Acid dyes, process for the production thereof and their use

The present invention relates to the technical field of dyestuffs for dyeing and printing of hydroxyl- and/or carboxamido-containing materials.

Acid dyes containing pyridine derivatives as couplers are known from the prior art and can be used as colorants in different applications, see for example US 5,468,848 A, wherein cationic mono- and bisazo dyes are disclosed, which may be used for dyeing poly acryl nitrile or polyester materials or US 3,959,250 A, GB 2 337 053 A, US 3,960,480 A, US 5,543,259 A and WO 2007 / 045825.

However, in the context of the dyeing and printing of hydroxyl- and/or carboxamido- containing material the known dyes have a number of technical disadvantages, which require improvement.

One such disadvantage is, that many of them are comprising heavy metals such as Cu, Cr or Ni. Such heavy metals are critical from a toxicological as well as an environmental point of view and shall thus be excluded. Surprisingly, it has now been found that the dyes of formula (1 ) as described below show highly advantageous properties over the known dyes. These include high tinctorial strength with high brilliancy as well as high fastness properties such as wash, contact and light fastness on the materials mentioned above, on blends containing them as well as on microfibres. Most importantly, dyes of formula (1 ) are substantially heavy metal free and provide dyeings that are levelled. Metals may only be present as counter ions and are selected from the groups of alkali and earth alkali metals, which do not have such effects as heavy metals.

If heavy meatals 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 is directed to dyes of formula (1 ) and mixtures thereof

wherein X is O, S or NH,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M, R ⁹ and R ¹⁸ independent of each other is cyano, carbamoyl, substituted carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen,

R ¹⁰ and R ¹⁹ independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyi- 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, acyl- amino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido, R ¹¹ , R ¹² , R ²⁰ and R ²¹ independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkyl- thioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocyclo- alkylalkyl

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, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloal- kyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono- aryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carba- moyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamo- yl and SO ₃ M

or alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl- amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl- monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N- alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N- monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl- sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyl and SO3M,

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²² , R ²³ , R ²⁴ and R ²⁵ independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkyl- thioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, hetero- cycloalkylalkyl

or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur

or

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

or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl- amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-mono- cycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl- amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N- monoalkyl-N-monoarylsulfamoyl and SO3M,

R ¹⁷ and R ²⁶ independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl- aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur

or

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

or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl- amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocyclo- alkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl- amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-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 an integer 1 , 2, 3 or 4, when n is 2, 3 or 4, R ¹³ contained in the 2, 3 or 4 units can be identical or different from unit to unit, and same applies to R ¹⁴ independently from R ¹³ ,

when m is 2, 3 or 4, R ¹⁵ contained in the 2, 3 or 4 units can be identical or different from unit to unit, and same applies to R ¹⁶ independently from R ¹⁵ ,

when o is 2, 3 or 4, R ²² contained in the 2, 3 or 4 units can be identical or different from unit to unit, and same applies to R ²³ independently from R ²² ,

and when p is 2, 3 or 4, R ²⁴ contained in the 2, 3 or 4 units can be identical or different from unit to unit, and same applies to R ²⁵ independently from R ²⁴

and

the dyes of formula (1 ) have two to six sulfonic acid groups.

This invention is directed to all tautomeric and geometric isomers of the dyes of formula (1 ) as well as to mixtures thereof. Alkyl groups appearing in this invention may be straight-chain or branched and are (Ci-Ci2)-alkyl groups, preferably (Ci-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 (Ci-C8)-alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (Ci-Cs)- thioalkoxy, for example -SCH3 or -SC2H5.

Cycloalkyl groups are preferably (C3-C8)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl. The term cycloalkyl comprises for the purpose of the present invention substituted cycloalkyl 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)-g roups for example vinyl and allyl. The term alkenyl comprises for the purpose of the present invention alkynyl groups as well, for example ethynyl and propargyl. Aryl groups appearing in this invention are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyi, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono- (hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy. Heteroaryl groups appearing in this invention are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1 ,3,4- thiadiazole, furane, oxazole, benzoxazole or isoxazole. The terms heteroayl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyi, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hy- droxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy. Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetra- hydrofuran or piperazine. The term heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxylalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, mono- alkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, aminocarbonyl- amino, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Halogen is preferably chlorine, bromine or fluorine. M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(Ci- C ₄ )-alkylammonium.

