylene radical of 1 to 4 carbon atoms in each case and
A is vinyl or is ethyl which is substituted in the β-position by a substituent which can be split off by means of alkali to form the vinyl group;
Y is chlorine, cyanoamino or a group of the general formula (5) in which
R³ is hydrogen or alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms, which is replaced by halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy , Sulfo, sulfato or phosphato is substituted, or a group of the formula -W-SO₂-A with W and A is one of the meanings mentioned above and
R⁴ is hydrogen or alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms, which is halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy , Sulfo, sulfato or phosphato is substituted, or cycloalkyl of 5 to 8 carbon atoms or a group of the formula -W-SO₂-A with W and A is one of the abovementioned meanings or is phenyl or naphthyl, both by 1, 2 or 3 substituents from the group halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfamoyl, sulfo and alkylsulfonyl with an alkyl radical of 1 to 4 carbon atoms, may be substituted, or
R³ and R⁴ together represent an alkylene radical of 3 to 6 carbon atoms or a through a group -NH-, -O-, -CO-, -S-, -SO₂- or -N (R⁵) - (wherein R⁵ by sulfato or Sulfato-substituted alkyl of 1 to 4 carbon atoms, such as ethyl, is an interrupted alkylene radical of 3 to 6 carbon atoms, which together with the nitrogen atom form a heterocyclic radical. 3. Azo compound according to claim 2, characterized in that R¹ Is hydrogen, methyl or ethyl. 4. Azo compound according to claim 2 or 3, characterized in that X Is chlorine or fluorine. 5. Azo compound according to at least one of claims 2 to 4, characterized in that Y is a group of the general formula (4) is in which
R² is hydrogen, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms, which is substituted by hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, carboxy, sulfo, sulfato or phosphato, or phenyl or Is naphthyl, both by 1, 2 or 3 substituents from the group halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, Sulfamoyl, sulfo and alkylsulfonyl can be substituted with an alkyl radical of 1 to 4 carbon atoms,
W is alkylene of 2 to 4 carbon atoms or phenylene or naphthylene, both of which are substituted by 1, 2 or 3 substituents from the group halogen, hydroxy, cyano, nitro, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 C atoms, alkoxycarbonyl of 2 to 5 C atoms, carboxy, sulfamoyl and sulfo can be substituted, or phenylene alkylene or alkylene phenylene with an alkylene radical of 1 to 4 carbon atoms in each case and
A is vinyl or is ethyl which is substituted in the β-position by a substituent which can be split off by means of alkali to form the vinyl group. 6. Azo compound according to at least one of claims 2 to 4, characterized characterized as Y being morpholino. 7. Azo compound according to at least one of claims 2 to 4, characterized characterized in that Y is mono- or disulfophenyl or mono-, di- or Is trisulfonaphthyl. 8. Azo compound according to claim 2, characterized in that Z is a radical of the general formula (8a) is in which X is chlorine, fluorine or cyanoamino, A has one of the particularly preferred meanings mentioned in claim 2, R² is hydrogen, ethyl, methyl, β-hydroxyethyl, β-sulfatoethyl, phenyl, 3-sulfophenyl or 4-sulfophenyl and W¹ is 1,2-ethylene, 1,3-propylene, 2-methyl-1,2-ethylene, 2-methyl-1,3-propylene, 2-ethoxy-ethyl, 1,4-phenylene, 1,3 -Phenylene, 2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene, 2-sulfo-1,4-phenylene, 2 -Hydroxy-1,5-phenylene, 2-bromo-1,5-phenylene or 4- (2'-eth) -phen-1,1'-ylene, where in these groups the 1-position with the N atom is connected, or 1-sulfonaphth-2,6-ylene, 6-sulfonaphth-2,8-ylene, naphth-2,6-ylene or naphth-2,8-ylene, in which the 2 position is connected to the N atom. 9. Azo compound according to claim 1 of the general formula (1A) in which E, v, K, R¹ and n have the meanings given in Claim 1, Z has one of the meanings given in one of Claims 1 to 7 and B represents -NH- or -O-. 10. Azo compound according to claim 1 of the general formula (1B) in which E, v, K, R¹ and n have the meanings given in Claim 1 and Z has one of the meanings given in at least one of Claims 2 to 8. 11. Azo compound according to claim 1 of the general formula (Z) in which E, v, K, R¹ and n have the meanings given in Claim 1 and Z has one of the meanings given in at least one of Claims 2 to 8 and R is hydrogen, methyl or methoxy. 12. A process for the preparation of an azo compound of the general formula (1) mentioned and defined in claim 1, characterized in that a compound of the general formula (12) in which R and G are one of those mentioned in claim 1, diazotized and with a compound of the general formula (13) in which E, v, K, R¹, Z and n have one of the meanings given in Claim 1,
or that a compound of the general formula (14) diazotized with G, R, E and v having one of the meanings given in Claim 1 and coupling it with a compound of the general formula HKN (R¹) -Z with K, R¹ and Z having the meaning given in Claim 1, or in that a compound of the general formula Formula (15) in which G, R, v, K, R¹ and n have one of the meanings mentioned in claim 1, with a compound of the general formula X ° -Z, in which X ° represents chlorine, bromine or fluorine and Z in which 1 has the meaning mentioned, implements. 13. Use of a dye of claim 1 or one of claim 12 dye prepared for dyeing (including printing) of material containing hydroxyl and / or carbonamide groups, in particular Fiber material. 14. Process for dyeing (including printing) of hydroxy and / or material containing carbonamide groups, in particular fiber material which one applies a dye to the material and the Dye on the material using heat or with the help of an alkaline fixed agent or by means of both measures, thereby characterized in that the dye is a dye of claim 1 or uses a dye prepared according to claim 12.