Reactive Dyes, process for the production thereof and their use

The present invention relates to the technical field of reactive dyestuffs for dyeing and printing of hydroxyl-, amino-, and carboxamido-containing material.

Reactive dyes based on bis- and polyazo moiety containing at least one reactive anchor are known from prior art and can be used as colorants in different applications, see for example: US 6,323,327, WO 99/064520, WO 97/027249, US 5,378,817, US 5,591 ,834, US 5,342,927, WO 97/025377, US 5,420,257, JP 2002/226,724, WO 03/040239, WO 03/033599, US20030172476.

In the context of the dyeing and printing of hydroxyl-, amino-, and/or carboxamido- containing material the known dyes have a number of technical disadvantages such as low fixation, moderate wet fastness and light fastness level. Hence, there is a need for developing new reactive dyes of superior technical performance.

Surprisingly, it has now been found that the dyes of the formula (I) as described below show highly advantageous properties over the known dyes. These include superior wet fastness and light fastness, superior ecological profile as well as the possibility to achieve a wide range of darker shades including dark violets, dark browns, dark navy and black shades.

The present invention refers to dyes of the formula (I) and mixtures thereof

wherein

n is an integer, either 0 or 1 ;

K is a radical of heterocyclic coupling component as described below;

A is a radical of middle component as described below;

B is a radical of diazo component as described below;

M is hydrogen, sodium, potassium, lithium or ammonium or mono-, di-, tri- or tetra-(Ci- C ₄ )-alkylammonium, one equivalent of an alkali earth metal, or a monovalent organic cation;

K is a coupling component of following general formula (K1 ) to (K3);

(K1 ) (K2) (K3) wherein

R ¹ and R ⁴ , independent from each other, are hydrogen, alkyl, cycloalkyl,

trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino; monoaryl-amino; diaryl-amino; monocycloalkyl monoarylamino; monoalkyl monoaryl amino; alkylthio; arylthio;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido; R ² , R ⁵ and R ¹¹ , independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, sulfomethyl or -SOsM;

R ³ ', R ⁶ to R ⁹ and R ¹² , independent from each other, are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N- monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, N,N- diarylamino, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N- alkyl-N-cycloalkyl-amino, N-aryl-Ncycloalkyl-amino, N-heteroarylamino, N- heterocycloalkylamino or hydroxyakylsulfonylalkyl,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkyl- amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or S0 ₃ M;

or alkyl or aryl substituted by -SO ₂ X; whereby

X is vinyl or a radical -CH ₂ CH ₂ -Y where Y is a group removable under alkaline conditions such as OS0 ₃ M, SS0 ₃ M, OCOCH ₃ , OPO ₃ M or halogen; and

R ¹⁰ is hydroxyl or amino group;

And whereby, in the general formula K2 the point of attachment and R ⁵ can be positioned ortho or para to the amino rest bearing the substituents R ⁶ and R ⁷ , meaning that when the point of attachment is positioned ortho to amino rest bearing the substituents R ⁶ and R ⁷ , R ⁵ is positioned para to the same, and vice versa. or

K is a coupling component of the following general formulae (K4) to (K6);

(K4) (K5)

whereby

T is a reactive anchor of general formulae (T1 ) to (T3);

wherein

R and R , independent from each other are halogen or

)30

R , R , R , R ^y and R ^JU independent from each other are halogen; or each of R to R , independent from each other are substituted by one of the groups selected from general formulae (1 a) to (1 c);

(1a) (1 b) (1 c) wherein

R , R , R and R , independent from one another, are hydrogen, alkyl, phenyl or phenyl substituted by one of the groups selected from alkyl, alkoxy, halogen, or -SOsM; alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N- monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, N,N- diarylamino, N-alkyl-N-aryl-amino, N-monocycloalkylamino, Ν,Ν-dicycloalkylamino, N- alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroarylamino, N- heterocycloalkylamino or hydroxyakylsulfonylalkyl,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkylamino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or S0 ₃ M; each of R ³³ , R ³⁴ and R ³³⁸ , independent from each other, are hydrogen, alkyl, alkoxyl, halogen, trifluoromethyl, cyano, nitro, ester, carbamoyl, SO ₃ M or -S0 ₂ X;

where M is hydrogen, sodium, potassium, lithium or ammonium;

X is vinyl or a radical -CH ₂ CH ₂ -Y where Y is a group removable under alkaline conditions such as OS0 ₃ M, SS0 ₃ M, OCOCH ₃ , OPO ₃ M or halogen; p is an integer from 1 to 5; R ¹³ and R ¹⁵ , independent from each other, are hydrogen, alkyl, cycloalkyl,

trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;

monoaryl-amino; diaryl-amino; monocycloalkyl monoarylamino; monoalkyl monoaryl amino; alkylthio; arylthio;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido;

R ¹² , R ¹⁶ and R ²² , independent from each other,

are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;

R ¹⁴ ', R ¹⁷ to R ²⁰ and R ²³ , independent from each other,

are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM; aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N- monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, N,N- diarylamino, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N- alkyl-N-cycloalkyl-amino, N-aryl-Ncycloalkyl-amino, N-heteroarylamino, N- heterocycloalkylamino or hydroxyakylsulfonylalkyl,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur; or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkyl- amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or S0 ₃ M;

R ²¹ is hydroxyl or amino group;

And whereby, in the general formula K5 the point of attachment and R ¹⁶ can be positioned ortho or para to the amino rest bearing the substituents R ¹⁷ and R ¹⁸ , meaning that when the point of attachment is positioned ortho to amino rest bearing the substituents R ¹⁷ and R ¹⁸ , R ¹⁶ is positioned para to the same, and vice versa.