Particular preferred embodiments of the present invention are dyes of formula (1 a) or mixtures thereof

(1 a)

wherein

X is O, S or NH,

R ^{1 a} , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,

R ^9a and R ^18a independent of each other is cyano, carbamoyl or alkoxycarbonyl,

R ^10a and R ^19a independent of each other is unsubstituted, linear or branched (Ci-C ₄ )- alkyl, unsubstiuted (Cs-CzJ-cycloalkyl or substituted (Cs-CzJ-cycloalkyl with one or more substituents, preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl,

R ^{11 a} , R ^12a , R ^20a and R ^{21 a} independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl- aminoalkyl, 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, Ν,Ν-dialkyl-amino, N- monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono- cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenyl- ureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfa-

or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M,

R ^13a , R ^14a , R ^15a , R ^16a , R ^22a , R ^23a , R ^24a and R ^25a independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, amino- alkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, h eteroary I a I ky I , h eterocycl oa I ky I a I ky I

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, Ν,Ν-dialkyl-amino, N- monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocy- cloalkyl-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 SOsM

or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M,

R ^17a and R ^26a , independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl- aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl or heterocycloalkylalkyl or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur

or

alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, Ν,Ν-dialkyl-amino, N- monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocy- cloalkyl-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 SOsM

or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M, m, n, o and p independent of each other is an integer of 1 , 2, 3 or 4, when n is 2, 3 or 4, R ^13a contained in the 2, 3 or 4 units can be identical or different from unit to unit, and same applies to R ^14a independently from R ^13a ,

when m is 2, 3 or 4, R ^15a contained in the 2, 3 or 4 units can be identical or different from unit to unit, and same applies to R ^16a independently from R ^15a ,

when o is 2, 3 or 4, R ^22a contained in the 2, 3 or 4 units can be identical or different from unit to unit, and same applies to R ^23a independently from R ^22a ,

and when p is 2, 3 or 4, R ^24a contained in the 2, 3 or 4 units can be identical or different from unit to unit, and same applies to R ^25a independently from R ^24a and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

Particularly preferred embodiments of the present invention are dyes of the formula (1 aa) and mixtures thereof:

(1 aa) wherein X is O,

R ^{1 AA} , R ^2AA , R ^3AA , R ^4AA , R ^5AA , R ^6AA , R ^7AA and R ^8AA independent of each other is SO ₃ M, hydrogen, alkyl or alkoxy, whereby at least two of them are SO3M ,

R ^9AA and R ^18AA independent of each other is cyano or carbamoyl,

_R 10aa _{a nd} Rl9aa j _s mgthyl, m, n, o and p independent of each other is an integer of 2, 3 or 4, p1 1 aa p13aa p14aa p15aa p16aa p17aa p20aa p22aa p23aa p24aa p25aa gp ₍ j p26aa jg hydrogen, pi2aa _{a nc} | p2iaa 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 -ethyl propyl, 1 ,2-dimethyl- propyl, tert-butyl, 3-methyl butyl, 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-hy- droxy-1 -[2-(2-hydroxyethylsulfanyl)-ethyl], 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(ethylsulfonyl)ethanol, 2-hydroxyethoxypropyl, 2-hydroxyethoxyethyl, 2-(ethylsulfo- nyl) 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 (1 aa) are the compounds of the formulae (1 aa ¹ to 1 aa ⁷⁵⁶ ), wherein R ^2aa and R ^5aa is hydrogen:

