The present invention relates to the technical field of dyestuffs for dyeing and printing of hydroxyl- and/or carboxamido-containing material.
Acid dyes containing pyridine derivatives as couplers are known from prior art and can be used as colorants in different applications, see for example GB 2 337 053 A, which discloses dyes as part of ink jet formulations, which bisazo-dyes are based on hydroxypyridone and pyridinium as structural elements. According to the examples the dyes disclosed are used as neutral molecules for printing paper. Other dyes are disclosed in e.g. U.S. Pat. No. 3,959,250 A, U.S. Pat. No. 5,468,848 A, U.S. Pat. No. 3,960,480 A, U.S. Pat. No. 5,543,259 A and WO 2007/045825 A.
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 the 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 formula (1)
![embedded image]()
wherein
R1, R2, R3, R4, R5, R6, R7 and R8 independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M whereby at least two of them are SO3M,
R9 and R18 independent of each other is cyano, carbamoyl, substituted carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen,
R10 and R19 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, R20 and R21 independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, 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, 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, phenyilureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamo-yl, 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 sulphur, 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, phenyilureido, 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,
R13, R14, R15, R16, R22, R23, R24 and R25 independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, 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, 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-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyilureido, 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 sulphur 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-alkyl-sulfonyl-amino, ureido, alkylureido, phenyilureido, 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,
R17 and R26 independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, 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, 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, phenyilureido, 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 sulphur 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, phenyilureido, 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,
m, n, o and p independent of each other is integer 1, 2, 3 or 4,
when n is 2, 3 or 4, R13 contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R14 independently from R13,
when m is 2, 3 or 4, R15 contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R16 independently from R15,
when o is 2, 3 or 4, R22 contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R23 independently from R22 and
when p is 2, 3 or 4, R24 contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R25 independently from R24,
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 to R17, 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 to R17 is positioned para to R9, and vice versa
and
the same applies to the amino rests bearing the substituents R20 and R21, and R22 to R26, respectively that can be positioned ortho or para to R18, meaning that when the amino rest bearing the substituents R20 and R21 is positioned ortho to R18, the amino rest bearing the substituents R22 to R26 is positioned para to R18, and vice versa.
The present invention refers to all tautomeric and geometric isomers of the dyes of formula (1) as well as 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 cycloalklyl groups and unsatured 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 the context of this invention are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl respectively. 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 or 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 or acyloxy.
Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine. The terms 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-(hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, amino-carbonylamino, aminosulfonylamino, alkoxycarbonyl or acyloxy.
Halogen is preferably chlorine, bromine or fluorine.
M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(C1-C4)-alkylammonium.
Preferred are dyes of formula (1a)
![embedded image]()
wherein
R1a, R2a, R3a, R4a, R5a, R6a, R7a and R8a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
R9a and R18a independent of each other is cyano, carbamoyl or alkoxycarbonyl,
R10a and R19a independent of each other is unsubstituted, linear or branched (C1-C4)-alkyl, unsubstituted (C5-C7)-cycloalkyl, substituted (C5-C7)-cycloalkyl with one or more substituents, preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl,
R11a, R12a, R20a and R21a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, 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-mono-cycloalkyl-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 sulphur 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,
R13a, R14a, R15a, R16a, R22a, R23a, R24a and R25a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, 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-mono-cycloalkyl-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 sulphur 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,
R17a and R26a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyakylsulfonylalkyl, 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-mono-cycloalkyl-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 sulphur 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,
M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation,
m, n, o and p independent of each other is integer and is 1, 2, 3 or 4,
when n is 2, 3 or 4, R13a contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R14a independently from R13a,
when m is 2, 3 or 4, R15a contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R16a independently from R15a,
when o is 2, 3 or 4, R22a contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R23a independently from R22a and
when p is 2, 3 or 4, R24a contained in the 2, 3, or 4 units can be identical or different from unit to unit, and same applies to R25a independently from R24a.
Particular preferred are dyes of formula (1aa)
![embedded image]()
wherein
R1aa, R2aa, R3aa, R4aa, R5aa, R6aa, R7aa and R8aa independent of each other is SO3M, hydrogen, alkyl or alkoxy whereby at least two of them are SO3M,
R9aa and R18aa independent of each other is cyano or carbamoyl,
R10aa and R19aa is methyl,
m, n, o and p, independent of each other is an integer and is 2, 3 or 4,
R11aa, R13aa, R14aa, R15aa, R16aa, R17aa, R20aa, R22aa, R23aa, R24aa, R25aa and R26aa is hydrogen,
R12aa and R21aa 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-ethylproyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-methoxyethyl, 3-methoxypropyl, 2-hydroxyethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 2-(2-hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(ethyl-sulfonyl)ethanol, 3-(4-hydroxybutoxy)propyl, 2-(2-hydroxyethoxy)ethyl, 4-(2-hydroxyethane-sulfonyl)phenyl, 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 (1aa) are the compounds of the formulae (1aa1 to 1aa816) and mixtures thereof, wherein R2aa and R7aa is hydrogen:
|
Structure
R1aa
R3aa
R4aa
R5aa
R6aa
R8aa
R9aa/R18aa
R12aa/R21aa
m
n
o
p
|
|
1aa1
H
SO3H
H
H
SO3H
H
CN
H
2
2
2
2
|
1aa2
H
H
SO3H
SO3H
H
H
|
1aa3
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa4
OMe
H
SO3H
SO3H
H
OMe
|
1aa5
H
SO3H
H
H
SO3H
H
CN
Ethyl
2
2
2
2
|
1aa6
H
H
SO3H
SO3H
H
H
|
1aa7
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa8
OMe
H
SO3H
SO3H
H
OMe
|
1aa9
H
SO3H
H
H
SO3H
H
CN
Propyl
2
2
2
2
|
1aa10
H
H
SO3H
SO3H
H
H
|
1aa11
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa12
OMe
H
SO3H
SO3H
H
OMe
|
1aa13
H
SO3H
H
H
SO3H
H
CN
Butyl
2
2
2
2
|
1aa14
H
H
SO3H
SO3H
H
H
|
1aa15
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa16
OMe
H
SO3H
SO3H
H
OMe
|
1aa17
H
SO3H
H
H
SO3H
H
CN
Pentyl
2
2
2
2
|
1aa18
H
H
SO3H
SO3H
H
H
|
1aa19
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa20
OMe
H
SO3H
SO3H
H
OMe
|
1aa21
H
SO3H
H
H
SO3H
H
CN
Cyclobutyl
2
2
2
2
|
1aa22
H
H
SO3H
SO3H
H
H
|
1aa23
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa24
OMe
H
SO3H
SO3H
H
OMe
|
1aa25
H
SO3H
H
H
SO3H
H
CN
Cyclopentyl
2
2
2
2
|
1aa26
H
H
SO3H
SO3H
H
H
|
1aa27
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa28
OMe
H
SO3H
SO3H
H
OMe
|
1aa29
H
SO3H
H
H
SO3H
H
CN
Isopropyl
2
2
2
2
|
1aa30
H
H
SO3H
SO3H
H
H
|
1aa31
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa32
OMe
H
SO3H
SO3H
H
OMe
|
1aa33
H
SO3H
H
H
SO3H
H
CN
Sec-butyl
2
2
2
2
|
1aa34
H
H
SO3H
SO3H
H
H
|
1aa35
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa36
OMe
H
SO3H
SO3H
H
OMe
|
1aa37
H
SO3H
H
H
SO3H
H
CN
2-Methyl
2
2
2
2
|
1aa38
H
H
SO3H
SO3H
H
H
butyl
|
1aa39
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa40
OMe
H
SO3H
SO3H
H
OMe
|
1aa41
H
SO3H
H
H
SO3H
H
CN
1-Ethyl
2
2
2
2
|
1aa42
H
H
SO3H
SO3H
H
H
propyl
|
1aa43
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa44
OMe
H
SO3H
SO3H
H
OMe
|
1aa45
H
SO3H
H
H
SO3H
H
CN
1,2-Dimethyl
2
2
2
2
|
1aa46
H
H
SO3H
SO3H
H
H
propyl
|
1aa47
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa48
OMe
H
SO3H
SO3H
H
OMe
|
1aa49
H
SO3H
H
H
SO3H
H
CN
Tert-butyl
2
2
2
2
|
1aa50
H
H
SO3H
SO3H
H
H
|
1aa51
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa52
OMe
H
SO3H
SO3H
H
OMe
|
1aa53
H
SO3H
H
H
SO3H
H
CN
3-Methyl
2
2
2
2
|
1aa54
H
H
SO3H
SO3H
H
H
butyl
|
1aa55
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa56
OMe
H
SO3H
SO3H
H
OMe
|
1aa57
H
SO3H
H
H
SO3H
H
CN
Pentan-2-yl
2
2
2
2
|
1aa58
H
H
SO3H
SO3H
H
H
|
1aa59
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa60
OMe
H
SO3H
SO3H
H
OMe
|
1aa61
H
SO3H
H
H
SO3H
H
CN
2-Ethylhexyl
2
2
2
2
|
1aa62
H
H
SO3H
SO3H
H
H
|
1aa63
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa64
OMe
H
SO3H
SO3H
H
OMe
|
1aa65
H
SO3H
H
H
SO3H
H
CN
2,2-Dimethyl
2
2
2
2
|
1aa66
H
H
SO3H
SO3H
H
H
propyl
|
1aa67
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa68
OMe
H
SO3H
SO3H
H
OMe
|
1aa69
H
SO3H
H
H
SO3H
H
CN
Phenyl
2
2
2
2
|
1aa70
H
H
SO3H
SO3H
H
H
|
1aa71
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa72
OMe
H
SO3H
SO3H
H
OMe
|
1aa73
H
SO3H
H
H
SO3H
H
CN
Benzyl
2
2
2
2
|
1aa74
H
H
SO3H
SO3H
H
H
|
1aa75
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa76
OMe
H
SO3H
SO3H
H
OMe
|
1aa77
H
SO3H
H
H
SO3H
H
CONH2
H
2
2
2
2
|
1aa78
H
H
SO3H
SO3H
H
H
|
1aa79
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa80
