# Patent

## Title
Acid dyes, process for the production thereof and their use

## Abstract

Dyes of formula (1)




a process for their production and their use are described.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage application (under 35 U.S.C. §371) of PCT/EP2014/072629, filed Oct. 22, 2014, which claims benefit of European Application No. 13190652.1, filed Oct. 29, 2013, both of which are incorporated herein by reference in their entirety.
The present invention relates to the technical field of dyestuffs for dyeing and printing of hydroxyl- and/or carboxamido-containing material.
Acid dyes with pyridine couplers are known from prior art and can be used as colorants in different applications, see for example U.S. Pat. No. 3,959,250 A1, U.S. Pat. No. 5,468,848 A1, JP 1 197578 A and WO 2007/045825 A2.
However, in the context of the dyeing and printing of hydroxyl- and/or carboxamido-containing material the known dyes have a number of technical disadvantages, which require improvement.
One such disadvantage is, that many of them are comprising heavy metals such as Cu, Cr or Ni. Such heavy metals are critical from a toxicological as well as an environmental point of view and shall thus be excluded.
Surprisingly, it has now been found that the dyes of formula (1) as described below show highly advantageous properties over the known dyes. These include high tinctorial strength with high brilliancy as well as high fastness properties such as wash, contact and light fastness on the materials mentioned above, on blends containing them as well as on microfibres. Most importantly, dyes of formula (1) are substantially heavy metal free and provide dyeings that are levelled. Metals may only be present as counter ions and are selected from the groups of alkali and earth alkali metals, which do not have such effects as heavy metals.
If heavy metals are present at all in the dyes of the present invention they do not result from being integral part of the dye but are coursed by the production process in general. Reasons in general for these impurities can be impurities resulting from educts and catalysts being used in the respective reactions—the levels of such impurities can be managed and be kept well below those recommended e.g. by ETAD® and would thus be below 100 ppm for Cr, below 250 ppm for Cu and below 200 ppm for Ni just to mention the values for the metals mentioned above. This is a significant improvement as compared to dyes where such metals are present at molar levels.
The present invention refers to dyes of the formula (1) and mixtures thereof




wherein

    R1, R2, R3 and R4 independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M whereby at least two of them are SO3M,
    R5, R6, R7 and R8 independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, —SO3M or alkylureido,
    R9 and R15 independent of each other is cyano, carbamoyl, carbamoyl substituted, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen,
    R10 and R16 independent of each other is 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, monocycloalkylmonoarylamino, monoalkyl 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 and phenylureido,
    R11, R12, R13, R14, R17, R18, R19, R20 independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and 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, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-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, N,N-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, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO3M
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and 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, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-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, N,N-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, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO3M,
    M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation,
    the dyes of formula (1) have two to six sulfonic acid groups
    and
    whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R11, R12, R13 and R14, respectively can be positioned ortho or para to R9, meaning that when the amino rest bearing the substituents R11 and R12 is positioned ortho to R9, the amino rest bearing the substituents R13 and R14 is positioned para to R9, and vice versa;
    and
    the same applies to the amino rests bearing the substituents R17, R18, R19 and R20, respectively that can be positioned ortho or para to R15, meaning that when the amino rest bearing the substituents R17 and R18 is positioned ortho to R15, the amino rest bearing the substituents R19 and R20 is positioned para to R15, and vice versa.


This invention refers to all tautomeric and geometric isomers of the dyes of formula (1) and mixtures thereof.
Alkyl groups appearing in this invention may be straight-chain or branched and are (C1-C12)-alkyl groups, preferably (C1-C8)-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.
The same applies to alkoxy groups which accordingly are preferably (C1-C8)-alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (C1-C8)-thioalkoxy, for example —SCH3 or —SC2H5.
Cycloalkyl groups are preferably (C3-C8)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl. The term cyloalkyl comprises for the purpose of the present invention substituted cycloalkyl groups and unsaturated cycloalkyl groups as well. A preferred group of this type is cyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
Alkenyl groups may be straight-chain or branched and are preferably (C2-C6)-groups for example vinyl and allyl. The term alkenyl comprises for the purpose of the present invention alkynyl groups as well, for example ethynyl and propargyl.
Aryl groups appearing in this invention are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
Heteroaryl groups appearing in this invention are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1,2,4-thiadiazole, 1,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1,3,4-thiadiazole, furane, oxazole, benzoxazole or isoxazole. The terms heteroaryl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine. The term heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalky)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, aminocarbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.
Halogen is preferably chlorine, bromine or fluorine.
M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(C1-C4)-alkylammonium.
Particularly preferred embodiments of the present invention are dyes of formula (1a) and mixtures thereof




    wherein
    R1a, R2a, R3a and R4a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
    R5a, R6a, R7a and R8a independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO3M or (C1-C4)-acylamino,
    R9a and R15a independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
    R10a and R16a independent of one another is unsubstituted, linear or branched (C1-C4)-alkyl, unsubstituted (C5-C7)-cycloalkyl or substituted (C5-C7)-cycloalkyl with one or more substituents such as methyl, ethyl, isobutyl, sec-butyl, tert-butyl or methylbutyl,
    R11a, R12a R13a, R14a, R17a, R18a, R19a and R20a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur
    or
    alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
    and
    M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.


In particularly preferred dyes of formula (1a):

    R1a, R2a, R3a and R4a independent of each other is SO3M, hydrogen, alkyl, alkoxy or halogen—whereby at least two of them are SO3M,
    R5a, R6a, R7a and R8a independent of each other is hydrogen, methyl, halogen, —SO3M or acetylamino,
    R9a and R15a independent of each other is cyano or carbamoyl,
    R10a and R16a is methyl,
    R11a, R12a R13a, R14a, R17a, R18a, R19a and R20a independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl
    and
    M is hydrogen, sodium, potassium, lithium or ammonium.


Examples of particularly preferred dyes of the formula (1a) are the compounds of formulae (1a1 to 1a462) and mixtures thereof:





















Struc-










R14a/


ture
R1a
R2a
R3a
R4a
R5a/R7a
R6a/R8a
R9a/R16a
R11a/R17a
R12a/R18a
R13a/R19a
R20a







1a1
SO3H
SO3H
H
H
Methyl
Methyl
CN
Methyl
H
Methyl
H


1a2
SO3H
H
H
SO3H


1a3
SO3H
SO3H
H
H
Methyl
Methyl
CN
Ethyl
H
Ethyl
H


1a4
SO3H
H
H
SO3H


1a5
SO3H
SO3H
H
H
Methyl
Methyl
CN
Propyl
H
Propyl
H


1a6
SO3H
H
H
SO3H


1a7
SO3H
SO3H
H
H
Methyl
Methyl
CN
Butyl
H
Butyl
H


1a8
SO3H
H
H
SO3H


1a9
SO3H
SO3H
H
H
Methyl
Methyl
CN
Pentyl
H
Pentyl
H


1a10
SO3H
H
H
SO3H


1a11
SO3H
SO3H
H
H
Methyl
Methyl
CN
Hexyl
H
Hexyl
H


1a12
SO3H
H
H
SO3H


1a13
SO3H
SO3H
H
H
Methyl
Methyl
CN
Cyclobutyl
H
Cyclobutyl
H


1a14
SO3H
H
H
SO3H


1a15
SO3H
SO3H
H
H
Methyl
Methyl
CN
Cyclopentyl
H
Cyclopentyl
H


1a16
SO3H
H
H
SO3H


1a17
SO3H
SO3H
H
H
Methyl
Methyl
CN
Cyclohexyl
H
Cyclohexyl
H


1a18
SO3H
H
H
SO3H


1a19
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-Methyl
H
2-Methyl
H


1a20
SO3H
H
H
SO3H



cyclohexyl

cyclohexyl


1a21
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-Methyl
H
3-Methyl
H


1a22
SO3H
H
H
SO3H



cyclohexyl

cyclohexyl


1a23
SO3H
SO3H
H
H
Methyl
Methyl
CN
Isopropyl
H
Isopropyl
H


1a24
SO3H
H
H
SO3H


1a25
SO3H
SO3H
H
H
Methyl
Methyl
CN
Sec-butyl
H
Sec-butyl
H


1a26
SO3H
H
H
SO3H


1a27
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-
H
2-
H


1a28
SO3H
H
H
SO3H



Methylbutyl

Methylbutyl


1a29
SO3H
SO3H
H
H
Methyl
Methyl
CN
1-
H
1-
H


1a30
SO3H
H
H
SO3H



Ethylpropyl

Ethylpropyl


1a31
SO3H
SO3H
H
H
Methyl
Methyl
CN
1,2-
H
1,2-
H


1a32
SO3H
H
H
SO3H



Dimethyl

Dimethyl










propyl

propyl


1a33
SO3H
SO3H
H
H
Methyl
Methyl
CN
Tert-butyl
H
Tert-butyl
H


1a34
SO3H
H
H
SO3H


1a35
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-Methyl
H
3-Methyl
H


1a36
SO3H
H
H
SO3H



butyl

butyl


1a37
SO3H
SO3H
H
H
Methyl
Methyl
CN
Pentan-2-yl
H
Pentan-2-yl
H


1a38
SO3H
H
H
SO3H


1a39
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-
H
2-
H


1a40
SO3H
H
H
SO3H



Ethylhexyl

Ethylhexyl


1a41
SO3H
SO3H
H
H
Methyl
Methyl
CN
2,2-Dimethyl
H
2,2-Dimethyl propyl
H


1a42
SO3H
H
H
SO3H



propyl


1a43
SO3H
SO3H
H
H
Methyl
Methyl
CN
Phenyl
H
Phenyl
H


1a44
SO3H
H
H
SO3H


1a45
SO3H
SO3H
H
H
Methyl
Methyl
CN
Benzyl
H
Benzyl
H


1a46
SO3H
H
H
SO3H


1a47
SO3H
SO3H
H
H
Methyl
Methyl
CN
Allyl
H
Allyl
H


1a48
SO3H
H
H
SO3H


1a49
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-Methoxy
H
Butyl
H


1a50
SO3H
H
H
SO3H



ethyl


1a51
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-Methoxy
H
3-Methoxy propyl
H


1a52
SO3H
H
H
SO3H



propyl


1a53
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-Methoxy
H
Butyl
H


1a54
SO3H
H
H
SO3H



propyl


1a55
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-Methyl
H
Sec-butyl
H


1a56
SO3H
H
H
SO3H



thioethyl


1a57
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-Methyl
H
2-Hydroxyethyl
H


1a58
SO3H
H
H
SO3H



thioethyl


1a59
SO3H
SO3H
H
H
Methyl
Methyl
CN
Butyl
Butyl
2-Hydroxyethyl
H


1a60
SO3H
H
H
SO3H


1a61
SO3H
SO3H
H
H
Methyl
Methyl
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1a62
SO3H
H
H
SO3H


1a63
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-Fluoroethyl
H
Butyl
H


1a64
SO3H
H
H
SO3H


1a65
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-
H
2-Ethylhexyl
H


1a66
SO3H
H
H
SO3H



Chloroethyl


1a67
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-Chloro
H
2-Ethylhexyl
H


1a68
SO3H
H
H
SO3H



propyl


1a69
SO3H
SO3H
H
H
Methyl
Methyl
CN
Tetrahydro
H
Butyl
H


1a70
SO3H
H
H
SO3H



furfuryl


1a71
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-Furan-2-yl-
H
Butyl
H


1a72
SO3H
H
H
SO3H



ethyl


1a73
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-(2-Hydroxy-
H
Butyl
H


1a74
SO3H
H
H
SO3H



ethyl










sulfanyl)-ethyl


1a75
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-(2-tert-Butyl
H
Butyl
H


1a76
SO3H
H
H
SO3H



sulfanyl-










ethane










sulfonyl)-ethyl


1a77
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-Hydroxy-
H
Butyl
H


1a78
SO3H
H
H
SO3H



ethoxy propyl


1a79
SO3H
SO3H
H
H
Methyl
Methyl
CN
2(2-hydroxy
H
Butyl
H


1a80
SO3H
H
H
SO3H



ethoxy)ethyl


1a81
SO3H
SO3H
H
H
Methyl
Methyl
CN
H
H
2-(2-Hydroxy ethoxy)
H


1a82
SO3H
H
H
SO3H





propyl


1a83
SO3H
SO3H
H
H
Methyl
Methyl
CN
H
H
2-(2-Hydroxy
H


1a84
SO3H
H
H
SO3H





ethoxy)ethyl


1a85
SO3H
SO3H
H
H
Methyl
Methyl
CN
H
H
3-(4-Hydroxy
H


1a86
SO3H
H
H
SO3H





butoxy)propyl


1a87
SO3H
SO3H
H
H
Methyl
Methyl
CN
2-(2-Hydroxy
H
H
H


1a88
SO3H
H
H
SO3H



ethoxy)ethyl


1a89
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-(4-Hydroxy
H
H
H


1a90
SO3H
H
H
SO3H



butoxy)propy


1a91
SO3H
SO3H
H
H
Methyl
Methyl
CN
Phenyl
H
2-(2-Hydroxy
H


1a92
SO3H
H
H
SO3H





ethoxy)ethyl


1a93
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-(2-
H
H
H


1a94
SO3H
H
H
SO3H



Phenoxy










ethoxy)-










propyl


1a95
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-
H
3-Isopropoxy-propyl
H


1a96
SO3H
H
H
SO3H



Isopropoxy-










propyl


1a97
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-
H
H
H


1a98
SO3H
H
H
SO3H



Isopropoxy-










propyl


1a99
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-
H
Phenyl
H


1a100
SO3H
H
H
SO3H



Isopropoxy-










propyl


1a101
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-Ethoxy-
H
3-Ethoxy-propyl
H


1a102
SO3H
H
H
SO3H



propyl


1a103
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-Ethoxy-
H
H
H


1a104
SO3H
H
H
SO3H



propyl


1a105
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-Ethoxy-
H
Phenyl
H


1a106
SO3H
H
H
SO3H



propyl


1a107
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-
H
3-Ethoxybutyl
H


1a108
SO3H
H
H
SO3H



Ethoxybutyl


1a109
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-
H
H
H


1a110
SO3H
H
H
SO3H



Ethoxybutyl


1a111
SO3H
SO3H
H
H
Methyl
Methyl
CN
3-
H
Phenyl
H


1a112
SO3H
H
H
SO3H



Ethoxybutyl


1a113
SO3H
SO3H
H
H
Methyl
Methyl
CN
4-(2-
H
H
H


1a114
SO3H
H
H
SO3H



Hydroxy-










ethanesulfonyl)-










phenyl


1a115
SO3H
SO3H
H
H
Methyl
F
CN
2-Methoxy
H
Butyl
H


1a116
SO3H
H
H
SO3H



ethyl


1a117
SO3H
SO3H
H
H
Methyl
F
CN
3-Methoxy
H
Butyl
H


1a118
SO3H
H
H
SO3H



propyl


1a119
SO3H
SO3H
H
H
Methyl
F
CN
Butyl
Butyl
2-
H


1a120
SO3H
H
H
SO3H





Hydroxyethyl


1a121
SO3H
SO3H
H
H
Methyl
F
CN
Isopropyl
Isopropyl
2-
H


1a122
SO3H
H
H
SO3H





Hydroxyethyl


1a123
SO3H
SO3H
H
H
Methyl
F
CN
2-Fluoro
H
Butyl
H


1a124
SO3H
H
H
SO3H



ethyl


1a125
SO3H
SO3H
H
H
Methyl
F
CN
2-Chloro
H
2-
H


1a126
SO3H
H
H
SO3H



ethyl

Ethylhexyl


1a127
SO3H
SO3H
H
H
Methyl
F
CN
3-Chloro
H
2-
H


1a128
SO3H
H
H
SO3H



propyl

Ethylhexyl


1a129
SO3H
SO3H
H
H
Methyl
F
CN
2-(2-
H
Butyl
H


1a130
SO3H
H
H
SO3H



Hydroxy-










ethyl










sulfanyl)-










ethyl


1a131
SO3H
SO3H
H
H
Methyl
F
CN
2-(2-tert-
H
Butyl
H


1a132
SO3H
H
H
SO3H



Butyl










sulfanyl-










ethane










sulfonyl)-










ethyl


1a133
SO3H
SO3H
H
H
Methyl
F
CN
2-Hydroxy
H
Butyl
H


1a134
SO3H
H
H
SO3H



ethoxy










propyl


1a135
SO3H
SO3H
H
H
Methyl
F
CN
2-Hydroxy
H
Butyl
H


1a136\
SO3H
H
H
SO3H



ethoxyethyl


1a137
SO3H
SO3H
H
H
Methyl
F
CN
2-(Ethyl sulfonyl)
H
Butyl
H


1a138
SO3H
H
H
SO3H



ethanol


1a139
SO3H
SO3H
H
H
Methyl
F
CN
H
H
2-(2-Hydroxy
H


1a140
SO3H
H
H
SO3H





ethoxy)












