AU2013279552A1

AU2013279552A1 - Reactive dyes, process for the production thereof and their use

Info

Publication number: AU2013279552A1
Application number: AU2013279552A
Authority: AU
Inventors: Roxana Barbieru; Hyeong Kyu Kim; Vedarethinam RAVI; Vajiravelu Sivamurugan; Han YUAN
Original assignee: Dystar Colours Distribution GmbH
Current assignee: Dystar Colours Distribution GmbH
Priority date: 2012-06-18
Filing date: 2013-06-13
Publication date: 2014-11-06

Description

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- C₄)-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

R¹ and R⁴, 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; R², R⁵ and R¹¹, independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, sulfomethyl or -SOsM;

R³', R⁶ to R⁹ and R¹², 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 S0₃M;

or alkyl or aryl substituted by -SO₂X; whereby

X is vinyl or a radical -CH₂CH₂-Y where Y is a group removable under alkaline conditions such as OS0₃M, SS0₃M, OCOCH₃, OPO₃M or halogen; and

R¹⁰ is hydroxyl or amino group;

And whereby, in the general formula K2 the point of attachment and R⁵ can be positioned ortho or para to the amino rest bearing the substituents R⁶ and R⁷, meaning that when the point of attachment is positioned ortho to amino rest bearing the substituents R⁶ and R⁷, R⁵ 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 S0₃M; each of R³³, R³⁴ and R³³⁸, independent from each other, are hydrogen, alkyl, alkoxyl, halogen, trifluoromethyl, cyano, nitro, ester, carbamoyl, SO₃M or -S0₂X;

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

X is vinyl or a radical -CH₂CH₂-Y where Y is a group removable under alkaline conditions such as OS0₃M, SS0₃M, OCOCH₃, OPO₃M or halogen; p is an integer from 1 to 5; R¹³ and R¹⁵, 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;

R¹², R¹⁶ and R²², independent from each other,

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

R¹⁴', R¹⁷ to R²⁰ and R²³, 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

R²¹ is hydroxyl or amino group;

And whereby, in the general formula K5 the point of attachment and R¹⁶ can be positioned ortho or para to the amino rest bearing the substituents R¹⁷ and R¹⁸, meaning that when the point of attachment is positioned ortho to amino rest bearing the substituents R¹⁷ and R¹⁸, R¹⁶ 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

R³⁴¹ to R³⁴⁸, 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, S0₃M, 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 SO₃M;

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 SO₃M;

or

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

whereby, R and R independent from each other, are hydrogen, alkyl, alkyl substituted by SO₃M, alkyl chain interrupted by one or two heteroatoms, or T, whereby T has the same meaning as above;

U is -0-, -S- or -N(R³²⁹)-;

R³²³, R³²⁷ and R³²⁹, independent from one another, are hydrogen, alkyl, alkyl substituted by SO₃M, alkyl chain interrupted by one or two heteroatoms;

R³²⁴, R³²⁵, R³²⁶ and R³²⁸, 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

R³⁵ to R⁴⁰ and R³⁵¹, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -S0₃M, trifluoromethyl, nitro, ester, NHC(0)R⁴¹, CONH₂, S(0)₂R⁴², - SO₂X or aminosubstituted by T or one of the general formulae (E1 ) to (E3);

(E1 (E2)

(E3) wherein

V is -0-, -S- or -N(R³⁵²)-;

R⁴³, R⁴⁷ and R³⁵², independent from one another are hydrogen, alkyl, alkyl substituted by SO3M, alkyl chain interrupted by one or two heteroatoms;

R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁸, independent from one another are hydrogen, alkyl or alkyl chain interrupted by one or two heteroatoms;

R³³⁰, R³³¹, R³³² and R³³³, independent from one another are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R³³⁴, CONH₂, S(0)₂R³³⁵ 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 SO₃M; alkyl containing a rest with free valence to link to rest reactive anchor T;

R⁴¹, R⁴², R³³⁴ and R³³⁵, 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;

R⁵⁰, R⁵⁴, R⁵⁹, R⁶⁷, R⁷⁵ and R⁷⁹ independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0₃M;

R⁵¹, R⁵⁵, R⁶⁰ and R⁶⁸ 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 SO₃M; or alkyl interrupted by one or more heteroatoms such as oxygen or sulphur; R⁵², R⁵³, R⁵⁶, R⁵⁷, R⁶⁴, R⁶⁵, R⁷², R⁷³, R⁷⁶, R⁷⁷, R⁸³ and R⁸⁴, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R⁸⁶, CONH₂, S(0)₂R⁸⁷ or -S0₂X;

R⁸⁶ and R⁸⁷ independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.