A is a phenylene or napthylene middle component and has the general formula (A1 ) or (A2);

(A1 ) (A2)

wherein

R ³⁴¹ to R ³⁴⁸ , independent from one another, are hydrogen, alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, halogen, trifluoromethyl; cycloalkyl;

heterocycloalkyl; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido, S0 ₃ M, COOM;

or

alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkylamino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl,

alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl- carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N- monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N- monoarylsulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoarylsulfamoyl or SO ₃ M;

or

alkyl interrupted by one or more heteroatoms such as oxygen or sulfur; or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkyl- amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or SO ₃ M;

or

a group of formulae (2a) to (2c)

whereby, R and R independent from each other, are hydrogen, alkyl, alkyl substituted by SO ₃ M, alkyl chain interrupted by one or two heteroatoms, or T, whereby T has the same meaning as above;

U is -0-, -S- or -N(R ³²⁹ )-;

R ³²³ , R ³²⁷ and R ³²⁹ , independent from one another, are hydrogen, alkyl, alkyl substituted by SO ₃ M, alkyl chain interrupted by one or two heteroatoms;

R ³²⁴ , R ³²⁵ , R ³²⁶ and R ³²⁸ , independent from one another are hydrogen, alkyl or alkyl chain interrupted by one or two heteroatoms; r is an integer of 0 to 6;

s is an integer of 1 to 6;

^** refers to attachment point with Al and A2;

^*** refers to attachment point with T;

B is the diazo component and has one of the general formula (B1 ) or (B2);

(B1 ) (B2)

wherein

R ³⁵ to R ⁴⁰ and R ³⁵¹ , independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -S0 ₃ M, trifluoromethyl, nitro, ester, NHC(0)R ⁴¹ , CONH ₂ , S(0) ₂ R ⁴² , - SO ₂ X or aminosubstituted by T or one of the general formulae (E1 ) to (E3);

(E1 (E2)

(E3) wherein

V is -0-, -S- or -N(R ³⁵² )-;

R ⁴³ , R ⁴⁷ and R ³⁵² , independent from one another are hydrogen, alkyl, alkyl substituted by SO3M, alkyl chain interrupted by one or two heteroatoms;

R ⁴⁴ , R ⁴⁵ , R ⁴⁶ and R ⁴⁸ , independent from one another are hydrogen, alkyl or alkyl chain interrupted by one or two heteroatoms;

R ³³⁰ , R ³³¹ , R ³³² and R ³³³ , independent from one another are hydrogen or alkyl, alkoxy, halogen, cyano, -SO ₃ M, trifluoromethyl, nitro, ester, NHC(0)R ³³⁴ , CONH ₂ , S(0) ₂ R ³³⁵ or a group of formula (3a);

(3a)

R and R , independent from one another are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N- monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, N,N- diarylamino, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N- alkyl-N-cycloalkyl-amino, N-aryl-Ncycloalkyl-amino, N-heteroarylamino, N- heterocycloalkylamino or hydroxyakylsulfonylalkyl,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkyl- amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or SO ₃ M; alkyl containing a rest with free valence to link to rest reactive anchor T;

R ⁴¹ , R ⁴² , R ³³⁴ and R ³³⁵ , independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

c is an integer of 0 to 6

d is an integer of 1 to 6

* ^*** refers to attachment point with B1 and B2

* ^**** refers to attachment point with T

* ^***** refers to attachement point with E3

T and X are the same as defined above;

with the general proviso that the dyes of general formula (I) contain at least one reactive anchor; and

This invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I).

Alkyl groups appearing in this application may be straight-chain or branched and are for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n- pentyl, isopentyl, methylbutyl and n-hexyl. The same logic applies to alkoxy groups which for example are methoxy and ethoxy.

Cycloalkyl groups are preferably cyclopentyl and cyclohexyl. The term cyloalkyl comprises for the purpose of the present application substituted cydoalklyl groups and unsaturated cycloalkyl groups as well. A preferred group of this type is cyclopentenyl.

Alkenyl groups may be straight-chain or branched and are for example vinyl and allyl. The term alkenyl comprises for the purpose of the present application alkynyl groups as well, for example ethynyl and propargyl.

Heterocycloalkyi groups are preferably pyrrolidine, piperidine, morpholine or piperazine, tetrahydrofuran, imidazole, triazole. The terms heterocycloalkyi comprises the above groups in unsubstituted as well as in substituted form.

Aryl is in particular phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl.

Halogen is preferably fluorine, chlorine or bromine.

Preferred embodiments of the present invention are dyes of the formulae (la) to (If) and mixtures thereof;

(lc)

(Id)

le)

(if)

wherein

R , R , R , R ,R'° and R independent from each other, are hydrogen, alkyl, cydoalkyi, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino; monoaryl-amino; diaryl-amino; monocycloalkyl monoarylamino; monoalkyl monoaryl amino; alkylthio; arylthio;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cydoalkyi, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido;

R ⁵⁰ , R ⁵⁴ , R ⁵⁹ , R ⁶⁷ , R ⁷⁵ and R ⁷⁹ independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0 ₃ M;

R ⁵¹ , R ⁵⁵ , R ⁶⁰ and R ⁶⁸ independent from each other, are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N- monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, N,N- diarylamino, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N- alkyl-N-cycloalkyl-amino, N-aryl-Ncycloalkyl-amino, N-heteroarylamino, N- heterocycloalkylamino or hydroxyakylsulfonylalkyl,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkyl- amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or SO ₃ M; or alkyl interrupted by one or more heteroatoms such as oxygen or sulphur; R ⁵² , R ⁵³ , R ⁵⁶ , R ⁵⁷ , R ⁶⁴ , R ⁶⁵ , R ⁷² , R ⁷³ , R ⁷⁶ , R ⁷⁷ , R ⁸³ and R ⁸⁴ , independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO ₃ M, trifluoromethyl, nitro, ester, NHC(0)R ⁸⁶ , CONH ₂ , S(0) ₂ R ⁸⁷ or -S0 ₂ X;

R ⁸⁶ and R ⁸⁷ independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.

R ⁶¹ to R ⁶³ , R ⁶⁹ to R ⁷¹ , R ⁸⁰ to R ⁸² , independent from one another, are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, SO3M, COOM; or a group of formulae (2a) to (2c) as defined above;

In the especially preferred dyes of general formulae (la) to (If),

R ⁴⁹ , R ⁸⁵ , R ⁵⁸ , R ⁶⁶ , R ⁷⁴ and R ⁷⁸ independent from one another, are hydrogen or (C ₁ -C4) alkyl or aryl;

R ⁵⁰ , R ⁵⁴ , R ⁵⁹ , R ⁶⁷ , R ⁷⁵ and R ⁷⁹ independent from one another, are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO ₃ M or -COOM;

R ⁵¹ , R ⁵⁵ , R ⁶⁰ and R ⁶⁸ independent from one another, are alkyl or aryl; Aryl substituted by one more substituents selected from alkyl, alkoxy, halogen or -SO ₃ M;

R ⁶¹ to R ⁶³ , R ⁶⁹ to R ⁷¹ , R ⁸⁰ to R ⁸² , independent from one another are hydrogen, (Ci- C )alkyl, (Ci-C )alkoxyl, hydroxyl, carbamido, halogen or -SO ₃ M or contain group of formulae (2a) to (2c) as defined above;