propyl


1a141
SO3H
SO3H
H
H
Methyl
F
CN
H
H
2-(2-Hydroxy
H


1a142
SO3H
H
H
SO3H





ethoxy)ethyl


1a143
SO3H
SO3H
H
H
Methyl
F
CN
H
H
3-(4-Hydroxy
H


1a144
SO3H
H
H
SO3H





butoxy)propyl


1a145
SO3H
SO3H
H
H
Methyl
F
CN
2-(2-Hydroxy
H
H
H


1a146
SO3H
H
H
SO3H



ethoxy)ethyl


1a147
SO3H
SO3H
H
H
Methyl
F
CN
3-(4-Hydroxy
H
H
H


1a148
SO3H
H
H
SO3H



butoxy)propyl


1a149
SO3H
SO3H
H
H
Methyl
F
CN
Phenyl
H
(2-Hydroxy
H


1a150
SO3H
H
H
SO3H





ethoxy)ethyl


1a151
SO3H
SO3H
H
H
Methyl
F
CN
3-(2-Phenoxy-
H
H
H


1a152
SO3H
H
H
SO3H



ethoxy)-propyl


1a153
SO3H
SO3H
H
H
Methyl
F
CN
3-Isopropoxy-
H
3-Isopropoxy-
H


1a154
SO3H
H
H
SO3H



propyl

propyl


1a155
SO3H
SO3H
H
H
Methyl
F
CN
3-Isopropoxy-
H
H
H


1a156
SO3H
H
H
SO3H



propyl


1a157
SO3H
SO3H
H
H
Methyl
F
CN
3-Isopropoxy-
H
Phenyl
H


1a158
SO3H
H
H
SO3H



propyl


1a159
SO3H
SO3H
H
H
Methyl
F
CN
3-Ethoxy-propyl
H
3-Ethoxy-
H


1a160
SO3H
H
H
SO3H





propyl


1a161
SO3H
SO3H
H
H
Methyl
F
CN
3-Ethoxy-propyl
H
H
H


1a162
SO3H
H
H
SO3H


1a163
SO3H
SO3H
H
H
Methyl
F
CN
3-Ethoxy-propyl
H
Phenyl
H


1a164
SO3H
H
H
SO3H


1a165
SO3H
SO3H
H
H
Methyl
F
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1a166
SO3H
H
H
SO3H


1a167
SO3H
SO3H
H
H
Methyl
F
CN
3-Ethoxybutyl
H
H
H


1a168
SO3H
H
H
SO3H


1a169
SO3H
SO3H
H
H
Methyl
F
CN
3-Ethoxybutyl
H
Phenyl
H


1a170
SO3H
H
H
SO3H


1a171
SO3H
SO3H
H
H
Methyl
F
CN
4-(2-Hydroxy-
H
H
H


1a172
SO3H
H
H
SO3H



ethanesulfonyl)-










phenyl


1a173
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
2-Methoxy ethyl
H
Butyl
H


1a174
SO3H
H
H
SO3H


1a175
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Methoxy
H
Butyl
H


1a176
SO3H
H
H
SO3H



propyl


1a177
SO3H
H
H
SO3H


1a178
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
Butyl
Butyl
2-Hydroxyethyl
H


1a179
SO3H
H
H
SO3H


1a180
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
Isopropyl
Iso-
2-Hydroxyethyl
H


1a181
SO3H
H
H
SO3H




propyl


1a182
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
2-Fluoroethyl
H
Butyl
H


1a183
SO3H
H
H
SO3H


1a184
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
2-Chloroethyl
H
2-Ethylhexyl
H


1a185
SO3H
H
H
SO3H


1a186
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Chloropropyl
H
2-Ethylhexyl
H


1a187
SO3H
H
H
SO3H


1a188
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
2-(2-Hydroxy-
H
Butyl
H


1a189
SO3H
H
H
SO3H



ethyl sulfanyl)-










ethyl]


1a190
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
2-(2-tert-Butyl
H
Butyl
H


1a191
SO3H
H
H
SO3H



sulfanyl-ethane










sulfonyl)-ethyl


1a192
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
2-
H
Butyl
H


1a193
SO3H
H
H
SO3H



Hydroxyethoxy










propyl


1a194
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
2-Hydroxy
H
Butyl
H


1a195
SO3H
H
H
SO3H



ethoxyethyl


1a196
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy ethoxy)
H


1a197
SO3H
H
H
SO3H





propyl


1a198
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy ethoxy)ethyl
H


1a199
SO3H
H
H
SO3H


1a200
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
H
H
3-(4-Hydroxy
H


1a201
SO3H
H
H
SO3H





butoxy)propyl


1a202
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
2-(2-Hydroxy ethoxy)ethyl
H
H
H


1a203
SO3H
H
H
SO3H


1a204
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-(4-Hydroxy butoxy)propyl
H
H
H


1a205
SO3H
H
H
SO3H


1a206
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy ethoxy)ethyl
H


1a207
SO3H
H
H
SO3H


1a208
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
Phenyl
H
2-(2-Hydroxy ethoxy)ethyl
H


1a209
SO3H
H
H
SO3H


1a210
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-(2-Phenoxy-ethoxy)-
H
H
H


1a211
SO3H
H
H
SO3H



propyl


1a212
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1a213
SO3H
H
H
SO3H


1a214
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
H
H


1a215
SO3H
H
H
SO3H


1a216
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
Phenyl
H


1a217
SO3H
H
H
SO3H


1a218
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1a219
SO3H
H
H
SO3H


1a220
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
H
H


1a221
SO3H
H
H
SO3H


1a222
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
Phenyl
H


1a223
SO3H
H
H
SO3H


1a224
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1a225
SO3H
H
H
SO3H


1a226
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
H
H


1a227
SO3H
H
H
SO3H


1a228
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
Phenyl
H


1a229
SO3H
H
H
SO3H


1a230
SO3H
SO3H
H
H
NHCOCH3
OMe
CN
4-(2-Hydroxy-
H
H
H


1a231
SO3H
H
H
SO3H



ethanesulfonyl)-










phenyl


1a232
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Methyl
H
Methyl
H


1a233
SO3H
H
H
SO3H


1a234
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Ethyl
H
Ethyl
H


1a235
SO3H
H
H
SO3H


1a236
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Propyl
H
Propyl
H


1a237
SO3H
H
H
SO3H


1a238
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Butyl
H
Butyl
H


1a239
SO3H
H
H
SO3H


1a240
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Pentyl
H
Pentyl
H


1a241
SO3H
H
H
SO3H


1a242
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Hexyl
H
Hexyl
H


1a243
SO3H
H
H
SO3H


1a244
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Cyclobutyl
H
Cyclobutyl
H


1a245
SO3H
H
H
SO3H


1a246
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Cyclopentyl
H
Cyclopentyl
H


1a247
SO3H
H
H
SO3H


1a248
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Cyclohexyl
H
Cyclohexyl
H


1a249
SO3H
H
H
SO3H


1a250
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Methyl cyclohexyl
H
2-Methyl
H


1a251
SO3H
H
H
SO3H





cyclohexyl


1a252
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Methyl cyclohexyl
H
3-Methyl
H


1a253
SO3H
H
H
SO3H





cyclohexyl


1a254
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Isopropyl
H
Isopropyl
H


1a255
SO3H
H
H
SO3H


1a256
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Sec-butyl
H
Sec-butyl
H


1a257
SO3H
H
H
SO3H


1a258
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Methylbutyl
H
2-Methylbutyl
H


1a259
SO3H
H
H
SO3H


1a260
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
1-Ethylpropyl
H
1-Ethylpropyl
H


1a261
SO3H
H
H
SO3H


1a262
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1a263
SO3H
H
H
SO3H


1a264
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Tert-butyl
H
Tert-butyl
H


1a265
SO3H
H
H
SO3H


1a266
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1a267
SO3H
H
H
SO3H


1a268
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1a269
SO3H
H
H
SO3H


1a270
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1a271
SO3H
H
H
SO3H


1a272
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1a273
SO3H
H
H
SO3H


1a274
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Phenyl
H
Phenyl
H


1a275
SO3H
H
H
SO3H


1a276
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Benzyl
H
Benzyl
H


1a277
SO3H
H
H
SO3H


1a278
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Allyl
H
Allyl
H


1a279
SO3H
H
H
SO3H


1a280
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Methoxy ethyl
H
Butyl
H


1a281
SO3H
H
H
SO3H


1a282
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1a283
SO3H
H
H
SO3H


1a284
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Methoxy propyl
H
Butyl
H


1a285
SO3H
H
H
SO3H


1a286
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Methyl thiothyl
H
Sec-butyl
H


1a287
SO3H
H
H
SO3H


1a288
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Methyl thiothyl
H
2-Hydroxyethyl
H


1a289
SO3H
H
H
SO3H


1a290
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Butyl
Butyl
2-Hydroxyethyl
H


1a291
SO3H
H
H
SO3H


1a292
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1a293
SO3H
H
H
SO3H


1a294
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Fluoroethyl
H
Butyl
H


1a295
SO3H
H
H
SO3H


1a296
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Chloroethyl
H
2-Ethylhexyl
H


1a297
SO3H
H
H
SO3H


1a298
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Chloro propyl
H
2-Ethylhexyl
H


1a299
SO3H
H
H
SO3H


1a300
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Tetrahydro
H
Butyl
H


1a301
SO3H
H
H
SO3H



furfuryl


1a302
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Furan-2-yl-
H
Butyl
H


1a303
SO3H
H
H
SO3H



ethyl


1a304
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-(2-Hydroxy-
H
Butyl
H


1a305
SO3H
H
H
SO3H



ethyl sulfanyl)-










ethyl


1a306
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-(2-tert-Butyl
H
Butyl
H


1a307
SO3H
H
H
SO3H



sulfanyl-ethane










sylfonyl)-ethyl


1a308
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-
H
Butyl
H


1a309
SO3H
H
H
SO3H



Hydroxyethoxy










propyl


1a310
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-Hydroxy
H
Butyl
H


1a311
SO3H
H
H
SO3H



ethoxyethyl


1a312
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
H
H
2-(2-Hydroxy ethoxy)
H


1a313
SO3H
H
H
SO3H





propyl


1a314
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
H
H
2-(2-Hydroxy ethoxy)ethyl
H


1a315
SO3H
H
H
SO3H


1a316
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
H
H
3-(4-Hydroxy
H


1a317
SO3H
H
H
SO3H





butoxy)propyl


1a318
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
2-(2-Hydroxy
H
H
H


1a319
SO3H
H
H
SO3H



ethoxy)ethyl


1a320
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-(4-Hydroxy
H
H
H


1a321
SO3H
H
H
SO3H



butoxy)propyl


1a322
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
Phenyl
H
2-(2-Hydroxy ethoxy)ethyl
H


1a323
SO3H
H
H
SO3H


1a324
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H


1a325
SO3H
H
H
SO3H



propyl


1a326
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1a327
SO3H
H
H
SO3H


1a328
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
H
H


1a329
SO3H
H
H
SO3H


1a330
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1a331
SO3H
H
H
SO3H


1a332
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1a333
SO3H
H
H
SO3H


1a334
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
H
H


1a335
SO3H
H
H
SO3H


1a336
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1a337
SO3H
H
H
SO3H


1a338
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1a339
SO3H
H
H
SO3H


1a340
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
H
H


1a341
SO3H
H
H
SO3H


1a342
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
Phenyl
H


1a343
SO3H
H
H
SO3H


1a344
SO3H
SO3H
H
H
Methyl
Methyl
CONH2
4-(2-Hydroxy-
H
H
H


1a345
SO3H
H
H
SO3H



ethanesulfonyl)-phenyl


1a346
SO3H
SO3H
H
H
Methyl
F
CONH2
2-Methoxy ethyl
H
Butyl
H


1a347
SO3H
H
H
SO3H


1a348
SO3H
SO3H
H
H
Methyl
F
CONH2
2-Methoxy propyl
H
Butyl
H


1a349
SO3H
H
H
SO3H


1a350
SO3H
SO3H
H
H
Methyl
F
CONH2
Butyl
Butyl
2-Hydroxyethyl
H


1a351
SO3H
H
H
SO3H


1a352
SO3H
SO3H
H
H
Methyl
F
CONH2
Isopropyl
Iso-propyl
2-Hydrox-yethyl
H


1a353
SO3H
H
H
SO3H


1a354
SO3H
SO3H
H
H
Methyl
F
CONH2
2-Fluoro ethyl
H
Butyl
H


1a355
SO3H
H
H
SO3H


1a356
SO3H
SO3H
H
H
Methyl
F
CONH2
2-Chloro ethyl
H
2-Ethylhexyl
H


1a357
SO3H
H
H
SO3H


1a358
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Chloro propyl
H
2-Ethylhexyl
H


1a359
SO3H
H
H
SO3H


1a360
SO3H
SO3H
H
H
Methyl
F
CONH2
2-(2-Hydroxy-ethyl
H
Butyl
H


1a361
SO3H
H
H
SO3H



sulfanyl)-ethyl


1a362
SO3H
SO3H
H
H
Methyl
F
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H


1a363
SO3H
H
H
SO3H



ethane sulfonyl)-ethyl


1a364
SO3H
SO3H
H
H
Methyl
F
CONH2
2-Hydroxy ethoxy
H
Butyl
H


1a365
SO3H
H
H
SO3H



propyl


1a366
SO3H
SO3H
H
H
Methyl
F
CONH2
2-Hydroxy ethoxyethyl
H
Butyl
H


1a367
SO3H
H
H
SO3H


1a368
SO3H
SO3H
H
H
Methyl
F
CONH2
2-(Ethyl sulfonyl) ethanol
H
Butyl
H


1a369
SO3H
H
H
SO3H


1a370
SO3H
SO3H
H
H
Methyl
F
CONH2
H
H
2-(2-Hydroxy ethoxy)
H


1a371
SO3H
H
H
SO3H





propyl


1a372
SO3H
SO3H
H
H
Methyl
F
CONH2
H
H
2-(2-Hydroxy
H


1a373
SO3H
H
H
SO3H





ethoxy)ethyl


1a374
SO3H
SO3H
H
H
Methyl
F
CONH2
H
H
3-(4-Hydroxy
H


1a375
SO3H
H
H
SO3H





butoxy)propyl


1a376
SO3H
SO3H
H
H
Methyl
F
CONH2
2-(2-Hydroxy
H
H
H


1a377
SO3H
H
H
SO3H



ethoxy)ethyl


1a378
SO3H
SO3H
H
H
Methyl
F
CONH2
3-(4-Hydroxy
H
H
H


1a379
SO3H
H
H
SO3H



butoxy)propyl


1a380
SO3H
SO3H
H
H
Methyl
F
CONH2
Phenyl
H
(2-Hydroxy ethoxy)ethyl
H


1a381
SO3H
H
H
SO3H


1a382
SO3H
SO3H
H
H
Methyl
F
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H


1a383
SO3H
H
H
SO3H



propyl


1a384
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1a385
SO3H
H
H
SO3H


1a386
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Isopropoxy-propyl
H
H
H