R⁶¹ to R⁶³, R⁶⁹ to R⁷¹, R⁸⁰ to R⁸², 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),

R⁴⁹, R⁸⁵, R⁵⁸, R⁶⁶, R⁷⁴ and R⁷⁸ independent from one another, are hydrogen or (C₁ -C4) alkyl or aryl;

R⁵⁰, R⁵⁴, R⁵⁹, R⁶⁷, R⁷⁵ and R⁷⁹ independent from one another, are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO₃M or -COOM;

R⁵¹, R⁵⁵, R⁶⁰ and R⁶⁸ independent from one another, are alkyl or aryl; Aryl substituted by one more substituents selected from alkyl, alkoxy, halogen or -SO₃M;

R⁶¹to R⁶³, R⁶⁹ to R⁷¹, R⁸⁰ to R⁸², independent from one another are hydrogen, (Ci- C )alkyl, (Ci-C )alkoxyl, hydroxyl, carbamido, halogen or -SO₃M or contain group of formulae (2a) to (2c) as defined above;

R⁸⁶ and R⁸⁷ 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

R⁹⁰ and R⁹⁴ 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;

R⁹¹ and R⁹⁵ independent from one another, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;

D¹ and D² 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 S0₃M;

R⁹², R⁹³, R⁹⁹ and R¹⁰⁰, independent from one another, are hydrogen or alkyi, alkoxy, halogen, cyano, -S0₃M, trifluoromethyl, nitro, ester, NHC(0)R¹⁰¹, CONH₂, S(0)₂R¹⁰² or -S0₂X;

R¹⁰¹ and R¹⁰² independent from one another are hydrogen, alkyi or alkyi substituted by hydroxy or halogen.

R⁹⁶ to R⁹⁸, 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, S0₃M, COOM; or a group of formulae (2a) to (2c) as defined above;

with the proviso D¹ and D² 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),

R⁹⁰ and R⁹⁴ independent from one another are hydrogen or (Ci-C₄)-alkyl or aryl;

R⁹¹ and R⁹⁵ independent from one another are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -S0₃M or -COOM;

D¹ and D² are alkyi or aryl; alkyi or aryl substituted by one more substituents selected from alkyi, alkoxy, halogen or -SO₃M, amino, N-alkyl amino;

R⁹⁶ to R⁹⁸, independent from one another are hydrogen, (Ci-C₄)-alkyl, (Ci-C₄)alkoxyl, hydroxyl, carbamido, halogen or -SO₃M or contain group of formulae (2a) to (2c) as defined above; R¹⁰¹ and R¹⁰² 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

R¹⁰⁵, R¹¹⁰, R¹¹⁵ and R¹²³ 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

R¹⁰⁶, R¹¹¹, R¹¹⁶ and R¹²⁴ are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;

R¹⁰⁷, R¹¹², R¹¹⁷ and R¹²⁵ 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 -SO₃M;

R¹⁰⁸, R¹⁰⁹, R¹¹³, R¹¹⁴, R¹²¹ , R¹²², R¹²⁹ and R¹³⁰, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester,

NHC(0)R¹³¹ , CONH2, S(0)₂R¹³² or -S0₂X;

R¹³¹ and R¹³², independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.

_Ri i8 _{10 R}i2o _{an d R}126 _{10 R}128_; j_nc|_ep_enc|_ent 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, S0₃M, COOM; or a group of formulae (2a) to (2c) as defined above;

E⁴ to E⁷, 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),

R¹⁰⁵, R¹¹⁰, R¹¹⁵ and R¹²³ independent from each other are hydrogen or (Ci-C₄)alkyl or aryl;

R¹⁰⁶, R¹¹¹, R¹¹⁶ and R¹²⁴ independent from each other are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO₃M or -COOM;

R¹⁰⁷, R¹¹², R¹¹⁷ and R¹²⁵ independent from each other are alkyl or aryl; Aryl substituted by one more substituents selected from alkyl, alkoxy, halogen or -SO3M;

R¹¹⁸ to R¹²⁰ and R¹²⁶ to R¹²⁸, independent from one another, are hydrogen, (Ci-C₄)alkyl, (Ci-C₄)alkoxyl, hydroxyl, carbamido, halogen or -SOsM or contain group of formulae (2a) to (2c);

R¹⁰⁸, R¹⁰⁹, R¹¹³, R¹¹⁴, R¹²¹ , R¹²², R¹²⁹ and R¹³⁰, independent from one another, are hydrogen or alkyl, alkoxy, halogen, -SO₃M or -SO₂X;

R¹³¹ and R¹³², independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxyl; E⁴ to E⁷, 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 R¹⁵⁰ 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;

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;

R¹³⁶, R¹⁴⁰, R¹⁴⁴ and R¹⁵¹ independent from each other are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0₃M;

D³, D⁴, D⁵ and D⁶ 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 S0₃M;

R¹³⁷, R¹³⁸, R¹⁴¹, R¹⁴², R¹⁴⁸, R¹⁴⁹, R¹⁵⁵ and R¹⁵⁶, independent from one another are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester,

NHC(0)R¹⁵⁷, CONH2, S(0)₂R¹⁵⁸ or -S0₂X;

R¹⁵⁷ and R¹⁵⁸, independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R¹⁴⁵, R¹⁴⁶, R¹⁴⁷, R¹⁵², R¹⁵³ and R¹⁵⁴, 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, S0₃M, COOM; or a group of formulae (2a) to (2c) as defined above;

E⁸to E¹¹, 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),

R¹³⁵, R¹³⁹, R¹⁴³ and R¹⁵⁰ independent from each other are hydrogen or (Ci-C₄)-alkyl or aryl;