R ⁸⁶ and R ⁸⁷ independent from one another are hydrogen, alkyl or alkyl substituted by hydroxyl;

T and X are the same as defined above. Further preferred embodiments of the present invention are dyes of the formulae (Ig) and (Ih) and mixtures thereof;

(ig)

wherein

R ⁹⁰ and R ⁹⁴ independent from one another, are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;

monoaryl-amino; diaryl-amino; monocycloalkyl monoarylamino; monoalkyi monoaryl amino; alkylthio; arylthio;

or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido;

R ⁹¹ and R ⁹⁵ independent from one another, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;

D ¹ and D ² independent from one another, are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N- monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, N,N- diarylamino, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N- alkyl-N-cycloalkyl-amino, N-aryl-Ncycloalkyl-amino, N-heteroarylamino, N- heterocycloalkylamino or hydroxyakylsulfonylalkyl,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkylamino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or S0 ₃ M;

R ⁹² , R ⁹³ , R ⁹⁹ and R ¹⁰⁰ , independent from one another, are hydrogen or alkyi, alkoxy, halogen, cyano, -S0 ₃ M, trifluoromethyl, nitro, ester, NHC(0)R ¹⁰¹ , CONH ₂ , S(0) ₂ R ¹⁰² or -S0 ₂ X;

R ¹⁰¹ and R ¹⁰² independent from one another are hydrogen, alkyi or alkyi substituted by hydroxy or halogen.

R ⁹⁶ to R ⁹⁸ , independent from one another are hydrogen, alkyi, alkyi substituted, alkyi chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted,

halogen , trifluoromethyl; cycloalkyl; heterocycloalkyl; cyano; nitro; acyloxy;

alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 ₃ M, COOM; or a group of formulae (2a) to (2c) as defined above;

with the proviso D ¹ and D ² contain a rest with free valence to link to rest reactive anchor T;

T is the same as defined above;

In the especially preferred dyes of the formulae (Ig) and (Ih),

R ⁹⁰ and R ⁹⁴ independent from one another are hydrogen or (Ci-C ₄ )-alkyl or aryl;

R ⁹¹ and R ⁹⁵ independent from one another are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -S0 ₃ M or -COOM;

D ¹ and D ² are alkyi or aryl; alkyi or aryl substituted by one more substituents selected from alkyi, alkoxy, halogen or -SO ₃ M, amino, N-alkyl amino;

R ⁹⁶ to R ⁹⁸ , independent from one another are hydrogen, (Ci-C ₄ )-alkyl, (Ci-C ₄ )alkoxyl, hydroxyl, carbamido, halogen or -SO ₃ M or contain group of formulae (2a) to (2c) as defined above; R ¹⁰¹ and R ¹⁰² independent from one another are hydrogen, alkyl or alkyi substituted by hydroxyl;

T and X are the same as defined above. Further preferred embodiments of the present invention are dyes of the formulae (li) to (II) and mixtures thereof;

(li)

wherein

R ¹⁰⁵ , R ¹¹⁰ , R ¹¹⁵ and R ¹²³ independent from each other are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;

monoaryl-amino; diaryl-amino; monocycloalkyi monoarylamino; monoalkyi monoaryl amino; alkylthio; arylthio;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido;

R ¹⁰⁶ , R ¹¹¹ , R ¹¹⁶ and R ¹²⁴ are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;

R ¹⁰⁷ , R ¹¹² , R ¹¹⁷ and R ¹²⁵ are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl- carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl- carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N- monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, Ν,Ν-diarylamino, N- alkyl-N-aryl-amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N-alkyl-N- cycloalkyl-amino, N-aryl-Ncycloalkyl-amino, N-heteroarylamino, N- heterocycloalkylamino or hydroxyakylsulfonylalkyl,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkylamino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or -SO ₃ M;

R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹³ , R ¹¹⁴ , R ¹²¹ , R ¹²² , R ¹²⁹ and R ¹³⁰ , independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO ₃ M, trifluoromethyl, nitro, ester,

NHC(0)R ¹³¹ , CONH2, S(0) ₂ R ¹³² or -S0 ₂ X;

R ¹³¹ and R ¹³² , independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.

_R i i8 _{10 R} i2o _{an d R} 126 _{10 R} 128 _; j _nc | _e p _enc | _en t f _{rom one} another, are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy

substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 ₃ M, COOM; or a group of formulae (2a) to (2c) as defined above;

E ⁴ to E ⁷ , independent from each other, are a group of general formulae (E1 ) to (E3) as defined above;

In the especially preferred dyes of the formulae (li) to (II),

R ¹⁰⁵ , R ¹¹⁰ , R ¹¹⁵ and R ¹²³ independent from each other are hydrogen or (Ci-C ₄ )alkyl or aryl;

R ¹⁰⁶ , R ¹¹¹ , R ¹¹⁶ and R ¹²⁴ independent from each other are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO ₃ M or -COOM;

R ¹⁰⁷ , R ¹¹² , R ¹¹⁷ and R ¹²⁵ independent from each other are alkyl or aryl; Aryl substituted by one more substituents selected from alkyl, alkoxy, halogen or -SO3M;

R ¹¹⁸ to R ¹²⁰ and R ¹²⁶ to R ¹²⁸ , independent from one another, are hydrogen, (Ci-C ₄ )alkyl, (Ci-C ₄ )alkoxyl, hydroxyl, carbamido, halogen or -SOsM or contain group of formulae (2a) to (2c);

R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹³ , R ¹¹⁴ , R ¹²¹ , R ¹²² , R ¹²⁹ and R ¹³⁰ , independent from one another, are hydrogen or alkyl, alkoxy, halogen, -SO ₃ M or -SO ₂ X;

R ¹³¹ and R ¹³² , independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxyl; E ⁴ to E ⁷ , independent from each other, are a group of general formulae (E1 ) to (E3); T and X is the same as defined above.