1a387
SO3H
H
H
SO3H


1a388
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1a389
SO3H
H
H
SO3H


1a390
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-
H


1a391
SO3H
H
H
SO3H





propyl


1a392
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Ethoxy-propyl
H
H
H


1a393
SO3H
H
H
SO3H


1a394
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1a395
SO3H
H
H
SO3H


1a396
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Ethoxybutyl
H
3-
H


1a397
SO3H
H
H
SO3H





Ethoxybutyl


1a398
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Ethoxybutyl
H
H
H


1a399
SO3H
H
H
SO3H


1a400
SO3H
SO3H
H
H
Methyl
F
CONH2
3-Ethoxybutyl
H
Phenyl
H


1a401
SO3H
H
H
SO3H


1a402
SO3H
SO3H
H
H
Methyl
F
CONH2
4-(2-Hydroxy-
H
H
H


1a403
SO3H
H
H
SO3H



ethanesulfonyl)-










phenyl


1a404
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
2-Methoxy
H
Butyl
H


1a405
SO3H
H
H
SO3H



ethyl


1a406
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Methoxy
H
Butyl
H


1a407
SO3H
H
H
SO3H



propyl


1a408
SO3H
H
H
SO3H


1a409
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
Butyl
Butyl
2-
H


1a410
SO3H
H
H
SO3H





Hydroxyethyl


1a411
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
Isopropyl
Iso-
2-
H


1a412
SO3H
H
H
SO3H




propyl
Hydroxyethyl


1a413
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
2-Fluoroethyl
H
Butyl
H


1a414
SO3H
H
H
SO3H


1a415
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
2-Chloroethyl
H
2-Ethylhexyl
H


1a416
SO3H
H
H
SO3H


1a417
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Chloropropyl
H
2-Ethylhexyl
H


1a418
SO3H
H
H
SO3H


1a419
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
2-(2-Hydroxy-
H
Butyl
H


1a420
SO3H
H
H
SO3H



ethyl sulfanyl)-










ethyl]


1a421
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
2-(2-tert-Butyl
H
Butyl
H


1a422
SO3H
H
H
SO3H



sulfanyl-ethane










sulfonyl)-ethyl


1a423
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
2-
H
Butyl
H


1a424
SO3H
H
H
SO3H



Hydroxyethoxy










propyl


1a425
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
2-Hydroxy
H
Butyl
H


1a426
SO3H
H
H
SO3H



ethoxyethyl


1a427
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy ethoxy)
H


1a428
SO3H
H
H
SO3H





propyl


1a429
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy
H


1a430
SO3H
H
H
SO3H





ethoxy)ethyl


1a431
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
H
H
3-(4-Hydroxy
H


1a432
SO3H
H
H
SO3H





butoxy)propyl


1a433
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
2-(2-Hydroxy ethoxy)ethyl
H
H
H


1a434
SO3H
H
H
SO3H


1a435
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-(4-Hydroxy butoxy)-
H
H
H


1a436
SO3H
H
H
SO3H



propyl


1a437
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy-
H


1a438
SO3H
H
H
SO3H





ethoxy)ethyl


1a439
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
Phenyl
H
2-(2-Hydroxy-
H


1a440
SO3H
H
H
SO3H





ethoxy)ethyl


1a441
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H


1a442
SO3H
H
H
SO3H



propyl


1a443
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1a444
SO3H
H
H
SO3H


1a445
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
H
H


1a446
SO3H
H
H
SO3H


1a447
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Isopropoxy-
H
Phenyl
H


1a448
SO3H
H
H
SO3H



propyl


1a449
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-
H


1a450
SO3H
H
H
SO3H





propyl


1a451
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
H
H


1a452
SO3H
H
H
SO3H


1a453
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1a454
SO3H
H
H
SO3H


1a455
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Ethoxybutyl
H
3-
H


1a456
SO3H
H
H
SO3H





Ethoxybutyl


1a457
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Ethoxybutyl
H
H
H


1a458
SO3H
H
H
SO3H


1a459
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
3-Ethoxybutyl
H
Phenyl
H


1a460
SO3H
H
H
SO3H


1a461
SO3H
SO3H
H
H
NHCOCH3
OMe
CONH2
4-(2-hydroxy-
H
H
H


1a462
SO3H
H
H
SO3H



ethanesulfonyl)-










phenyl









Further particularly preferred embodiments of the present invention are dyes of formula (1b) and mixtures thereof




    wherein
    R1b, R2b, R3b and R4b independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
    R5b, R6b, R7b and R8b independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO3M or (C1-C4)-acylamino,
    R9b and R15b independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
    R10b and R16b independent of each other is unsubstituted, linear or branched (C1-C4)-alkyl, unsubstiuted (C5-C7)-cycloalkyl or substituted (C5-C7)-cycloalkyl with one or more substituents such as methyl, ethyl, isobutyl, sec-butyl, tert-butyl or methylbutyl,
    R11b, R12b R13b, R14b, R17b, R18b, R19b and R20b independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur
    or
    alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyi-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyi-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsuifonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
    and
    M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.


In particularly preferred dyes of formula (1b):

    R3b and R4b is SO3M,
    R1b and R2b is hydrogen,
    R5b, R6b, R7b and R8b independent of each other is hydrogen, methyl, halogen, —SO3M or acetylamino,
    R9b and R15b independent of each other is cyano or carbamoyl,
    R1b and R16b is methyl,
    R11b, R12b R13b, R14b, R17b, R18b, R19b and R20b independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl
    and
    M is hydrogen, sodium, potassium, lithium or ammonium.


Examples of such particularly preferred dyes of formula (1b) are the compounds of formulae (1b1 to 1b364) and mixtures thereof:

















Structure
R5b/R7b
R6b/R8b
R9b/R16b
R11b/R17b
R12b/R18b
R13b/R19b
R14b/R20b







1b1
Methyl
Methyl
CN
Methyl
H
Methyl
H


1b2
Methyl
Methyl
CN
Ethyl
H
Ethyl
H


1b3
Methyl
Methyl
CN
Propyl
H
Propyl
H


1b4
Methyl
Methyl
CN
Butyl
H
Butyl
H


1b5
Methyl
Methyl
CN
Pentyl
H
Pentyl
H


1b6
Methyl
Methyl
CN
Hexyl
H
Hexyl
H


1b7
Methyl
Methyl
CN
Cyclobutyl
H
Cyclobutyl
H


1b8
Methyl
Methyl
CN
Cyclopentyl
H
Cyclopentyl
H


1b9
Methyl
Methyl
CN
Cyclohexyl
H
Cyclohexyl
H


1b10
Methyl
Methyl
CN
2-Methylcyclohexyl
H
2-Methylcyclohexyl
H


1b11
Methyl
Methyl
CN
3-Methylcyclohexyl
H
3-Methylcyclohexyl
H


1b12
Methyl
Methyl
CN
Isopropyl
H
Isopropyl
H


1b13
Methyl
Methyl
CN
Sec-butyl
H
Sec-butyl
H


1b14
Methyl
Methyl
CN
2-Methylbutyl
H
2-Methylbutyl
H


1b15
Methyl
Methyl
CN
1-Ethylpropyl
H
1-Ethylpropyl
H


1b16
Methyl
Methyl
CN
1,2-Dimethylpropyl
H
1,2-Dimethylpropyl
H


1b17
Methyl
Methyl
CN
Tert-butyl
H
Tert-butyl
H


1b18
Methyl
Methyl
CN
3-Methylbutyl
H
3-Methylbutyl
H


1b19
Methyl
Methyl
CN
Pentan-2-yl
H
Pentan-2-yl
H


1b20
Methyl
Methyl
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1b21
Methyl
Methyl
CN
2,2-Dimethylpropyl
H
2,2-Dimethylpropyl
H


1b22
Methyl
Methyl
CN
Phenyl
H
Phenyl
H


1b23
Methyl
Methyl
CN
Benzyl
H
Benzyl
H


1b24
Methyl
Methyl
CONH2
Methyl
H
Methyl
H


1b25
Methyl
Methyl
CONH2
Ethyl
H
Ethyl
H


1b26
Methyl
Methyl
CONH2
Propyl
H
Propyl
H


1b27
Methyl
Methyl
CONH2
Butyl
H
Butyl
H


1b28
Methyl
Methyl
CONH2
Pentyl
H
Pentyl
H


1b29
Methyl
Methyl
CONH2
Hexyl
H
Hexyl
H


1b30
Methyl
Methyl
CONH2
Cyclobutyl
H
Cyclobutyl
H


1b31
Methyl
Methyl
CONH2
Cyclopentyl
H
Cyclopentyl
H


1b32
Methyl
Methyl
CONH2
Cyclohexyl
H
Cyclohexyl
H


1b33
Methyl
Methyl
CONH2
2-Methylcyclohexyl
H
2-Methylcyclohexyl
H


1b34
Methyl
Methyl
CONH2
3-Methylcyclohexyl
H
3-Methylcyclohexyl
H


1b35
Methyl
Methyl
CONH2
Isopropyl
H
Isopropyl
H


1b36
Methyl
Methyl
CONH2
Sec-butyl
H
Sec-butyl
H


1b37
Methyl
Methyl
CONH2
2-Methylbutyl
H
2-Methylbutyl
H


1b38
Methyl
Methyl
CONH2
1-Ethylpropyl
H
1-Ethylpropyl
H


1b39
Methyl
Methyl
CONH2
1,2-Dimethylpropyl
H
1,2-Dimethylpropyl
H


1b40
Methyl
Methyl
CONH2
Tert-butyl
H
Tert-butyl
H


1b41
Methyl
Methyl
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1b42
Methyl
Methyl
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1b43
Methyl
Methyl
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1b44
Methyl
Methyl
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1b45
Methyl
Methyl
CONH2
Phenyl
H
Phenyl
H


1b46
Methyl
Methyl
CONH2
Benzyl
H
Benzyl
H


1b47
Methyl
F
CN
Methyl
H
Methyl
H


1b48
Methyl
F
CN
Ethyl
H
Ethyl
H


1b49
Methyl
F
CN
Propyl
H
Propyl
H


1b50
Methyl
F
CN
Butyl
H
Butyl
H


1b51
Methyl
F
CN
Pentyl
H
Pentyl
H


1b52
Methyl
F
CN
Hexyl
H
Hexyl
H


1b53
Methyl
F
CN
Cyclobutyl
H
Cyclobutyl
H


1b54
Methyl
F
CN
Cyclopentyl
H
Cyclopentyl
H


1b55
Methyl
F
CN
Cyclohexyl
H
Cyclohexyl
H


1b56
Methyl
F
CN
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1b57
Methyl
F
CN
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1b58
Methyl
F
CN
Isopropyl
H
Isopropyl
H


1b59
Methyl
F
CN
Sec-butyl
H
Sec-butyl
H


1b60
Methyl
F
CN
2-Methyl butyl
H
2-Methyl
H








butyl


1b61
Methyl
F
CN
1-Ethyl propyl
H
1-Ethyl propyl
H


1b62
Methyl
F
CN
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1b63
Methyl
F
CN
Tert-butyl
H
Tert-butyl
H


1b64
Methyl
F
CN
3-Methyl butyl
H
3-Methyl butyl
H


1b65
Methyl
F
CN
Pentan-2-yl
H
Pentan-2-yl
H


1b66
Methyl
F
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1b67
Methyl
F
CN
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1b68
Methyl
F
CN
Phenyl
H
Phenyl
H


1b69
Methyl
F
CN
Benzyl
H
Benzyl
H


1b70
Methyl
F
CONH2
Methyl
H
Methyl
H


1b71
Methyl
F
CONH2
Ethyl
H
Ethyl
H


1b72
Methyl
F
CONH2
Propyl
H
Propyl
H


1b73
Methyl
F
CONH2
Butyl
H
Butyl
H


1b74
Methyl
F
CONH2
Pentyl
H
Pentyl
H


1b75
Methyl
F
CONH2
Hexyl
H
Hexyl
H


1b76
Methyl
F
CONH2
Cyclobutyl
H
Cyclobutyl
H


1b77
Methyl
F
CONH2
Cyclopentyl
H
Cyclopentyl
H


1b78
Methyl
F
CONH2
Cyclohexyl
H
Cyclohexyl
H


1b79
Methyl
F
CONH2
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1b80
Methyl
F
CONH2
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1b81
Methyl
F
CONH2
Isopropyl
H
Isopropyl
H


1b82
Methyl
F
CONH2
Sec-butyl
H
Sec-butyl
H


1b83
Methyl
F
CONH2
2-Methyl butyl
H
2-Methyl
H








butyl


1b84
Methyl
F
CONH2
1-Ethyl propyl
H
1-Ethyl propyl
H


1b85
Methyl
F
CONH2
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1b86
Methyl
F
CONH2
Tert-butyl
H
Tert-butyl
H


1b87
Methyl
F
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1b88
Methyl
F
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1b89
Methyl
F
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1b90
Methyl
F
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1b91
Methyl
F
CONH2
Phenyl
H
Phenyl
H


1b92
Methyl
F
CONH2
Benzyl
H
Benzyl
H


1b93
NHCOCH3
OMe
CN
Methyl
H
Methyl
H


1b94
NHCOCH3
OMe
CN
Ethyl
H
Ethyl
H


1b95
NHCOCH3
OMe
CN
Propyl
H
Propyl
H


1b96
NHCOCH3
OMe
CN
Butyl
H
Butyl
H


1b97
NHCOCH3
OMe
CN
Pentyl
H
Pentyl
H


1b98
NHCOCH3
OMe
CN
Hexyl
H
Hexyl
H


1b99
NHCOCH3
OMe
CN
Cyclobutyl
H
Cyclobutyl
H


1b100
NHCOCH3
OMe
CN
Cyclopentyl
H
Cyclopentyl
H


1b101
NHCOCH3
OMe
CN
Cyclohexyl
H
Cyclohexyl
H


1b102
NHCOCH3
OMe
CN
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1b103
NHCOCH3
OMe
CN
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1b104
NHCOCH3
OMe
CN
Isopropyl
H
Isopropyl
H


1b105
NHCOCH3
OMe
CN
Sec-butyl
H
Sec-butyl
H


1b106
NHCOCH3
OMe
CN
2-Methyl butyl
H
2-Methyl
H








butyl


1b107
NHCOCH3
OMe
CN
1-Ethyl propyl
H
1-Ethyl propyl
H


1b108
NHCOCH3
OMe
CN
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1b109
NHCOCH3
OMe
CN
Tert-butyl
H
Tert-butyl
H


1b110
NHCOCH3
OMe
CN
3-Methyl butyl
H
3-Methyl butyl
H


1b111
NHCOCH3
OMe
CN
Pentan-2-yl
H
Pentan-2-yl
H


1b112
NHCOCH3
OMe
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1b113
NHCOCH3
OMe
CN
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1b114
NHCOCH3
OMe
CN
Phenyl
H
Phenyl
H


1b115
NHCOCH3
OMe
CN
Benzyl
H
Benzyl
H


1b116
NHCOCH3
OMe
CONH2
Methyl
H
Methyl
H


1b117
NHCOCH3
OMe
CONH2
Ethyl
H
Ethyl
H


1b118
NHCOCH3
OMe
CONH2
Propyl
H
Propyl
H


1b119
NHCOCH3
OMe
CONH2
Butyl
H
Butyl
H


1b120
NHCOCH3
OMe
CONH2
Pentyl
H
Pentyl
H


1b121
NHCOCH3
OMe
CONH2
Hexyl
H
Hexyl
H


1b122
NHCOCH3
OMe
CONH2
Cyclobutyl
H
Cyclobutyl
H


1b123
NHCOCH3
OMe
CONH2
Cyclopentyl
H
Cyclopentyl
H


1b124
NHCOCH3
OMe
CONH2
Cyclohexyl
H
Cyclohexyl
H


1b125
NHCOCH3
OMe
CONH2
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1b126
NHCOCH3
OMe
CONH2
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1b127
NHCOCH3
OMe
CONH2
Isopropyl
H
Isopropyl
H


1b128
NHCOCH3
OMe
CONH2
Sec-butyl
H
Sec-butyl
H


1b129
NHCOCH3
OMe
CONH2
2-Methyl butyl
H
2-Methyl
H








butyl


1b130
NHCOCH3
OMe
CONH2
1-Ethyl propyl
H
1-Ethyl propyl
H


1b131
NHCOCH3
OMe
CONH2
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1b132
NHCOCH3
OMe
CONH2
Tert-butyl
H
Tert-butyl
H


1b133
NHCOCH3
OMe
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1b134
NHCOCH3
OMe
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1b135
NHCOCH3
OMe
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1b136
NHCOCH3
OMe
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1b137
NHCOCH3
OMe
CONH2
Phenyl
H
Phenyl
H


1b138
NHCOCH3
OMe
CONH2
Benzyl
H
Benzyl
H


1b139
Methyl
Methyl
CN
2-Methoxyethyl
H
Butyl
H


1b140
Methyl
Methyl
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1b141
Methyl
Methyl
CN
3-Methoxy propyl
H
Butyl
H