OMe
H
SO3H
SO3H
H
OMe
|
1aa81
H
SO3H
H
H
SO3H
H
CONH2
Ethyl
2
2
2
2
|
1aa82
H
H
SO3H
SO3H
H
H
|
1aa83
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa84
OMe
H
SO3H
SO3H
H
OMe
|
1aa85
H
SO3H
H
H
SO3H
H
CONH2
Propyl
2
2
2
2
|
1aa86
H
H
SO3H
SO3H
H
H
|
1aa87
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa88
OMe
H
SO3H
SO3H
H
OMe
|
1aa89
H
SO3H
H
H
SO3H
H
CONH2
Butyl
2
2
2
2
|
1aa90
H
H
SO3H
SO3H
H
H
|
1aa91
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa92
OMe
H
SO3H
SO3H
H
OMe
|
1aa93
H
SO3H
H
H
SO3H
H
CONH2
Pentyl
2
2
2
2
|
1aa94
H
H
SO3H
SO3H
H
H
|
1aa95
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa96
OMe
H
SO3H
SO3H
H
OMe
|
1aa97
H
SO3H
H
H
SO3H
H
CONH2
Cyclobutyl
2
2
2
2
|
1aa98
H
H
SO3H
SO3H
H
H
|
1aa99
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa100
OMe
H
SO3H
SO3H
H
OMe
|
1aa101
H
SO3H
H
H
SO3H
H
CONH2
Cyclopentyl
2
2
2
2
|
1aa102
H
H
SO3H
SO3H
H
H
|
1aa103
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa104
OMe
H
SO3H
SO3H
H
OMe
|
1aa105
H
SO3H
H
H
SO3H
H
CONH2
Isopropyl
2
2
2
2
|
1aa106
H
H
SO3H
SO3H
H
H
|
1aa107
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa108
OMe
H
SO3H
SO3H
H
OMe
|
1aa109
H
SO3H
H
H
SO3H
H
CONH2
Sec-butyl
2
2
2
2
|
1aa110
H
H
SO3H
SO3H
H
H
|
1aa111
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa112
OMe
H
SO3H
SO3H
H
OMe
|
1aa113
H
SO3H
H
H
SO3H
H
CONH2
|
1aa114
H
H
SO3H
SO3H
H
H
2-Methyl
2
2
2
2
|
1aa115
Methyl
H
SO3H
SO3H
H
Methyl
butyl
|
1aa116
OMe
H
SO3H
SO3H
H
OMe
|
1aa117
H
SO3H
H
H
SO3H
H
CONH2
1-Ethyl
2
2
2
2
|
1aa118
H
H
SO3H
SO3H
H
H
propyl
|
1aa119
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa120
OMe
H
SO3H
SO3H
H
OMe
|
1aa121
H
SO3H
H
H
SO3H
H
CONH2
1,2-Dimethyl
2
2
2
2
|
1aa122
H
H
SO3H
SO3H
H
H
propyl
|
1aa123
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa124
OMe
H
SO3H
SO3H
H
OMe
|
1aa125
H
SO3H
H
H
SO3H
H
CONH2
Tert-butyl
2
2
2
2
|
1aa126
H
H
SO3H
SO3H
H
H
|
1aa127
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa128
OMe
H
SO3H
SO3H
H
OMe
|
1aa129
H
SO3H
H
H
SO3H
H
CONH2
3-Methyl
2
2
2
2
|
1aa130
H
H
SO3H
SO3H
H
H
butyl
|
1aa131
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa132
OMe
H
SO3H
SO3H
H
OMe
|
1aa133
H
SO3H
H
H
SO3H
H
CONH2
Pentan-2-yl
2
2
2
2
|
1aa134
H
H
SO3H
SO3H
H
H
|
1aa135
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa136
OMe
H
SO3H
SO3H
H
OMe
|
1aa137
H
SO3H
H
H
SO3H
H
CONH2
2-Ethylhexyl
2
2
2
2
|
1aa138
H
H
SO3H
SO3H
H
H
|
1aa139
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa140
OMe
H
SO3H
SO3H
H
OMe
|
1aa141
H
SO3H
H
H
SO3H
H
CONH2
2,2-Dimethyl
2
2
2
2
|
1aa142
H
H
SO3H
SO3H
H
H
propyl
|
1aa143
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa144
OMe
H
SO3H
SO3H
H
OMe
|
1aa145
H
SO3H
H
H
SO3H
H
CONH2
Phenyl
2
2
2
2
|
1aa146
H
H
SO3H
SO3H
H
H
|
1aa147
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa148
OMe
H
SO3H
SO3H
H
OMe
|
1aa149
H
SO3H
H
H
SO3H
H
CONH2
Benzyl
2
2
2
2
|
1aa150
H
H
SO3H
SO3H
H
H
|
1aa151
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa152
OMe
H
SO3H
SO3H
H
OMe
|
1aa153
H
SO3H
H
H
SO3H
H
CN
H
3
4
3
4
|
1aa154
H
H
SO3H
SO3H
H
H
|
1aa155
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa156
OMe
H
SO3H
SO3H
H
OMe
|
1aa157
H
SO3H
H
H
SO3H
H
CN
Ethyl
3
4
3
4
|
1aa158
H
H
SO3H
SO3H
H
H
|
1aa159
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa160
OMe
H
SO3H
SO3H
H
OMe
|
1aa161
H
SO3H
H
H
SO3H
H
CN
Propyl
3
4
3
4
|
1aa162
H
H
SO3H
SO3H
H
H
|
1aa163
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa164
OMe
H
SO3H
SO3H
H
OMe
|
1aa165
H
SO3H
H
H
SO3H
H
CN
Butyl
3
4
3
4
|
1aa166
H
H
SO3H
SO3H
H
H
|
1aa167
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa168
OMe
H
SO3H
SO3H
H
OMe
|
1aa169
H
SO3H
H
H
SO3H
H
CN
Pentyl
3
4
3
4
|
1aa170
H
H
SO3H
SO3H
H
H
|
1aa171
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa172
OMe
H
SO3H
SO3H
H
OMe
|
1aa173
H
SO3H
H
H
SO3H
H
CN
Cyclobutyl
3
4
3
4
|
1aa174
H
H
SO3H
SO3H
H
H
|
1aa175
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa176
OMe
H
SO3H
SO3H
H
OMe
|
1aa177
H
SO3H
H
H
SO3H
H
CN
Cyclopentyl
3
4
3
4
|
1aa178
H
H
SO3H
SO3H
H
H
|
1aa179
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa180
OMe
H
SO3H
SO3H
H
OMe
|
1aa181
H
SO3H
H
H
SO3H
H
CN
Isopropyl
3
4
3
4
|
1aa182
H
H
SO3H
SO3H
H
H
|
1aa183
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa184
OMe
H
SO3H
SO3H
H
OMe
|
1aa185
H
SO3H
H
H
SO3H
H
CN
Sec-butyl
3
4
3
4
|
1aa186
H
H
SO3H
SO3H
H
H
|
1aa187
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa188
OMe
H
SO3H
SO3H
H
OMe
|
1aa189
H
SO3H
H
H
SO3H
H
CN
2-Methyl
3
4
3
4
|
1aa190
H
H
SO3H
SO3H
H
H
butyl
|
1aa191
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa192
OMe
H
SO3H
SO3H
H
OMe
|
1aa193
H
SO3H
H
H
SO3H
H
CN
1-Ethyl
3
4
3
4
|
1aa194
H
H
SO3H
SO3H
H
H
propyl
|
1aa195
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa196
OMe
H
SO3H
SO3H
H
OMe
|
1aa197
H
SO3H
H
H
SO3H
H
CN
1,2-Dimethyl
3
4
3
4
|
1aa198
H
H
SO3H
SO3H
H
H
propyl
|
1aa199
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa200
OMe
H
SO3H
SO3H
H
OMe
|
1aa201
H
SO3H
H
H
SO3H
H
CN
Tert-butyl
3
4
3
4
|
1aa202
H
H
SO3H
SO3H
H
H
|
1aa203
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa204
OMe
H
SO3H
SO3H
H
OMe
|
1aa205
H
SO3H
H
H
SO3H
H
CN
3-Methyl
3
4
3
4
|
1aa206
H
H
SO3H
SO3H
H
H
butyl
|
1aa207
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa208
OMe
H
SO3H
SO3H
H
OMe
|
1aa209
H
SO3H
H
H
SO3H
H
CN
Pentan-2-yl
3
4
3
4
|
1aa210
H
H
SO3H
SO3H
H
H
|
1aa211
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa212
OMe
H
SO3H
SO3H
H
OMe
|
1aa213
H
SO3H
H
H
SO3H
H
CN
2-Ethylhexyl
3
4
3
4
|
1aa214
H
H
SO3H
SO3H
H
H
|
1aa215
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa216
OMe
H
SO3H
SO3H
H
OMe
|
1aa217
H
SO3H
H
H
SO3H
H
CN
2,2-Dimethyl
3
4
3
4
|
1aa218
H
H
SO3H
SO3H
H
H
propyl
|
1aa219
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa220
OMe
H
SO3H
SO3H
H
OMe
|
1aa221
H
SO3H
H
H
SO3H
H
CN
Phenyl
3
4
3
4
|
1aa222
H
H
SO3H
SO3H
H
H
|
1aa223
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa224
OMe
H
SO3H
SO3H
H
OMe
|
1aa225
H
SO3H
H
H
SO3H
H
CN
Benzyl
3
4
3
4
|
1aa226
H
H
SO3H
SO3H
H
H
|
1aa227
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa228
OMe
H
SO3H
SO3H
H
OMe
|
1aa229
H
SO3H
H
H
SO3H
H
CONH2
H
3
4
3
4
|
1aa230
H
H
SO3H
SO3H
H
H
|
1aa231
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa232
OMe
H
SO3H
SO3H
H
OMe
|
1aa233
H
SO3H
H
H
SO3H
H
CONH2
Ethyl
3
4
3
4
|
1aa234
H
H
SO3H
SO3H
H
H
|
1aa235
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa236
OMe
H
SO3H
SO3H
H
OMe
|
1aa237
H
SO3H
H
H
SO3H
H
CONH2
Propyl
3
4
3
4
|
1aa238
H
H
SO3H
SO3H
H
H
|
1aa239
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa240
OMe
H
SO3H
SO3H
H
OMe
|
1aa241
H
SO3H
H
H
SO3H
H
CONH2
Butyl
3
4
3
4
|
1aa242
H
H
SO3H
SO3H
H
H
|
1aa243
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa244
OMe
H
SO3H
SO3H
H
OMe
|
1aa245
H
SO3H
H
H
SO3H
H
CONH2
Pentyl
3
4
3
4
|
1aa246
H
H
SO3H
SO3H
H
H
|
1aa247
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa248
OMe
H
SO3H
SO3H
H
OMe
|
1aa249
H
SO3H
H
H
SO3H
H
CONH2
Cyclopentyl
3
4
3
4
|
1aa250
H
H
SO3H
SO3H
H
H
|
1aa251
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa252
OMe
H
SO3H
SO3H
H
OMe
|
1aa253
H
SO3H
H
H
SO3H
H
CONH2
Cyclopentyl
3
4
3
4
|
1aa254
H
H
SO3H
SO3H
H
H
|
1aa255
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa256
OMe
H
SO3H
SO3H
H
OMe
|
1aa257
H
SO3H
H
H
SO3H
H
CONH2
Isopropyl
3
4
3
4
|
1aa258
H
H
SO3H
SO3H
H
H
|
1aa259
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa260
OMe
H
SO3H
SO3H
H
OMe
|
1aa261
H
SO3H
H
H
SO3H
H
CONH2
Sec-butyl
3
4
3
4
|
1aa262
H
H
SO3H
SO3H
H
H
|
1aa263
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa264
OMe
H
SO3H
SO3H
H
OMe
|
1aa265
H
SO3H
H
H
SO3H
H
CONH2
2-Methyl
3
4
3
4
|
1aa266
H
H
SO3H
SO3H
H
H
butyl
|
1aa267
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa268
OMe
H
SO3H
SO3H
H
OMe
|
1aa269
H
SO3H
H
H
SO3H
H
CONH2
1-Ethyl
3
4
3
4
|
1aa270
H
H
SO3H
SO3H
H
H
propyl
|
1aa271
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa272
OMe
H
SO3H
SO3H
H
OMe
|
1aa273
H
SO3H
H
H
SO3H
H
CONH2
1,2-Dimethyl
3
4
3
4
|
1aa274
H
H
SO3H
SO3H
H
H
propyl
|
1aa275
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa276
OMe
H
SO3H
SO3H
H
OMe
|
1aa277
H
SO3H
H
H
SO3H
H
CONH2
Tert-butyl
3
4
3
4
|
1aa278
H
H
SO3H
SO3H
H
H
|
1aa279
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa280
OMe
H
SO3H
SO3H
H
OMe
|
1aa281
H
SO3H
H
H
SO3H
H
CONH2
3-Methyl
3
4
3
4
|
1aa282
H
H
SO3H
SO3H
H
H
butyl
|
1aa283
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa284
OMe
H
SO3H
SO3H
H
OMe
|
1aa285
H
SO3H
H
H
SO3H
H
CONH2
Pentan-2-yl
3
4
3
4
|
1aa286
H
H
SO3H
SO3H
H
H
|
1aa287
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa288
OMe
H
SO3H
SO3H
H
OMe
|
1aa289
H
SO3H
H
H
SO3H
H
CONH2
2-Ethylhexyl
3
4
3
4
|
1aa290
H
H
SO3H
SO3H
H
H
|
1aa291
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa292
OMe
H
SO3H
SO3H
H
OMe
|
1aa293
H
SO3H
H
H
SO3H
H
CONH2
2,2-Dimethyl
3
4
3
4
|
1aa294
H
H
SO3H
SO3H
H
H
propyl
|
1aa295
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa296
OMe
H
SO3H
SO3H
H
OMe
|
1aa297
H
SO3H
H
H
SO3H
H
CONH2
Phenyl
3
4
3
4
|
1aa298
H
H
SO3H
SO3H
H
H
|
1aa299
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa300
OMe
H
SO3H
SO3H
H
OMe
|
1aa301
H
SO3H
H
H
SO3H
H
CONH2
Benzyl
3
4
3
4
|
1aa302
H
H
SO3H
SO3H
H
H
|
1aa303
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa304
OMe
H
SO3H
SO3H
H
OMe
|
1aa305
H
SO3H
H
H
SO3H
H
CN
H
3
3
3
3
|
1aa306
H
H
SO3H
SO3H
H
H
|
1aa307
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa308
OMe
H
SO3H
SO3H
H
OMe
|
1aa309
H
SO3H
H
H
SO3H
H
CN
Ethyl
3
3
3
3
|
1aa310
H
H
SO3H
SO3H
H
H
|
1aa311
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa312
OMe
H
SO3H
SO3H
H
OMe
|
1aa313
H
SO3H
H
H
SO3H
H
CN
Propyl
3
3
3
3
|
1aa314
H
H
SO3H
SO3H
H
H
|
1aa315
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa316
OMe
H
SO3H
SO3H
H
OMe
|
1aa317
H
SO3H
H
H
SO3H
H
CN
Butyl
3
3
3
3
|
1aa318
H
H
SO3H
SO3H
H
H
|
1aa319
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa320
OMe
H
SO3H
SO3H
H
OMe
|
1aa321
H
SO3H
H
H
SO3H
H
CN
Pentyl
3
3
3
3
|
1aa322
H
H
SO3H
SO3H
H
H
|
1aa323
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa324
OMe
H
SO3H
SO3H
H
OMe
|
1aa325
H
SO3H
H
H
SO3H
H
CN
|
1aa326
H
H
SO3H
SO3H
H
H
Cyclobutyl
3
3
3
3
|
1aa327
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa328
OMe
H
SO3H
SO3H
H
OMe
|
1aa329
H
SO3H
H
H
SO3H
H
CN
Cyclopentyl
3
3
3
3
|
1aa330
H
H
SO3H
SO3H
H
H
|
1aa331
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa332
OMe
H
SO3H
SO3H
H
OMe
|
1aa333
H
SO3H
H
H
SO3H
H
CN
Isopropyl
3
3
3
3
|
1aa334
H
H
SO3H
SO3H
H
H
|
1aa335
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa336
OMe
H
SO3H
SO3H
H