Further preferred emodiments of the present invention are dyes of the formulae (Im) to (Ip) and mixtures thereof;

(Im)

(In)

( lo)

wherein

p135 p139 p and R ¹⁵⁰ independent from each other are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;

monoaryl-amino; diaryl-amino; monocycloalkyi monoarylamino; monoalkyi monoaryl amino; alkylthio; arylthio;

or are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido;

R ¹³⁶ , R ¹⁴⁰ , R ¹⁴⁴ and R ¹⁵¹ independent from each other are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0 ₃ M;

D ³ , D ⁴ , D ⁵ and D ⁶ independent from each other are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N- monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, N,N- diarylamino, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N- alkyl-N-cycloalkyl-amino, N-aryl-Ncycloalkyl-amino, N-heteroarylamino, N- heterocycloalkylamino or hydroxyakylsulfonylalkyl;

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkylamino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, Ν,Ν-diaryl- sulfamoyi, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or S0 ₃ M;

R ¹³⁷ , R ¹³⁸ , R ¹⁴¹ , R ¹⁴² , R ¹⁴⁸ , R ¹⁴⁹ , R ¹⁵⁵ and R ¹⁵⁶ , independent from one another are hydrogen or alkyl, alkoxy, halogen, cyano, -SO ₃ M, trifluoromethyl, nitro, ester,

NHC(0)R ¹⁵⁷ , CONH2, S(0) ₂ R ¹⁵⁸ or -S0 ₂ X;

R ¹⁵⁷ and R ¹⁵⁸ , independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁵² , R ¹⁵³ and R ¹⁵⁴ , independent from one another are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 ₃ M, COOM; or a group of formulae (2a) to (2c) as defined above;

E ⁸ to E ¹¹ , independent from each other, are a group of general formulae (E1 ) to (E3) as defined above;

T and X is the same as defined above.

In the especially preferred dyes of the formulae (Im) to (Ip),

R ¹³⁵ , R ¹³⁹ , R ¹⁴³ and R ¹⁵⁰ independent from each other are hydrogen or (Ci-C ₄ )-alkyl or aryl;

R ¹³⁶ , R ¹⁴⁰ , R ¹⁴⁴ and R ¹⁵¹ independent from each other are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO ₃ M or -COOM;

D ³ , D ⁴ , D ⁵ and D ⁶ independent from each other are alkyl or aryl; alkyl or aryl

substituted by one more substituents selected from alkyl, alkoxy, halogen or -SOsM, amino, N-alkyl amino or amino group substituted by T;

R ¹³⁷ , R ¹³⁸ , R ¹⁴¹ , R ¹⁴² , R ¹⁴⁸ , R ¹⁴⁹ , R ¹⁵⁵ and R ¹⁵⁶ , independent from one another, are hydrogen or alkyl, alkoxy, halogen, -SO ₃ M or -SO ₂ X; R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁵² , R ¹⁵³ and R ¹⁵⁴ , independent from one another, are hydrogen, (d- C )-alkyl, (Ci-C )alkoxyl, hydroxyl, carbamido, halogen or -S0 ₃ M or contain group of formulae (2a) to (2c) as defined above;

E ⁸ to E ¹¹ , independent from each other, are a group of general formulae (E1 ) to (E3) as defined above;

T and X is the same as defined above.

Further preferred embodiments of the present invention are dyes of the formulae (Iq) to (It) and mixtures thereof;

wherein

R ¹⁶¹ , R ¹⁶⁸ , R ¹⁷⁵ and R ¹⁸⁵ independent from each other are alkyl, cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -

R ¹⁶² , R ¹⁶⁹ , R ¹⁷⁶ and R ¹⁸⁶ independent from each other are hydroxyl or amino; _R 163 _{tQ R} i65 _{j R} i 7o _{tQ R} 172 _{> R} 177 _{{q R} 179 _{and R} 187 _{fo R} i∞ j _ndepenc | _en t f _rom each other, are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl,

heterocycloalkyl, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoaryl- sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N- monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, Ν,Ν-diarylamino, N -a Iky I- N -aryl - amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N-alkyl-N-cycloalkyl-amino, N- aryl-Ncycloalkyl-amino, N-heteroarylamino, N-heterocycloalkylamino or

hyd roxya ky I s u If o ny I a I ky I ,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkyl- amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or -SO ₃ M; or alkyl interrupted by one or more heteroatoms such as oxygen or sulphur; or alkyl or aryl substituted by -SO ₂ X; whereby

X is vinyl or a radical -CH ₂ CH ₂ -Y where Y is a group removable under alkaline conditions such as OSO ₃ M; or contain a rest with free valence to link to rest reactive anchor T;

R ¹⁶⁶ , R ¹⁶⁷ , R ¹⁷³ , R ¹⁷⁴ , R ¹⁸³ , R ¹⁸⁴ , R ¹⁹³ and R ¹⁹⁴ , independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO ₃ M, trifluoromethyl, nitro, ester,

NHC(0)R ¹⁹⁵ , CONH2, S(0) ₂ R ¹⁹⁶ or -S0 ₂ X;

R ¹⁹⁵ and R ¹⁹⁶ , independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R ¹⁸⁰ to R ¹⁸² and R ¹⁹⁰ to R ¹⁹² , independent from one another are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen, trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido, SO ₃ M, COOM; or a group of formulae (2a) to (2c) as defined above;

X is the same as defined above.

In the especially preferred dyes of the formulae (Iq) to (It),

R ¹⁶¹ , R ¹⁶⁸ , R ¹⁷⁵ and R ¹⁸⁵ , independent from each other are (Ci-C ₄ )alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;

R ¹⁶² , R ¹⁶⁹ , R ¹⁷⁶ and R ¹⁸⁶ , independent from each other are hydroxyl or amino;

_R 163 _{tQ R} i65 _{j R} i7o _{{q R} 172 _{> R} 177 _{{q R} 179 _{and R} 187 _toR i89 j _ndepenc | _en t f _rom one another are hydrogen, (Ci-C )alkyl, (Ci-C )alkyloxy, halogen, -SO ₃ M or -S0 ₂ X or free valence substituted with T;

R ¹⁶⁶ , R ¹⁶⁷ , R ¹⁷³ , R ¹⁷⁴ , R ¹⁸³ , R ¹⁸⁴ , R ¹⁹³ and R ¹⁹⁴ , independent from one another, are hydrogen, (Ci-C )alkyl, (Ci-C )alkoxyl, halogen or -S0 ₃ M;

_R i8o _{t0 R} 182 _{and R} i9o _{t0 R} 192^ independent from one another are hydrogen, (C ₁ -C ₄ )alkyl, (Ci-C ₄ )alkoxyl, hydroxyl, carbamido, halogen or -SOsM or contain the group of formulae (2a) to (2c);

T and X have the same meanings as above. Further preferred embodiments of the present invention are dyes of the formulae (lu) to (Ix) and mixtures thereof;