1b142
Methyl
Methyl
CN
Butyl
Butyl
2-Hydroxyethyl
H


1b143
Methyl
Methyl
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1b144
Methyl
Methyl
CN
2-Fluoro ethyl
H
Butyl
H


1b145
Methyl
Methyl
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1b146
Methyl
Methyl
CN
3-Chloro propyl
H
2-Ethylhexyl
H


1b147
Methyl
Methyl
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1b148
Methyl
Methyl
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1b149
Methyl
Methyl
CN
2-(2-Hydroxy ethoxy)
H
Butyl
H






propyl


1b150
Methyl
Methyl
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1b151
Methyl
Methyl
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1b152
Methyl
Methyl
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b153
Methyl
Methyl
CN
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1b154
Methyl
Methyl
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1b155
Methyl
Methyl
CN
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1b156
Methyl
Methyl
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b157
Methyl
Methyl
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1b158
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1b159
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
H
H


1b160
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
Phenyl
H


1b161
Methyl
Methyl
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1b162
Methyl
Methyl
CN
3-Ethoxy-propyl
H
H
H


1b163
Methyl
Methyl
CN
3-Ethoxy-propyl
H
Phenyl
H


1b164
Methyl
Methyl
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1b165
Methyl
Methyl
CN
3-Ethoxybutyl
H
H
H


1b166
Methyl
Methyl
CN
3-Ethoxybutyl
H
Phenyl
H


1b167
Methyl
Methyl
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1b168
Methyl
F
CN
2-Methoxyethyl
H
Butyl
H


1b169
Methyl
F
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1b170
Methyl
F
CN
3-Methoxy propyl
H
Butyl
H


1b171
Methyl
F
CN
Butyl
Butyl
2-Hydroxyethyl
H


1b172
Methyl
F
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1b173
Methyl
F
CN
2-Fluoro ethyl
H
Butyl
H


1b174
Methyl
F
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1b175
Methyl
F
CN
3-Chloro propyl
H
2-Ethylhexyl
H


1b176
Methyl
F
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1b177
Methyl
F
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1b178
Methyl
F
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1b179
Methyl
F
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1b180
Methyl
F
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1b181
Methyl
F
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b182
Methyl
F
CN
H
H
3-(4-Hydroxy
H








ethoxy)propyl


1b183
Methyl
F
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1b184
Methyl
F
CN
3-(4-Hydroxy
H
H
H






ethoxy)propyl


1b185
Methyl
F
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b186
Methyl
F
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1b187
Methyl
F
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1b188
Methyl
F
CN
3-Isopropoxy-propyl
H
H
H


1b189
Methyl
F
CN
3-Isopropoxy-propyl
H
Phenyl
H


1b190
Methyl
F
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1b191
Methyl
F
CN
3-Ethoxy-propyl
H
H


1b192
Methyl
F
CN
3-Ethoxy-propyl
H
Phenyl
H


1b193
Methyl
F
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1b194
Methyl
F
CN
3-Ethoxybutyl
H
H


1b195
Methyl
F
CN
3-Ethoxybutyl
H
Phenyl
H


1b196
Methyl
F
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1b197
NHCOCH3
OMe
CN
2-Methoxyethyl
H
Butyl
H


1b198
NHCOCH3
OMe
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1b199
NHCOCH3
OMe
CN
3-Methoxy propyl
H
Butyl
H


1b200
NHCOCH3
OMe
CN
Butyl
Butyl
2-Hydroxyethyl
H


1b201
NHCOCH3
OMe
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1b202
NHCOCH3
OMe
CN
2-Fluoro ethyl
H
Butyl
H


1b203
NHCOCH3
OMe
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1b204
NHCOCH3
OMe
CN
3-Chloro propyl
H
2-Ethylhexyl
H


1b205
NHCOCH3
OMe
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1b206
NHCOCH3
OMe
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1b207
NHCOCH3
OMe
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1b208
NHCOCH3
OMe
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1b209
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1b210
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b211
NHCOCH3
OMe
CN
H
H
3-(4-Hydroxy
H








ethoxy)propyl


1b212
NHCOCH3
OMe
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1b213
NHCOCH3
OMe
CN
3-(4-Hydroxy
H
H
H






ethoxy)propyl


1b214
NHCOCH3
OMe
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b215
NHCOCH3
OMe
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1b216
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1b217
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
H
H


1b218
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
Phenyl
H


1b219
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1b220
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
H
H


1b221
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
Phenyl
H


1b222
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1b223
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
H
H


1b224
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
Phenyl
H


1b225
NHCOCH3
OMe
CN
3-Methoxy propyl
H
Butyl
H


1b226
NHCOCH3
OMe
CN

Butyl
2-Hydroxyethyl
H


1b227
NHCOCH3
OMe
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1b228
NHCOCH3
OMe
CN
2-Fluoro ethyl
H
Butyl
H


1b229
NHCOCH3
OMe
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1b230
NHCOCH3
OMe
CN
3-Chloro propyl
H
2-Ethylhexyl
H


1b231
NHCOCH3
OMe
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1b232
NHCOCH3
OMe
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1b233
NHCOCH3
OMe
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1b234
NHCOCH3
OMe
CN
2-Hydroxy ethoxyethyl
H
Butyl
H


1b235
NHCOCH3
OMe
CN
2-(Ethyl sulfonyl) ethanol
H
Butyl
H


1b236
NHCOCH3
OMe
CN
H
H
(2-Hydroxy ethoxy)
H








propyl


1b237
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b238
NHCOCH3
OMe
CN
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1b239
NHCOCH3
OMe
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1b240
NHCOCH3
OMe
CN
3-(4-Hydroxy
H
H
H






ethoxy)propyl


1b241
NHCOCH3
OMe
CN
H
H
(2-Hydroxy
H








ethoxy)ethyl


1b242
NHCOCH3
OMe
CN
Phenyl
H
(2-Hydroxy
H








ethoxy)ethyl


1b243
NHCOCH3
OMe
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1b244
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1b245
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
H
H


1b246
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
Phenyl
H


1b247
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1b248
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
H
H


1b249
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
Phenyl
H


1b250
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1b251
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
H
H


1b252
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
Phenyl
H


1b253
NHCOCH3
OMe
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1b254
Methyl
Methyl
CONH2
2-Methoxyethyl
H
Butyl
H


1b255
Methyl
Methyl
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1b256
Methyl
Methyl
CONH2
3-Methoxy propyl
H
Butyl
H


1b257
Methyl
Methyl
CONH2
Butyl
Butyl
2-Hydroxyethyl
H


1b258
Methyl
Methyl
CONH2
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1b259
Methyl
Methyl
CONH2
2-Fluoro ethyl
H
Butyl
H


1b260
Methyl
Methyl
CONH2
2-Chloro ethyl
H
2-Ethylhexyl
H


1b261
Methyl
Methyl
CONH2
3-Chloro propyl
H
2-Ethylhexyl
H


1b262
Methyl
Methyl
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1b263
Methyl
Methyl
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1b264
Methyl
Methyl
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1b265
Methyl
Methyl
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1b266
Methyl
Methyl
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1b267
Methyl
Methyl
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b268
Methyl
Methyl
CONH2
H
H
3-(4-Hydroxy
H








ethoxy)propyl


1b269
Methyl
Methyl
CONH2
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1b270
Methyl
Methyl
CONH2
3-(4-Hydroxy
H
H
H






ethoxy)propyl


1b271
Methyl
Methyl
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b272
Methyl
Methyl
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1b273
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1b274
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
H
H


1b275
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1b276
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1b277
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
H
H


1b278
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1b279
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
3-Ethoxy butyl
H


1b280
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
H
H


1b281
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
Phenyl
H


1b282
Methyl
Methyl
CONH2
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1b283
Methyl
F
CONH2
2-Methoxyethyl
H
Butyl
H


1b284
Methyl
F
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1b285
Methyl
F
CONH2
3-Methoxy propyl
H
Butyl
H


1b286
Methyl
F
CONH2
Butyl
Butyl
2-Hydroxyethyl
H


1b287
Methyl
F
CONH2
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1b288
Methyl
F
CONH2
2-Fluoro ethyl
H
Butyl
H


1b289
Methyl
F
CONH2
2-Chloro ethyl
H
2-Ethylhexyl
H


1b290
Methyl
F
CONH2
2-Chloro propyl
H
2-Ethylhexyl
H


1b291
Methyl
F
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1b292
Methyl
F
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1b293
Methyl
F
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1b294
Methyl
F
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1b295
Methyl
F
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1b296
Methyl
F
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b297
Methyl
F
CONH2
H
H
3-(2-Hydroxy
H








ethoxy)ethyl


1b298
Methyl
F
CONH2
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1b299
Methyl
F
CONH2
3-(4-Hydroxy
H
H
H






ethoxy)propyl


1b300
Methyl
F
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b301
Methyl
F
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1b302
Methyl
F
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1b303
Methyl
F
CONH2
3-Isopropoxy-propyl
H
H
H


1b304
Methyl
F
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1b305
Methyl
F
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1b306
Methyl
F
CONH2
3-Ethoxy-propyl
H
H
H


1b307
Methyl
F
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1b308
Methyl
F
CONH2
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1b309
Methyl
F
CONH2
3-Ethoxybutyl
H
H
H


1b310
Methyl
F
CONH2
3-Ethoxybutyl
H
Phenyl
H


1b311
Methyl
F
CONH2
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1b312
NHCOCH3
OMe
CONH2
2-Methoxyethyl
H
Butyl
H


1b313
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1b314
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
Butyl
H


1b315
NHCOCH3
OMe
CONH2
Butyl
Butyl
2-Hydroxyethyl
H


1b316
NHCOCH3
OMe
CONH2
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1b317
NHCOCH3
OMe
CONH2
2-Fluoro ethyl
H
Butyl
H


1b318
NHCOCH3
OMe
CONH2
2-Chloro ethyl
H
2-Ethylhexyl
H


1b319
NHCOCH3
OMe
CONH2
2-Chloro propyl
H
2-Ethylhexyl
H


1b320
NHCOCH3
OMe
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1b321
NHCOCH3
OMe
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1b322
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1b323
NHCOCH3
OMe
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1b324
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1b325
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b326
NHCOCH3
OMe
CONH2
H
H
3-(4-Hydroxy
H








ethoxy)propyl


1b327
NHCOCH3
OMe
CONH2
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1b328
NHCOCH3
OMe
CONH2
3-(4-Hydroxy
H
H
H






ethoxy)propyl


1b329
NHCOCH3
OMe
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b330
NHCOCH3
OMe
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1b331
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1b332
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
H
H


1b333
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1b334
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1b335
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
H
H


1b336
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1b337
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1b338
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
H
H


1b339
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
Phenyl
H


1b340
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
Butyl
H


1b341
NHCOCH3
OMe
CONH2
Butyl
Bu
2-Hydroxy ethyl
H


1b342
NHCOCH3
OMe
CONH2
Isopropyl
Isopropyl
2-Hydroxy ethyl
H


1b343
NHCOCH3
OMe
CONH2
2-Fluoro ethyl
H
Butyl
H


1b344
NHCOCH3
OMe
CONH2
2-Chloro ethyl
H
2-Ethyl hexyl
H


1b345
NHCOCH3
OMe
CONH2
3-Chloro propyl
H
2-Ethyl hexyl
H


1b346
NHCOCH3
OMe
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1b347
NHCOCH3
OMe
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1b348
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1b349
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxyethyl
H
Butyl
H


1b350
NHCOCH3
OMe
CONH2
2-(Ethyl sulfonyl) ethanol
H
Butyl
H


1b351
NHCOCH3
OMe
CONH2
H
H
3-(2-Hydroxy ethoxy)
H








propyl


1b352
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b353
NHCOCH3
OMe
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1b354
NHCOCH3
OMe
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1b355
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1b356
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
H
H


1b357
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1b358
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1b359
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
H
H


1b360
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1b361
NHCOCH3
OMe
CONH2
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1b362
NHCOCH3
OMe
CONH2
3-Ethoxybutyl
H
H
H


1b363
NHCOCH3
OMe
CONH2
3-Ethoxybutyl
H
Phenyl
H


1b364
NHCOCH3
OMe
CONH2
4-(2-hydroxy-
H
H
H






ethanesulfonyl)-phenyl









Further particularly preferred embodiments of the present invention are dyes of formula (1c) and mixtures thereof:




wherein

    R1c, R2c, R3c and R4c independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
    R5c, R6c, R7c and R8c independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO3M or (C1-C4)-acylamino,
    R9c and R15c independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
    R10c and R16c independent of each other is unsubstituted, linear or branched (C1-C4)-alkyl, unsubstiuted (C5-C7)-cycloalkyl or substituted (C5-C7)-cycloalkyl with one or more substituents such as methyl, ethyl, isobutyl, sec-butyl, tert-butyl or methylbutyl,
    R11c, R12c R13c, R14c, R17c, R18c, R19c and R20c independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur
    or
    alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
    or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
    and
    M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.


In the most preferred dyes of formula (1c):

    R2c and R4c is SO3M,
    R1c and R2c is hydrogen,
    R5c, R6c, R7c and R8c independent of each other is hydrogen, methyl, halogen, —SO3M or acetylamino,
    R9c and R15c independent of each other is cyano or carbamoyl,
    R10c and F16c is methyl,
    R11c, R12c R13c, R14c, R17c, R18c, R19c and R20c independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl
    and
    M is hydrogen, sodium, potassium, lithium or ammonium.


Examples of such preferred dyes of formula (1c) are the compounds of the formulae (1c1 to 1c364) and mixtures thereof:

















Structure
R5c/R7c
R6c/R8c
R9c/R16c
R11c/R17c
R12c/R18c
R13c/R19c
R14c/R20c







1c1
Methyl
Methyl
CN
Methyl
H
Methyl
H


1c2
Methyl
Methyl
CN
Ethyl
H
Ethyl
H


1c3
Methyl
Methyl
CN
Propyl
H
Propyl
H


1c4
Methyl
Methyl
CN
Butyl
H
Butyl
H


1c5
Methyl
Methyl
CN
Pentyl
H
Pentyl
H


1c6
Methyl
Methyl
CN
Hexyl
H
Hexyl
H


1c7
Methyl
Methyl
CN
Cyclobutyl
H
Cyclobutyl
H


1c8
Methyl
Methyl
CN
Cyclopentyl
H
Cyclopentyl
H


1c9
Methyl
Methyl
CN
Cyclohexyl
H
Cyclohexyl
H


1c10
Methyl
Methyl
CN
2-Methylcyclohexyl
H
2-Methylcyclohexyl
H


1c11
Methyl
Methyl
CN
3-Methylcyclohexyl
H
3-Methylcyclohexyl
H


1c12
Methyl
Methyl
CN
Isopropyl
H
Isopropyl
H


1c13
Methyl
Methyl
CN
Sec-butyl
H
Sec-butyl
H


1c14
Methyl
Methyl
CN
2-Methylbutyl
H
2-Methylbutyl
H


1c15
Methyl
Methyl
CN
1-Ethylpropyl
H
1-Ethylpropyl
H


1c16
Methyl
Methyl
CN
1,2-Dimethylpropyl
H
1,2-Dimethylpropyl
H


1c17
Methyl
Methyl
CN
Tert-butyl
H
Tert-butyl
H


1c18
Methyl
Methyl
CN
3-Methylbutyl
H
3-Methylbutyl
H


1c19
Methyl
Methyl
CN
Pentan-2-yl
H
Pentan-2-yl
H


1c20
Methyl
Methyl
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1c21
Methyl
Methyl
CN
2,2-Dimethylpropyl
H
2,2-Dimethylpropyl
H