OMe
|
1aa337
H
SO3H
H
H
SO3H
H
CN
Sec-butyl
3
3
3
3
|
1aa338
H
H
SO3H
SO3H
H
H
|
1aa339
Me
H
SO3H
SO3H
H
Me
|
1aa340
OMe
H
SO3H
SO3H
H
OMe
|
1aa341
H
SO3H
H
H
SO3H
H
CN
2-Methyl
3
3
3
3
|
1aa342
H
H
SO3H
SO3H
H
H
butyl
|
1aa343
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa344
OMe
H
SO3H
SO3H
H
OMe
|
1aa345
H
SO3H
H
H
SO3H
H
CN
1-Ethyl
3
3
3
3
|
1aa346
H
H
SO3H
SO3H
H
H
propyl
|
1aa347
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa348
OMe
H
SO3H
SO3H
H
OMe
|
1aa349
H
SO3H
H
H
SO3H
H
CN
1,2-Dimethyl
3
3
3
3
|
1aa350
H
H
SO3H
SO3H
H
H
propyl
|
1aa351
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa352
OMe
H
SO3H
SO3H
H
OMe
|
1aa353
H
SO3H
H
H
SO3H
H
CN
Tert-butyl
3
3
3
3
|
1aa354
H
H
SO3H
SO3H
H
H
|
1aa355
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa356
OMe
H
SO3H
SO3H
H
OMe
|
1aa357
H
SO3H
H
H
SO3H
H
CN
3-Methyl
3
3
3
3
|
1aa358
H
H
SO3H
SO3H
H
H
butyl
|
1aa359
Me
H
SO3H
SO3H
H
Me
|
1aa360
OMe
H
SO3H
SO3H
H
OMe
|
1aa361
H
SO3H
H
H
SO3H
H
CN
Pentan-2-yl
3
3
3
3
|
1aa362
H
H
SO3H
SO3H
H
H
|
1aa363
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa364
OMe
H
SO3H
SO3H
H
OMe
|
1aa365
H
SO3H
H
H
SO3H
H
CN
2-Ethylhexyl
3
3
3
3
|
1aa366
H
H
SO3H
SO3H
H
H
|
1aa367
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa368
OMe
H
SO3H
SO3H
H
OMe
|
1aa369
H
SO3H
H
H
SO3H
H
CN
2,2-Dimethyl
3
3
3
3
|
1aa370
H
H
SO3H
SO3H
H
H
propyl
|
1aa371
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa372
OMe
H
SO3H
SO3H
H
OMe
|
1aa373
H
SO3H
H
H
SO3H
H
CN
Phenyl
3
3
3
3
|
1aa374
H
H
SO3H
SO3H
H
H
|
1aa375
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa376
OMe
H
SO3H
SO3H
H
OMe
|
1aa377
H
SO3H
H
H
SO3H
H
CN
Benzyl
3
3
3
3
|
1aa378
H
H
SO3H
SO3H
H
H
|
1aa379
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa380
OMe
H
SO3H
SO3H
H
OMe
|
1aa381
H
SO3H
H
H
SO3H
H
CONH2
H
3
3
3
3
|
1aa382
H
H
SO3H
SO3H
H
H
|
1aa383
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa384
OMe
H
SO3H
SO3H
H
OMe
|
1aa385
H
SO3H
H
H
SO3H
H
CONH2
Ethyl
3
3
3
3
|
1aa386
H
H
SO3H
SO3H
H
H
|
1aa387
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa388
OMe
H
SO3H
SO3H
H
OMe
|
1aa389
H
SO3H
H
H
SO3H
H
CONH2
Propyl
3
3
3
3
|
1aa390
H
H
SO3H
SO3H
H
H
|
1aa391
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa392
OMe
H
SO3H
SO3H
H
OMe
|
1aa393
H
SO3H
H
H
SO3H
H
CONH2
Butyl
3
3
3
3
|
1aa394
H
H
SO3H
SO3H
H
H
|
1aa395
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa396
OMe
H
SO3H
SO3H
H
OMe
|
1aa397
H
SO3H
H
H
SO3H
H
CONH2
Pentyl
3
3
3
3
|
1aa398
H
H
SO3H
SO3H
H
H
|
1aa399
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa400
OMe
H
SO3H
SO3H
H
OMe
|
1aa401
H
SO3H
H
H
SO3H
H
CONH2
Cyclobutyl
3
3
3
3
|
1aa402
H
H
SO3H
SO3H
H
H
|
1aa403
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa404
OMe
H
SO3H
SO3H
H
OMe
|
1aa405
H
SO3H
H
H
SO3H
H
CONH2
Cyclopentyl
3
3
3
3
|
1aa406
H
H
SO3H
SO3H
H
H
|
1aa407
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa408
OMe
H
SO3H
SO3H
H
OMe
|
1aa409
H
SO3H
H
H
SO3H
H
CONH2
Isopropyl
3
3
3
3
|
1aa410
H
H
SO3H
SO3H
H
H
|
1aa411
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa412
OMe
H
SO3H
SO3H
H
OMe
|
1aa413
H
SO3H
H
H
SO3H
H
CONH2
Sec-butyl
3
3
3
3
|
1aa414
H
H
SO3H
SO3H
H
H
|
1aa415
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa416
OMe
H
SO3H
SO3H
H
OMe
|
1aa417
H
SO3H
H
H
SO3H
H
CONH2
2-Methyl
3
3
3
3
|
1aa418
H
H
SO3H
SO3H
H
H
butyl
|
1aa419
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa420
OMe
H
SO3H
SO3H
H
OMe
|
1aa421
H
SO3H
H
H
SO3H
H
CONH2
1-Ethyl
3
3
3
3
|
1aa422
H
H
SO3H
SO3H
H
H
propyl
|
1aa423
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa424
OMe
H
SO3H
SO3H
H
OMe
|
1aa425
H
SO3H
H
H
SO3H
H
CONH2
1,2-Dimethyl
3
3
3
3
|
1aa426
H
H
SO3H
SO3H
H
H
propyl
|
1aa427
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa428
OMe
H
SO3H
SO3H
H
OMe
|
1aa429
H
SO3H
H
H
SO3H
H
CONH2
Tert-butyl
3
3
3
3
|
1aa430
H
H
SO3H
SO3H
H
H
|
1aa431
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa432
OMe
H
SO3H
SO3H
H
OMe
|
1aa433
H
SO3H
H
H
SO3H
H
CONH2
3-Methyl
3
3
3
3
|
1aa434
H
H
SO3H
SO3H
H
H
butyl
|
1aa435
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa436
OMe
H
SO3H
SO3H
H
OMe
|
1aa437
H
SO3H
H
H
SO3H
H
CONH2
Pentan-2-yl
3
3
3
3
|
1aa438
H
H
SO3H
SO3H
H
H
|
1aa439
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa440
OMe
H
SO3H
SO3H
H
OMe
|
1aa441
H
SO3H
H
H
SO3H
H
CONH2
2-Ethylhexyl
3
3
3
3
|
1aa442
H
H
SO3H
SO3H
H
H
|
1aa443
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa444
OMe
H
SO3H
SO3H
H
OMe
|
1aa445
H
SO3H
H
H
SO3H
H
CONH2
2,2-Dimethyl
3
3
3
3
|
1aa446
H
H
SO3H
SO3H
H
H
propyl
|
1aa447
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa448
OMe
H
SO3H
SO3H
H
OMe
|
1aa449
H
SO3H
H
H
SO3H
H
CONH2
Phenyl
3
3
3
3
|
1aa450
H
H
SO3H
SO3H
H
H
|
1aa451
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa452
OMe
H
SO3H
SO3H
H
OMe
|
1aa453
H
SO3H
H
H
SO3H
H
CONH2
Benzyl
3
3
3
3
|
1aa454
H
H
SO3H
SO3H
H
H
|
1aa455
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa456
OMe
H
SO3H
SO3H
H
OMe
|
1aa457
H
SO3H
H
H
SO3H
H
CN
2-Methoxy
2
2
2
2
|
1aa458
H
H
SO3H
SO3H
H
H
ethyl
|
1aa459
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa460
OMe
H
SO3H
SO3H
H
OMe
|
1aa461
H
SO3H
H
H
SO3H
H
CN
3-Methoxy
2
2
2
2
|
1aa462
H
H
SO3H
SO3H
H
H
propyl
|
1aa463
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa464
OMe
H
SO3H
SO3H
H
OMe
|
1aa465
H
SO3H
H
H
SO3H
H
CN
2-Hydroxy
2
2
2
2
|
1aa466
H
H
SO3H
SO3H
H
H
ethyl
|
1aa467
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa468
OMe
H
SO3H
SO3H
H
OMe
|
1aa469
H
SO3H
H
H
SO3H
H
CN
2-Fluoro
2
2
2
2
|
1aa470
H
H
SO3H
SO3H
H
H
ethyl
|
1aa471
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa472
OMe
H
SO3H
SO3H
H
OMe
|
1aa473
H
SO3H
H
H
SO3H
H
CN
2-Chloro
2
2
2
2
|
1aa474
H
H
SO3H
SO3H
H
H
ethyl
|
1aa475
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa476
OMe
H
SO3H
SO3H
H
OMe
|
1aa477
H
SO3H
H
H
SO3H
H
CN
3-Chloro
2
2
2
2
|
1aa478
H
H
SO3H
SO3H
H
H
propyl
|
1aa479
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa480
OMe
H
SO3H
SO3H
H
OMe
|
1aa481
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy-
2
2
2
2
|
1aa482
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1aa483
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1aa484
OMe
H
SO3H
SO3H
H
OMe
|
1aa485
H
SO3H
H
H
SO3H
H
CN
2-(2-tert-Butyl
2
2
2
2
|
1aa486
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1aa487
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1aa488
OMe
H
SO3H
SO3H
H
OMe
|
1aa489
H
SO3H
H
H
SO3H
H
CN
3-(4-Hydroxy
2
2
2
2
|
1aa490
H
H
SO3H
SO3H
H
H
butoxy)
|
1aa491
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1aa492
OMe
H
SO3H
SO3H
H
OMe
|
1aa493
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy
2
2
2
2
|
1aa494
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1aa495
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa496
OMe
H
SO3H
SO3H
H
OMe
|
1aa497
H
SO3H
H
H
SO3H
H
CN
4-(2-Hydroxy-
2
2
2
2
|
1aa498
H
H
SO3H
SO3H
H
H
ethane
|
1aa499
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1aa500
OMe
H
SO3H
SO3H
H
OMe
|
1aa501
H
SO3H
H
H
SO3H
H
CN
3-(2-Phenoxy-
2
2
2
2
|
1aa502
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1aa503
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa504
OMe
H
SO3H
SO3H
H
OMe
|
1aa505
H
SO3H
H
H
SO3H
H
CN
3-Isopropoxy-
2
2
2
2
|
1aa506
H
H
SO3H
SO3H
H
H
propyl
|
1aa507
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa508
OMe
H
SO3H
SO3H
H
OMe
|
1aa509
H
SO3H
H
H
SO3H
H
CN
3-Ethoxy propyl
2
2
2
2
|
1aa510
H
H
SO3H
SO3H
H
H
|
1aa511
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa512
OMe
H
SO3H
SO3H
H
OMe
|
1aa513
H
SO3H
H
H
SO3H
H
CN
4-Ethoxy butyl
2
2
2
2
|
1aa514
H
H
SO3H
SO3H
H
H
|
1aa515
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa516
OMe
H
SO3H
SO3H
H
OMe
|
1aa517
H
SO3H
H
H
SO3H
H
CONH2
2-Methoxy ethyl
2
2
2
2
|
1aa518
H
H
SO3H
SO3H
H
H
|
1aa519
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa520
OMe
H
SO3H
SO3H
H
OMe
|
1aa521
H
SO3H
H
H
SO3H
H
CONH2
3-Methoxy
2
2
2
2
|
1aa522
H
H
SO3H
SO3H
H
H
propyl
|
1aa523
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa524
OMe
H
SO3H
SO3H
H
OMe
|
1aa525
H
SO3H
H
H
SO3H
H
CONH2
2-Hydroxy ethyl
2
2
2
2
|
1aa526
H
H
SO3H
SO3H
H
H
|
1aa527
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa528
OMe
H
SO3H
SO3H
H
OMe
|
1aa529
H
SO3H
H
H
SO3H
H
CONH2
2-Fluoro ethyl
2
2
2
2
|
1aa530
H
H
SO3H
SO3H
H
H
|
1aa531
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa532
OMe
H
SO3H
SO3H
H
OMe
|
1aa533
H
SO3H
H
H
SO3H
H
CONH2
2-Chloro ethyl
2
2
2
2
|
1aa534
H
H
SO3H
SO3H
H
H
|
1aa535
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa536
OMe
H
SO3H
SO3H
H
OMe
|
1aa537
H
SO3H
H
H
SO3H
H
CONH2
3-Chloro propyl
2
2
2
2
|
1aa538
H
H
SO3H
SO3H
H
H
|
1aa539
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa540
OMe
H
SO3H
SO3H
H
OMe
|
1aa541
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy-
2
2
2
2
|
1aa542
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1aa543
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1aa544
OMe
H
SO3H
SO3H
H
OMe
|
1aa545
H
SO3H
H
H
SO3H
H
CONH2
2-(2-tert-Butyl
2
2
2
2
|
1aa546
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1aa547
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1aa548
OMe
H
SO3H
SO3H
H
OMe
|
1aa549
H
SO3H
H
H
SO3H
H
CONH2
3-(4-Hydroxy
2
2
2
2
|
1aa550
H
H
SO3H
SO3H
H
H
butoxy)
|
1aa551
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1aa552
OMe
H
SO3H
SO3H
H
OMe
|
1aa553
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy
2
2
2
2
|
1aa554
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1aa555
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa556
OMe
H
SO3H
SO3H
H
OMe
|
1aa557
H
SO3H
H
H
SO3H
H
CONH2
4-(2-Hydroxy-
2
2
2
2
|
1aa558
H
H
SO3H
SO3H
H
H
ethane
|
1aa559
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1aa560
OMe
H
SO3H
SO3H
H
OMe
|
1aa561
H
SO3H
H
H
SO3H
H
CONH2
3-(2-Phenoxy-
2
2
2
2
|
1aa562
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1aa563
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa564
OMe
H
SO3H
SO3H
H
OMe
|
1aa565
H
SO3H
H
H
SO3H
H
CONH2
3-Isopropoxy-
2
2
2
2
|
1aa566
H
H
SO3H
SO3H
H
H
propyl
|
1aa567
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa568
OMe
H
SO3H
SO3H
H
OMe
|
1aa569
H
SO3H
H
H
SO3H
H
CONH2
3-Ethoxy-propyl
2
2
2
2
|
1aa570
H
H
SO3H
SO3H
H
H
|
1aa571
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa572
OMe
H
SO3H
SO3H
H
OMe
|
1aa573
H
SO3H
H
H
SO3H
H
CONH2
4-Ethoxy butyl
2
2
2
2
|
1aa574
H
H
SO3H
SO3H
H
H
|
1aa575
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa576
OMe
H
SO3H
SO3H
H
OMe
|
1aa577
H
SO3H
H
H
SO3H
H
CN
2-Methoxy ethyl
3
4
3
4
|
1aa578
H
H
SO3H
SO3H
H
H
|
1aa579
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa580
OMe
H