R ¹⁹⁹ , R ²⁰⁶ , R ^{2 3} and R ²²³ independent from each other are alkyl, cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0 ₃ M;

R ²⁰⁰ , R ²⁰⁷ , R ²¹⁴ and R ²²⁴ independent from each other are hydroxyl or amino;

_R 201 _{tQ R} 2Q3^ _R 208 _{tQ R} 210 _{; R} 215 _{[q r} 217 _R 225 _{{q r} 227 _^ j _ndependent f _{rom each othe} are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl,

heterocycloalkyi, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl- sulfamoyi, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoaryl- sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N- monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, N,N-diarylamino, N-alkyl-N-aryl- amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N-alkyl-N-cycloalkyl-amino, N- aryl-Ncycloalkyl-amino, N-heteroarylamino, N-heterocycloalkylamino or

hydroxyakylsulfonylalkyl,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkylamino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or -SO ₃ M; or alkyl interrupted by one or more heteroatoms such as oxygen or sulphur; or alkyl or aryl substituted by -SO ₂ X or contains a rest with free valence to link to rest reactive anchor T;

whereby X is vinyl or a radical -CH ₂ CH ₂ -Y where Y is a group removable under alkaline conditions such as OSO ₃ M; R ²⁰⁴ , R ²⁰⁵ , R ²¹¹ , R ²¹² , R ²²¹ , R ²²² , R ²³¹ and R ²³² , independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -S0 ₃ M, trifluoromethyl, nitro, ester,

NHC(0)R ²³³ , CONH ₂ , S(0) ₂ R ²³⁴ or -S0 ₂ X;

R ²³³ and R ²³⁴ , independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R ²¹⁸ to R ²²⁰ and R ²²⁸ to R ²³⁰ , independent from one another, are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy

substituted, halogen, trifluoromethyl; cycloalkyi; heterocycloalkyl; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido, S0 ₃ M, COOM; or a group of formulae (2a) to (2c) as defined above;

E ¹² to E ¹⁵ , independent from each other, are a group of general formulae (E1 ) to (E3) as defined above;

X is the same as defined above.

In the especially preferred dyes of the formulae (lu) to (Ix),

R ¹⁹⁹ , R ²⁰⁶ , R ^{2 3} and R ²²³ are (Ci-C ₄ )alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;

R ²⁰⁰ , R ²⁰⁷ , R ²¹⁴ and R ²²⁴ are hydroxyl or amino;

R ²⁰¹ to R ²⁰³ , R ²⁰⁸ to R ²¹⁰ , R ²¹⁵ toR ²¹⁷ and R ²²⁵ to R ²²⁷ , independent from one another, are hydrogen, (Ci-C ₄ )alkyl, (Ci-C ₄ )alkyloxy, halogen, -SO3M or -SO ₂ X or free valence substituted with T;

R ²⁰⁴ , R ²⁰⁵ , R ² , R ²¹² , R ²²¹ , R ²²² , R ²³ and R ²³² , independent from one another, are hydrogen, (Ci-C ₄ )alkyl, (Ci-C ₄ )alkoxyl, halogen or -SO ₃ M;

R ²¹⁸ to R ²²⁰ and R ²²⁸ to R ²³⁰ , independent from one another, are hydrogen, (Ci-C ₄ )alkyl, (Ci-C )alkoxyl, hydroxyl, carbamido, halogen or -SO ₃ M or contain the group of formulae (2a) to (2c);

E ¹² to E ¹⁵ , independent from each other, are a group of general formulae (E1 ) to (E3); T and X have the same meanings as above. Further preferred embodiments of the present invention are dyes of the formulae (ly) to lab) and mixtures thereof;

(lz)

(lab) wherein

R ²³⁷ , R ²⁴⁵ , R ²⁵³ and R ²⁶⁴ independent from each other are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;

monoaryl-amino; diaryl-amino; monocycloalkyi monoarylamino; monoalkyi monoaryl amino; alkylthio; arylthio;

or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido;

R ²³⁸ , R ²⁴⁶ , R ²⁵⁴ and R ²⁶⁵ independent from each other are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0 ₃ M;

_R 239 _{tQ R} 24 _{2i R} 247 _{{q r} 250 ^ _R 255 _{to R} 258 _R 267 _{to R} 270 _j j _ndepenc | _en t f _r0 m each Other are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl,

heterocycloalkyl, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoarylcarbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N, N -diary I- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoaryl- sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N- monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, Ν,Ν-diarylamino, N-alkyl-N-aryl- amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N-alkyl-N-cycloalkyl-amino, N- aryl-Ncycloalkyl-amino, N-heteroarylamino, N-heterocycloalkylamino or

hyd roxya ky I s u If 0 ny I a I ky I ,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkylamino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or SO ₃ M; or alkyl interrupted by one or more heteroatoms such as oxygen or sulphur; or contains a rest with free valence to link to rest reactive anchor T;

R ²⁴³ , R ²⁴⁴ , R ²⁵¹ , R ²⁵² , R ²⁶² , R ²⁶³ , R ²⁷⁴ and R ²⁷⁵ , independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO ₃ M, trifluoromethyl, nitro, ester,

NHC(0)R ²⁷⁶ , CONH2, S(0) ₂ R ²⁷⁷ or -S0 ₂ X;

R ²⁷⁶ and R ²⁷⁷ , independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R ²⁵⁹ to R ²⁶¹ and R ²⁷¹ to R ²⁷³ , independent from one another, are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 ₃ M, COOM; or a group of formulae (2a) to (2c) as defined above;

In the especially preferred dyes of the formulae (ly) to (lab),

R ²³⁷ , R ²⁴⁵ , R ²⁵³ and R ²⁶⁴ are hydrogen or (C1-C4) alkyl, aryl, (C1-C4) alkyloxy;

R ²³⁸ , R ²⁴⁶ , R ²⁵⁴ and R ²⁶⁵ are (Ci-C ₄ )alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;

R ²³⁹ to R ²⁴² , R ²⁴⁷ to R ²⁵⁰ , R ²⁵⁵ to R ²⁵⁸ and R ²⁶⁷ to R ²⁷⁰ , independent from one another, are hydrogen, (Ci-C )alkyl, (Ci-C ₆ )alkyloxy, aryl;

Or -Alk-S0 ₂ X,

Or aryl substituted by one or more groups selected from halogen, -SO ₃ M or -SO ₂ X or free valence substituted with T;

R ²⁴³ , R ²⁴⁴ , R ²⁵¹ , R ²⁵² , R ²⁶² , R ²⁶³ , R ²⁷⁴ and R ²⁷⁵ , independent from one another, are hydrogen, (Ci-C )alkyl, (Ci-C )alkoxyl, halogen or -SO ₃ M; R ²⁵⁹ to R ²⁶¹ and R ²⁷¹ to R ²⁷³ , independent from one another, are hydrogen, (Ci-C ₄ )alkyl, (Ci-C ₄ )alkoxyl, hydroxyl, carbamido, halogen or -SOsM or contain the group of formulae (2a) to (2c);

T and X have the same meanings as defined above.