R¹³⁶, R¹⁴⁰, R¹⁴⁴ and R¹⁵¹ independent from each other are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO₃M or -COOM;

D³, D⁴, D⁵ and D⁶ 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;

R¹³⁷, R¹³⁸, R¹⁴¹, R¹⁴², R¹⁴⁸, R¹⁴⁹, R¹⁵⁵ and R¹⁵⁶, independent from one another, are hydrogen or alkyl, alkoxy, halogen, -SO₃M or -SO₂X; R¹⁴⁵, R¹⁴⁶, R¹⁴⁷, R¹⁵², R¹⁵³ and R¹⁵⁴, independent from one another, are hydrogen, (d- C )-alkyl, (Ci-C )alkoxyl, hydroxyl, carbamido, halogen or -S0₃M or contain group of formulae (2a) to (2c) as defined above;

E⁸ to E¹¹, 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

R¹⁶¹, R¹⁶⁸, R¹⁷⁵ and R¹⁸⁵ independent from each other are alkyl, cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -

R¹⁶², R¹⁶⁹, R¹⁷⁶ and R¹⁸⁶ independent from each other are hydroxyl or amino; _R163 _{tQ R}i65_{j R}i 7o _{tQ R}172_{> R}177 _{{q R}179 _{and R}187 _{fo R}i∞ j_ndepenc|_ent 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 -SO₃M; or alkyl interrupted by one or more heteroatoms such as oxygen or sulphur; or alkyl or aryl substituted by -SO₂X; whereby

X is vinyl or a radical -CH₂CH₂-Y where Y is a group removable under alkaline conditions such as OSO₃M; or contain a rest with free valence to link to rest reactive anchor T;

R¹⁶⁶, R¹⁶⁷, R¹⁷³, R¹⁷⁴, R¹⁸³, R¹⁸⁴, R¹⁹³ and R¹⁹⁴, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester,

NHC(0)R¹⁹⁵, CONH2, S(0)₂R¹⁹⁶ or -S0₂X;

R¹⁹⁵ and R¹⁹⁶, independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R¹⁸⁰ to R¹⁸² and R¹⁹⁰ to R¹⁹², 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, SO₃M, 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),

R¹⁶¹ , R¹⁶⁸, R¹⁷⁵ and R¹⁸⁵, independent from each other are (Ci-C₄)alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;

R¹⁶², R¹⁶⁹, R¹⁷⁶ and R¹⁸⁶, independent from each other are hydroxyl or amino;

_R163 _{tQ R}i65_{j R}i7o _{{q R}172_{> R}177 _{{q R}179 _{and R}187 _toRi89 j_ndepenc|_ent f_rom one another are hydrogen, (Ci-C )alkyl, (Ci-C )alkyloxy, halogen, -SO₃M or -S0₂X or free valence substituted with T;

R¹⁶⁶, R¹⁶⁷, R¹⁷³, R¹⁷⁴, R¹⁸³, R¹⁸⁴, R¹⁹³ and R¹⁹⁴, independent from one another, are hydrogen, (Ci-C )alkyl, (Ci-C )alkoxyl, halogen or -S0₃M;

_Ri8o _{t0 R}182 _{and R}i9o _{t0 R}192^ independent from one another are hydrogen, (C₁-C₄)alkyl, (Ci-C₄)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;

R¹⁹⁹, R²⁰⁶, R^{2 3} and R²²³ independent from each other are alkyl, cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0₃M;

R²⁰⁰, R²⁰⁷, R²¹⁴ and R²²⁴ independent from each other are hydroxyl or amino;

_R201 _{tQ R}2Q3^ _R208 _{tQ R}210_{; R}215 _{[q r}217 _R225 _{{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 -SO₃M; or alkyl interrupted by one or more heteroatoms such as oxygen or sulphur; or alkyl or aryl substituted by -SO₂X or contains a rest with free valence to link to rest reactive anchor T;

whereby X is vinyl or a radical -CH₂CH₂-Y where Y is a group removable under alkaline conditions such as OSO₃M; R²⁰⁴, R²⁰⁵, R²¹¹, R²¹², R²²¹, R²²², R²³¹ and R²³², independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -S0₃M, trifluoromethyl, nitro, ester,

NHC(0)R²³³, CONH₂, S(0)₂R²³⁴ or -S0₂X;

R²³³ and R²³⁴, independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R²¹⁸ to R²²⁰ and R²²⁸ to R²³⁰, 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, S0₃M, COOM; or a group of formulae (2a) to (2c) as defined above;

E¹² to E¹⁵, 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),

R¹⁹⁹, R²⁰⁶, R^{2 3} and R²²³ are (Ci-C₄)alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;

R²⁰⁰, R²⁰⁷, R²¹⁴ and R²²⁴ are hydroxyl or amino;

R²⁰¹ to R²⁰³, R²⁰⁸ to R²¹⁰, R²¹⁵ toR²¹⁷ and R²²⁵ to R²²⁷, independent from one another, are hydrogen, (Ci-C₄)alkyl, (Ci-C₄)alkyloxy, halogen, -SO3M or -SO₂X or free valence substituted with T;