SO3H
SO3H
H
OMe
|
1aa581
H
SO3H
H
H
SO3H
H
CN
3-Methoxy
3
4
3
4
|
1aa582
H
H
SO3H
SO3H
H
H
propyl
|
1aa583
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa584
OMe
H
SO3H
SO3H
H
OMe
|
1aa585
H
SO3H
H
H
SO3H
H
CN
2-Hydroxy ethyl
3
4
3
4
|
1aa586
H
H
SO3H
SO3H
H
H
|
1aa587
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa588
OMe
H
SO3H
SO3H
H
OMe
|
1aa589
H
SO3H
H
H
SO3H
H
CN
2-Fluoro ethyl
3
4
3
4
|
1aa590
H
H
SO3H
SO3H
H
H
|
1aa591
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa592
OMe
H
SO3H
SO3H
H
OMe
|
1aa593
H
SO3H
H
H
SO3H
H
CN
2-Chloro ethyl
3
4
3
4
|
1aa594
H
H
SO3H
SO3H
H
H
|
1aa595
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa596
OMe
H
SO3H
SO3H
H
OMe
|
1aa597
H
SO3H
H
H
SO3H
H
CN
3-Chloro propyl
3
4
3
4
|
1aa598
H
H
SO3H
SO3H
H
H
|
1aa599
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa600
OMe
H
SO3H
SO3H
H
OMe
|
1aa601
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy-
3
4
3
4
|
1aa602
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1aa603
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1aa604
OMe
H
SO3H
SO3H
H
OMe
|
1aa605
H
SO3H
H
H
SO3H
H
CN
2-(2-tert-Butyl
3
4
3
4
|
1aa606
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1aa607
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1aa608
OMe
H
SO3H
SO3H
H
OMe
|
1aa609
H
SO3H
H
H
SO3H
H
CN
3-(4-Hydroxy
3
4
3
4
|
1aa610
H
H
SO3H
SO3H
H
H
butoxy)
|
1aa611
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1aa612
OMe
H
SO3H
SO3H
H
OMe
|
1aa613
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy
3
4
3
4
|
1aa614
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1aa615
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa616
OMe
H
SO3H
SO3H
H
OMe
|
1aa617
H
SO3H
H
H
SO3H
H
CN
4-(2-Hydroxy-
3
4
3
4
|
1aa618
H
H
SO3H
SO3H
H
H
ethane
|
1aa619
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1aa620
OMe
H
SO3H
SO3H
H
OMe
|
1aa621
H
SO3H
H
H
SO3H
H
CN
3-(2-Phenoxy-
3
4
3
4
|
1aa622
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1aa623
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa624
OMe
H
SO3H
SO3H
H
OMe
|
1aa625
H
SO3H
H
H
SO3H
H
CN
3-Isopropoxy-
3
4
3
4
|
1aa626
H
H
SO3H
SO3H
H
H
propyl
|
1aa627
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa628
OMe
H
SO3H
SO3H
H
OMe
|
1aa629
H
SO3H
H
H
SO3H
H
CN
3-Ethoxy propyl
3
4
3
4
|
1aa630
H
H
SO3H
SO3H
H
H
|
1aa631
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa632
OMe
H
SO3H
SO3H
H
OMe
|
1aa633
H
SO3H
H
H
SO3H
H
CN
4-Ethoxy butyl
3
4
3
4
|
1aa634
H
H
SO3H
SO3H
H
H
|
1aa635
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa636
OMe
H
SO3H
SO3H
H
OMe
|
1aa637
H
SO3H
H
H
SO3H
H
CONH2
2-Methoxy ethyl
3
4
3
4
|
1aa638
H
H
SO3H
SO3H
H
H
|
1aa639
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa640
OMe
H
SO3H
SO3H
H
OMe
|
1aa641
H
SO3H
H
H
SO3H
H
CONH2
3-Methoxy
3
4
3
4
|
1aa642
H
H
SO3H
SO3H
H
H
propyl
|
1aa643
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa644
OMe
H
SO3H
SO3H
H
OMe
|
1aa645
H
SO3H
H
H
SO3H
H
CONH2
2-Hydroxy ethyl
3
4
3
4
|
1aa646
H
H
SO3H
SO3H
H
H
|
1aa647
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa648
OMe
H
SO3H
SO3H
H
OMe
|
1aa649
H
SO3H
H
H
SO3H
H
CONH2
2-Fluoro ethyl
3
4
3
4
|
1aa650
H
H
SO3H
SO3H
H
H
|
1aa651
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa652
OMe
H
SO3H
SO3H
H
OMe
|
1aa653
H
SO3H
H
H
SO3H
H
CONH2
2-Chloro ethyl
3
4
3
4
|
1aa654
H
H
SO3H
SO3H
H
H
|
1aa655
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa656
OMe
H
SO3H
SO3H
H
OMe
|
1aa657
H
SO3H
H
H
SO3H
H
CONH2
3-Chloro propyl
3
4
3
4
|
1aa658
H
H
SO3H
SO3H
H
H
|
1aa659
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa660
OMe
H
SO3H
SO3H
H
OMe
|
1aa661
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy-
3
4
3
4
|
1aa662
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1aa663
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1aa664
OMe
H
SO3H
SO3H
H
OMe
|
1aa665
H
SO3H
H
H
SO3H
H
CONH2
2-(2-tert-Butyl
3
4
3
4
|
1aa666
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1aa667
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1aa668
OMe
H
SO3H
SO3H
H
OMe
|
1aa669
H
SO3H
H
H
SO3H
H
CONH2
3-(4-Hydroxy
3
4
3
4
|
1aa670
H
H
SO3H
SO3H
H
H
butoxy)
|
1aa671
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1aa672
OMe
H
SO3H
SO3H
H
OMe
|
1aa673
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy
3
4
3
4
|
1aa674
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1aa675
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa676
OMe
H
SO3H
SO3H
H
OMe
|
1aa677
H
SO3H
H
H
SO3H
H
CONH2
4-(2-Hydroxy-
3
4
3
4
|
1aa678
H
H
SO3H
SO3H
H
H
ethane
|
1aa679
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1aa680
OMe
H
SO3H
SO3H
H
OMe
|
1aa681
H
SO3H
H
H
SO3H
H
CONH2
3-(2-Phenoxy-
3
4
3
4
|
1aa682
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1aa683
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa684
OMe
H
SO3H
SO3H
H
OMe
|
1aa685
H
SO3H
H
H
SO3H
H
CONH2
3-Isopropoxy-
3
4
3
4
|
1aa686
H
H
SO3H
SO3H
H
H
propyl
|
1aa687
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa688
OMe
H
SO3H
SO3H
H
OMe
|
1aa689
H
SO3H
H
H
SO3H
H
CONH2
3-Ethoxy-propyl
3
4
3
4
|
1aa690
H
H
SO3H
SO3H
H
H
|
1aa691
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa692
OMe
H
SO3H
SO3H
H
OMe
|
1aa693
H
SO3H
H
H
SO3H
H
CONH2
3-Ethoxybutyl
3
4
3
4
|
1aa694
H
H
SO3H
SO3H
H
H
|
1aa695
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa696
OMe
H
SO3H
SO3H
H
OMe
|
1aa697
H
SO3H
H
H
SO3H
H
CN
2-Methoxy ethyl
3
3
3
3
|
1aa698
H
H
SO3H
SO3H
H
H
|
1aa699
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa700
OMe
H
SO3H
SO3H
H
OMe
|
1aa701
H
SO3H
H
H
SO3H
H
CN
3-Methoxy
3
3
3
3
|
1aa702
H
H
SO3H
SO3H
H
H
propyl
|
1aa703
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa704
OMe
H
SO3H
SO3H
H
OMe
|
1aa705
H
SO3H
H
H
SO3H
H
CN
2-Hydroxy ethyl
3
3
3
3
|
1aa706
H
H
SO3H
SO3H
H
H
|
1aa707
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa708
OMe
H
SO3H
SO3H
H
OMe
|
1aa709
H
SO3H
H
H
SO3H
H
CN
2-Fluoro ethyl
3
3
3
3
|
1aa710
H
H
SO3H
SO3H
H
H
|
1aa711
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa712
OMe
H
SO3H
SO3H
H
OMe
|
1aa713
H
SO3H
H
H
SO3H
H
CN
2-Chloro ethyl
3
3
3
3
|
1aa714
H
H
SO3H
SO3H
H
H
|
1aa715
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa716
OMe
H
SO3H
SO3H
H
OMe
|
1aa717
H
SO3H
H
H
SO3H
H
CN
3-Chloro propyl
3
3
3
3
|
1aa718
H
H
SO3H
SO3H
H
H
|
1aa719
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa720
OMe
H
SO3H
SO3H
H
OMe
|
1aa721
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy-
3
3
3
3
|
1aa722
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1aa723
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1aa724
OMe
H
SO3H
SO3H
H
OMe
|
1aa725
H
SO3H
H
H
SO3H
H
CN
2-(2-tert-Butyl
3
3
3
3
|
1aa726
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1aa727
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1aa728
OMe
H
SO3H
SO3H
H
OMe
|
1aa729
H
SO3H
H
H
SO3H
H
CN
3-(4-Hydroxy
3
3
3
3
|
1aa730
H
H
SO3H
SO3H
H
H
butoxy)
|
1aa731
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1aa732
OMe
H
SO3H
SO3H
H
OMe
|
1aa733
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy
3
3
3
3
|
1aa734
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1aa735
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa736
OMe
H
SO3H
SO3H
H
OMe
|
1aa737
H
SO3H
H
H
SO3H
H
CN
4-(2-Hydroxy-
3
3
3
3
|
1aa738
H
H
SO3H
SO3H
H
H
ethane
|
1aa739
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1aa740
OMe
H
SO3H
SO3H
H
OMe
|
1aa741
H
SO3H
H
H
SO3H
H
CN
3-(2-Phenoxy-
3
3
3
3
|
1aa742
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1aa743
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa744
OMe
H
SO3H
SO3H
H
OMe
|
1aa745
H
SO3H
H
H
SO3H
H
CN
3-Isopropoxy-
3
3
3
3
|
1aa746
H
H
SO3H
SO3H
H
H
propyl
|
1aa747
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa748
OMe
H
SO3H
SO3H
H
OMe
|
1aa749
H
SO3H
H
H
SO3H
H
CN
3-Ethoxy propyl
3
3
3
3
|
1aa750
H
H
SO3H
SO3H
H
H
|
1aa751
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa752
OMe
H
SO3H
SO3H
H
OMe
|
1aa753
H
SO3H
H
H
SO3H
H
CN
4-Ethoxy butyl
3
3
3
3
|
1aa754
H
H
SO3H
SO3H
H
H
|
1aa755
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa756
OMe
H
SO3H
SO3H
H
OMe
|
1aa757
H
SO3H
H
H
SO3H
H
CONH2
2-Methoxy ethyl
3
3
3
3
|
1aa758
H
H
SO3H
SO3H
H
H
|
1aa759
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa760
OMe
H
SO3H
SO3H
H
OMe
|
1aa761
H
SO3H
H
H
SO3H
H
CONH2
3-Methoxy
3
3
3
3
|
1aa762
H
H
SO3H
SO3H
H
H
propyl
|
1aa763
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa764
OMe
H
SO3H
SO3H
H
OMe
|
1aa765
H
SO3H
H
H
SO3H
H
CONH2
2-Hydroxy ethyl
3
3
3
3
|
1aa766
H
H
SO3H
SO3H
H
H
|
1aa767
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa768
OMe
H
SO3H
SO3H
H
OMe
|
1aa769
H
SO3H
H
H
SO3H
H
CONH2
2-Fluoro ethyl
3
3
3
3
|
1aa770
H
H
SO3H
SO3H
H
H
|
1aa771
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa772
OMe
H
SO3H
SO3H
H
OMe
|
1aa773
H
SO3H
H
H
SO3H
H
CONH2
2-Chloro ethyl
3
3
3
3
|
1aa774
H
H
SO3H
SO3H
H
H
|
1aa775
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa776
OMe
H
SO3H
SO3H
H
OMe
|
1aa777
H
SO3H
H
H
SO3H
H
CONH2
3-Chloro propyl
3
3
3
3
|
1aa778
H
H
SO3H
SO3H
H
H
|
1aa779
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa780
OMe
H
SO3H
SO3H
H
OMe
|
1aa781
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy-
3
3
3
3
|
1aa782
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1aa783
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1aa784
OMe
H
SO3H
SO3H
H
OMe
|
1aa785
H
SO3H
H
H
SO3H
H
CONH2
2-(2-tert-Butyl
3
3
3
3
|
1aa786
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1aa787
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1aa788
OMe
H
SO3H
SO3H
H
OMe
|
1aa789
H
SO3H
H
H
SO3H
H
CONH2
3-(4-Hydroxy
3
3
3
3
|
1aa790
H
H
SO3H
SO3H
H
H
butoxy)
|
1aa791
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1aa792
OMe
H
SO3H
SO3H
H
OMe
|
1aa793
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy
3
3
3
3
|
1aa794
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1aa795
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa796
OMe
H
SO3H
SO3H
H
OMe
|
1aa797
H
SO3H
H
H
SO3H
H
CONH2
4-(2-Hydroxy-
3
3
3
3
|
1aa798
H
H
SO3H
SO3H
H
H
ethane
|
1aa799
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1aa800
OMe
H
SO3H
SO3H
H
OMe
|
1aa801
H
SO3H
H
H
SO3H
H
CONH2
3-(2-Phenoxy-
3
3
3
3
|
1aa802
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1aa803
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa804
OMe
H
SO3H
SO3H
H
OMe
|
1aa805
H
SO3H
H
H
SO3H
H
CONH2
3-Isopropoxy-
3
3
3
3
|
1aa806
H
H
SO3H
SO3H
H
H
propyl
|
1aa807
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa808
OMe
H
SO3H
SO3H
H
OMe
|
1aa809
H
SO3H
H
H
SO3H
H
CONH2
3-Ethoxy-propyl
3
3
3
3
|
1aa810
H
H
SO3H
SO3H
H
H
|
1aa811