1c22
Methyl
Methyl
CN
Phenyl
H
Phenyl
H


1c23
Methyl
Methyl
CN
Benzyl
H
Benzyl
H


1c24
Methyl
Methyl
CONH2
Methyl
H
Methyl
H


1c25
Methyl
Methyl
CONH2
Ethyl
H
Ethyl
H


1c26
Methyl
Methyl
CONH2
Propyl
H
Propyl
H


1c27
Methyl
Methyl
CONH2
Butyl
H
Butyl
H


1c28
Methyl
Methyl
CONH2
Pentyl
H
Pentyl
H


1c29
Methyl
Methyl
CONH2
Hexyl
H
Hexyl
H


1c30
Methyl
Methyl
CONH2
Cyclobutyl
H
Cyclobutyl
H


1c31
Methyl
Methyl
CONH2
Cyclopentyl
H
Cyclopentyl
H


1c32
Methyl
Methyl
CONH2
Cyclohexyl
H
Cyclohexyl
H


1c33
Methyl
Methyl
CONH2
2-Methylcyclohexyl
H
2-Methylcyclohexyl
H


1c34
Methyl
Methyl
CONH2
3-Methylcyclohexyl
H
3-Methylcyclohexyl
H


1c35
Methyl
Methyl
CONH2
Isopropyl
H
Isopropyl
H


1c36
Methyl
Methyl
CONH2
Sec-butyl
H
Sec-butyl
H


1c37
Methyl
Methyl
CONH2
2-Methylbutyl
H
2-Methylbutyl
H


1c38
Methyl
Methyl
CONH2
1-Ethylpropyl
H
1-Ethylpropyl
H


1c39
Methyl
Methyl
CONH2
1,2-Dimethylpropyl
H
1,2-Dimethylpropyl
H


1c40
Methyl
Methyl
CONH2
Tert-butyl
H
Tert-butyl
H


1c41
Methyl
Methyl
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1c42
Methyl
Methyl
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1c43
Methyl
Methyl
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1c44
Methyl
Methyl
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1c45
Methyl
Methyl
CONH2
Phenyl
H
Phenyl
H


1c46
Methyl
Methyl
CONH2
Benzyl
H
Benzyl
H


1c47
Methyl
F
CN
Methyl
H
Methyl
H


1c48
Methyl
F
CN
Ethyl
H
Ethyl
H


1c49
Methyl
F
CN
Propyl
H
Propyl
H


1c50
Methyl
F
CN
Butyl
H
Butyl
H


1c51
Methyl
F
CN
Pentyl
H
Pentyl
H


1c52
Methyl
F
CN
Hexyl
H
Hexyl
H


1c53
Methyl
F
CN
Cyclobutyl
H
Cyclobutyl
H


1c54
Methyl
F
CN
Cyclopentyl
H
Cyclopentyl
H


1c55
Methyl
F
CN
Cyclohexyl
H
Cyclohexyl
H


1c56
Methyl
F
CN
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1c57
Methyl
F
CN
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1c58
Methyl
F
CN
Isopropyl
H
Isopropyl
H


1c59
Methyl
F
CN
Sec-butyl
H
Sec-butyl
H


1c60
Methyl
F
CN
2-Methyl butyl
H
2-Methyl
H








butyl


1c61
Methyl
F
CN
1-Ethyl propyl
H
1-Ethyl propyl
H


1c62
Methyl
F
CN
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1c63
Methyl
F
CN
Tert-butyl
H
Tert-butyl
H


1c64
Methyl
F
CN
3-Methyl butyl
H
3-Methyl butyl
H


1c65
Methyl
F
CN
Pentan-2-yl
H
Pentan-2-yl
H


1c66
Methyl
F
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1c67
Methyl
F
CN
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1c68
Methyl
F
CN
Phenyl
H
Phenyl
H


1c69
Methyl
F
CN
Benzyl
H
Benzyl
H


1c70
Methyl
F
CONH2
Methyl
H
Methyl
H


1c71
Methyl
F
CONH2
Ethyl
H
Ethyl
H


1c72
Methyl
F
CONH2
Propyl
H
Propyl
H


1c73
Methyl
F
CONH2
Butyl
H
Butyl
H


1c74
Methyl
F
CONH2
Pentyl
H
Pentyl
H


1c75
Methyl
F
CONH2
Hexyl
H
Hexyl
H


1c76
Methyl
F
CONH2
Cyclobutyl
H
Cyclobutyl
H


1c77
Methyl
F
CONH2
Cyclopentyl
H
Cyclopentyl
H


1c78
Methyl
F
CONH2
Cyclohexyl
H
Cyclohexyl
H


1c79
Methyl
F
CONH2
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1c80
Methyl
F
CONH2
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1c81
Methyl
F
CONH2
Isopropyl
H
Isopropyl
H


1c82
Methyl
F
CONH2
Sec-butyl
H
Sec-butyl
H


1c83
Methyl
F
CONH2
2-Methyl butyl
H
2-Methyl
H








butyl


1c84
Methyl
F
CONH2
1-Ethyl propyl
H
1-Ethyl propyl
H


1c85
Methyl
F
CONH2
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1c86
Methyl
F
CONH2
Tert-butyl
H
Tert-butyl
H


1c87
Methyl
F
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1c88
Methyl
F
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1c89
Methyl
F
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1c90
Methyl
F
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1c91
Methyl
F
CONH2
Phenyl
H
Phenyl
H


1c92
Methyl
F
CONH2
Benzyl
H
Benzyl
H


1c93
NHCOCH3
OMe
CN
Methyl
H
Methyl
H


1c94
NHCOCH3
OMe
CN
Ethyl
H
Ethyl
H


1c95
NHCOCH3
OMe
CN
Propyl
H
Propyl
H


1c96
NHCOCH3
OMe
CN
Butyl
H
Butyl
H


1c97
NHCOCH3
OMe
CN
Pentyl
H
Pentyl
H


1c98
NHCOCH3
OMe
CN
Hexyl
H
Hexyl
H


1c99
NHCOCH3
OMe
CN
Cyclobutyl
H
Cyclobutyl
H


1c100
NHCOCH3
OMe
CN
Cyclopentyl
H
Cyclopentyl
H


1c101
NHCOCH3
OMe
CN
Cyclohexyl
H
Cyclohexyl
H


1c102
NHCOCH3
OMe
CN
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1c103
NHCOCH3
OMe
CN
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1c104
NHCOCH3
OMe
CN
Isopropyl
H
Isopropyl
H


1c105
NHCOCH3
OMe
CN
Sec-butyl
H
Sec-butyl
H


1c106
NHCOCH3
OMe
CN
2-Methyl butyl
H
2-Methyl
H








butyl


1c107
NHCOCH3
OMe
CN
1-Ethyl propyl
H
1-Ethyl propyl
H


1c108
NHCOCH3
OMe
CN
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1c109
NHCOCH3
OMe
CN
Tert-butyl
H
Tert-butyl
H


1c110
NHCOCH3
OMe
CN
3-Methyl butyl
H
3-Methyl butyl
H


1c111
NHCOCH3
OMe
CN
Pentan-2-yl
H
Pentan-2-yl
H


1c112
NHCOCH3
OMe
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1c113
NHCOCH3
OMe
CN
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1c114
NHCOCH3
OMe
CN
Phenyl
H
Phenyl
H


1c115
NHCOCH3
OMe
CN
Benzyl
H
Benzyl
H


1c116
NHCOCH3
OMe
CONH2
Methyl
H
Methyl
H


1c117
NHCOCH3
OMe
CONH2
Ethyl
H
Ethyl
H


1c118
NHCOCH3
OMe
CONH2
Propyl
H
Propyl
H


1c119
NHCOCH3
OMe
CONH2
Butyl
H
Butyl
H


1c120
NHCOCH3
OMe
CONH2
Pentyl
H
Pentyl
H


1c121
NHCOCH3
OMe
CONH2
Hexyl
H
Hexyl
H


1c122
NHCOCH3
OMe
CONH2
Cyclobutyl
H
Cyclobutyl
H


1c123
NHCOCH3
OMe
CONH2
Cyclopentyl
H
Cyclopentyl
H


1c124
NHCOCH3
OMe
CONH2
Cyclohexyl
H
Cyclohexyl
H


1c125
NHCOCH3
OMe
CONH2
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1c126
NHCOCH3
OMe
CONH2
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1c127
NHCOCH3
OMe
CONH2
Isopropyl
H
Isopropyl
H


1c128
NHCOCH3
OMe
CONH2
Sec-butyl
H
Sec-butyl
H


1c129
NHCOCH3
OMe
CONH2
2-Methyl butyl
H
2-Methyl
H








butyl


1c130
NHCOCH3
OMe
CONH2
1-Ethyl propyl
H
1-Ethyl propyl
H


1c131
NHCOCH3
OMe
CONH2
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1c132
NHCOCH3
OMe
CONH2
Tert-butyl
H
Tert-butyl
H


1c133
NHCOCH3
OMe
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1c134
NHCOCH3
OMe
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1c135
NHCOCH3
OMe
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1c136
NHCOCH3
OMe
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1c137
NHCOCH3
OMe
CONH2
Phenyl
H
Phenyl
H


1c138
NHCOCH3
OMe
CONH2
Benzyl
H
Benzyl
H


1c139
Methyl
Methyl
CN
2-Methoxyethyl
H
Butyl
H


1c140
Methyl
Methyl
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1c141
Methyl
Methyl
CN
3-Methoxy propyl
H
Butyl
H


1c142
Methyl
Methyl
CN
Butyl
Butyl
2-Hydroyethyl
H


1c143
Methyl
Methyl
CN
Isopropyl
Isopropyl
2-Hydroyethyl
H


1c144
Methyl
Methyl
CN
2-Fluoro ethyl
H
Butyl
H


1c145
Methyl
Methyl
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1c146
Methyl
Methyl
CN
3-Chloro propyl
H
2-Ethylhexyl
H


1c147
Methyl
Methyl
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1c148
Methyl
Methyl
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1c149
Methyl
Methyl
CN
2-(2-Hydroxy ethoxy)
H
Butyl
H






propyl


1c150
Methyl
Methyl
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1c151
Methyl
Methyl
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1c152
Methyl
Methyl
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c153
Methyl
Methyl
CN
H
H
3-(4-Hydroxy
H








ethoxy)propyl


1c154
Methyl
Methyl
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1c155
Methyl
Methyl
CN
3-(4-Hydroxy
H
H
H






ethoxy)propyl


1c156
Methyl
Methyl
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c157
Methyl
Methyl
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1c158
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1c159
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
H
H


1c160
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
Phenyl
H


1c161
Methyl
Methyl
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1c162
Methyl
Methyl
CN
3-Ethoxy-propyl
H
H
H


1c163
Methyl
Methyl
CN
3-Ethoxy-propyl
H
Phenyl
H


1c164
Methyl
Methyl
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1c165
Methyl
Methyl
CN
3-Ethoxybutyl
H
H
H


1c166
Methyl
Methyl
CN
3-Ethoxybutyl
H
Phenyl
H


1c167
Methyl
Methyl
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1c168
Methyl
F
CN
2-Methoxyethyl
H
Butyl
H


1c169
Methyl
F
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1c170
Methyl
F
CN
3-Methoxy propyl
H
Butyl
H


1c171
Methyl
F
CN
Butyl
Butyl
2-Hydoxy ethyl
H


1c172
Methyl
F
CN
Isopropyl
Isopropyl
2-Hydoxy ethyl
H


1c173
Methyl
F
CN
2-Fluoro ethyl
H
Butyl
H


1c174
Methyl
F
CN
2-Chloro ethyl
H
2-Ethyl hexyl
H


1c175
Methyl
F
CN
3-Chloro propyl
H
2-Ethyl hexyl
H


1c176
Methyl
F
CN
2-(2-
H
Butyl
H






Hydroxethylsulfanyl)-






ethyl


1c177
Methyl
F
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1c178
Methyl
F
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1c179
Methyl
F
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1c180
Methyl
F
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1c181
Methyl
F
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c182
Methyl
F
CN
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1c183
Methyl
F
CN
2-(2-Hydoxy
H
H
H






ethoxy)ethyl


1c184
Methyl
F
CN
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1c185
Methyl
F
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c186
Methyl
F
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1c187
Methyl
F
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1c188
Methyl
F
CN
3-Isopropoxy-propyl
H
H
H


1c189
Methyl
F
CN
3-Isopropoxy-propyl
H
Phenyl
H


1c190
Methyl
F
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1c191
Methyl
F
CN
3-Ethoxy-propyl
H
H


1c192
Methyl
F
CN
3-Ethoxy-propyl
H
Phenyl
H


1c193
Methyl
F
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1c194
Methyl
F
CN
3-Ethoxybutyl
H
H


1c195
Methyl
F
CN
3-Ethoxybutyl
H
Phenyl
H


1c196
Methyl
F
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1c197
NHCOCH3
OMe
CN
2-Methoxyethyl
H
Butyl
H


1c198
NHCOCH3
OMe
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1c199
NHCOCH3
OMe
CN
3-Methoxy propyl
H
Butyl
H


1c200
NHCOCH3
OMe
CN
Butyl
Butyl
2-Hydroxyethyl
H


1c201
NHCOCH3
OMe
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1c202
NHCOCH3
OMe
CN
2-Fluoro ethyl
H
Butyl
H


1c203
NHCOCH3
OMe
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1c204
NHCOCH3
OMe
CN
3-Chloro propyl
H
2-Ethylhexyl
H


1c205
NHCOCH3
OMe
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1c206
NHCOCH3
OMe
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1c207
NHCOCH3
OMe
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1c208
NHCOCH3
OMe
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1c209
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1c210
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c211
NHCOCH3
OMe
CN
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1c212
NHCOCH3
OMe
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1c213
NHCOCH3
OMe
CN
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1c214
NHCOCH3
OMe
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c215
NHCOCH3
OMe
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1c216
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1c217
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
H
H


1c218
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
Phenyl
H


1c219
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1c220
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
H
H


1c221
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
Phenyl
H


1c222
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1c223
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
H
H


1c224
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
Phenyl
H


1c225
NHCOCH3
OMe
CN
3-Methoxy propyl
H
Butyl
H


1c226
NHCOCH3
OMe
CN
Butyl
Bu
2-Hydroxyethyl
H


1c227
NHCOCH3
OMe
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1c228
NHCOCH3
OMe
CN
2-Fluoro ethyl
H
Butyl
H


1c229
NHCOCH3
OMe
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1c230
NHCOCH3
OMe
CN
2-Chloro propyl
H
2-Ethylhexyl
H


1c231
NHCOCH3
OMe
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1c232
NHCOCH3
OMe
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1c233
NHCOCH3
OMe
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1c234
NHCOCH3
OMe
CN
2-Hydroxy ethoxyethyl
H
Butyl
H


1c235
NHCOCH3
OMe
CN
2-(Ethyl sulfonyl) ethanol
H
Butyl
H


1c236
NHCOCH3
OMe
CN
H
H
(2-Hydroxy ethoxy)
H








propyl


1c237
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c238
NHCOCH3
OMe
CN
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1c239
NHCOCH3
OMe
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1c240
NHCOCH3
OMe
CN
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1c241
NHCOCH3
OMe
CN
H
H
(2-Hydroxy
H








ethoxy)ethyl


1c242
NHCOCH3
OMe
CN
Phenyl
H
(2-Hydroxy
H








ethoxy)ethyl


1c243
NHCOCH3
OMe
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1c244
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1c245
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
H
H


1c246
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
Phenyl
H


1c247
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1c248
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
H
H


1c249
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
Phenyl
H


1c250
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1c251
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
H
H


1c252
NHCOCH3
OMe
CN
3-Ethoxybutyl
H
Phenyl
H


1c253
NHCOCH3
OMe
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1c254
Methyl
Methyl
CONH2
2-Methoxyethyl
H
Butyl
H


1c255
Methyl
Methyl
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1c256
Methyl
Methyl
CONH2
3-Methoxy propyl
H
Butyl
H


1c257
Methyl
Methyl
CONH2
Butyl
Butyl
2-Hydroxyethyl
H


1c258
Methyl
Methyl
CONH2
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1c259
Methyl
Methyl
CONH2
2-Fluoro ethyl
H
Butyl
H


1c260
Methyl
Methyl
CONH2
2-Chloro ethyl
H
2-Ethylhexyl
H


1c261
Methyl
Methyl
CONH2
3-Chloro propyl
H
2-Ethylhexyl
H


1c262
Methyl
Methyl
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1c263
Methyl
Methyl
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1c264
Methyl
Methyl
CONH2
2-Hydroxy ethoxy propyl
H
Butyl
H