R²⁰⁴, R²⁰⁵, R² , R²¹², R²²¹, R²²², R²³ and R²³², independent from one another, are hydrogen, (Ci-C₄)alkyl, (Ci-C₄)alkoxyl, halogen or -SO₃M;

R²¹⁸ to R²²⁰ and R²²⁸ to R²³⁰, independent from one another, are hydrogen, (Ci-C₄)alkyl, (Ci-C )alkoxyl, hydroxyl, carbamido, halogen or -SO₃M or contain the group of formulae (2a) to (2c);

E¹² to E¹⁵, 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

R²³⁷, R²⁴⁵, R²⁵³ and R²⁶⁴ 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;

R²³⁸, R²⁴⁶, R²⁵⁴ and R²⁶⁵ independent from each other are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0₃M;

_R239 _{tQ R}24_{2i R}247 _{{q r}250 ^ _R255 _{to R}258 _R267 _{to R}270_j j_ndepenc|_ent f_r0m 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 SO₃M; 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;

R²⁴³, R²⁴⁴, R²⁵¹, R²⁵², R²⁶², R²⁶³, R²⁷⁴ and R²⁷⁵, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester,

NHC(0)R²⁷⁶, CONH2, S(0)₂R²⁷⁷ or -S0₂X;

R²⁷⁶ and R²⁷⁷, independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R²⁵⁹ to R²⁶¹ and R²⁷¹ to R²⁷³, 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, S0₃M, COOM; or a group of formulae (2a) to (2c) as defined above;

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

R²³⁷, R²⁴⁵, R²⁵³ and R²⁶⁴ are hydrogen or (C1-C4) alkyl, aryl, (C1-C4) alkyloxy;

R²³⁸, R²⁴⁶, R²⁵⁴ and R²⁶⁵ are (Ci-C₄)alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;

R²³⁹ to R²⁴², R²⁴⁷ to R²⁵⁰, R²⁵⁵ to R²⁵⁸ and R²⁶⁷ to R²⁷⁰, independent from one another, are hydrogen, (Ci-C )alkyl, (Ci-C₆)alkyloxy, aryl;

Or -Alk-S0₂X,

Or aryl substituted by one or more groups selected from halogen, -SO₃M or -SO₂X or free valence substituted with T;

R²⁴³, R²⁴⁴, R²⁵¹, R²⁵², R²⁶², R²⁶³, R²⁷⁴ and R²⁷⁵, independent from one another, are hydrogen, (Ci-C )alkyl, (Ci-C )alkoxyl, halogen or -SO₃M; R²⁵⁹ to R²⁶¹ and R²⁷¹ to R²⁷³, independent from one another, are hydrogen, (Ci-C₄)alkyl, (Ci-C₄)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

R²⁸⁰, R²⁸⁸, R²⁹⁶ and R³⁰⁷ 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

R²⁸¹, R²⁸⁹, R²⁹⁷ and R³⁰⁸ are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;

_R282 _{tQ R}2∞ _R290 _{{q r}293 ^ _R298 _{to R}301 _R309 _{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 SO₃M; 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;

R²⁸⁶, R²⁸⁷, R²⁹⁴, R²⁹⁵, R³⁰⁵, R³⁰⁶, R³¹⁶ and R³¹⁷, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester,

NHC(0)R³¹⁸, CONH2, S(0)₂R³¹⁹ or -S0₂X;

R³¹⁸ and R³¹⁹, independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R³⁰² to R³⁰⁴ and R³¹³ to R³¹⁵, 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, S0₃M, COOM; or a group of formulae (2a) to (2c) as defined above;

E¹⁶ to E¹⁹, 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),

R²⁸⁰, R²⁸⁸, R²⁹⁶ and R³⁰⁷ independent from each other are hydrogen or (d-C₄) alkyl, aryl, (Ci-C ) alkyloxy;

R²⁸¹, R²⁸⁹, R²⁹⁷ and R³⁰⁸ independent from each other are (Ci-C₄)alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;

_R282 _{tQ R}28_{5i R}290 _{to R}293_{> R}298 _{{q r}301 _R309 _{q pSH ^ j_ndependent f_{rom Qne an0}ther, are hydrogen, (Ci-C )alkyl, (Ci-C₆)alkyloxy, aryl

Or -Alk-S0₂X,

Or aryl substituted by one or more groups selected from halogen, -SO₃M or -SO₂X or free valence substituted with T; R²⁸⁶, R²⁸⁷, R²⁹⁴, R²⁹⁵, R³⁰⁵, R³⁰⁶, R³¹⁶ and R³¹⁷, independent from one another, are hydrogen, (Ci-C )alkyl, (Ci-C )alkoxyl, halogen or -S0₃M;

_R302 _{10 R}304 _{and R}313 _{tQ R}315^ j_nc|_ep_enc|_ent f_{rom one} another are hydrogen, (C₁-C₄)alkyl, (Ci-C₄)alkoxyl, hydroxyl, carbamido, halogen or -S0₃M or contains the group of formulae (2a) to (2c);