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa812
OMe
H
SO3H
SO3H
H
OMe
|
1aa813
H
SO3H
H
H
SO3H
H
CONH2
4-Ethoxy butyl
3
3
3
3
|
1aa814
H
H
SO3H
SO3H
H
H
|
1aa815
Methyl
H
SO3H
SO3H
H
Methyl
|
1aa816
OMe
H
SO3H
SO3H
H
OMe
|
|
Further preferred embodiments of the present invention are dyes of formula (1ab)
![embedded image]()
wherein
R1ab, R2ab, R3ab, R4ab, R5ab, R6ab, R7ab and R8ab independent of each other is SO3M, hydrogen, alkyl or alkoxy, whereby at least two of them are SO3M,
R9ab and R18ab independent of each other is cyano or carbamoyl,
R10ab and R19ab is methyl,
m, n, o and p independent of each other is an integer and is 2, 3 or 4,
R11ab, R13ab, R14ab, R15ab, R16ab, R17ab, R20ab, R22ab, R23ab, R24ab, R25ab, and R26ab is hydrogen
R12ab and R21ab 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-ethylproyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-methoxyethyl, 3-methoxypropyl, 2-hydroxyethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, tetrahydrofurfuryl, 2-furan-2-yl-ethyl, 6-hydroxy-1-[2-(2-hydroxyethylsulfanyl)-ethyl], 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(ethylsulfonyl)ethanol, 2-hydroxyethoxypropyl, 2-hydroxyethoxyethyl, 2-(ethyl sulfonyl) ethanol, 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 (1ab) are the compounds of the formulae (1ab1 to 1ab816), wherein R2ab and R7ab is hydrogen:
|
Structure
R1ab
R3ab
R4ab
R5ab
R6ab
R8ab
R9ab/R18ab
R12ab/R21ab
m
n
o
p
|
|
1ab1
H
SO3H
H
H
SO3H
H
CN
H
2
2
2
2
|
1ab2
H
H
SO3H
SO3H
H
H
|
1ab3
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab4
OMe
H
SO3H
SO3H
H
OMe
|
1ab5
H
SO3H
H
H
SO3H
H
CN
Ethyl
2
2
2
2
|
1ab6
H
H
SO3H
SO3H
H
H
|
1ab7
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab8
OMe
H
SO3H
SO3H
H
OMe
|
1ab9
H
SO3H
H
H
SO3H
H
CN
Propyl
2
2
2
2
|
1ab10
H
H
SO3H
SO3H
H
H
|
1ab11
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab12
OMe
H
SO3H
SO3H
H
OMe
|
1ab13
H
SO3H
H
H
SO3H
H
CN
Butyl
2
2
2
2
|
1ab14
H
H
SO3H
SO3H
H
H
|
1ab15
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab16
OMe
H
SO3H
SO3H
H
OMe
|
1ab17
H
SO3H
H
H
SO3H
H
CN
Pentyl
2
2
2
2
|
1ab18
H
H
SO3H
SO3H
H
H
|
1ab19
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab20
OMe
H
SO3H
SO3H
H
OMe
|
1ab21
H
SO3H
H
H
SO3H
H
CN
Cyclobutyl
2
2
2
2
|
1ab22
H
H
SO3H
SO3H
H
H
|
1ab23
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab24
OMe
H
SO3H
SO3H
H
OMe
|
1ab25
H
SO3H
H
H
SO3H
H
CN
Cyclopentyl
2
2
2
2
|
1ab26
H
H
SO3H
SO3H
H
H
|
1ab27
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab28
OMe
H
SO3H
SO3H
H
OMe
|
1ab29
H
SO3H
H
H
SO3H
H
CN
Isopropyl
2
2
2
2
|
1ab30
H
H
SO3H
SO3H
H
H
|
1ab31
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab32
OMe
H
SO3H
SO3H
H
OMe
|
1ab33
H
SO3H
H
H
SO3H
H
CN
Sec-butyl
2
2
2
2
|
1ab34
H
H
SO3H
SO3H
H
H
|
1ab35
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab36
OMe
H
SO3H
SO3H
H
OMe
|
1ab37
H
SO3H
H
H
SO3H
H
CN
2-Methyl butyl
2
2
2
2
|
1ab38
H
H
SO3H
SO3H
H
H
|
1ab39
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab40
OMe
H
SO3H
SO3H
H
OMe
|
1ab41
H
SO3H
H
H
SO3H
H
CN
1-Ethyl propyl
2
2
2
2
|
1ab42
H
H
SO3H
SO3H
H
H
|
1ab43
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab44
OMe
H
SO3H
SO3H
H
OMe
|
1ab45
H
SO3H
H
H
SO3H
H
CN
1,2-Dimethyl
2
2
2
2
|
1ab46
H
H
SO3H
SO3H
H
H
propyl
|
1ab47
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab48
OMe
H
SO3H
SO3H
H
OMe
|
1ab49
H
SO3H
H
H
SO3H
H
CN
Tert-butyl
2
2
2
2
|
1ab50
H
H
SO3H
SO3H
H
H
|
1ab51
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab52
OMe
H
SO3H
SO3H
H
OMe
|
1ab53
H
SO3H
H
H
SO3H
H
CN
3-Methyl butyl
2
2
2
2
|
1ab54
H
H
SO3H
SO3H
H
H
|
1ab55
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab56
OMe
H
SO3H
SO3H
H
OMe
|
1ab57
H
SO3H
H
H
SO3H
H
CN
Pentan-2-yl
2
2
2
2
|
1ab58
H
H
SO3H
SO3H
H
H
|
1ab59
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab60
OMe
H
SO3H
SO3H
H
OMe
|
1ab61
H
SO3H
H
H
SO3H
H
CN
2-Ethylhexyl
2
2
2
2
|
1ab62
H
H
SO3H
SO3H
H
H
|
1ab63
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab64
OMe
H
SO3H
SO3H
H
OMe
|
1ab65
H
SO3H
H
H
SO3H
H
CN
2,2-Dimethyl
2
2
2
2
|
1ab66
H
H
SO3H
SO3H
H
H
propyl
|
1ab67
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab68
OMe
H
SO3H
SO3H
H
OMe
|
1ab69
H
SO3H
H
H
SO3H
H
CN
Phenyl
2
2
2
2
|
1ab70
H
H
SO3H
SO3H
H
H
|
1ab71
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab72
OMe
H
SO3H
SO3H
H
OMe
|
1ab73
H
SO3H
H
H
SO3H
H
CN
Benzyl
2
2
2
2
|
1ab74
H
H
SO3H
SO3H
H
H
|
1ab75
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab76
OMe
H
SO3H
SO3H
H
OMe
|
1ab77
H
SO3H
H
H
SO3H
H
CONH2
H
2
2
2
2
|
1ab78
H
H
SO3H
SO3H
H
H
|
1ab79
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab80
OMe
H
SO3H
SO3H
H
OMe
|
1ab81
H
SO3H
H
H
SO3H
H
CONH2
Ethyl
2
2
2
2
|
1ab82
H
H
SO3H
SO3H
H
H
|
1ab83
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab84
OMe
H
SO3H
SO3H
H
OMe
|
1ab85
H
SO3H
H
H
SO3H
H
CONH2
Propyl
2
2
2
2
|
1ab86
H
H
SO3H
SO3H
H
H
|
1ab87
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab88
OMe
H
SO3H
SO3H
H
OMe
|
1ab89
H
SO3H
H
H
SO3H
H
CONH2
Butyl
2
2
2
2
|
1ab90
H
H
SO3H
SO3H
H
H
|
1ab91
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab92
OMe
H
SO3H
SO3H
H
OMe
|
1ab93
H
SO3H
H
H
SO3H
H
CONH2
Pentyl
2
2
2
2
|
1ab94
H
H
SO3H
SO3H
H
H
|
1ab95
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab96
OMe
H
SO3H
SO3H
H
OMe
|
1ab97
H
SO3H
H
H
SO3H
H
CONH2
Cyclobutyl
2
2
2
2
|
1ab98
H
H
SO3H
SO3H
H
H
|
1ab99
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab100
OMe
H
SO3H
SO3H
H
OMe
|
1ab101
H
SO3H
H
H
SO3H
H
CONH2
Cyclopentyl
2
2
2
2
|
1ab102
H
H
SO3H
SO3H
H
H
|
1ab103
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab104
OMe
H
SO3H
SO3H
H
OMe
|
1ab105
H
SO3H
H
H
SO3H
H
CONH2
Isopropyl
2
2
2
2
|
1ab106
H
H
SO3H
SO3H
H
H
|
1ab107
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab108
OMe
H
SO3H
SO3H
H
OMe
|
1ab109
H
SO3H
H
H
SO3H
H
CONH2
Sec-butyl
2
2
2
2
|
1ab110
H
H
SO3H
SO3H
H
H
|
1ab111
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab112
OMe
H
SO3H
SO3H
H
OMe
|
1ab113
H
SO3H
H
H
SO3H
H
CONH2
2-Methyl butyl
2
2
2
2
|
1ab114
H
H
SO3H
SO3H
H
H
|
1ab115
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab116
OMe
H
SO3H
SO3H
H
OMe
|
1ab117
H
SO3H
H
H
SO3H
H
CONH2
1-Ethyl propyl
2
2
2
2
|
1ab118
H
H
SO3H
SO3H
H
H
|
1ab119
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab120
OMe
H
SO3H
SO3H
H
OMe
|
1ab121
H
SO3H
H
H
SO3H
H
CONH2
1,2-Dimethyl
2
2
2
2
|
1ab122
H
H
SO3H
SO3H
H
H
propyl
|
1ab123
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab124
OMe
H
SO3H
SO3H
H
OMe
|
1ab125
H
SO3H
H
H
SO3H
H
CONH2
Tert-butyl
2
2
2
2
|
1ab126
H
H
SO3H
SO3H
H
H
|
1ab127
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab128
OMe
H
SO3H
SO3H
H
OMe
|
1ab129
H
SO3H
H
H
SO3H
H
CONH2
3-Methyl butyl
2
2
2
2
|
1ab130
H
H
SO3H
SO3H
H
H
|
1ab131
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab132
OMe
H
SO3H
SO3H
H
OMe
|
1ab133
H
SO3H
H
H
SO3H
H
CONH2
Pentan-2-yl
2
2
2
2
|
1ab134
H
H
SO3H
SO3H
H
H
|
1ab135
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab136
OMe
H
SO3H
SO3H
H
OMe
|
1ab137
H
SO3H
H
H
SO3H
H
CONH2
2-Ethylhexyl
2
2
2
2
|
1ab138
H
H
SO3H
SO3H
H
H
|
1ab139
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab140
OMe
H
SO3H
SO3H
H
OMe
|
1ab141
H
SO3H
H
H
SO3H
H
CONH2
2,2-Dimethyl
2
2
2
2
|
1ab142
H
H
SO3H
SO3H
H
H
propyl
|
1ab143
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab144
OMe
H
SO3H
SO3H
H
OMe
|
1ab145
H
SO3H
H
H
SO3H
H
CONH2
Phenyl
2
2
2
2
|
1ab146
H
H
SO3H
SO3H
H
H
|
1ab147
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab148
OMe
H
SO3H
SO3H
H
OMe
|
1ab149
H
SO3H
H
H
SO3H
H
CONH2
Benzyl
2
2
2
2
|
1ab150
H
H
SO3H
SO3H
H
H
|
1ab151
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab152
OMe
H
SO3H
SO3H
H
OMe
|
1ab153
H
SO3H
H
H
SO3H
H
CN
H
3
4
3
4
|
1ab154
H
H
SO3H
SO3H
H
H
|
1ab155
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab156
OMe
H
SO3H
SO3H
H
OMe
|
1ab157
H
SO3H
H
H
SO3H
H
CN
Ethyl
3
4
3
4
|
1ab158
H
H
SO3H
SO3H
H
H
|
1ab159
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab160
OMe
H
SO3H
SO3H
H
OMe
|
1ab161
H
SO3H
H
H
SO3H
H
CN
Propyl
3
4
3
4
|
1ab162
H
H
SO3H
SO3H
H
H
|
1ab163
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab164
OMe
H
SO3H
SO3H
H
OMe
|
1ab165
H
SO3H
H
H
SO3H
H
CN
Butyl
3
4
3
4
|
1ab166
H
H
SO3H
SO3H
H
H
|
1ab167
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab168
OMe
H
SO3H
SO3H
H
OMe
|
1ab169
H
SO3H
H
H
SO3H
H
CN
Pentyl
3
4
3
4
|
1ab170
H
H
SO3H
SO3H
H
H
|
1ab171
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab172
OMe
H
SO3H
SO3H
H
OMe
|
1ab173
H
SO3H
H
H
SO3H
H
CN
Cyclobutyl
3
4
3
4
|
1ab174
H
H
SO3H
SO3H
H
H
|
1ab175
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab176
OMe
H
SO3H
SO3H
H
OMe
|
1ab177
H
SO3H
H
H
SO3H
H
CN
Cyclopentyl
3
4
3
4
|
1ab178
H
H
SO3H
SO3H
H
H
|
1ab179
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab180
OMe
H
SO3H
SO3H
H
OMe
|
1ab181
H
SO3H
H
H
SO3H
H
CN
Isopropyl
3
4
3
4
|
1ab182
H
H
SO3H
SO3H
H
H
|
1ab183
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab184
OMe
H
SO3H
SO3H
H
OMe
|
1ab185
H
SO3H
H
H
SO3H
H
CN
Sec-butyl
3
4
3
4
|
1ab186
H
H
SO3H
SO3H
H
H
|
1ab187
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab188
OMe
H
SO3H
SO3H
H
OMe
|
1ab189
H
SO3H
H
H
SO3H
H
CN
2-Methyl butyl
3
4
3
4
|
1ab190
H
H
SO3H
SO3H
H
H
|
1ab191
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab192
OMe
H
SO3H
SO3H
H
OMe
|
1ab193
H
SO3H
H
H
SO3H
H
CN
1-Ethyl propyl
3
4
3
4
|
1ab194
H
H
SO3H
SO3H
H
H
|
1ab195
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab196
OMe
H
SO3H
SO3H
H
OMe
|
1ab197
H
SO3H
H
H
SO3H
H
CN
1,2-Dimethyl
3
4
3
4
|
1ab198
H
H
SO3H
SO3H
H
H
propyl
|
1ab199
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab200
OMe
H
SO3H
SO3H
H
OMe
|
1ab201
H
SO3H
H
H
SO3H
H
CN
Tert-butyl
3
4
3
4
|
1ab202
H
H
SO3H
SO3H
H
H
|
1ab203
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab204
OMe
H
SO3H
SO3H
H
OMe
|
1ab205
H
SO3H
H
H
SO3H
H
CN
3-Methyl butyl
3
4
3
4
|
1ab206
H
H
SO3H
SO3H
H
H
|
1ab207
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab208
OMe
H
SO3H
SO3H
H
OMe
|
1ab209
H
SO3H
H
H
SO3H
H
CN
Pentan-2-yl
3
4
3
4
|
1ab210
H
H
SO3H
SO3H
H
H
|
1ab211
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab212
OMe
H
SO3H
SO3H
H
OMe
|
1ab213
H
SO3H
H
H
SO3H
H
CN
2-Ethylhexyl
3
4
3
4
|
1ab214
H
H
SO3H
SO3H
H
H
|
1ab215
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab216
OMe
H
SO3H
SO3H
H
OMe
|
1ab217
H
SO3H
H
H
SO3H
H
CN
2,2-Dimethyl
3
4
3
4
|
1ab218
H
H
SO3H
SO3H
H
H
propyl
|
1ab219
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab220
OMe
H
SO3H
SO3H
H
OMe
|
1ab221
H
SO3H
H
H
SO3H
H
CN
Phenyl
3
4
3
4
|
1ab222
H
H
SO3H
SO3H
H
H
|
1ab223
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab224