Further preferred embodiments of the present invention are dyes of the formulae (lac) to (laf) and mixtures thereof;

2

wherein

R ²⁸⁰ , R ²⁸⁸ , R ²⁹⁶ and R ³⁰⁷ independent from each other are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;

monoaryl-amino; diaryl-amino; monocydoalkyi monoarylamino; monoalkyi monoaryl amino; alkylthio; arylthio;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido;

R ²⁸¹ , R ²⁸⁹ , R ²⁹⁷ and R ³⁰⁸ are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;

_R 282 _{tQ R} 2∞ _R 290 _{{q r} 293 ^ _R 298 _{to R} 301 _R 309 _{to R} 312 j _ndependent f _{rom each otheri} are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl,

heterocycloalkyl, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoarylcarbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoaryl- sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N- monoalkylamino, Ν,Ν-dialkyl-amino, N-arylamino, Ν,Ν-diarylamino, N-alkyl-N-aryl- amino, N-monocycloalkylamino, N;N-dicycloalkylamino, N-alkyl-N-cycloalkyl-amino, N- aryl-Ncycloalkyl-amino, N-heteroarylamino, N-heterocycloalkylamino or

hyd roxya ky I s u If o ny I a I ky I ,

or

are alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-di alkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo alkyl- amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl- carbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N- dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyi, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N-monoarylsulfamoyl or SO ₃ M; or alkyl interrupted by one or more heteroatoms such as oxygen or sulphur; or a rest with free valence to link to rest reactive anchor T;

R ²⁸⁶ , R ²⁸⁷ , R ²⁹⁴ , R ²⁹⁵ , R ³⁰⁵ , R ³⁰⁶ , R ³¹⁶ and R ³¹⁷ , independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO ₃ M, trifluoromethyl, nitro, ester,

NHC(0)R ³¹⁸ , CONH2, S(0) ₂ R ³¹⁹ or -S0 ₂ X;

R ³¹⁸ and R ³¹⁹ , independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R ³⁰² to R ³⁰⁴ and R ³¹³ to R ³¹⁵ , independent from one another, are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 ₃ M, COOM; or a group of formulae (2a) to (2c) as defined above;

E ¹⁶ to E ¹⁹ , independent from each other, are a group of general formulae (E1 ) to (E3) as defined above;

T and X have the same meanings as defined above.

In the especially preferred dyes of the formulae (lac) to (laf),

R ²⁸⁰ , R ²⁸⁸ , R ²⁹⁶ and R ³⁰⁷ independent from each other are hydrogen or (d-C ₄ ) alkyl, aryl, (Ci-C ) alkyloxy;

R ²⁸¹ , R ²⁸⁹ , R ²⁹⁷ and R ³⁰⁸ independent from each other are (Ci-C ₄ )alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;

_R 282 _{tQ R} 28 _{5i R} 290 _{to R} 293 _{> R} 298 _{{q r} 301 _R 309 _{q pSH ^ j _ndependent f _{rom Qne an0} ther, are hydrogen, (Ci-C )alkyl, (Ci-C ₆ )alkyloxy, aryl

Or -Alk-S0 ₂ X,

Or aryl substituted by one or more groups selected from halogen, -SO ₃ M or -SO ₂ X or free valence substituted with T; R ²⁸⁶ , R ²⁸⁷ , R ²⁹⁴ , R ²⁹⁵ , R ³⁰⁵ , R ³⁰⁶ , R ³¹⁶ and R ³¹⁷ , independent from one another, are hydrogen, (Ci-C )alkyl, (Ci-C )alkoxyl, halogen or -S0 ₃ M;

_R 302 _{10 R} 304 _{and R} 313 _{tQ R} 315^ j _nc | _e p _enc | _en t f _{rom one} another are hydrogen, (C ₁ -C ₄ )alkyl, (Ci-C ₄ )alkoxyl, hydroxyl, carbamido, halogen or -S0 ₃ M or contains the group of formulae (2a) to (2c);

E ¹⁶ to E ¹⁹ , independent from each other, are a group of general formulae (E1 ) to (E3); T and X are the same as defined above.

Examples of the preferred dyes of this invention are the dyes from 1 to 194 (Tablel ) corresponding to the general formula (II).

wherein

n is 0 or 1 ;

K ⁷ is a radical of heterocyclic coupling component and has the same meaning as described above for K;

A ³ is a radical of middle component and has the same meaning as described above for A; B ³ is a radical of diazo component and has the same meaning as described above for B; M is hydrogen, sodium, potassium, lithium or ammonium; Table 1

51

52



90

92

93

94

95

96

103

109

114

115

116

117

118

119

120

121

ı22









130

ı32

ı33





140

141







^* refers to the attachment point of B ³ and the rest containing K ⁷ when n is an integer of 0;

^* refers to the attachment point between B ³ and A ³ ;

^** refers to the attachment point of A ³ and of the rest containing K ⁷ when n is an integer of 1.

Further examples of the preferred dyes of this invention are the dyes from 195 to 391 (Table 2) corresponding to the general formula (III).

wherein

n is 0 or 1 ;

K ⁸ is a radical of heterocyclic coupling component and has the same meaning as described above for K;

A ⁴ is a radical of middle component and has the same meaning as described above for A; B ⁴ is a radical of diazo component and has the same meaning as described above for B; M is hydrogen, sodium, potassium, lithium or ammonium;

ı52

ı53





190

ı94

ı96

210

214

215

216

218

220

221

222

223

224

227

IJ33





^* refers to the attachment point of B ⁴ and of the rest containing K ⁸ when n is an integer of 0;

^* refers to the attachment point between B ⁴ and A ⁴ ;

^** refers to the attachment point of A ⁴ and of the rest containing K ⁸ when n is an integer of 1.