E¹⁶ to E¹⁹, 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 ;

K⁷ is a radical of heterocyclic coupling component and has the same meaning as described above for K;

A³ is a radical of middle component and has the same meaning as described above for A; B³ 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 B³ and the rest containing K⁷ when n is an integer of 0;

^*refers to the attachment point between B³ and A³;

^**refers to the attachment point of A³ and of the rest containing K⁷ 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 ;

K⁸ is a radical of heterocyclic coupling component and has the same meaning as described above for K;

A⁴ is a radical of middle component and has the same meaning as described above for A; B⁴ 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 B⁴ and of the rest containing K⁸ when n is an integer of 0;

^*refers to the attachment point between B⁴ and A⁴;

^**refers to the attachment point of A⁴ and of the rest containing K⁸ 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-NH₂) is diazotised and coupled onto the intermediate V to obtain the bisazo d e product of general formula (VI).

Alternatively, the diazo component (B-NH₂) can be diazotised and coupled onto the compound (A-NH₂) 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-NH₂ 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-NH₂ 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).

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.

Claims

Claims:

1. Chemical compound of formula (I):

wherein n is 0 or 1 ;

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

A is a radical of a middle component as described below;

B is a radical of a diazo component as described below;

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

K is a coupling component of one of general formulae (K1 ) to (K3);

(K1 ) (K2) (K3) wherein, R¹ and R⁴, 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;

R², R⁵ and R¹¹, independent from each other, are cyano, carbamoyl,

alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, sulfomethyl or -SO₃M;

R³, R⁶, R⁷, R⁸, R⁹ and R¹², independent from 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, Ν,Ν-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, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N- monoarylsulfamoyl, N-monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, N,N- 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 alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;

or

alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl 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, 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, N,N-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-monoaryl sulfamoyl, N,N- diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N- monoarylsulfamoyl or SO₃M;

or

alkyl or aryl substituted by -SO₂X; whereby

X is vinyl or a radical -CH₂CH₂-Y where Y is a group removable under alkaline conditions such as OS0₃M, SS0₃M, OCOCH₃, OPO₃M or halogen; and

R¹⁰ is hydroxyl or amino group;

And whereby, in the general formula K2 the point of attachment and R⁵ can be positioned ortho or para to the amino rest bearing the substituents R⁶ and R⁷, meaning that when the point of attachment is positioned ortho to amino rest bearing the substituents R⁶ and R⁷, R⁵ is positioned para to the same, and vice versa. or K is a coupling component of one of general formulae (K4) to (K6);

(K4) (K5)

(K6)

whereby

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

wherein

R²⁴ and R²⁵, independent from each other are halogen or

R , R , R , R and R , independent from each other are halogen; or

each of R , R , R , R , R , R and R^M, 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, alky, phenyl or phenyl substituted by one member of the group selected from alkyl, alkoxy, halogen, or -S0₃M; alkenyl, cycloalkyi, 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, sulfamoyl, 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, N,N- dialkyl-amino, N-arylamino, Ν,Ν-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 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-monoalkylamino, Ν,Ν-dialkyl 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, 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, N,N- 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-monoaryl sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or SO₃M;

R³³, R³⁴ and R³³⁸, independent from each other, are hydrogen, alkyl, alkoxyl, halogen, trifluoromethyl, cyano, nitro, ester, carbamoyl, SO₃M or -SO₂X;

where M is hydrogen, sodium, potassium, lithium or ammonium; X is vinyl or a radical -CH₂CH₂-Y where Y is a group removable under alkaline conditions such as OS0₃M, SS0₃M, OCOCH₃, OPO₃M or halogen; p is an integer from 1 to 5;

R¹³ and R¹⁵, 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;

R¹², R¹⁶ and R²², independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SO₃M;

R¹⁴, R¹⁷ to R²⁰ and R²³, independent from each other, are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SO₃M; 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, 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

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 alkyl-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, N,N-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-monoaryl sulfamoyl, N,N- diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N- monoarylsulfamoyl or SOsM; R²¹ is hydroxyl or amino group;

And whereby, in the general formula K5 the point of attachment and R¹⁶ can be positioned ortho or para to the amino rest bearing the substituents R¹⁷ and R¹⁸, meaning that when the point of attachment is positioned ortho to amino rest bearing the substituents R¹⁷ and R¹⁸, R¹⁶ is positioned para to the same, and vice versa.