1c265
Methyl
Methyl
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1c266
Methyl
Methyl
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1c267
Methyl
Methyl
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c268
Methyl
Methyl
CONH2
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1c269
Methyl
Methyl
CONH2
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1c270
Methyl
Methyl
CONH2
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1c271
Methyl
Methyl
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c272
Methyl
Methyl
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1c273
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1c274
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
H
H


1c275
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1c276
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1c277
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
H
H


1c278
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1c279
Methyl
Methyl
CONH2
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1c280
Methyl
Methyl
CONH2
3-Ethoxy butyl
H
H
H


1c281
Methyl
Methyl
CONH2
3-Ethoxy butyl
H
Phenyl
H


1c282
Methyl
Methyl
CONH2
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1c283
Methyl
F
CONH2
2-Methoxyethyl
H
Butyl
H


1c284
Methyl
F
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1c285
Methyl
F
CONH2
3-Methoxy propyl
H
Butyl
H


1c286
Methyl
F
CONH2
Butyl
Butyl
2-Hydroxyethyl
H


1c287
Methyl
F
CONH2
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1c288
Methyl
F
CONH2
2-Fluoro ethyl
H
Butyl
H


1c289
Methyl
F
CONH2
2-Chloro ethyl
H
2-Ethyl hexyl
H


1c290
Methyl
F
CONH2
3-Chloro propyl
H
2-Ethyl hexyl
H


1c291
Methyl
F
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1c292
Methyl
F
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1c293
Methyl
F
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1c294
Methyl
F
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1c295
Methyl
F
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1c296
Methyl
F
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c297
Methyl
F
CONH2
H
H
3-(2-Hydroxy
H








ethoxy)ethyl


1c298
Methyl
F
CONH2
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1c299
Methyl
F
CONH2
3-(2-Hydroxy
H
H
H






ethoxy)ethyl


1c300
Methyl
F
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1c301
Methyl
F
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1c302
Methyl
F
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1c303
Methyl
F
CONH2
3-Isopropoxy-propyl
H
H
H


1c304
Methyl
F
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1c305
Methyl
F
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1c306
Methyl
F
CONH2
3-Ethoxy-propyl
H
H
H


1c307
Methyl
F
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1c308
Methyl
F
CONH2
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1c309
Methyl
F
CONH2
3-Ethoxy butyl
H
H
H


1c310
Methyl
F
CONH2
3-Ethoxy butyl
H
Phenyl
H


1c311
Methyl
F
CONH2
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1c312
NHCOCH3
OMe
CONH2
2-Methoxyethyl
H
Butyl
H


1c313
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1c314
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
Butyl
H


1c315
NHCOCH3
OMe
CONH2
Butyl
Butyl
2-Hydroxyethyl
H


1c316
NHCOCH3
OMe
CONH2
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1c317
NHCOCH3
OMe
CONH2
2-Fluoro ethyl
H
Butyl
H


1c318
NHCOCH3
OMe
CONH2
2-Chloro ethyl
H
2-Ethylhexyl
H


1c319
NHCOCH3
OMe
CONH2
2-Chloro propyl
H
2-Ethylhexyl
H


1c320
NHCOCH3
OMe
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1c321
NHCOCH3
OMe
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1c322
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1c323
NHCOCH3
OMe
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1c324
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1c325
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy-
H








ethoxy)ethyl


1c326
NHCOCH3
OMe
CONH2
H
H
3-(2-Hydroxy-
H








ethoxy)propyl


1c327
NHCOCH3
OMe
CONH2
2-(2-Hydroxy-
H
H
H






ethoxy)ethyl


1c328
NHCOCH3
OMe
CONH2
3-(2-Hydroxy-
H
H
H






ethoxy)propyl


1c329
NHCOCH3
OMe
CONH2
Phenyl
H
2-(2-Hydroxy-
H








ethoxy)ethyl


1c330
NHCOCH3
OMe
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1c331
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1c332
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
H
H


1c333
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1c334
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1c335
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
H
H


1c336
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1c337
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
3-Ethoxybutyl
H


1c338
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
H
H


1c339
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
Phenyl
H


1c340
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
Butyl
H


1c341
NHCOCH3
OMe
CONH2
Butyl
Butyl
2-Hydroxy ethyl
H


1c342
NHCOCH3
OMe
CONH2
Isopropyl
Isopropyl
2-Hydroxy ethyl
H


1c343
NHCOCH3
OMe
CONH2
2-Fluoro ethyl
H
Butyl
H


1c344
NHCOCH3
OMe
CONH2
2-Chloro ethyl
H
2-Ethylhexyl
H


1c345
NHCOCH3
OMe
CONH2
3-Chloro propyl
H
2-Ethylhexyl
H


1c346
NHCOCH3
OMe
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1c347
NHCOCH3
OMe
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1c348
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1c349
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxyethyl
H
Butyl
H


1c350
NHCOCH3
OMe
CONH2
2-(Ethyl sulfonyl) ethanol
H
Butyl
H


1c351
NHCOCH3
OMe
CONH2
H
H
3-(2-Hydroxy ethoxy)
H








propyl


1c352
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy-
H








ethoxy)ethyl


1c353
NHCOCH3
OMe
CONH2
Phenyl
H
2-(2-Hydroxy-
H








ethoxy)ethyl


1c354
NHCOCH3
OMe
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1c355
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1c356
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
H
H


1c357
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1c358
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1c359
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
H
H


1c360
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1c361
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1c362
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
H
H


1c363
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
Phenyl
H


1c364
NHCOCH3
OMe
CONH2
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl









Further particularly preferred embodiments of the present invention are dyes of formula (1d) and mixtures thereof




    wherein
    R1d, R2d, R3d and R4d independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M whereby at least two of them are SO3M,
    R5d, R6d, R7d and R8d independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO3M or (C1-C4)-acylamino,
    R9d and R15d independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
    R10d and R16d independent of each other is unsubstituted, linear or branched (C1-C4)-alkyl, (C5-C7)-cycloalkyi or substituted (C5-C7)-cycloalkyl with one or more substituents such as methyl, ethyl, isobutyl, sec-butyl, Cert-butyl and methylbutyl,
    R11d, R12d R13d, R14d, R17d, R18d, R19d and R20d independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
    or
    alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
    or
    alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
    and
    M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.


In the most preferred dyes of formula (1d):

    R1d and R3d is SO3M,
    R2d and R4d is hydrogen,
    R5d, R6d, R7d and R8d independent of each other is hydrogen, methyl, halogen, —SO3M or acetylamino,
    R9d and R15d independent of each other is cyano or carbamoyl,
    R10d and R16d is methyl,
    R11d, R12d R13d, R14d, R17d, R16d, R19d and R20d independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl
    and
    M is hydrogen, sodium, potassium, lithium or ammonium.


Examples of preferred dyes of the formula (1d) are the compounds of formulae (1d1 to 1 d364) and mixtures thereof:
























R14d/


Structure
R5d/R7d
R6d/R8d
R9d/R16d
R11d/R17d
R12d/R18d
R13d/R19d
R20d







1d1
Methyl
Methyl
CN
Methyl
H
Methyl
H


1d2
Methyl
Methyl
CN
Ethyl
H
Ethyl
H


1d3
Methyl
Methyl
CN
Propyl
H
Propyl
H


1d4
Methyl
Methyl
CN
Butyl
H
Butyl
H


1d5
Methyl
Methyl
CN
Pentyl
H
Pentyl
H


1d6
Methyl
Methyl
CN
Hexyl
H
Hexyl
H


1d7
Methyl
Methyl
CN
Cyclobutyl
H
Cyclobutyl
H


1d8
Methyl
Methyl
CN
Cyclopentyl
H
Cyclopentyl
H


1d9
Methyl
Methyl
CN
Cyclohexyl
H
Cyclohexyl
H


1d10
Methyl
Methyl
CN
2-Methylcyclohexyl
H
2-Methylcyclohexyl
H


1d11
Methyl
Methyl
CN
3-Methylcyclohexyl
H
3-Methylcyclohexyl
H


1d12
Methyl
Methyl
CN
Isopropyl
H
Isopropyl
H


1d13
Methyl
Methyl
CN
Sec-butyl
H
Sec-butyl
H


1d14
Methyl
Methyl
CN
2-Methylbutyl
H
2-Methylbutyl
H


1d15
Methyl
Methyl
CN
1-Ethylpropyl
H
1-Ethylpropyl
H


1d16
Methyl
Methyl
CN
1,2-Dimethylpropyl
H
1,2-Dimethylpropyl
H


1d17
Methyl
Methyl
CN
Tert-butyl
H
Tert-butyl
H


1d18
Methyl
Methyl
CN
3-Methylbutyl
H
3-Methylbutyl
H


1d19
Methyl
Methyl
CN
Pentan-2-yl
H
Pentan-2-yl
H


1d20
Methyl
Methyl
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1d21
Methyl
Methyl
CN
2,2-Dimethylpropyl
H
2,2-Dimethylpropyl
H


1d22
Methyl
Methyl
CN
Phenyl
H
Phenyl
H


1d23
Methyl
Methyl
CN
Benzyl
H
Benzyl
H


1d24
Methyl
Methyl
CONH2
Methyl
H
Methyl
H


1d25
Methyl
Methyl
CONH2
Ethyl
H
Ethyl
H


1d26
Methyl
Methyl
CONH2
Propyl
H
Propyl
H


1d27
Methyl
Methyl
CONH2
Butyl
H
Butyl
H


1d28
Methyl
Methyl
CONH2
Pentyl
H
Pentyl
H


1d29
Methyl
Methyl
CONH2
Hexyl
H
Hexyl
H


1d30
Methyl
Methyl
CONH2
Cyclobutyl
H
Cyclobutyl
H


1d31
Methyl
Methyl
CONH2
Cyclopentyl
H
Cyclopentyl
H


1d32
Methyl
Methyl
CONH2
Cyclohexyl
H
Cyclohexyl
H


1d33
Methyl
Methyl
CONH2
2-Methylcyclohexyl
H
2-Methylcyclohexyl
H


1d34
Methyl
Methyl
CONH2
3-Methylcyclohexyl
H
3-Methylcyclohexyl
H


1d35
Methyl
Methyl
CONH2
Isopropyl
H
Isopropyl
H


1d36
Methyl
Methyl
CONH2
Sec-butyl
H
Sec-butyl
H


1d37
Methyl
Methyl
CONH2
2-Methylbutyl
H
2-Methylbutyl
H


1d38
Methyl
Methyl
CONH2
1-Ethylpropyl
H
1-Ethylpropyl
H


1d39
Methyl
Methyl
CONH2
1,2-Dimethylpropyl
H
1,2-Dimethylpropyl
H


1d40
Methyl
Methyl
CONH2
Tert-butyl
H
Tert-butyl
H


1d41
Methyl
Methyl
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1d42
Methyl
Methyl
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1d43
Methyl
Methyl
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1d44
Methyl
Methyl
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1d45
Methyl
Methyl
CONH2
Phenyl
H
Phenyl
H


1d46
Methyl
Methyl
CONH2
Benzyl
H
Benzyl
H


1d47
Methyl
F
CN
Methyl
H
Methyl
H


1d48
Methyl
F
CN
Ethyl
H
Ethyl
H


1d49
Methyl
F
CN
Propyl
H
Propyl
H


1d50
Methyl
F
CN
Butyl
H
Butyl
H


1d51
Methyl
F
CN
Pentyl
H
Pentyl
H


1d52
Methyl
F
CN
Hexyl
H
Hexyl
H


1d53
Methyl
F
CN
Cyclobutyl
H
Cyclobutyl
H


1d54
Methyl
F
CN
Cyclopentyl
H
Cyclopentyl
H


1d55
Methyl
F
CN
Cyclohexyl
H
Cyclohexyl
H


1d56
Methyl
F
CN
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1d57
Methyl
F
CN
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1d58
Methyl
F
CN
Isopropyl
H
Isopropyl
H


1d59
Methyl
F
CN
Sec-butyl
H
Sec-butyl
H


1d60
Methyl
F
CN
2-Methyl butyl
H
2-Methyl
H








butyl


1d61
Methyl
F
CN
1-Ethyl propyl
H
1-Ethyl propyl
H


1d62
Methyl
F
CN
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1d63
Methyl
F
CN
Tert-butyl
H
Tert-butyl
H


1d64
Methyl
F
CN
3-Methyl butyl
H
3-Methyl butyl
H


1d65
Methyl
F
CN
Pentan-2-yl
H
Pentan-2-yl
H


1d66
Methyl
F
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1d67
Methyl
F
CN
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1d68
Methyl
F
CN
Phenyl
H
Phenyl
H


1d69
Methyl
F
CN
Benzyl
H
Benzyl
H


1d70
Methyl
F
CONH2
Methyl
H
Methyl
H


1d71
Methyl
F
CONH2
Ethyl
H
Ethyl
H


1d72
Methyl
F
CONH2
Propyl
H
Propyl
H


1d73
Methyl
F
CONH2
Butyl
H
Butyl
H


1d74
Methyl
F
CONH2
Pentyl
H
Pentyl
H


1d75
Methyl
F
CONH2
Hexyl
H
Hexyl
H


1d76
Methyl
F
CONH2
Cyclobutyl
H
Cyclobutyl
H


1d77
Methyl
F
CONH2
Cyclopentyl
H
Cyclopentyl
H


1d78
Methyl
F
CONH2
Cyclohexyl
H
Cyclohexyl
H


1d79
Methyl
F
CONH2
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1d80
Methyl
F
CONH2
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1d81
Methyl
F
CONH2
Isopropyl
H
Isopropyl
H


1d82
Methyl
F
CONH2
Sec-butyl
H
Sec-butyl
H


1d83
Methyl
F
CONH2
2-Methyl butyl
H
2-Methyl
H








butyl


1d84
Methyl
F
CONH2
1-Ethyl propyl
H
1-Ethyl propyl
H


1d85
Methyl
F
CONH2
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1d86
Methyl
F
CONH2
Tert-butyl
H
Tert-butyl
H


1d87
Methyl
F
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1d88
Methyl
F
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1d89
Methyl
F
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1d90
Methyl
F
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1d91
Methyl
F
CONH2
Phenyl
H
Phenyl
H


1d92
Methyl
F
CONH2
Benzyl
H
Benzyl
H


1d93
NHCOCH3
OMe
CN
Methyl
H
Methyl
H


1d94
NHCOCH3
OMe
CN
Ethyl
H
Ethyl
H


1d95
NHCOCH3
OMe
CN
Propyl
H
Propyl
H


1d96
NHCOCH3
OMe
CN
Butyl
H
Butyl
H


1d97
NHCOCH3
OMe
CN
Pentyl
H
Pentyl
H


1d98
NHCOCH3
OMe
CN
Hexyl
H
Hexyl
H


1d99
NHCOCH3
OMe
CN
Cyclobutyl
H
Cyclobutyl
H


1d100
NHCOCH3
OMe
CN
Cyclopentyl
H
Cyclopentyl
H


1d101
NHCOCH3
OMe
CN
Cyclohexyl
H
Cyclohexyl
H


1d102
NHCOCH3
OMe
CN
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1d103
NHCOCH3
OMe
CN
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1d104
NHCOCH3
OMe
CN
Isopropyl
H
Isopropyl
H


1d105
NHCOCH3
OMe
CN
Sec-butyl
H
Sec-butyl
H


1d106
NHCOCH3
OMe
CN
2-Methyl butyl
H
2-Methyl
H








butyl


1d107
NHCOCH3
OMe
CN
1-Ethyl propyl
H
1-Ethyl propyl
H


1d108
NHCOCH3
OMe
CN
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1d109
NHCOCH3
OMe
CN
Tert-butyl
H
Tert-butyl
H


1d110
NHCOCH3
OMe
CN
3-Methyl butyl
H
3-Methyl butyl
H


1d111
NHCOCH3
OMe
CN
Pentan-2-yl
H
Pentan-2-yl
H


1d112
NHCOCH3
OMe
CN
2-Ethylhexyl
H
2-Ethylhexyl
H


1d113
NHCOCH3
OMe
CN
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1d114
NHCOCH3
OMe
CN
Phenyl
H
Phenyl
H