DYS2012/S00

1 aa ³³⁵ H H SOsH H SOsH H

1 aa ³³⁶ H SOsH H H SOsH H

1aa ³³⁷ H SOsH H H H SOsH

1 ,2-Dimethyl

1 aa ³³⁸ H H SOsH H SOsH H CN 3 3 3 3 propyl

1aa ³³⁹ H SOsH H H SOsH H

_{1 aa} 340 H SOsH H H H SOsH

1aa ³⁴¹ H H SOsH H SOsH H CN Tert-butyl 3 3 3 3

1aa ³⁴² H SOsH H H SOsH H

1aa ³⁴³ H SOsH H H H SOsH

1aa ³⁴⁴ H H SOsH H SOsH H CN 3-Methyl butyl 3 3 3 3

1aa ³⁴⁵ H SOsH H H SOsH H

1aa ³⁴⁶ H SOsH H H H SOsH

1aa ³⁴⁷ H H SOsH H SOsH H CN Pentan-2-yl 3 3 3 3

1aa ³⁴⁸ H SOsH H H SOsH H

1aa ³⁴⁹ H SOsH H H H SOsH

1aa ³⁵⁰ H H SOsH H SOsH H CN 2-Ethylhexyl 3 3 3 3

1aa ³⁵¹ H SOsH H H SOsH H

1aa ³⁵² H SOsH H H H SOsH

1 aa ³⁵³ H H SOsH H SOsH H CN 2,2-Dimethyl 3 3 3 3 propyl

1aa ³⁵⁴ H SOsH H H SOsH H

1 aa ³⁵⁵ H SOsH H H H SOsH CN Phenyl 3 3 3 3

1 aa ³⁵⁶ H H SOsH H SOsH H

1aa ³⁵⁷ H SOsH H H SOsH H

1 aa ³⁵⁸ H SOsH H H H SOsH

1aa ³⁵⁹ H H SOsH H SOsH H CN Benzyl 3 3 3 3

1aa ³⁶⁰ H SOsH H H SOsH H

1aa ³⁶¹ H SOsH H H H SOsH

1aa ³⁶² H H SOsH H SOsH H CONH ₂ H 3 3 3 3

1 aa ³⁶³ H SOsH H H SOsH H

1aa ³⁶⁴ H SOsH H H H SOsH

1 aa ³⁶⁵ H H SOsH H SOsH H CONH2 Methyl 3 3 3 3

1 aa ³⁶⁶ H SOsH H H SOsH H

1aa ³⁶⁷ H SOsH H H H SOsH

1 aa ³⁶⁸ H H SOsH H SOsH H CONH2 Ethyl 3 3 3 3

1aa ³⁶⁹ H SOsH H H SOsH H

_{1 aa} 370 H SOsH H H H SOsH

1aa ³⁷¹ H H SOsH H SOsH H CONH2 Propyl 3 3 3 3

1aa ³⁷² H SOsH H H SOsH H

1aa ³⁷³ H SOsH H H H SOsH

1aa ³⁷⁴ H H SOsH H SOsH H CONH2 Butyl 3 3 3 3

1aa ³⁷⁵ H SOsH H H SOsH H

_{1 aa} 376 H SOsH H H H SOsH CONH2 Pentyl 3 3 3 3

1aa ³⁷⁷ H H SOsH H SOsH H

1aa ³⁷⁸ H SOsH H H SOsH H

1aa ³⁷⁹ H SOsH H H H SOsH

1aa ³⁸⁰ H H SOsH H SOsH H CONH ₂ Hexyl 3 3 3 3

1aa ³⁸¹ H SOsH H H SOsH H

1aa ³⁸² H SOsH H H H SOsH

1 aa ³⁸³ H H SOsH H SOsH H CONH2 Cyclobutyl 3 3 3 3

1aa ³⁸⁴ H SOsH H H SOsH H

1 aa ³⁸⁵ H SOsH H H H SOsH

1 aa ³⁸⁶ H H SOsH H SOsH H CONH2 Cyclopentyl 3 3 3 3

1aa ³⁸⁷ H SOsH H H SOsH H