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

(A1 ) (A2)

wherein

R³⁴¹ to R³⁴⁸, 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, S0₃M, COOM; or

are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkylamino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N -a Iky I- 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, N,N- 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 SO₃M;

or

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

alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl 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, 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, N,N-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-monoaryl sulfamoyl, N,N- diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl- N- monoarylsulfamoyl or SO₃M;

or

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

whereby, R and R independent from each other, are hydrogen, alkyl, alkyl substituted by SO₃M, 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^^a)-;

R³²³, R³²⁷ and R³²⁹, independent from one another, are hydrogen, alkyl, alkyl substituted by SO₃M, alkyl chain interrupted by one or two heteroatoms;

R³²⁴, R³²⁵, R³²⁶ and R³²⁸, 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 formulae (B1 ) or (B2);

(B1 ) (B2)

wherein

R³⁴ to R⁴⁰ and R³⁵¹, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R⁴¹, CONH₂, S(0)₂R⁴², -SO₂X or aminosubstituted by T or one of the general formulae (E1 ) to (E3);

(E3)

wherein

V is -0-, -S- or -N(R^JO ;

R⁴³, R⁴⁷ and R³⁵², independent from one another are hydrogen, alkyl, alkyl substituted by S0₃M, alkyl chain interrupted by one or two heteroatoms;

R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁸, independent from one another are hydrogen, alkyl or alkyl chain interrupted by one or two heteroatoms;

R³³⁰, R³³¹, R³³² and R³³³, independent from one another are hydrogen or alkyl, alkoxy, halogen, cyano, -S0₃M, trifluoromethyl, nitro, ester, NHC(0)R³³⁴, CONH₂, S(0)₂R³³⁵ or a group of formula (3a);

R and R , independent from one another are hydrogen, alkyl, alkenyl, cycloalkyi, trifluoromethyl, aryl, heteroaryl, heterocycloalkyi, 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, 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-monoalkylamino, Ν,Ν-dialkyl 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, 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, N,N- 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-monoaryl sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or SO₃M;

containing a rest with free valence to link to rest reactive anchor T;

R⁴¹, R⁴², R³³⁴ and R³³⁵, 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.

Chemical compound according to claim 1 having one of formulae (la) to (If):

(lc)

(Id)

le)

(if)

wherein

R , R , R , R , R and R 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;

R⁵⁰, R⁵⁴, R⁵⁹, R⁶⁷, R⁷⁵ and R⁷⁹ independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;

R⁵¹, R⁵⁵, R⁶⁰ and R⁶⁸ independent from 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, 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-monoalkylamino, Ν,Ν-dialkyl 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, 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, 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-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or SO₃M;

R⁵², R⁵³, R⁵⁶, R⁵⁷, R⁶⁴, R⁶⁵, R⁷², R⁷³, R⁷⁶, R⁷⁷, R⁸³ and R⁸⁴, independent from one another, are hydrogen or alkyi, alkoxy, halogen, cyano, -SO₃M,

trifluoromethyl, nitro, ester, NHC(0)R⁸⁶, CONH₂, S(0)₂R⁸⁷ or -S0₂X;

R⁸⁶ and R⁸⁷ independent from one another, are hydrogen, alkyi or alkyi substituted by hydroxy or halogen.

R⁶¹ to R⁶³, R⁶⁹ to R⁷¹ , R⁸⁰ to R⁸², independent from one another, are hydrogen, alkyi, alkyi substituted, alkyi 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, S0₃M, COOM; or a group of formulae (2a) to (2c)

And X and M are as defined in claim 1 . 3. Chemical compound according to claim 1 having one of formulae (Ig) and (Ih) and mixtures thereof;

S0₃M

(ig)

wherein

R⁹⁰ and R⁹⁴ 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;

R⁹¹ and R⁹⁵ independent from each other, are cyano, carbamoyl,

alkoxycarbonyl, tnfluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -S0₃M;

D¹ and D² independent from each other, are hydrogen, alkyl, alkenyl, cycloalkyl, tnfluoromethyl, 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, sulfamoyl, 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, Ν,Ν-dialkyl amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N -a Iky I- N-arylamino, N-monocyclo alkyl-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, tnfluoromethyl, 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, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl- sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or SO₃M;

R⁹², R⁹³, R⁹⁹ and R¹⁰⁰, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R¹⁰¹, CONH2, S(0)₂R¹⁰² or -S0₂X;

R¹⁰¹ and R¹⁰² independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.

R⁹⁶ to R⁹⁸, independent from one another are hydrogen, alkyl, alkyl substituted, alkyl 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, sulfamoyl, ureido, alkylureido, SO₃M, COOM; or a group of formulae (2a) to (2c);

with the proviso D¹ and D² contain a rest with free valence to link to rest reactive anchor T;

M, X and T are the same as defined in claim 1 .

4. Chemical compound according to claim 1 having one of formulae (li) to (II) and mixtures thereof;

(li)

wherein

R¹⁰⁵, R¹¹⁰, R¹¹⁵ and R¹²³ independent from each other, are hydrogen, alkyl, cycloalkyi, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino; monoaryl-amino; diaryl-amino; monocycloalkyi monoarylamino; monoalkyl monoaryl amino; alkylthio; arylthio;

or

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

R¹⁰⁶, R¹¹¹, R¹¹⁶ and R¹²⁴ independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -S0₃M;

R¹⁰⁷, R¹¹², R¹¹⁷ and R¹²⁵ independent from 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, 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-monoalkylamino, Ν,Ν-dialkyl 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, 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, 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-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or -SO₃M;

R¹⁰⁸, R¹⁰⁹, R¹¹³, R¹¹⁴, R¹²¹, R¹²², R¹²⁹ and R¹³⁰, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R¹³¹, CONH₂, S(0)₂R¹³² or -S0₂X;

R¹³¹ and R¹³², independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.