OMe
H
SO3H
SO3H
H
OMe
|
1ab225
H
SO3H
H
H
SO3H
H
CN
Benzyl
3
4
3
4
|
1ab226
H
H
SO3H
SO3H
H
H
|
1ab227
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab228
OMe
H
SO3H
SO3H
H
OMe
|
1ab229
H
SO3H
H
H
SO3H
H
CONH2
H
3
4
3
4
|
1ab230
H
H
SO3H
SO3H
H
H
|
1ab231
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab232
OMe
H
SO3H
SO3H
H
OMe
|
1ab233
H
SO3H
H
H
SO3H
H
CONH2
Ethyl
3
4
3
4
|
1ab234
H
H
SO3H
SO3H
H
H
|
1ab235
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab236
OMe
H
SO3H
SO3H
H
OMe
|
1ab237
H
SO3H
H
H
SO3H
H
CONH2
Propyl
3
4
3
4
|
1ab238
H
H
SO3H
SO3H
H
H
|
1ab239
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab240
OMe
H
SO3H
SO3H
H
OMe
|
1ab241
H
SO3H
H
H
SO3H
H
CONH2
Butyl
3
4
3
4
|
1ab242
H
H
SO3H
SO3H
H
H
|
1ab243
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab244
OMe
H
SO3H
SO3H
H
OMe
|
1ab245
H
SO3H
H
H
SO3H
H
CONH2
Pentyl
3
4
3
4
|
1ab246
H
H
SO3H
SO3H
H
H
|
1ab247
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab248
OMe
H
SO3H
SO3H
H
OMe
|
1ab249
H
SO3H
H
H
SO3H
H
CONH2
Cyclobutyl
3
4
3
4
|
1ab250
H
H
SO3H
SO3H
H
H
|
1ab251
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab252
OMe
H
SO3H
SO3H
H
OMe
|
1ab253
H
SO3H
H
H
SO3H
H
CONH2
Cyclopentyl
3
4
3
4
|
1ab254
H
H
SO3H
SO3H
H
H
|
1ab255
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab256
OMe
H
SO3H
SO3H
H
OMe
|
1ab257
H
SO3H
H
H
SO3H
H
CONH2
Isopropyl
3
4
3
4
|
1ab258
H
H
SO3H
SO3H
H
H
|
1ab259
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab260
OMe
H
SO3H
SO3H
H
OMe
|
1ab261
H
SO3H
H
H
SO3H
H
CONH2
Sec-butyl
3
4
3
4
|
1ab262
H
H
SO3H
SO3H
H
H
|
1ab263
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab264
OMe
H
SO3H
SO3H
H
OMe
|
1ab265
H
SO3H
H
H
SO3H
H
CONH2
2-Methyl butyl
3
4
3
4
|
1ab266
H
H
SO3H
SO3H
H
H
|
1ab267
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab268
OMe
H
SO3H
SO3H
H
OMe
|
1ab269
H
SO3H
H
H
SO3H
H
CONH2
1-Ethyl propyl
3
4
3
4
|
1ab270
H
H
SO3H
SO3H
H
H
|
1ab271
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab272
OMe
H
SO3H
SO3H
H
OMe
|
1ab273
H
SO3H
H
H
SO3H
H
CONH2
1,2-Dimethyl
3
4
3
4
|
1ab274
H
H
SO3H
SO3H
H
H
propyl
|
1ab275
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab276
OMe
H
SO3H
SO3H
H
OMe
|
1ab277
H
SO3H
H
H
SO3H
H
CONH2
Tert-butyl
3
4
3
4
|
1ab278
H
H
SO3H
SO3H
H
H
|
1ab279
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab280
OMe
H
SO3H
SO3H
H
OMe
|
1ab281
H
SO3H
H
H
SO3H
H
CONH2
3-Methyl butyl
3
4
3
4
|
1ab282
H
H
SO3H
SO3H
H
H
|
1ab283
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab284
OMe
H
SO3H
SO3H
H
OMe
|
1ab285
H
SO3H
H
H
SO3H
H
CONH2
Pentan-2-yl
3
4
3
4
|
1ab286
H
H
SO3H
SO3H
H
H
|
1ab287
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab288
OMe
H
SO3H
SO3H
H
OMe
|
1ab289
H
SO3H
H
H
SO3H
H
CONH2
2-Ethylhexyl
3
4
3
4
|
1ab290
H
H
SO3H
SO3H
H
H
|
1ab291
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab292
OMe
H
SO3H
SO3H
H
OMe
|
1ab293
H
SO3H
H
H
SO3H
H
CONH2
2,2-Dimethyl
3
4
3
4
|
1ab294
H
H
SO3H
SO3H
H
H
propyl
|
1ab295
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab296
OMe
H
SO3H
SO3H
H
OMe
|
1ab297
H
SO3H
H
H
SO3H
H
CONH2
Phenyl
3
4
3
4
|
1ab298
H
H
SO3H
SO3H
H
H
|
1ab299
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab300
OMe
H
SO3H
SO3H
H
OMe
|
1ab301
H
SO3H
H
H
SO3H
H
CONH2
Benzyl
3
4
3
4
|
1ab302
H
H
SO3H
SO3H
H
H
|
1ab303
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab304
OMe
H
SO3H
SO3H
H
OMe
|
1ab305
H
SO3H
H
H
SO3H
H
CN
H
3
3
3
3
|
1ab306
H
H
SO3H
SO3H
H
H
|
1ab307
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab308
OMe
H
SO3H
SO3H
H
OMe
|
1ab309
H
SO3H
H
H
SO3H
H
CN
Ethyl
3
3
3
3
|
1ab310
H
H
SO3H
SO3H
H
H
|
1ab311
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab312
OMe
H
SO3H
SO3H
H
OMe
|
1ab313
H
SO3H
H
H
SO3H
H
CN
Propyl
3
3
3
3
|
1ab314
H
H
SO3H
SO3H
H
H
|
1ab315
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab316
OMe
H
SO3H
SO3H
H
OMe
|
1ab317
H
SO3H
H
H
SO3H
H
CN
Butyl
3
3
3
3
|
1ab318
H
H
SO3H
SO3H
H
H
|
1ab319
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab320
OMe
H
SO3H
SO3H
H
OMe
|
1ab321
H
SO3H
H
H
SO3H
H
CN
Pentyl
3
3
3
3
|
1ab322
H
H
SO3H
SO3H
H
H
|
1ab323
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab324
OMe
H
SO3H
SO3H
H
OMe
|
1ab325
H
SO3H
H
H
SO3H
H
CN
Cyclobutyl
3
3
3
3
|
1ab326
H
H
SO3H
SO3H
H
H
|
1ab327
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab328
OMe
H
SO3H
SO3H
H
OMe
|
1ab329
H
SO3H
H
H
SO3H
H
CN
Cyclopentyl
3
3
3
3
|
1ab330
H
H
SO3H
SO3H
H
H
|
1ab331
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab332
OMe
H
SO3H
SO3H
H
OMe
|
1ab333
H
SO3H
H
H
SO3H
H
CN
Isopropyl
3
3
3
3
|
1ab334
H
H
SO3H
SO3H
H
H
|
1ab335
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab336
OMe
H
SO3H
SO3H
H
OMe
|
1ab337
H
SO3H
H
H
SO3H
H
CN
Sec-butyl
3
3
3
3
|
1ab338
H
H
SO3H
SO3H
H
H
|
1ab339
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab340
OMe
H
SO3H
SO3H
H
OMe
|
1ab341
H
SO3H
H
H
SO3H
H
CN
2-Methyl butyl
3
3
3
3
|
1ab342
H
H
SO3H
SO3H
H
H
|
1ab343
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab344
OMe
H
SO3H
SO3H
H
OMe
|
1ab345
H
SO3H
H
H
SO3H
H
CN
1-Ethyl propyl
3
3
3
3
|
1ab346
H
H
SO3H
SO3H
H
H
|
1ab347
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab348
OMe
H
SO3H
SO3H
H
OMe
|
1ab349
H
SO3H
H
H
SO3H
H
CN
1,2-Dimethyl
3
3
3
3
|
1ab350
H
H
SO3H
SO3H
H
H
propyl
|
1ab351
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab352
OMe
H
SO3H
SO3H
H
OMe
|
1ab353
H
SO3H
H
H
SO3H
H
CN
Tert-butyl
3
3
3
3
|
1ab354
H
H
SO3H
SO3H
H
H
|
1ab355
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab356
OMe
H
SO3H
SO3H
H
OMe
|
1ab357
H
SO3H
H
H
SO3H
H
CN
3-Methyl butyl
3
3
3
3
|
1ab358
H
H
SO3H
SO3H
H
H
|
1ab359
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab360
OMe
H
SO3H
SO3H
H
OMe
|
1ab361
H
SO3H
H
H
SO3H
H
CN
Pentan-2-yl
3
3
3
3
|
1ab362
H
H
SO3H
SO3H
H
H
|
1ab363
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab364
OMe
H
SO3H
SO3H
H
OMe
|
1ab365
H
SO3H
H
H
SO3H
H
CN
2-Ethylhexyl
3
3
3
3
|
1ab366
H
H
SO3H
SO3H
H
H
|
1ab367
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab368
OMe
H
SO3H
SO3H
H
OMe
|
1ab369
H
SO3H
H
H
SO3H
H
CN
2,2-Dimethyl
3
3
3
3
|
1ab370
H
H
SO3H
SO3H
H
H
propyl
|
1ab371
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab372
OMe
H
SO3H
SO3H
H
OMe
|
1ab373
H
SO3H
H
H
SO3H
H
CN
Phenyl
3
3
3
3
|
1ab374
H
H
SO3H
SO3H
H
H
|
1ab375
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab376
OMe
H
SO3H
SO3H
H
OMe
|
1ab377
H
SO3H
H
H
SO3H
H
CN
Benzyl
3
3
3
3
|
1ab378
H
H
SO3H
SO3H
H
H
|
1ab379
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab380
OMe
H
SO3H
SO3H
H
OMe
|
1ab381
H
SO3H
H
H
SO3H
H
CONH2
H
3
3
3
3
|
1ab382
H
H
SO3H
SO3H
H
H
|
1ab383
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab384
OMe
H
SO3H
SO3H
H
OMe
|
1ab385
H
SO3H
H
H
SO3H
H
CONH2
Ethyl
3
3
3
3
|
1ab386
H
H
SO3H
SO3H
H
H
|
1ab387
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab388
OMe
H
SO3H
SO3H
H
OMe
|
1ab389
H
SO3H
H
H
SO3H
H
CONH2
Propyl
3
3
3
3
|
1ab390
H
H
SO3H
SO3H
H
H
|
1ab391
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab392
OMe
H
SO3H
SO3H
H
OMe
|
1ab393
H
SO3H
H
H
SO3H
H
CONH2
Butyl
3
3
3
3
|
1ab394
H
H
SO3H
SO3H
H
H
|
1ab395
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab396
OMe
H
SO3H
SO3H
H
OMe
|
1ab397
H
SO3H
H
H
SO3H
H
CONH2
Pentyl
3
3
3
3
|
1ab398
H
H
SO3H
SO3H
H
H
|
1ab399
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab400
OMe
H
SO3H
SO3H
H
OMe
|
1ab401
H
SO3H
H
H
SO3H
H
CONH2
Cyclobutyl
3
3
3
3
|
1ab402
H
H
SO3H
SO3H
H
H
|
1ab403
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab404
OMe
H
SO3H
SO3H
H
OMe
|
1ab405
H
SO3H
H
H
SO3H
H
CONH2
Cyclopentyl
3
3
3
3
|
1ab406
H
H
SO3H
SO3H
H
H
|
1ab407
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab408
OMe
H
SO3H
SO3H
H
OMe
|
1ab409
H
SO3H
H
H
SO3H
H
CONH2
Isopropyl
3
3
3
3
|
1ab410
H
H
SO3H
SO3H
H
H
|
1ab411
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab412
OMe
H
SO3H
SO3H
H
OMe
|
1ab413
H
SO3H
H
H
SO3H
H
CONH2
Sec-butyl
3
3
3
3
|
1ab414
H
H
SO3H
SO3H
H
H
|
1ab415
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab416
OMe
H
SO3H
SO3H
H
OMe
|
1ab417
H
SO3H
H
H
SO3H
H
CONH2
2-Methyl butyl
3
3
3
3
|
1ab418
H
H
SO3H
SO3H
H
H
|
1ab419
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab420
OMe
H
SO3H
SO3H
H
OMe
|
1ab421
H
SO3H
H
H
SO3H
H
CONH2
1-Ethyl propyl
3
3
3
3
|
1ab422
H
H
SO3H
SO3H
H
H
|
1ab423
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab424
OMe
H
SO3H
SO3H
H
OMe
|
1ab425
H
SO3H
H
H
SO3H
H
CONH2
1,2-Dimethyl
3
3
3
3
|
1ab426
H
H
SO3H
SO3H
H
H
propyl
|
1ab427
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab428
OMe
H
SO3H
SO3H
H
OMe
|
1ab429
H
SO3H
H
H
SO3H
H
CONH2
Tert-butyl
3
3
3
3
|
1ab430
H
H
SO3H
SO3H
H
H
|
1ab431
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab432
OMe
H
SO3H
SO3H
H
OMe
|
1ab433
H
SO3H
H
H
SO3H
H
CONH2
3-Methyl butyl
3
3
3
3
|
1ab434
H
H
SO3H
SO3H
H
H
|
1ab435
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab436
OMe
H
SO3H
SO3H
H
OMe
|
1ab437
H
SO3H
H
H
SO3H
H
CONH2
Pentan-2-yl
3
3
3
3
|
1ab438
H
H
SO3H
SO3H
H
H
|
1ab439
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab440
OMe
H
SO3H
SO3H
H
OMe
|
1ab441
H
SO3H
H
H
SO3H
H
CONH2
2-Ethylhexyl
3
3
3
3
|
1ab442
H
H
SO3H
SO3H
H
H
|
1ab443
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab444
OMe
H
SO3H
SO3H
H
OMe
|
1ab445
H
SO3H
H
H
SO3H
H
CONH2
2,2-Dimethyl
3
3
3
3
|
1ab446
H
H
SO3H
SO3H
H
H
propyl
|
1ab447
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab448
OMe
H
SO3H
SO3H
H
OMe
|
1ab449
H
SO3H
H
H
SO3H
H
CONH2
Phenyl
3
3
3
3
|
1ab450
H
H
SO3H
SO3H
H
H
|
1ab451
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab452
OMe
H
SO3H
SO3H
H
OMe
|
1ab453
H
SO3H
H
H
SO3H
H
CONH2
Benzyl
3
3
3
3
|
1ab454
H
H
SO3H
SO3H
H
H
|
1ab455
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab456
OMe
H
SO3H
SO3H
H
OMe
|
1ab457
H
SO3H
H
H
SO3H
H
CN
2-Methoxy ethyl
2
2
2
2
|
1ab458
H
H
SO3H
SO3H
H
H
|
1ab459
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab460
OMe
H
SO3H
SO3H
H
OMe
|
1ab461
H
SO3H
H
H
SO3H
H
CN
3-Methoxy
2
2
2
2
|
1ab462
H
H
SO3H
SO3H
H
H
propyl
|
1ab463
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab464
OMe
H
SO3H
SO3H
H
OMe
|
1ab465
H
SO3H
H
H
SO3H
H
CN
2-Hydroxy ethyl
2
2
2
2
|
1ab466
H
H
SO3H
SO3H
H
H
|
1ab467
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab468
OMe
H
SO3H
SO3H
H
OMe
|
1ab469
H
SO3H
H
H
SO3H
H
CN
2-Fluoro ethyl
2
2
2
2
|
1ab470
H
H
SO3H
SO3H
H
H
|
1ab471
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab472
OMe
H
SO3H
SO3H
H
OMe
|
1ab473
H
SO3H
H
H
SO3H
H
CN
2-Chloro ethyl
2
2
2
2
|
1ab474
H
H
SO3H
SO3H
H
H
|
1ab475
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab476
OMe
H
SO3H
SO3H
H
OMe
|
1ab477
H
SO3H
H
H
SO3H
H
CN