1 aa ³⁸⁸ H SOsH H H H SOsH

1aa ³⁸⁹ H H SOsH H SOsH H CONH2 Cyclohexyl 3 3 3 3

1aa ³⁹⁰ H SOsH H H SOsH H

1aa ³⁹¹ H SOsH H H H SOsH

1aa ³⁹² H H SOsH H SOsH H 2-Methyl

CONH2 3 3 3 3 cyclohexyl

1aa ³⁹³ H SOsH H H SOsH H

1aa ³⁹⁴ H SOsH H H H SOsH

1aa ³⁹⁵ H H SOsH H SOsH H CONH2 3-Methyl 3 3 3 3 cyclohexyl

1aa ³⁹⁶ H SOsH H H SOsH H

_{1 aa} 397 H SOsH H H H SOsH CONH2 Isopropyl 3 3 3 3

1aa ⁴⁸¹ H SOsH H H H SOsH

1aa ⁴⁸² H H SOsH H SOsH H CN 3-lsopropoxy- 2 2 2 2 propyl

1aa ⁴⁸³ H SOsH H H SOsH H

1aa ⁴⁸⁴ H SOsH H H H SOsH

1aa ⁴⁸⁵ H H SOsH H SOsH H CN 3-Ethoxy propyl 2 2 2 2

1aa ⁴⁸⁶ H SOsH H H SOsH H

1aa ⁴⁸⁷ H SOsH H H H SOsH

1aa ⁴⁸⁸ H H SOsH H SOsH H CONH2 Ally I 2 2 2 2

1aa ⁴⁸⁹ H SOsH H H SOsH H

_{1 aa} 490 H SOsH H H H SOsH

1aa ⁴⁹¹ H H SOsH H SOsH H CONH2 2-Methoxy ethyl 2 2 2 2

1aa ⁴⁹² H SOsH H H SOsH H

1aa ⁴⁹³ H SOsH H H H SOsH

1aa ⁴⁹⁴ H H SOsH H SOsH H CONH2 3-Methoxy propyl 2 2 2 2

1aa ⁴⁹⁵ H SOsH H H SOsH H

1aa ⁴⁹⁶ H SOsH H H H SOsH

1aa ⁴⁹⁷ H H SOsH H SOsH H CONH2 2-Methyl thioethyl 2 2 2 2

1aa ⁴⁹⁸ H SOsH H H SOsH H

1aa ⁴⁹⁹ H SOsH H H H SOsH

1aa ⁵⁰⁰ H H SOsH H SOsH H CONH2 2-Hydroxyethyl 2 2 2 2

_{1 aa} 501 H SOsH H H SOsH H

1aa ⁵⁰² H SOsH H H H SOsH

1aa ⁵⁰³ H H SOsH H SOsH H CONH2 2-Fluoro ethyl 2 2 2 2

1aa ⁵⁰⁴ H SOsH H H SOsH H

1aa ⁵⁰⁵ H SOsH H H H SOsH

1aa ⁵⁰⁶ H H SOsH H SOsH H CONH2 2-Chloro ethyl 2 2 2 2

1aa ⁵⁰⁷ H SOsH H H SOsH H

1aa ⁵⁰⁸ H SOsH H H H SOsH

1aa ⁵⁰⁹ H H SOsH H SOsH H CONH2 3-Chloro propyl 2 2 2 2

_{1 aa} 510 H SOsH H H SOsH H

1aa ⁵¹¹ H SOsH H H H SOsH

1aa ⁵¹² H H SOsH H SOsH H CONH2 Tetrahydro 2 2 2 2 furfuryl

1aa ⁵¹³ H SOsH H H SOsH H

1aa ⁵¹⁴ H SOsH H H H SOsH

1aa ⁵¹⁵ H H SOsH H SOsH H CONH2 2-Furan-2-yl-ethyl 2 2 2 2

1aa ⁵¹⁶ H SOsH H H SOsH H

1aa ⁵¹⁷ H SOsH H H H SOsH

6-Hydroxy-1-[2-

1aa ⁵¹⁸ H H SOsH H SOsH H CONH2 (2-hydroxy-ethyl 2 2 2 2

1aa ⁵¹⁹ H SOsH H H SOsH H sulfanyl)-ethyl]