_Ri i8 _{t0 R}i2o _{an d R}126 _{10 R}128 j_nc|_ep_enc|_ent f_{rom one} another, are hydrogen, alkyl, alkyl substituted, alkyl 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, S0₃M, COOM; or a group of formulae (2a) to (2c);

E⁴ to E⁷, independent from each other, are a group of general formulae (E1 ) to (E3),

and M as defined in claim 1.

5. Chemical compound according to claim 1 having one of formulae (Im) to (Ip) and mixtures thereof;

(Im)

(In)

(lo)

wherein

R¹³⁵, R¹³⁹, R¹⁴³ and R¹⁵⁰ independent from each other, are hydrogen, alkyl, cycloalkyi, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino; monoaryl-amino; diaryl-amino; monocycloalkyi 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;

R¹³⁶, R¹⁴⁰, R¹⁴⁴ and R¹⁵¹ independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -S0₃M;

D³, D⁴, D⁵ and D⁶ independent from 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, 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-monoalkylamino, Ν,Ν-dialkyl 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, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N- alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyi, 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, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl- sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or SO₃M;

R¹³⁷, R¹³⁸, R¹⁴¹, R¹⁴², R¹⁴⁸, R¹⁴⁹, R¹⁵⁵ and R¹⁵⁶, independent from one another are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R¹⁵⁷, CONH₂, S(0)₂R¹⁵⁸ or -S0₂X;

R¹⁵⁷ and R¹⁵⁸, independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R¹⁴⁵, R¹⁴⁶, R¹⁴⁷, R¹⁵², R¹⁵³ and R¹⁵⁴, independent from one another are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen , trifluoromethyl; cycloalkyl; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido, S0₃M, COOM; or a group of formulae (2a) to (2c);

E⁸to E¹¹, independent from each other, are a group of general formulae (E1 ) to

(E3);

T, M and X are the same as defined in claim 1 . 6. Chemical compound according to claim 1 having one of formulae (Iq) to (It) and mixtures thereof;

and mixtures thereof;

wherein

R¹⁶¹, R¹⁶⁸, R¹⁷⁵ and R¹⁸⁵ independent from each other, are alkyl, cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM; R¹⁶², R¹⁶⁹, R¹⁷⁶ and R¹⁸⁶ independent from each other, are hydroxyl or amino;

_R163 _{tQ R}165_{j R}170 _{{q r}172_{> r}177 _{{q r}179 _R187 _{{q r}1∞ j_ndepenc|_ent f_r0m 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, Ν,Ν-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, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N- monoarylsulfamoyl, N-monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino,

N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, N,N- 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-monoalkylamino, Ν,Ν-dialkyl 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, 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, N,N- 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-monoaryl sulfamoyi, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or -SO₃M;

or alkyl or aryl substituted by -SO₂X; whereby

X is vinyl or a radical -CH2CH2-Y where Y is a group removable under alkaline conditions such as OSO₃M; or contain a rest with free valence to link to rest reactive anchor T;

R¹⁶⁶, R¹⁶⁷, R¹⁷³, R¹⁷⁴, R¹⁸³, R¹⁸⁴, R¹⁹³ and R¹⁹⁴, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R¹⁹⁵, CONH₂, S(0)₂R¹⁹⁶ or -S0₂X;

R¹⁹⁵ and R¹⁹⁶, independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

_R ⁱ⁸o _{t0 R} ¹⁸² _{and R} ⁱ⁹o _{t0 R} ¹⁹² _; j_nc|_ep_enc|_ent 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, S0₃M, COOM; or a group of formulae (2a) to (2c);

X is the same as defined above,

M and T are as defined in claim 1.

7. Chemical compound according to claim 1 having one of formulae (lu) to (Ix) and mixtures thereof;

299

(Ix)

R ⁹⁹, R²⁰⁶, R²¹³ and R²²³ independent from each other, are alkyl, cyano, carbamoyl, alkoxycarbonyl, thfluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOaM;

R²⁰⁰, R²⁰⁷, R²¹⁴ and R²²⁴ independent from each other, are hydroxyl or amino; _R201 _{tQ R}203^ _R208 _{tQ R}210_{j R}215 _{{q r}217 _R225 _{{q r}227 _^ j_ndependent 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, Ν,Ν-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, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N- monoarylsulfamoyl, N-monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, N,N- 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, Ν,Ν-dialkyl 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, 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, N,N- 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-monoaryl sulfamoyi, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or -SO₃M;

or

alkyl or aryl substituted by -SO2X or contains a rest with free valence to link to rest reactive anchor T;

whereby X is vinyl or a radical -CH₂CH₂-Y where Y is a group removable under alkaline conditions such as OSO₃M;

R²⁰⁴, R²⁰⁵, R²¹¹, R²¹², R²²¹ , R²²², R²³¹ and R²³², independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R²³³, CONH₂, S(0)₂R²³⁴ or -S0₂X;

R²³³ and R²³⁴, independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

_R218 _{t0 R}22o _{and R}228 _{tQ R}23o^ j_nc|_ep_enc|_ent f_{rom one} another, are hydrogen, alkyl, alkyl substituted, alkyl 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, S0₃M, COOM; or a group of formulae (2a) to (2c);

E¹² to E¹⁵, independent from each other, are a group of general formulae (E1 ) to (E3);

X is the same as defined above,

M and T are as defined in claim 1 .