1d115
NHCOCH3
OMe
CN
Benzyl
H
Benzyl
H


1d116
NHCOCH3
OMe
CONH2
Methyl
H
Methyl
H


1d117
NHCOCH3
OMe
CONH2
Ethyl
H
Ethyl
H


1d118
NHCOCH3
OMe
CONH2
Propyl
H
Propyl
H


1d119
NHCOCH3
OMe
CONH2
Butyl
H
Butyl
H


1d120
NHCOCH3
OMe
CONH2
Pentyl
H
Pentyl
H


1d121
NHCOCH3
OMe
CONH2
Hexyl
H
Hexyl
H


1d122
NHCOCH3
OMe
CONH2
Cyclobutyl
H
Cyclobutyl
H


1d123
NHCOCH3
OMe
CONH2
Cyclopentyl
H
Cyclopentyl
H


1d124
NHCOCH3
OMe
CONH2
Cyclohexyl
H
Cyclohexyl
H


1d125
NHCOCH3
OMe
CONH2
2-Methyl cyclohexyl
H
2-Methyl cyclohexyl
H


1d126
NHCOCH3
OMe
CONH2
3-Methyl cyclohexyl
H
3-Methyl cyclohexyl
H


1d127
NHCOCH3
OMe
CONH2
Isopropyl
H
Isopropyl
H


1d128
NHCOCH3
OMe
CONH2
Sec-butyl
H
Sec-butyl
H


1d129
NHCOCH3
OMe
CONH2
2-Methyl butyl
H
2-Methyl
H








butyl


1d130
NHCOCH3
OMe
CONH2
1-Ethyl propyl
H
1-Ethyl propyl
H


1d131
NHCOCH3
OMe
CONH2
1,2-Dimethyl propyl
H
1,2-Dimethyl propyl
H


1d132
NHCOCH3
OMe
CONH2
Tert-butyl
H
Tert-butyl
H


1d133
NHCOCH3
OMe
CONH2
3-Methyl butyl
H
3-Methyl butyl
H


1d134
NHCOCH3
OMe
CONH2
Pentan-2-yl
H
Pentan-2-yl
H


1d135
NHCOCH3
OMe
CONH2
2-Ethylhexyl
H
2-Ethylhexyl
H


1d136
NHCOCH3
OMe
CONH2
2,2-Dimethyl propyl
H
2,2-Dimethyl propyl
H


1d137
NHCOCH3
OMe
CONH2
Phenyl
H
Phenyl
H


1d138
NHCOCH3
OMe
CONH2
Benzyl
H
Benzyl
H


1d139
Methyl
Methyl
CN
2-Methoxyethyl
H
Butyl
H


1d140
Methyl
Methyl
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1d141
Methyl
Methyl
CN
3-Methoxy propyl
H
Butyl
H


1d142
Methyl
Methyl
CN
Butyl
Butyl
2-Hydroxyethyl
H


1d143
Methyl
Methyl
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1d144
Methyl
Methyl
CN
2-Fluoro ethyl
H
Butyl
H


1d145
Methyl
Methyl
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1d146
Methyl
Methyl
CN
3-Chloro propyl
H
2-Ethylhexyl
H


1d147
Methyl
Methyl
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1d148
Methyl
Methyl
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1d149
Methyl
Methyl
CN
2-(2-Hydroxy ethoxy)
H
Butyl
H






propyl


1d150
Methyl
Methyl
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1d151
Methyl
Methyl
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1d152
Methyl
Methyl
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d153
Methyl
Methyl
CN
H
H
3-(2-Hydroxy
H








ethoxy)ethyl


1d154
Methyl
Methyl
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d155
Methyl
Methyl
CN
3-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d156
Methyl
Methyl
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d157
Methyl
Methyl
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1d158
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1d159
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
H
H


1d160
Methyl
Methyl
CN
3-Isopropoxy-propyl
H
Phenyl
H


1d161
Methyl
Methyl
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1d162
Methyl
Methyl
CN
3-Ethoxy-propyl
H
H
H


1d163
Methyl
Methyl
CN
3-Ethoxy-propyl
H
Phenyl
H


1d164
Methyl
Methyl
CN
3-Ethoxy butyl
H
3-Ethoxybutyl
H


1d165
Methyl
Methyl
CN
3-Ethoxy butyl
H
H
H


1d166
Methyl
Methyl
CN
3-Ethoxy butyl
H
Phenyl
H


1d167
Methyl
Methyl
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1d168
Methyl
F
CN
2-Methoxyethyl
H
Butyl
H


1d169
Methyl
F
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1d170
Methyl
F
CN
3-Methoxy propyl
H
Butyl
H


1d171
Methyl
F
CN
Butyl
Butyl
2-Hydroxy ethyl
H


1d172
Methyl
F
CN
Isopropyl
Isopropyl
2-Hydroxy ethyl
H


1d173
Methyl
F
CN
2-Fluoro ethyl
H
Butyl
H


1d174
Methyl
F
CN
2-Chloro ethyl
H
2-Ethyl hexyl
H


1d175
Methyl
F
CN
3-Chloro propyl
H
2-Ethyl hexyl
H


1d176
Methyl
F
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1d177
Methyl
F
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1d178
Methyl
F
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1d179
Methyl
F
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1d180
Methyl
F
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1d181
Methyl
F
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d182
Methyl
F
CN
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1d183
Methyl
F
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d184
Methyl
F
CN
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1d185
Methyl
F
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d186
Methyl
F
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1d187
Methyl
F
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1d188
Methyl
F
CN
3-Isopropoxy-propyl
H
H
H


1d189
Methyl
F
CN
3-Isopropoxy-propyl
H
Phenyl
H


1d190
Methyl
F
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1d191
Methyl
F
CN
3-Ethoxy-propyl
H
H


1d192
Methyl
F
CN
3-Ethoxy-propyl
H
Phenyl
H


1d193
Methyl
F
CN
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1d194
Methyl
F
CN
3-Ethoxy butyl
H
H


1d195
Methyl
F
CN
3-Ethoxy butyl
H
Phenyl
H


1d196
Methyl
F
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1d197
NHCOCH3
OMe
CN
2-Methoxyethyl
H
Butyl
H


1d198
NHCOCH3
OMe
CN
3-Methoxy propyl
H
3-Methoxy propyl
H


1d199
NHCOCH3
OMe
CN
3-Methoxy propyl
H
Butyl
H


1d200
NHCOCH3
OMe
CN
Butyl
Butyl
2-Hydroxyethyl
H


1d201
NHCOCH3
OMe
CN
Isopropyl
Isopropyl
2-Hydroxyethyl
H


1d202
NHCOCH3
OMe
CN
2-Fluoro ethyl
H
Butyl
H


1d203
NHCOCH3
OMe
CN
2-Chloro ethyl
H
2-Ethylhexyl
H


1d204
NHCOCH3
OMe
CN
3-Chloro propyl
H
2-Ethylhexyl
H


1d205
NHCOCH3
OMe
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1d206
NHCOCH3
OMe
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1d207
NHCOCH3
OMe
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1d208
NHCOCH3
OMe
CN
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1d209
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1d210
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d211
NHCOCH3
OMe
CN
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1d212
NHCOCH3
OMe
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d213
NHCOCH3
OMe
CN
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1d214
NHCOCH3
OMe
CN
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d215
NHCOCH3
OMe
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1d216
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1d217
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
H
H


1d218
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
Phenyl
H


1d219
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1d220
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
H
H


1d221
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
Phenyl
H


1d222
NHCOCH3
OMe
CN
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1d223
NHCOCH3
OMe
CN
3-Ethoxy butyl
H
H
H


1d224
NHCOCH3
OMe
CN
3-Ethoxy butyl
H
Phenyl
H


1d225
NHCOCH3
OMe
CN
3-Methoxy propyl
H
Butyl
H


1d226
NHCOCH3
OMe
CN
Butyl
Butyl
2-Hydroxy ethyl
H


1d227
NHCOCH3
OMe
CN
Isopropyl
Isopropyl
2-Hydroxy ethyl
H


1d228
NHCOCH3
OMe
CN
2-Fluoro ethyl
H
Butyl
H


1d229
NHCOCH3
OMe
CN
2-Chloro ethyl
H
2-Ethyl hexyl
H


1d230
NHCOCH3
OMe
CN
2-Chloro propyl
H
2-Ethyl hexyl
H


1d231
NHCOCH3
OMe
CN
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1d232
NHCOCH3
OMe
CN
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1d233
NHCOCH3
OMe
CN
2-Hydroxy ethoxy
H
Butyl
H






propyl


1d234
NHCOCH3
OMe
CN
2-Hydroxy ethoxyethyl
H
Butyl
H


1d235
NHCOCH3
OMe
CN
2-(Ethyl sulfonyl) ethanol
H
Butyl
H


1d236
NHCOCH3
OMe
CN
H
H
(2-Hydroxy ethoxy)
H








propyl


1d237
NHCOCH3
OMe
CN
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d238
NHCOCH3
OMe
CN
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1d239
NHCOCH3
OMe
CN
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d240
NHCOCH3
OMe
CN
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1d241
NHCOCH3
OMe
CN
H
H
(2-Hydroxy
H








ethoxy)ethyl


1d242
NHCOCH3
OMe
CN
Phenyl
H
(2-Hydroxy
H








ethoxy)ethyl


1d243
NHCOCH3
OMe
CN
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1d244
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1d245
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
H
H


1d246
NHCOCH3
OMe
CN
3-Isopropoxy-propyl
H
Phenyl
H


1d247
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1d248
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
H
H


1d249
NHCOCH3
OMe
CN
3-Ethoxy-propyl
H
Phenyl
H


1d250
NHCOCH3
OMe
CN
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1d251
NHCOCH3
OMe
CN
3-Ethoxy butyl
H
H
H


1d252
NHCOCH3
OMe
CN
3-Ethoxy butyl
H
Phenyl
H


1d253
NHCOCH3
OMe
CN
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1d254
Methyl
Methyl
CONH2
2-Methoxyethyl
H
Butyl
H


1d255
Methyl
Methyl
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1d256
Methyl
Methyl
CONH2
3-Methoxy propyl
H
Butyl
H


1d257
Methyl
Methyl
CONH2
Butyl
Butyl
2-Hydroxy ethyl
H


1d258
Methyl
Methyl
CONH2
Isopropyl
Isopropyl
2-Hydroxy ethyl
H


1d259
Methyl
Methyl
CONH2
2-Fluoro ethyl
H
Butyl
H


1d260
Methyl
Methyl
CONH2
2-Chloro ethyl
H
2-Ethyl hexyl
H


1d261
Methyl
Methyl
CONH2
3-Chloro propyl
H
2-Ethyl hexyl
H


1d262
Methyl
Methyl
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1d263
Methyl
Methyl
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1d264
Methyl
Methyl
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1d265
Methyl
Methyl
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1d266
Methyl
Methyl
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1d267
Methyl
Methyl
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d268
Methyl
Methyl
CONH2
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1d269
Methyl
Methyl
CONH2
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d270
Methyl
Methyl
CONH2
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1d271
Methyl
Methyl
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d272
Methyl
Methyl
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1d273
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1d274
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
H
H


1d275
Methyl
Methyl
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1d276
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1d277
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
H
H


1d278
Methyl
Methyl
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1d279
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
3-Ethoxybutyl
H


1d280
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
H
H


1d281
Methyl
Methyl
CONH2
3-Ethoxybutyl
H
Phenyl
H


1d282
Methyl
Methyl
CONH2
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1d283
Methyl
F
CONH2
2-Methoxyethyl
H
Butyl
H


1d284
Methyl
F
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1d285
Methyl
F
CONH2
3-Methoxy propyl
H
Butyl
H


1d286
Methyl
F
CONH2
Butyl
Butyl
2-Hydroxy ethyl
H


1d287
Methyl
F
CONH2
Isopropyl
Isopropyl
2-Hydroxy ethyl
H


1d288
Methyl
F
CONH2
2-Fluoro ethyl
H
Butyl
H


1d289
Methyl
F
CONH2
2-Chloro ethyl
H
2-Ethyl hexyl
H


1d290
Methyl
F
CONH2
3-Chloro propyl
H
2-Ethyl hexyl
H


1d291
Methyl
F
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1d292
Methyl
F
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1d293
Methyl
F
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1d294
Methyl
F
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1d295
Methyl
F
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1d296
Methyl
F
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d297
Methyl
F
CONH2
H
H
3-(2-Hydroxy
H








ethoxy)ethyl


1d298
Methyl
F
CONH2
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d299
Methyl
F
CONH2
3-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d300
Methyl
F
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d301
Methyl
F
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1d302
Methyl
F
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1d303
Methyl
F
CONH2
3-Isopropoxy-propyl
H
H
H


1d304
Methyl
F
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1d305
Methyl
F
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1d306
Methyl
F
CONH2
3-Ethoxy-propyl
H
H
H


1d307
Methyl
F
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1d308
Methyl
F
CONH2
3-Ethoxy butyl
H
3-Ethoxybutyl
H


1d309
Methyl
F
CONH2
3-Ethoxy butyl
H
H
H


1d310
Methyl
F
CONH2
3-Ethoxy butyl
H
Phenyl
H


1d311
Methyl
F
CONH2
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl


1d312
NHCOCH3
OMe
CONH2
2-Methoxyethyl
H
Butyl
H


1d313
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
3-Methoxy propyl
H


1d314
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
Butyl
H


1d315
NHCOCH3
OMe
CONH2
Butyl
Butyl
2-Hydroxy ethyl
H


1d316
NHCOCH3
OMe
CONH2
Isopropyl
Isopropyl
2-Hydroxy ethyl
H


1d317
NHCOCH3
OMe
CONH2
2-Fluoro ethyl
H
Butyl
H


1d318
NHCOCH3
OMe
CONH2
2-Chloro ethyl
H
2-Ethyl hexyl
H


1d319
NHCOCH3
OMe
CONH2
3-Chloro propyl
H
2-Ethyl hexyl
H


1d320
NHCOCH3
OMe
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1d321
NHCOCH3
OMe
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1d322
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1d323
NHCOCH3
OMe
CONH2
2-(2-Hydroxyethoxy)ethyl
H
Butyl
H


1d324
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy ethoxy)
H








propyl


1d325
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d326
NHCOCH3
OMe
CONH2
H
H
3-(2-Hydroxy
H








ethoxy)propyl


1d327
NHCOCH3
OMe
CONH2
2-(2-Hydroxy
H
H
H






ethoxy)ethyl


1d328
NHCOCH3
OMe
CONH2
3-(2-Hydroxy
H
H
H






ethoxy)propyl


1d329
NHCOCH3
OMe
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d330
NHCOCH3
OMe
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1d331
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1d332
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
H
H


1d333
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1d334
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1d335
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
H
H


1d336
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1d337
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1d338
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
H
H


1d339
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
Phenyl
H


1d340
NHCOCH3
OMe
CONH2
3-Methoxy propyl
H
Butyl
H


1d341
NHCOCH3
OMe
CONH2
Butyl
Butyl
2-Hydroxy ethyl
H


1d342
NHCOCH3
OMe
CONH2
Isopropyl
Isopropyl
2-Hydroxy ethyl
H


1d343
NHCOCH3
OMe
CONH2
2-Fluoro ethyl
H
Butyl
H


1d344
NHCOCH3
OMe
CONH2
2-Chloro ethyl
H
2-Ethyl hexyl
H


1d345
NHCOCH3
OMe
CONH2
3-Chloro propyl
H
2-Ethyl hexyl
H


1d346
NHCOCH3
OMe
CONH2
2-(2-
H
Butyl
H






Hydroxyethylsulfanyl)-






ethyl


1d347
NHCOCH3
OMe
CONH2
2-(2-tert-Butyl sulfanyl-
H
Butyl
H






ethane sulfonyl)-ethyl


1d348
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxy
H
Butyl
H






propyl


1d349
NHCOCH3
OMe
CONH2
2-Hydroxy ethoxyethyl
H
Butyl
H


1d350
NHCOCH3
OMe
CONH2
2-(Ethyl sulfonyl) ethanol
H
Butyl
H


1d351
NHCOCH3
OMe
CONH2
H
H
3-(2-Hydroxy ethoxy)
H








propyl


1d352
NHCOCH3
OMe
CONH2
H
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d353
NHCOCH3
OMe
CONH2
Phenyl
H
2-(2-Hydroxy
H








ethoxy)ethyl


1d354
NHCOCH3
OMe
CONH2
3-(2-Phenoxy-ethoxy)-
H
H
H






propyl


1d355
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
3-Isopropoxy-propyl
H


1d356
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
H
H


1d357
NHCOCH3
OMe
CONH2
3-Isopropoxy-propyl
H
Phenyl
H


1d358
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
3-Ethoxy-propyl
H


1d359
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
H
H


1d360
NHCOCH3
OMe
CONH2
3-Ethoxy-propyl
H
Phenyl
H


1d361
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
3-Ethoxy butyl
H


1d362
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
H
H


1d363
NHCOCH3
OMe
CONH2
3-Ethoxy butyl
H
Phenyl
H


1d364
NHCOCH3
OMe
CONH2
4-(2-Hydroxy-
H
H
H






ethanesulfonyl)-phenyl









The present invention also provides a process for the preparation of dyes of formula (1) and mixtures thereof as discribed above comprising the steps

    a) diazotization of a compound of formula (2)






wherein R1 to R4 are defined as given above,

    b) reacting the diazonium salt obtained in step a) with stoichiometric amounts of compounds of formula (3) and (4)






wherein R9 to R12 are defined as given above, to yield an intermediate of formula (5)





    c) diazotization of the compound of formula (5),
    d) reacting the diazonium salt obtained in step c) with the compounds of formula (6), (7), (8) and (9) or mixtures thereof






wherein R9 to R20 are defined as given above.