_{1 aa} 520 H SOsH H H H SOsH

2-(2-tert-Butyl

1aa ⁵²¹ H H SOsH H SOsH H CONH2 sulfanyl-ethane 2 2 2 2

1aa ⁵²² H SOsH H H SOsH H sulfonyl)-ethyl

1aa ⁵²³ H SOsH H H H SOsH

1aa ⁵²⁴ H H SOsH H SOsH H CONH ₂ 2-Hydroxy ethoxy 2 2 2 2 propyl

1aa ⁵²⁵ H SOsH H H SOsH H

1aa ⁵²⁶ H SOsH H H H SOsH

1aa ⁵²⁷ H H SOsH H SOsH H CONH2 2-Hydroxy 2 2 2 2 ethoxyethyl

1aa ⁵²⁸ H SOsH H H SOsH H

1aa ⁵²⁹ H SOsH H H H SOsH

2-

1aa ⁵³⁰ H H SOsH H SOsH H CONH2 (Ethylsulfonyl)eth 2 2 2 2

1aa ⁵³¹ H SOsH H H SOsH H anol

1aa ⁵³² H SOsH H H H SOsH

1 aa ⁵³³ H H SOsH H SOsH H CONH2 3-(2-Phenoxy- 2 2 2 2 ethoxy)-propyl

1aa ⁵³⁴ H SOsH H H SOsH H

1 aa ⁵³⁵ H SOsH H H H SOsH

1 aa ⁵³⁶ H H SOsH H SOsH H CONH2 3-lsopropoxy- 2 2 2 2 propyl

1aa ⁵³⁷ H SOsH H H SOsH H

1 aa ⁵³⁸ H SOsH H H H SOsH

1aa ⁵³⁹ H H SOsH H SOsH H CONH2 3-Ethoxy propyl 2 2 2 2

_{1 aa} 540 H SOsH H H SOsH H

1aa ⁵⁴¹ H SOsH H H H SOsH

1aa ⁵⁴² H H SOsH H SOsH H CN Ally I 3 4 3 4

_{1 aa} 543 H SOsH H H SOsH H

1aa ⁵⁴⁴ H SOsH H H H SOsH

1aa ⁵⁴⁵ H H SOsH H SOsH H CN 2-Methoxy ethyl 3 4 3 4

1aa ⁵⁴⁶ H SOsH H H SOsH H

1aa ⁵⁴⁷ H SOsH H H H SOsH

1aa ⁵⁴⁸ H H SOsH H SOsH H CN 3-Methoxy propyl 3 4 3 4

1aa ⁵⁴⁹ H SOsH H H SOsH H

1aa ⁵⁵⁰ H SOsH H H H SOsH

1aa ⁵⁵¹ H H SOsH H SOsH H CN 2-Methyl thioethyl 3 4 3 4

1aa ⁵⁵² H SOsH H H SOsH H

1 aa ⁵⁵³ H SOsH H H H SOsH

1aa ⁵⁵⁴ H H SOsH H SOsH H CN 2-Hydroxy ethyl 3 4 3 4

1 aa ⁵⁵⁵ H SOsH H H SOsH H

1 aa ⁵⁵⁶ H SOsH H H H SOsH

1aa ⁵⁵⁷ H H SOsH H SOsH H CN 2-Fluoro ethyl 3 4 3 4

1 aa ⁵⁵⁸ H SOsH H H SOsH H

1aa ⁵⁵⁹ H SOsH H H H SOsH

1aa ⁵⁶⁰ H H SOsH H SOsH H CN 2-Chloro ethyl 3 4 3 4

1aa ⁵⁶¹ H SOsH H H SOsH H

1aa ⁵⁶² H SOsH H H H SOsH

1 aa ⁵⁶³ H H SOsH H SOsH H CN 3-Chloro propyl 3 4 3 4

_{1 aa} 564 H SOsH H H SOsH H

1 aa ⁵⁶⁵ H SOsH H H H SOsH

1 aa ⁵⁶⁶ H H SOsH H SOsH H CN Tetrahydro 3 4 3 4 furfuryl

1aa ⁵⁶⁷ H SOsH H H SOsH H

1aa ⁵⁶⁸ H SOsH H H H SOsH

1aa ⁵⁶⁹ H H SOsH H SOsH H CN 2-Furan-2-yl-ethyl 3 4 3 4

_{1 aa} 570 H SOsH H H SOsH H

1aa ⁵⁷¹ H SOsH H H H SOsH 6-Hydroxy-1-[2-

1aa ⁵⁷² H H SOsH H SOsH H CN (2-hydroxy-ethyl 3 4 3 4 sulfanyl)-ethyl]