8. Chemical compound according to claim 1 having one of formulae (ly) to (lab) and mixtures thereof;

(lab) wherein

R²³⁷, R²⁴⁵, R²⁵³ and R²⁶⁴ independent from each other, are hydrogen, alkyl, cycloalkyi, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino; monoaryl-amino; diaryl-amino; monocycloalkyi 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;

R²³⁸, R²⁴⁶, R²⁵⁴ and R²⁶⁵ independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -S0₃M;

_R239 _{tQ R}24_{2i R}247 _{{q r}250 ^ _R255 _{to R}258 _R267 _{to R}270_j j_ndepenc|_ent f_r0m 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, Ν,Ν-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, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N- monoarylsulfamoyl, N-monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, N,N- 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-monoalkylamino, Ν,Ν-dialkyl 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, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N- alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, t fluoromethyl, 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, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or SO₃M; or alkyl contains a rest with free valence to link to rest reactive anchor T;

R²⁴³, R²⁴⁴, R²⁵¹, R²⁵², R²⁶², R²⁶³, R²⁷⁴ and R²⁷⁵, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R²⁷⁶, CONH₂, S(0)₂R²⁷⁷ or -S0₂X;

R²⁷⁶ and R²⁷⁷, independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R²⁵⁹ to R²⁶¹ and R²⁷¹ to R²⁷³, independent from one another, are hydrogen, alkyl, alkyl substituted, alkyl 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, S0₃M, COOM; or a group of formulae (2a) to (2c)

And X, M and T are as defined in claim 1.

9. Chemical compound according to claim 1 having one of formulae (lac) to (laf) and mixtures thereof; 307

(lae)

2

wherein

R²⁸⁰, R²⁸⁸, R²⁹⁶ and R³⁰⁷ independent from each other, are hydrogen, alkyl, cycloalkyi, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino; monoaryl-amino; diaryl-amino; monocycloalkyi 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;

R²⁸¹, R²⁸⁹, R²⁹⁷ and R³⁰⁸ are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SO₃M;

_R282 _{tQ R}2∞ _R290 _{{q r}293 ^ _R298 _{to R}301 _R309 _{to R}312 j_ndependent 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, Ν,Ν-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, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N- monoarylsulfamoyl, N-monoalkyl-N-monoaryl-sulfamoyl, amino, N-acylamino, N-thioacylamino, ureido, alkylureido, phenylureido, N-monoalkylamino, N,N- 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-monoalkylamino, Ν,Ν-dialkyl 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, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N- alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyi, 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, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl- N-monoarylsulfamoyl or SO₃M; or alkyl contains a rest with free valence to link to rest reactive anchor T;

R²⁸⁶, R²⁸⁷, R²⁹⁴, R²⁹⁵, R³⁰⁵, R³⁰⁶, R³¹⁶ and R³¹⁷, independent from one another, are hydrogen or alkyl, alkoxy, halogen, cyano, -SO₃M, trifluoromethyl, nitro, ester, NHC(0)R³¹⁸, CONH₂, S(0)₂R³¹⁹ or -S0₂X;

R³¹⁸ and R³¹⁹, independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;

R³⁰² to R³⁰⁴ and R³¹³ to R³¹⁵, 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, S0₃M, COOM; or a group of formulae (2a) to (2c);

E¹⁶ to E¹⁹, independent from each other, are a group of general formulae (E1 ) to (E3);

T, M and X have the same meanings as defined in claim 1 .

10. Chemical composition consisting of two or more chemical compounds according to any one of claims 1 to 9.

1 1. Chemical composition comprising one or more chemical compounds according to any one of claims 1 to 9. Aqueous solution for dying comprising one or more chemical compounds according to any one of claims 1 to 9.

13. Process for the production of chemical compounds according to formula (I) of claim 1 comprising the steps:

a) diazotizing compounds of formula (IV),

b) reacting the diazonium salts obtained in step a) with a compound of formula K to obtain an intermediate of formula (V)

K

c) diazotizing component (B-NH₂),

cx1 ) optionally coupling the diazotized product of step c) onto the compound (A- cx2) diazotizing the coupling product of step cx1 )

d) coupling the diazotized product of step c) onto the intermediate V to obtain the bisazo- roduct of general formula (VI) in case of step c)

or coupling the diazotized coupling product of cx2) onto the intermediate V to obtain the trisazo-product of general formula (VIII),

(VIII)

14. Use of a chemical compound according to any one of claims 1 to 9, a chemical composition according to claim 10 or 1 1 or of an aqueous solution according to claim 12 for dying fibers, as well as blends of such fibres selected from the group consisting of: vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers; and synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres.

15. Fiber and blends containing such fiber selected from the group consisting of: vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers; and synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres

comprising one or more chemical compounds according to any one of claims 1 to 9 either in chemically and/or physically bound form.