3-Chloro propyl
2
2
2
2
|
1ab478
H
H
SO3H
SO3H
H
H
|
1ab479
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab480
OMe
H
SO3H
SO3H
H
OMe
|
1ab481
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy-
2
2
2
2
|
1ab482
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1ab483
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1ab484
OMe
H
SO3H
SO3H
H
OMe
|
1ab485
H
SO3H
H
H
SO3H
H
CN
2-(2-tert-Butyl
2
2
2
2
|
1ab486
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1ab487
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1ab488
OMe
H
SO3H
SO3H
H
OMe
|
1ab489
H
SO3H
H
H
SO3H
H
CN
3-(4-Hydroxy
2
2
2
2
|
1ab490
H
H
SO3H
SO3H
H
H
butoxy)
|
1ab491
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1ab492
OMe
H
SO3H
SO3H
H
OMe
|
1ab493
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy
2
2
2
2
|
1ab494
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1ab495
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab496
OMe
H
SO3H
SO3H
H
OMe
|
1ab497
H
SO3H
H
H
SO3H
H
CN
4-(2-Hydroxy-
2
2
2
2
|
1ab498
H
H
SO3H
SO3H
H
H
ethane
|
1ab499
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1ab500
OMe
H
SO3H
SO3H
H
OMe
|
1ab501
H
SO3H
H
H
SO3H
H
CN
3-(2-Phenoxy-
2
2
2
2
|
1ab502
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1ab503
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab504
OMe
H
SO3H
SO3H
H
OMe
|
1ab505
H
SO3H
H
H
SO3H
H
CN
3-Isopropoxy-
2
2
2
2
|
1ab506
H
H
SO3H
SO3H
H
H
propyl
|
1ab507
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab508
OMe
H
SO3H
SO3H
H
OMe
|
1ab509
H
SO3H
H
H
SO3H
H
CN
3-Ethoxy-propyl
2
2
2
2
|
1ab510
H
H
SO3H
SO3H
H
H
|
1ab511
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab512
OMe
H
SO3H
SO3H
H
OMe
|
1ab513
H
SO3H
H
H
SO3H
H
CN
3-Ethoxybutyl
2
2
2
2
|
1ab514
H
H
SO3H
SO3H
H
H
|
1ab515
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab516
OMe
H
SO3H
SO3H
H
OMe
|
1ab517
H
SO3H
H
H
SO3H
H
CONH2
2-Methoxy ethyl
2
2
2
2
|
1ab518
H
H
SO3H
SO3H
H
H
|
1ab519
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab520
OMe
H
SO3H
SO3H
H
OMe
|
1ab521
H
SO3H
H
H
SO3H
H
CONH2
3-Methoxy
2
2
2
2
|
1ab522
H
H
SO3H
SO3H
H
H
propyl
|
1ab523
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab524
OMe
H
SO3H
SO3H
H
OMe
|
1ab525
H
SO3H
H
H
SO3H
H
CONH2
2-Hydroxyethyl
2
2
2
2
|
1ab526
H
H
SO3H
SO3H
H
H
|
1ab527
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab528
OMe
H
SO3H
SO3H
H
OMe
|
1ab529
H
SO3H
H
H
SO3H
H
CONH2
2-Fluoro ethyl
2
2
2
2
|
1ab530
H
H
SO3H
SO3H
H
H
|
1ab531
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab532
OMe
H
SO3H
SO3H
H
OMe
|
1ab533
H
SO3H
H
H
SO3H
H
CONH2
2-Chloro ethyl
2
2
2
2
|
1ab534
H
H
SO3H
SO3H
H
H
|
1ab535
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab536
OMe
H
SO3H
SO3H
H
OMe
|
1ab537
H
SO3H
H
H
SO3H
H
CONH2
3-Chloro propyl
2
2
2
2
|
1ab538
H
H
SO3H
SO3H
H
H
|
1ab539
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab540
OMe
H
SO3H
SO3H
H
OMe
|
1ab541
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy-
2
2
2
2
|
1ab542
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1ab543
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1ab544
OMe
H
SO3H
SO3H
H
OMe
|
1ab545
H
SO3H
H
H
SO3H
H
CONH2
2-(2-tert-Butyl
2
2
2
2
|
1ab546
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1ab547
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1ab548
OMe
H
SO3H
SO3H
H
OMe
|
1ab549
H
SO3H
H
H
SO3H
H
CONH2
3-(4-Hydroxy
2
2
2
2
|
1ab550
H
H
SO3H
SO3H
H
H
butoxy)
|
1ab551
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1ab552
OMe
H
SO3H
SO3H
H
OMe
|
1ab553
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy
2
2
2
2
|
1ab554
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1ab555
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab556
OMe
H
SO3H
SO3H
H
OMe
|
1ab557
H
SO3H
H
H
SO3H
H
CONH2
4-(2-Hydroxy-
2
2
2
2
|
1ab558
H
H
SO3H
SO3H
H
H
ethane
|
1ab559
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1ab560
OMe
H
SO3H
SO3H
H
OMe
|
1ab561
H
SO3H
H
H
SO3H
H
CONH2
3-(2-Phenoxy-
2
2
2
2
|
1ab562
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1ab563
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab564
OMe
H
SO3H
SO3H
H
OMe
|
1ab565
H
SO3H
H
H
SO3H
H
CONH2
3-Isopropoxy-
2
2
2
2
|
1ab566
H
H
SO3H
SO3H
H
H
propyl
|
1ab567
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab568
OMe
H
SO3H
SO3H
H
OMe
|
1ab569
H
SO3H
H
H
SO3H
H
CONH2
3-Ethoxy propyl
2
2
2
2
|
1ab570
H
H
SO3H
SO3H
H
H
|
1ab571
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab572
OMe
H
SO3H
SO3H
H
OMe
|
1ab573
H
SO3H
H
H
SO3H
H
CONH2
4-Ethoxy butyl
2
2
2
2
|
1ab574
H
H
SO3H
SO3H
H
H
|
1ab575
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab576
OMe
H
SO3H
SO3H
H
OMe
|
1ab577
H
SO3H
H
H
SO3H
H
CN
2-Methoxy ethyl
3
4
3
4
|
1ab578
H
H
SO3H
SO3H
H
H
|
1ab579
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab580
OMe
H
SO3H
SO3H
H
OMe
|
1ab581
H
SO3H
H
H
SO3H
H
CN
3-Methoxy
3
4
3
4
|
1ab582
H
H
SO3H
SO3H
H
H
propyl
|
1ab583
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab584
OMe
H
SO3H
SO3H
H
OMe
|
1ab585
H
SO3H
H
H
SO3H
H
CN
2-Hydroxyethyl
3
4
3
4
|
1ab586
H
H
SO3H
SO3H
H
H
|
1ab587
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab588
OMe
H
SO3H
SO3H
H
OMe
|
1ab589
H
SO3H
H
H
SO3H
H
CN
2-Fluoro ethyl
3
4
3
4
|
1ab590
H
H
SO3H
SO3H
H
H
|
1ab591
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab592
OMe
H
SO3H
SO3H
H
OMe
|
1ab593
H
SO3H
H
H
SO3H
H
CN
2-Chloro ethyl
3
4
3
4
|
1ab594
H
H
SO3H
SO3H
H
H
|
1ab595
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab596
OMe
H
SO3H
SO3H
H
OMe
|
1ab597
H
SO3H
H
H
SO3H
H
CN
3-Chloro propyl
3
4
3
4
|
1ab598
H
H
SO3H
SO3H
H
H
|
1ab599
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab600
OMe
H
SO3H
SO3H
H
OMe
|
1ab601
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy-
3
4
3
4
|
1ab602
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1ab603
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1ab604
OMe
H
SO3H
SO3H
H
OMe
|
1ab605
H
SO3H
H
H
SO3H
H
CN
2-(2-tert-Butyl
3
4
3
4
|
1ab606
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1ab607
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1ab608
OMe
H
SO3H
SO3H
H
OMe
|
1ab609
H
SO3H
H
H
SO3H
H
CN
3-(4-Hydroxy
3
4
3
4
|
1ab610
H
H
SO3H
SO3H
H
H
butoxy)
|
1ab611
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1ab612
OMe
H
SO3H
SO3H
H
OMe
|
1ab613
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy
3
4
3
4
|
1ab614
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1ab615
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab616
OMe
H
SO3H
SO3H
H
OMe
|
1ab617
H
SO3H
H
H
SO3H
H
CN
4-(2-Hydroxy-
3
4
3
4
|
1ab618
H
H
SO3H
SO3H
H
H
ethane
|
1ab619
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1ab620
OMe
H
SO3H
SO3H
H
OMe
|
1ab621
H
SO3H
H
H
SO3H
H
CN
3-(2-Phenoxy-
3
4
3
4
|
1ab622
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1ab623
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab624
OMe
H
SO3H
SO3H
H
OMe
|
1ab625
H
SO3H
H
H
SO3H
H
CN
3-Isopropoxy-
3
4
3
4
|
1ab626
H
H
SO3H
SO3H
H
H
propyl
|
1ab627
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab628
OMe
H
SO3H
SO3H
H
OMe
|
1ab629
H
SO3H
H
H
SO3H
H
CN
3-Ethoxy propyl
3
4
3
4
|
1ab630
H
H
SO3H
SO3H
H
H
|
1ab631
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab632
OMe
H
SO3H
SO3H
H
OMe
|
1ab633
H
SO3H
H
H
SO3H
H
CN
4-Ethoxy butyl
3
4
3
4
|
1ab634
H
H
SO3H
SO3H
H
H
|
1ab635
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab636
OMe
H
SO3H
SO3H
H
OMe
|
1ab637
H
SO3H
H
H
SO3H
H
CONH2
2-Methoxy ethyl
3
4
3
4
|
1ab638
H
H
SO3H
SO3H
H
H
|
1ab639
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab640
OMe
H
SO3H
SO3H
H
OMe
|
1ab641
H
SO3H
H
H
SO3H
H
CONH2
3-Methoxy
3
4
3
4
|
1ab642
H
H
SO3H
SO3H
H
H
propyl
|
1ab643
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab644
OMe
H
SO3H
SO3H
H
OMe
|
1ab645
H
SO3H
H
H
SO3H
H
CONH2
2-Hydroxyethyl
3
4
3
4
|
1ab646
H
H
SO3H
SO3H
H
H
|
1ab647
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab648
OMe
H
SO3H
SO3H
H
OMe
|
1ab649
H
SO3H
H
H
SO3H
H
CONH2
2-Fluoro ethyl
3
4
3
4
|
1ab650
H
H
SO3H
SO3H
H
H
|
1ab651
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab652
OMe
H
SO3H
SO3H
H
OMe
|
1ab653
H
SO3H
H
H
SO3H
H
CONH2
2-Chloro ethyl
3
4
3
4
|
1ab654
H
H
SO3H
SO3H
H
H
|
1ab655
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab656
OMe
H
SO3H
SO3H
H
OMe
|
1ab657
H
SO3H
H
H
SO3H
H
CONH2
3-Chloro propyl
3
4
3
4
|
1ab658
H
H
SO3H
SO3H
H
H
|
1ab659
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab660
OMe
H
SO3H
SO3H
H
OMe
|
1ab661
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy-
3
4
3
4
|
1ab662
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1ab663
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1ab664
OMe
H
SO3H
SO3H
H
OMe
|
1ab665
H
SO3H
H
H
SO3H
H
CONH2
2-(2-tert-Butyl
3
4
3
4
|
1ab666
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1ab667
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1ab668
OMe
H
SO3H
SO3H
H
OMe
|
1ab669
H
SO3H
H
H
SO3H
H
CONH2
3-(4-Hydroxy
3
4
3
4
|
1ab670
H
H
SO3H
SO3H
H
H
butoxy)
|
1ab671
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1ab672
OMe
H
SO3H
SO3H
H
OMe
|
1ab673
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy
3
4
3
4
|
1ab674
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1ab675
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab676
OMe
H
SO3H
SO3H
H
OMe
|
1ab677
H
SO3H
H
H
SO3H
H
CONH2
4-(2-Hydroxy-
3
4
3
4
|
1ab678
H
H
SO3H
SO3H
H
H
ethane
|
1ab679
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1ab680
OMe
H
SO3H
SO3H
H
OMe
|
1ab681
H
SO3H
H
H
SO3H
H
CONH2
3-(2-Phenoxy-
3
4
3
4
|
1ab682
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1ab683
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab684
OMe
H
SO3H
SO3H
H
OMe
|
1ab685
H
SO3H
H
H
SO3H
H
CONH2
3-Isopropoxy-
3
4
3
4
|
1ab686
H
H
SO3H
SO3H
H
H
propyl
|
1ab687
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab688
OMe
H
SO3H
SO3H
H
OMe
|
1ab689
H
SO3H
H
H
SO3H
H
CONH2
3-Ethoxy propyl
3
4
3
4
|
1ab690
H
H
SO3H
SO3H
H
H
|
1ab691
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab692
OMe
H
SO3H
SO3H
H
OMe
|
1ab693
H
SO3H
H
H
SO3H
H
CONH2
4-Ethoxy butyl
3
4
3
4
|
1ab694
H
H
SO3H
SO3H
H
H
|
1ab695
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab696
OMe
H
SO3H
SO3H
H
OMe
|
1ab697
H
SO3H
H
H
SO3H
H
CN
2-Methoxy ethyl
3
3
3
3
|
1ab698
H
H
SO3H
SO3H
H
H
|
1ab699
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab700
OMe
H
SO3H
SO3H
H
OMe
|
1ab701
H
SO3H
H
H
SO3H
H
CN
3-Methoxy
3
3
3
3
|
1ab702
H
H
SO3H
SO3H
H
H
propyl
|
1ab703
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab704
OMe
H
SO3H
SO3H
H
OMe
|
1ab705
H
SO3H
H
H
SO3H
H
CN
2-Hydroxy ethyl
3
3
3
3
|
1ab706
H
H
SO3H
SO3H
H
H
|
1ab707