The present invention also provides a process for the preparation of the dyes of the formula (I) which comprises diazotization of the compounds of the formula (IV) and reacting the correspondingly obtained diazonium salts with a compound of the formula K to obtain the intermediate of general formula (V).

In a further step the diazo component (B-NH ₂ ) is diazotised and coupled onto the intermediate V to obtain the bisazo d e product of general formula (VI).

Alternatively, the diazo component (B-NH ₂ ) can be diazotised and coupled onto the compound (A-NH ₂ ) to obtain intermediate (VII). Further, the intermediate (VII) is diazotised and coupled onto compound (V) to obtain the t sazo dye product of general formula (VIII).

.NH _{2 +} „NH,

(VII I)

Wherein A, B and K have the same meaning as described above.

The diazotization of the compounds of the formulae (IV), B-NH ₂ and (VII) can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used.

The coupling reaction of the diazotized compounds of the formulae (IV), B-NH ₂ and (VII) onto the compound of formula (K) and (V) can likewise be performed by known methods. The compounds of the formula A, B and K are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art. The present invention also provides for the use of the present invention's dyes for dyeing or printing of hydroxyl-, amino-, and/or carboxamido-containing material, or a process for dyeing or printing of hydroxyl- and/or carboxamido-containing material whereby a dye is applied to the material and fixed on the material by usual means, the process utilizing a dye in accordance with the present invention.

Hydroxyl-containing materials can be of natural or synthetic origin. Examples are cellulose fiber materials, preferably cotton, linen, hemp, jute and ramie fibers, regenerated cellulose fibers such as preferably staple viscose and filament viscose, chemically modified cellulose fibers, such as for example aminated cellulose fibers, and also polyvinyl alcohols.

Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-1 1 and nylon-4.

The hydroxyl- and/or carboxamido-containing materials mentioned can be present in various forms. For instance in the form of sheetlike structures, such as paper and leather, in the form of films, such as nylon films, or in the form of a bulk mass, for example composed of polyamide and polyurethane, in particular in the form of fibers, for example cellulose fibers. The fibers are preferably textile fibers, for example in the form of woven fabrics or yarns or in the form of hanks or wound packages.

The dyes of the present invention and their salts or mixtures can be used as a single dyeing product in dyeing or printing processes or it can be part of a di/tri or multi- component combination product in dyeing or in printing compositions. Dyes of this invention and their salts or mixtures are highly compatible with other known and/or commercially available dyes and they can be used together with such dyes to obtain specific hues of similarly good technical performance. Technical performance includes build-up, fastness properties and levelness.

The dyes according to the invention can be applied to the materials mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes. This applies to both, dyeing and printing processes.

It applies in particular to the production of dyeings on fiber materials composed of wool or other natural polyamides or of synthetic polyamides and their mixtures with other fiber material. In general, the material to be dyed is introduced into the bath at a temperature of about 40°C, agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98°C. However, the dyeings can also be carried out at the boil or in sealed dyeing apparatus at temperatures of up to 106°C.

Since the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.

The dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing. For this the dyes of the present invention need to be formulated in inks. Aqueous inks for digital printing which comprise a dye in

accordance with the present invention likewise form part of the subject matter of the present invention.

The inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 % by weight to 50% by weight, more preferably from 1 % by weight to 30% by weight and most preferably from 1 % by weight to 15% by weight, based on the total weight of the ink.

The inks, as well as the dye of the present invention, may if desired contain further dyes used in digital printing. For the inks of the present invention to be used in the continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present invention may include organic solvents at a total level of 1 -50% and preferably 5-30% by weight. Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5- pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2,6-hexanetriol, 1 ,2- octanediol, polyalkylene glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols having 1 to 8 alkylene groups, for example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydric alcohols, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers, such as for example: polyethylene glycol monomethyl ether,

polypropylene glycol glycerol ether, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as for example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine,

diethanolamine, triethanolamine, N-acetylethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives, such as for example: urea, thiourea, N-methylurea, Ν,Ν'-epsilon dimethylurea, ethyleneurea, 1 , 1 ,3,3-tetramethylurea, amides, such as for example: dimethylformamide, dimethylacetamide, acetamide, ketones or keto alcohols, such as for example: acetone, diacetone alcohol, cyclic ethers, such as for example: tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma butyrolactone, epsilon-caprolactam, further sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide, N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone, 1 -(2-hydroxyethyl)- 2-pyrrolidone, 1 -(3-hydroxypropyl)-2-pyrrolidone, 1 ,3-dimethyl-2-imidazolidinone, 1 ,3-dimethyl-2-imidazolinone, 1 ,3-bismethoxymethylimidazolidine, 2-(2- methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2- propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, trimethylpropane,

1 ,2-dimethoxypropane, dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether, 1 ,2-dimethoxypropane and trimethylpropane.

The inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1 .5 to 40.0 mPas in a temperature range from 20 to 50°C. Preferred inks have a viscosity of 1 .5 to 20 mPas and particularly preferred inks have a viscosity of 1 .5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example:

polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified

galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.

As further additives the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a function of the process used (thermal or piezo technology). Useful surface-active substances include for example: all surfactants, preferably nonionic surfactants, butyldiglycol, 1 ,2- hexanediol.

The inks of the present invention may further include customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink. The inks may be prepared in a conventional manner by mixing the components in water.

The inks of the invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and cellulosic fiber materials of any kind. Blend fabrics, for example blends of cotton, silk, wool with polyester fibers or polyamide fibers can similarly be printed. In contrast to conventional textile printing, where the printing ink already contains all necessary chemicals, in digital or inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.

The pretreatment of the textile substrate, for example cellulose and regenerated cellulose fibers and also silk and wool, is effected with an aqueous alkaline liquor prior to printing. In addition there is a need for thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans. These pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried. The examples below serve to illustrate the invention. Parts and percentages are by weight unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.

Synthesizing procedure for example 1 6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (a) was added into 70 parts of water. The reaction vessel was cooled to 0-5 °C using ice. 1.5 parts of sodium nitrite was added into the reaction mixture. After stirring for 10 min, 20.7 parts of 37% hydrochloric acid was added. The reaction was stirred at 0-5 °C for 0.5 h and then 0.2 parts of sulfamic acid was added.

3.6 parts of 1 -Ethyl-6-hydroxy-4-methyl-2-oxo-1 ,2-dihydropyridine-3-carbonitrile (e) was dissolved in water/methanol mixture. The reaction vessel was cooled to 0-5 °C using ice. The diazonium salt was added into the coupler solution slowly while maintaining the pH at in the slightly acidic range. The reaction was stirred until completion to yield the intermediate (f).