The diazotization of the compound of the formula (2) and (5), respectively 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 diazonium salts obtained by diazotization of the compound of formula (2) onto the compounds of formulae (3) and (4) as well as the coupling reaction of the diazonium salts obtained by diazotization of the compound of formula (5) onto the compounds of formulae (6), (7), (8) and (9) can likewise be performed by known methods.
The compounds of formula (2) are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art such as the methods dosclosed in DE79780, DE72665, DE61174 and U.S. Pat. No. 4,801,694 A1.
The pyridines of formula (6), (7), (8) and (9) in which R13 and R19 represent cyano are commercially available or can be synthesized via methods disclosed in the literature such as DE2230392. Through analogy, all the diamino pyridines that are used in this patent can be synthesized with the protocol. The obtained pyridines can be further derivatized by reactions known to persons skilled in the art, such as hydrolysis to form pyridines of formula (6), (7), (8) and (9) in which R13 and R19 represent carbonamide or by hydrolysis and further esterification to form pyridines of formula (10), (11), (12) and (13) in which R13 and R19 are alkoxycarbonyl.
The above-mentioned derivatization reactions can be carried out in alkaline or acidic media, preferably in acidic media using strong inorganic acids such as sulfuric acid or hydrochloric acid gaseous or solution, acidic resins or chlorotrimethylsilane or other suitable acid catalyst in the presence of the corresponding alkohol. The reactions are advantageously carried out under inert atmosphere at temperatures in the range from 40° C. to 150° C.
Alternatively, the above mentioned derivatization reactions can be undertaken as a final step after the synthesis of the corresponding dyes with pyridine nitriles.
The dyes of the present invention can be used alone or as a mixture with other dyes according to the present invention and/or other substances.
Thus a chemical composition comprising one or more dye(s) as described above is also an aspect of the present invention.
A chemical composition consisting of two or more dyes as described above forms another preferred aspect of the present invention.
Also an aqueous solution for dying comprising one or more dye(s) as described above forms an aspect of the present invention.
The dyes of the present invention are suitable for dyeing and printing of natural, manufactured, regenerated, modified or synthetic hydroxyl- amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for acid dyes.
Therefore, the present invention also is directed to a Process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with a dye as described above.
The use of a dye as described above, a chemical composition as described above or of an aqueous solution as described above for dying fibers, as well as blends of such fibres selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, 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 forms another aspect of the present invention.
Still another aspect of the present invention is/are: Fiber and blends containing such fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6,6 and aramid fibres, 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 comprising one or more dye(s) of the present invention either in chemically and/or physically bound form.
The above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet. 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 and/or mixtures can be used as a single dyeing colorant in dyeing or printing processes or can be part of a di-, tri- or multi-component combination colorant in dyeing or in printing compositions. The di-, tri- or multi-component shade dyeings show similar fastness level as compared to dyeing performed with a single colorant component.
Dyes of the present invention and their salts or mixtures are highly compatible with other known and/or commercially available acid dyes and they can be used together with such dyes of related chromophores and similar technical performance to obtain specific hues. Similar technical performance includes: comparable build-up, comparable fastness properties and comparable exhaustion rates during dyeings.
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 a 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 aqueous inks.
An Ink for digital textile printing, comprising a dye of the present invention is another aspect 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 to 50% by weight, more preferably from 0.5 to 30% by weight and most preferably from 1 to 15% by weight, based on the total weight of the ink.
If desired the inks may contain further dyes used in digital printing in addition to the one or more dyes of the present invention.
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 to 50% by weight and preferably 5 to 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, N,N′-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 present 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 comprise 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 weigh unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.


EXAMPLE 1
7.96 g of 3,7-Diamino-naphthalene-1,5-disulfonic acid were first dissolved in water at slightly acidic pH to give a complete solution. Ice was added to the solution and when the temperature reached 10 to 15° C., 10.6 ml of 5N of sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8° C. when the mixture was added dropwise into 12.38 g of concentrated HCl with 12 g of ice. Yellow suspension was formed and the reaction mixture was completed within an hour.
6.30 g of 2,5-Dimethyl-phenylamine were added directly into the diazo suspension and stirred. A violet precipitate was observed upon addition. The intermediate precipitate, 3,7-Bis-(4-amino-2,5-dimethyl-phenylazo)-naphthalene-1,5-disulfonic acid obtained was filtered off with suction, washed with organic solvent and dried.
15.22 g of the dried intermediate, 3,7-Bis-(4-amino-2,5-dimethyl-phenylazo)-naphthalene-1,5-disulfonic acid, was then dissolved in water at slightly acidic pH to give a complete reddish orange solution. Ice was added to the solution and when the temperature reached 10 to 15° C., 10.1 ml of 5N of sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8° C. when the mixture was added dropwise into concentrated HCl with ice. Violet suspension was formed and the reaction mixture was completed in 90 mins.
The obtained reaction mixture was used in the next step as described below: 14.62 g of 2,6-Bis-(3-methoxy-propylamino)-4-methyl-nicotinonitrile were stirred in methanol and adjusted to slightly acidic. The reaction mixture was added dropwise into the methanol solution and stirred. Brilliant orange precipitate was observed upon addition. The precipitate obtained was filtered off with suction and washed with brine giving the product of the formula 1a52. The analytic data are consistent with the assigned structure for product 1a52. The product dyes the targeted fibre materials in brilliant red to reddish violet shades.
Through analogy, all the dyes of formulae (1) can be synthesized according to the method described above.
DYEING EXAMPLE 1
1 part of the dye 1a52 of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on 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 dyebath was heated to 50° C. for 10 minutes and then entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98° C. over the course of 50 minutes and than dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60° C. and removal of the dyed material. The polyamide-6 fabric was washed with hot and cold water, soaped and then spun and dried. The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.
DYEING EXAMPLE 2
1 part of the dye 1a52 of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5.5 using acetic acid (80%). The dyebath was heated to 50° C. for 10 minutes and then entered with 100 parts of a woven polyamide-6,6 fabric. The temperature was raised to 120° C. over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60° C. and removal of the dyed material. The polyamide-6,6 fabric was washed with hot and cold water, soaped and then spun and dried.
The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.
DYEING EXAMPLE 3
100 parts of polyamide-6 material were padded with a 1000 parts 50° C. liquor solution that consisted of 40 parts of the dye 1 m52, 100 parts of urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 815 parts of water. The material was rolled up and placed into a steaming chamber at 85 to 98° C. for 3 to 6 hours. After fixation, the fabric was washed with hot and cold water, soaped and then spun and dried.
The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.
DYEING EXAMPLE 4
1 part of the dye 1a52 of this invention was dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were added. The pH was then adjusted to 4.5 using acetic acid (80%). The dyebath was heated to 50° C. for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature was raised to 100° C. over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 90° C. and removal of the dyed material. The wool fabric was washed with hot and cold water, soaped and then spun and dried.
The dyeing obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.
DYEING EXAMPLE 5
1 part of the dye 1a52 of this invention was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate, and 1 part of a wetting agent (anionic) was added. 100 parts of bleached cotton knitted fabric were added to this solution. The dye bath was then heated up to 98° C. with a gradient of 2° C./min then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling down to 80° C. At 80° C. the dyeing was continued for another 20 minutes. The dyed material was then removed and was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained gave dark red shade and has very good light and wet fastness and also good levelness in the fibre.
DYEING EXAMPLE 6
3 parts of the dye 1a52 of this invention dissolved in 82 parts of deionized water is added into the dyebath with 15 parts of diethylene glycol at 60° C. On cooling, a red printing ink is obtained. The red printing ink can be used for ink jet printing on paper, polyamide or wool textiles.
DYEING EXAMPLE 7
4 parts of chemically bleached (pine wood) sulphite pulp is mixed up with 100 parts of 55° C. water. 1 part of the dye 1a52 of this invention is dissolved in 100 parts of hot water. 80 parts of this solution is given to the mixed-up pulp and mixed for 2 minutes. After that the mixture is sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution is then diluted with 2000 parts of cold water and the paper is produced out of this solution. The red paper produced from the mixture has good wet fastnesses.

## Claims

1. A dye of formula (1)



wherein
R1, R2, R3 and R4 independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M—whereby at least two of them are SO3M,
R5, R6, R7 and R8 independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, —SO3M or alkylureido,
R9 and R15 independent of each other is cyano, carbamoyl, carbamoyl substituted, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen,
R10 and R16 independent of each other is 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, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, or 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, alkyl-ureido and phenylureido,
R11, R12, R13, R14, R17, R18, R19, R20 independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyakyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and 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, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo-alkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono-aryl-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, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbarnoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalk yl-N-monoarylsulfamo-yl and SO3M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and 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, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-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, N,N-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, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO3M,
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation,
the dyes of formula (1) have two to six sulfonic acid groups,
and
whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R11 and R12, and R13 and R14, respectively can be positioned ortho or para to R9, meaning that when the amino rest bearing the substituents R11 and R12 is positioned ortho to R9, the amino rest bearing the substituents R13 and R14 is positioned para to R9, and vice versa;
and
the same applies to the amino rests bearing the substituents R17 and R18, and R19 to R20 , respectively that can be positioned ortho or para to R15, meaning that when the amino rest bearing the substituents R17 and R18 is positioned ortho to R15, the amino rest bearing the substituents R19 to R20 is positioned para to R15, and vice versa.

2. The dye according to claim 1, having formula (1a)



wherein
R1a, R2a, R3a and R4a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
R5a, R6a, R7a and R8a independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO3M or (C1-C4)-acylamino,
R9a and R15a independent of one another is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
R10a and R16a independent of each other is unsubstituted, linear or branched (C1-C4)-alkyl, unsubstiuted (C5-C7)-cycloalkyl or substituted (C5-C7)-cycloalkyl with one or more substituents,
R11a, R12a R13a, R14a, R17a, R18a, R19a and R20a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
and
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

3. The dye according to claim 2, wherein R1a, R2a, R3a and R4a independent of each other is SO3M, hydrogen, alkyl, alkoxy or halogen—whereby at least two of them are SO3M,
R5a, R6a, R7a and R8a independent of each other is hydrogen, methyl, halogen, —SO3M or acetylamino,
R9a and R15a independent of each other is cyano or carbamoyl,
R10a and R16a is methyl,
R11a, R12a R13a, R14a, R17a, R18a, R19a and R20a independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxy-ethoxy)ethyl, 3-(4-hydroxyetlaoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl, alkyl substituted by SO3M or alkyl substituted by COOM
and
M is hydrogen, sodium, potassium, lithium or ammonium.

4. The dye according to claim 1, having formula (1b)



wherein
R1b, R2b, R3b and R4b independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
R5b, R6b, R7b and R8b independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO3M or (C1-C4)-acylamino,
R9b and R15b independent of each other is cyano, carbamoyl, carbamoyl substituted, sulfonylalkyl or alkoxycarbonyl,
R10b and R16b independent of each other is unsubstituted, linear or branched (C1-C4)-alkyl, unsubstiuted (C5-C7)-cycloalkyl or substituted (C5-C7)-cycloalkyl with one or more substituents,
R11b, R12b R13b, R14b, R17b, R18b, R19b and R20b independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl-ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
and
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

5. The dye according to claim 4, wherein
R3b and R4b is SO3M,
R1b and R2b is hydrogen,
R5b, R6b, R7b and R8b independent of each other is hydrogen, methyl, halogen, —SO3M or acetylamino,
R9b and R15b independent of each other is cyano or carbamoyl,
R10b and R16b is methyl,
R11b, R12b R13b, R14b, R17b, R18b, R19b and R20b independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO3M or alkyl substituted by COOM
and
M is hydrogen, sodium, potassium, lithium or ammonium.

6. The dye according to claim 1, having formula (1c)



wherein
R1c, R2c, R3c and R4c independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
R5c, R6c, R7c and R8c independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO3M or (C1-C4)-acylamino,
R9c and R15c independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
R10c and R16c independent of each other is unsubstituted, linear or branched (C1-C4)-alkyl, unsubstiuted (C5-C7)-cycloalkyl or substituted (C5-C7)-cycloalkyl with one or more substituents,
R11c, R12c R13c, R14c, R17c, R18c, R19c and R20c independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, amino alkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur, and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
and
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

7. The dye according to claim 6, wherein
R2c and R4c is SO3M,
R1c and R2c is hydrogen,
R5c, R6c, R7c and R8c independent of each other is hydrogen, methyl, halogen, —SO3M or acetylamino,
R9c and R15c independent of each other is cyano or carbamoyl,
R10c and R16c is methyl,
R11c, R12c R13c, R14c, R17c, R18c, R19c and R20c independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO3M or alkyl substituted by COOM
and
M is hydrogen, sodium, potassium, lithium or ammonium.

8. The dye according to claim 1, having formula (1d)



wherein
R1d, R2d, R3d and R4d independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M whereby at least two of them are SO3M,
R5d, R6d, R7d and R8d independent of each other is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO3M or (C1-C4)-acylamino,
R9d and R15d independent of each other is cyano, carbamoyl, carbamoyl substituted, sulfonylalkyl or alkoxycarbonyl,
R10d and R16d independent of each other is unsubstituted, linear or branched (C1-C4)-alkyl, unsubstiuted (C5-C7)-cycloalkyl or substituted (C5-C7)-cycloalkyl with one or more substituents,
R11d, R12d R14d, R17d, R18d, R19d and R20d independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, or heterocycloalkylalkyl,
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur,
or
alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
or
alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M
and
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

9. The dye according to claim 8, wherein
R1d and R3d is SO3M,
R2d and R4d is hydrogen,
R5d, R6d, R7d R8d independent of each other is hydrogen, methyl, halogen, —SO3M or acetylamino,
R9d and R15d independent of each other is cyano or carbamoyl,
R10d R16d is methyl,
R11d, R12d R13d, R14d, R17d, R18d, R19d and R20d independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 4-(2-hydroxy-ethanesulfonyl)-phenyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxypropyl), 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxyethoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, alkyl substituted by SO3M or alkyl substituted by COOM
and
M is hydrogen, sodium, potassium, lithium or ammonium.

10. A process for the preparation of the dye according to claim 1 and mixtures thereof comprising the steps
a) diazotization of a compound of formula (2)




wherein R1 to R4 are defined as in claim 1,
b) reacting the diazonium salt obtained in step a) with stoichiometric amounts of compounds of formula (3) and (4)




wherein R5 to R8 are defined as in claim 1, to yield an intermediate of formula (5)




c) diazotization of the compound of formula (5),
d) reacting the diazonium salt obtained in step c) with the compounds of formula (6), (7), (8) and (9) or mixtures thereof




wherein R11 to R20 are defined as in claim 1.

11. A chemical composition comprising one or more dye(s) according to claim 1.

12. A chemical composition consisting essentially of two or more dyes according to claim 1.

13. An aqueous solution for dying comprising one or more dyes according to claim 1.

14. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with the dye according to claim 1.

15. An ink for digital textile printing comprising the dye according to claim 1.

16. A fiber and blend containing the fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, 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 comprising one or more dye(s) according to claim 1 either in chemically and/or physically bound form.