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab708
OMe
H
SO3H
SO3H
H
OMe
|
1ab709
H
SO3H
H
H
SO3H
H
CN
2-Fluoro ethyl
3
3
3
3
|
1ab710
H
H
SO3H
SO3H
H
H
|
1ab711
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab712
OMe
H
SO3H
SO3H
H
OMe
|
1ab713
H
SO3H
H
H
SO3H
H
CN
2-Chloro ethyl
3
3
3
3
|
1ab714
H
H
SO3H
SO3H
H
H
|
1ab715
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab716
OMe
H
SO3H
SO3H
H
OMe
|
1ab717
H
SO3H
H
H
SO3H
H
CN
3-Chloro propyl
3
3
3
3
|
1ab718
H
H
SO3H
SO3H
H
H
|
1ab719
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab720
OMe
H
SO3H
SO3H
H
OMe
|
1ab721
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy-
3
3
3
3
|
1ab722
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1ab723
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1ab724
OMe
H
SO3H
SO3H
H
OMe
|
1ab725
H
SO3H
H
H
SO3H
H
CN
2-(2-tert-Butyl
3
3
3
3
|
1ab726
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1ab727
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1ab728
OMe
H
SO3H
SO3H
H
OMe
|
1ab729
H
SO3H
H
H
SO3H
H
CN
3-(4-Hydroxy
3
3
3
3
|
1ab730
H
H
SO3H
SO3H
H
H
butoxy)
|
1ab731
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1ab732
OMe
H
SO3H
SO3H
H
OMe
|
1ab733
H
SO3H
H
H
SO3H
H
CN
2-(2-Hydroxy
3
3
3
3
|
1ab734
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1ab735
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab736
OMe
H
SO3H
SO3H
H
OMe
|
1ab737
H
SO3H
H
H
SO3H
H
CN
4-(2-Hydroxy-
3
3
3
3
|
1ab738
H
H
SO3H
SO3H
H
H
ethane
|
1ab739
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1ab740
OMe
H
SO3H
SO3H
H
OMe
|
1ab741
H
SO3H
H
H
SO3H
H
CN
3-(2-Phenoxy-
3
3
3
3
|
1ab742
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1ab743
H
SO3H
SO3H
H
Methyl
|
1ab744
OMe
H
SO3H
SO3H
H
OMe
|
1ab745
H
SO3H
H
H
SO3H
H
CN
3-Isopropoxy-
3
3
3
3
|
1ab746
H
H
SO3H
SO3H
H
H
propyl
|
1ab747
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab748
OMe
H
SO3H
SO3H
H
OMe
|
1ab749
H
SO3H
H
H
SO3H
H
CN
3-Ethoxypropyl
3
3
3
3
|
1ab750
H
H
SO3H
SO3H
H
H
|
1ab751
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab752
OMe
H
SO3H
SO3H
H
OMe
|
1ab753
H
SO3H
H
H
SO3H
H
CN
3-Ethoxybutyl
3
3
3
3
|
1ab754
H
H
SO3H
SO3H
H
H
|
1ab755
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab756
OMe
H
SO3H
SO3H
H
OMe
|
1ab757
H
SO3H
H
H
SO3H
H
CONH2
2-Methoxyethyl
3
3
3
3
|
1ab758
H
H
SO3H
SO3H
H
H
|
1ab759
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab760
OMe
H
SO3H
SO3H
H
OMe
|
1ab761
H
SO3H
H
H
SO3H
H
CONH2
3-Methoxy
3
3
3
3
|
1ab762
H
H
SO3H
SO3H
H
H
propyl
|
1ab763
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab764
OMe
H
SO3H
SO3H
H
OMe
|
1ab765
H
SO3H
H
H
SO3H
H
CONH2
2-Hydroxy ethyl
3
3
3
3
|
1ab766
H
H
SO3H
SO3H
H
H
|
1ab767
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab768
OMe
H
SO3H
SO3H
H
OMe
|
1ab769
H
SO3H
H
H
SO3H
H
CONH2
2-Fluoro ethyl
3
3
3
3
|
1ab770
H
H
SO3H
SO3H
H
H
|
1ab771
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab772
OMe
H
SO3H
SO3H
H
OMe
|
1ab773
H
SO3H
H
H
SO3H
H
CONH2
2-Chloro ethyl
3
3
3
3
|
1ab774
H
H
SO3H
SO3H
H
H
|
1ab775
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab776
OMe
H
SO3H
SO3H
H
OMe
|
1ab777
H
SO3H
H
H
SO3H
H
CONH2
3-Chloro propyl
3
3
3
3
|
1ab778
H
H
SO3H
SO3H
H
H
|
1ab779
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab780
OMe
H
SO3H
SO3H
H
OMe
|
1ab781
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy-
3
3
3
3
|
1ab782
H
H
SO3H
SO3H
H
H
ethyl sulfanyl)-
|
1ab783
Methyl
H
SO3H
SO3H
H
Methyl
ethyl
|
1ab784
OMe
H
SO3H
SO3H
H
OMe
|
1ab785
H
SO3H
H
H
SO3H
H
CONH2
2-(2-tert-Butyl
3
3
3
3
|
1ab786
H
H
SO3H
SO3H
H
H
sulfanyl-ethane
|
1ab787
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-ethyl
|
1ab788
OMe
H
SO3H
SO3H
H
OMe
|
1ab789
H
SO3H
H
H
SO3H
H
CONH2
3-(4-Hydroxy
3
3
3
3
|
1ab790
H
H
SO3H
SO3H
H
H
butoxy)
|
1ab791
Methyl
H
SO3H
SO3H
H
Methyl
propyl
|
1ab792
OMe
H
SO3H
SO3H
H
OMe
|
1ab793
H
SO3H
H
H
SO3H
H
CONH2
2-(2-Hydroxy
3
3
3
3
|
1ab794
H
H
SO3H
SO3H
H
H
ethoxy)ethyl
|
1ab795
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab796
OMe
H
SO3H
SO3H
H
OMe
|
1ab797
H
SO3H
H
H
SO3H
H
CONH2
4-(2-Hydroxy-
3
3
3
3
|
1ab798
H
H
SO3H
SO3H
H
H
ethane
|
1ab799
Methyl
H
SO3H
SO3H
H
Methyl
sulfonyl)-phenyl
|
1ab800
OMe
H
SO3H
SO3H
H
OMe
|
1ab801
H
SO3H
H
H
SO3H
H
CONH2
3-(2-Phenoxy-
3
3
3
3
|
1ab802
H
H
SO3H
SO3H
H
H
ethoxy)-propyl
|
1ab803
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab804
OMe
H
SO3H
SO3H
H
OMe
|
1ab805
H
SO3H
H
H
SO3H
H
CONH2
3-Isopropoxy-
3
3
3
3
|
1ab806
H
H
SO3H
SO3H
H
H
propyl
|
1ab807
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab808
OMe
H
SO3H
SO3H
H
OMe
|
1ab809
H
SO3H
H
H
SO3H
H
CONH2
3-Ethoxy-propyl
3
3
3
3
|
1ab810
H
H
SO3H
SO3H
H
H
|
1ab811
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab812
OMe
H
SO3H
SO3H
H
OMe
|
1ab813
H
SO3H
H
H
SO3H
H
CONH2
3-Ethoxybutyl
3
3
3
3
|
1ab814
H
H
SO3H
SO3H
H
H
|
1ab815
Methyl
H
SO3H
SO3H
H
Methyl
|
1ab816
OMe
H
SO3H
SO3H
H
OMe
|
|
The present invention is also directed to a process for the preparation of the dyes of formula (1) and mixtures thereof, comprising
- a) diazotization of a compound of formula (2)
![embedded image]()
- wherein R1 to R8 are defined as above,
- b) reacting the corresponding diazonium salt obtained in step a) with the compounds of formula (3), (4), (5) and (6)
![embedded image]()
wherein R9 to R26 are as defined above.
The diazotization of the compound of formula (2) 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 advantageously be used.
The coupling reaction of the diazonium salt obtained by diazotization of the compound of the formula (2) onto the compounds of formulae (3), (4), (5) and (6) can be performed by known methods.
The compounds of the 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 disclosed in U.S. Pat. No. 5,728,874 or DE 172 106.
The pyridines of formula (3), (4), (5) and (6) in which R9 and R18 represent cyano are commercially available or can be synthesized via methods disclosed in the literature such as in DE 22 30 392. Through analogy, all the diamino pyridines that are used in this invention can be synthesized as described. The obtained pyridines can be further derivatized by reactions known to persons skilled in the art, such as hydrolysis to form pyridines in which R9 and R18 represent carbonamide or by hydrolysis and further esterification to form pyridines in which R9 and R18 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 alcohol. The reactions are advantageously carried out under inert atmosphere at temperatures in the range from 40 to 150° C.
Alternatively, the above-mentioned derivatization reactions could be undertaken as a final step after the synthesis of the corresponding dyes with pyridone 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° A) 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
8.62 g of 4,4′-diamino-biphenyl-2,2′-disulfonic acid were first dissolved in water at slightly acidic pH to give a complete solution. Ice was added to the solution and when temperature reaches 10 to 15° C., 10.6 ml of 5 N sodium nitrite solution were added dropwise into the 4,4′-diamino-biphenyl-2,2′-disulfonic acid solution. The reaction mixture was further cooled down to 0 to 8° C. using ice-salt-water bath. When temperature reached 0 to 8° C., the mixture was added dropwise into 12.38 g of concentrated HCl with 12 g of ice. Yellow suspension was formed and reaction mixture was completed within an hour.
13.21 g of a mixture of 2-amino-6-[3-(4-hydroxy-butoxy)-propylamino]-4-methyl-nicotinonitrile, 6-amino-2-[3-(4-hydroxy-butoxy)-propylamino]-4-methyl-nicotinonitrile, 2-amino-6-[2-(2-hydroxy-ethoxy)-ethylamino]-4-methyl-nicotinonitrile and 6-amino-2-[2-(2-hydroxy-ethoxy)-ethylamino]-4-methyl-nicotinonitrile were stirred in acidic water and added dropwise into the diazonium salt solution and stirred. Brilliant yellow precipitate was observed upon addition. Precipitate obtained was filtered off with suction and washed with brine giving an yellow product consisting of a mixture of the dyes 1aa154, 1ab154, 1aa2 and 1ab2. The analytic data are consistent with the assigned structure for the obtained products. The obtained products dye the targeted fibre materials in brilliant yellow shades.
Through analogy, all the dyes of formulae (1aa1-1aa816) and (1ab1-1ab816) and mixtures thereof can be synthesized according to the method described above.
Dyeing Example 1
1 part of the above-mentioned yellow product 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 than entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98° 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 fabric was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained give yellow shades and have very good light and wet fastness and also good levelness in the fibre.
Dyeing Example 2
1 part of the above-mentioned yellow product 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 dyeings obtained give yellow shades and have 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 consists of 40 parts of the above-mentioned yellow product, 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 810 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 dyeings obtained give yellow shades and have very good light and wet fastness and also good levelness in the fibre.
Dyeing Example 4
1 part of the above-mentioned yellow product 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 dyeings obtained give yellow shades and have very good light and wet fastness and also good levelness in the fibre.
Dyeing Example 5
1 part of the above-mentioned yellow product was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate, and 1 parts of a wetting agent (anionic) were added. 100 part of bleached cotton knitted fabric was 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 give yellow shades and have very good light and wet fastness and also good levelness in the fibre.
Dyeing Example 6
3 parts of the above-mentioned yellow product were dissolved in 82 parts of deionized water was added into the dyebath with 15 parts of diethylene glycol at 60° C. On cooling, a yellow printing ink was obtained. The yellow 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 were mixed up with 100 parts of 55° C. water. 1 part of the above-mentioned yellow product was dissolved in 100 parts of hot water. 80 parts of this solution were given to the mixed-up pulp and mixed for 2 minutes. After that the mixture was sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution were then diluted with 2000 parts of cold water and the paper was produced out of this solution. The yellow paper produced from the mixture has good wet fastnesses.
Patent Application
20160264783