5.9 parts of {2-[(4-aminobenzene)sulfonyl]ethoxy}sulfonic acid (g) was suspended in 50 parts of water. The reaction vessel was cooled to 0-5 °C using ice. 6.2 parts of 37% hydrochloric acid was added into the reaction mixture. After stirring for 10 min, 1.5 parts of sodium nitrite was added. The reaction was stirred at 0-5 °C for 1 h and then 0.2 parts of sulfamic acid was added.

The obtained diazonium salt was added slowly into the solution of (f) while maintaining the pH in the slightly acidic range. The reaction was stirred for 2 h. After completion, 15.2 parts of example 1 was obtained as black solid by precipitation, filtration and drying.

(f) (g) (1 )

Synthesizing procedure for Example 2

8.0 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (a) was dissolved in 50 parts of water. 5.1 parts of sodium nitrite solution was added into the reaction mixture. The reaction vessel was cooled down to 0 - 5 °C using ice-salt mixture. After 10 mins 7.5 parts of 37% hydrochloric acid was added to the reaction mixture. The reaction mixture was stirred for 1 -2 hrs. After completion 0.2 parts of sulfamic acid was added into the reaction mixture.

8.7 parts of coupling component (b) was suspended in 50 parts of water. The diazo component was added. The reaction mixture was stirred for 2 hrs. After completion, 16.1 parts of the product (c) was obtained by addition of salt and followed by filtration.

8.6 parts of 2,5-dimethoxyphenyl-4(2-sulfatoethyl)sulfonyl aniline (d) was suspended in 50 parts of water and stirred for 10 mins. 7.5 parts of 37% hydrochloric acid was added to the reaction mixture. The reaction vessel was cooled down to 0 - 5 °C using ice-salt mixture. 5.1 parts of sodium nitrite solution was added into the reaction mixture. The reaction mixture was stirred for 1 to 2 hrs.

After completion 0.2 parts of sulfamic acid was added into the reaction mixture. 17.7 parts of coupler (c) was dissolved in 50 parts of water. To this solution the diazo component was added dropwise during 1 hr. The reaction mixture was stirred for 2 hrs. After completion, 26.3 parts of the example 3 was obtained by addition of salt and followed by filtration.

Synthesizing procedure for example 124

6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (a) was added into 70 parts of water. The reaction vessel was cooled to 0-5 °C using ice. 1 .5 parts of sodium nitrite was added into the reaction mixture. After stirring for 10 min, 20.7 parts of 37% hydrochloric acid was added. The reaction was stirred at 0-5 °C for 0.5 h and then 0.2 parts of sulfamic acid was added.

7.66 parts of 1 -(sulfatoethyl sulfonyl ethyl)-6-hydroxy-4-methyl-2-oxo-1 ,2- dihydropyridine-3-carbonamide (h) was dissolved in water/methanol mixture. The reaction vessel was cooled to 0-5 °C using ice. The diazonium salt was added into the coupler solution slowly while maintaining the pH at in the slightly acidic range. The reaction was stirred until completion to yield the intermediate (i).

5.9 parts of {2-[(4-aminobenzene)sulfonyl]ethoxy}sulfonic acid (g) was suspended in 50 parts of water. The reaction vessel was cooled to 0-5 °C using ice. 6.2 parts of 37% hydrochloric acid was added into the reaction mixture. After stirring for 10 min, 1.5 parts of sodium nitrite was added. The reaction was stirred at 0-5 °C for 1 h and then 0.2 parts of sulfamic acid was added.

The obtained diazonium salt was added slowly into the solution of (i) while maintaining the pH in the slightly acidic range. The reaction was stirred for 2 h. After completion, 20.08 parts of example 121 was obtained as black solid by precipitation, filtration and drying.

Dyeing example 1

2 parts of a dye obtained as per formula (I) and 50 parts of sodium chloride were dissolved in 999 parts of water, and 5 parts of sodium carbonate and 1 part of a leveling agent were added. This dyebath was enetered with 100 parts of a woven cotton fabric. The temperature of the dyebath was increased to 30 °C and maintained for 30 mins. Further, the dyebath temperature was increased to 60 °C and maintained for 60 mins at 60 °C. Thereafter the dyed fabric was initially rinsed with water. Then, the dyed fabric was neutralized using 1000 parts of an aqueous solution containing 1 part of 60% acetic acid and heated at 50 °C for 30 to 40 minutes. The dyed fabric was rinsed with water at 70 °C and then soaped off at the boil with the laundry detergent for 30 to 40 minutes, and then rinsed again in water and spun dried. Dyeing example 2

1 part of the dye of the formula (I) was dissolved in 2000 parts of water and heated to 80 °C. for 20 minutes and 1 part of a leveling agent was added. The pH was then adjusted to 4.5 using acetic acid (60%) and 100 parts of wool fabric entered into the dyebath. The dye bath was heated to 40 °C. for 15 minutes. The temperature was raised to 98 °C. and maintained at 98 °C for 90 minutes. Then dyeing was lowered to 60 °C. and the fabric was removed from dyebath. The dyed fabric was washed with water and spun dried. Dyeing example 3

1 part of the dye of the formula (I) was dissolved in 2000 parts of water and 1 part of a leveling agent (based on a condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5 using acetic acid (80%). The dye bath was heated to 50 °C. for 10 minutes and then entered with 100 parts of a woven polyamide fabric. The temperature was raised to 1 10 °C. over the course of 50 minutes and then dyeing was lowered by cooling to 60 °C. and the dyed material was removed. The polyamide fabric was washed with hot and cold water, soaped and spun dried. Dyeing example 4

A textile fabric consisting of mercerized cotton was padded with a liquor containing 35g/l of calcium sodium carbonate, 100 g/l of urea and 150 g/l of a low-viscosity sodium alginate solution (6%), and then dried. The liquor pickup was 70%. The textile thus pretreated was printed with an aqueous ink containing 2% of the dye of example (I), 20% of sulfolane, 0.01 % of Mergal K9N and 77.99% of water using a drop-on- demand (bubblejet) ink-jet printing head. The print was fully dried. It was fixed by means of saturated steam at 102 °C for 8 minutes. The print was then rinsed warm, subjected to a fastness wash with hot water at 95 °C. Again rinsed with warm water and then dried.