1aa ⁵⁷³ H SOsH H H SOsH H

1aa ⁵⁷⁴ H SOsH H H H SOsH

2-(2-tert-Butyl

1aa ⁵⁷⁵ H H SOsH H SOsH H CN sulfanyl-ethane 3 4 3 4

1aa ⁵⁷⁶ H SOsH H H SOsH H sulfonyl)-ethyl

1aa ⁵⁷⁷ H SOsH H H H SOsH

1aa ⁵⁷⁸ H H SOsH H SOsH H CN 2-Hydroxy ethoxy 3 4 3 4 propyl

1aa ⁵⁷⁹ H SOsH H H SOsH H

1aa ⁵⁸⁰ H SOsH H H H SOsH

1aa ⁵⁸¹ H H SOsH H SOsH H CN 2-Hydroxy 3 4 3 4 ethoxyethyl

1aa ⁵⁸² H SOsH H H SOsH H

1 aa ⁵⁸³ H SOsH H H H SOsH

1aa ⁵⁸⁴ H H SOsH H SOsH H CN 2-(Ethylsulfonyl)- 3 4 3 4 ethanol

1 aa ⁵⁸⁵ H SOsH H H SOsH H

1aa ⁵⁸⁶ H SOsH H H H SOsH

1aa ⁵⁸⁷ H H SOsH H SOsH H CN 3-(2-Phenoxy- 3 4 3 4 ethoxy)-propyl

1 aa ⁵⁸⁸ H SOsH H H SOsH H

1aa ⁵⁸⁹ H SOsH H H H SOsH

1aa ⁵⁹⁰ H H SOsH H SOsH H CN 3-lsopropoxy- 3 4 3 4 propyl

1aa ⁵⁹¹ H SOsH H H SOsH H

1aa ⁵⁹² H SOsH H H H SOsH

1aa ⁵⁹³ H H SOsH H SOsH H CN 3-Ethoxy-propyl 3 4 3 4

1aa ⁵⁹⁴ H SOsH H H SOsH H

1aa ⁵⁹⁵ H SOsH H H H SOsH

1aa ⁵⁹⁶ H H SOsH H SOsH H CONH2 Ally I 3 4 3 4

1aa ⁵⁹⁷ H SOsH H H SOsH H

1aa ⁵⁹⁸ H SOsH H H H SOsH

1aa ⁵⁹⁹ H H SOsH H SOsH H CONH2 2-Methoxy ethyl 3 4 3 4

1aa ⁶⁰⁰ H SOsH H H SOsH H

1aa ⁶⁰¹ H SOsH H H H SOsH

1aa ⁶⁰² H H SOsH H SOsH H CONH2 3-Methoxy propyl 3 4 3 4

1aa ⁶⁰³ H SOsH H H SOsH H

1aa ⁶⁰⁴ H SOsH H H H SOsH

1aa ⁶⁰⁵ H H SOsH H SOsH H CONH2 2-Methyl thioethyl 3 4 3 4

_{1 aa} 606 H SOsH H H SOsH H

1aa ⁶⁰⁷ H SOsH H H H SOsH

1aa ⁶⁰⁸ H H SOsH H SOsH H CONH2 2-Hydroxy ethyl 3 4 3 4

1aa ⁶⁰⁹ H SOsH H H SOsH H

_{1 aa} 610 H SOsH H H H SOsH

1aa ⁶¹¹ H H SOsH H SOsH H CONH2 2-Fluoro ethyl 3 4 3 4

1aa ⁶¹² H SOsH H H SOsH H

1aa ⁶¹³ H SOsH H H H SOsH

1aa ⁶¹⁴ H H SOsH H SOsH H CONH2 2-Chloro ethyl 3 4 3 4

1aa ⁶¹⁵ H SOsH H H SOsH H

1aa ⁶¹⁶ H SOsH H H H SOsH

1aa ⁶¹⁷ H H SOsH H SOsH H CONH2 3-Chloro propyl 3 4 3 4

1aa ⁶¹⁸ H SOsH H H SOsH H

1aa ⁶¹⁹ H SOsH H H H SOsH

_{1 aa} 620 H H SOsH H SOsH H CONH2 Tetrahydro 3 4 3 4 furfuryl

1aa ⁶²¹ H SOsH H H SOsH H

1aa ⁶²² H SOsH H H H SOsH

1aa ⁶²³ H H SOsH H SOsH H CONH2 2-Furan-2-yl-ethyl 3 4 3 4

1aa ⁶²⁴ H SOsH H H SOsH H

1aa ⁶²⁵ H SOsH H H H SOsH

6-Hydroxy-1-[2-

_{1 ag} 626 H H SOsH H SOsH H CONH2 (2-hydroxy-ethyl 3 4 3 4

1aa ⁶²⁷ H SOsH H H SOsH H sulfanyl)-ethyl]

1aa ⁶²⁸ H SOsH H H H SOsH

2-(2-tert-Butyl

1aa ⁶²⁹ H H SOsH H SOsH H CONH ₂ sulfanyl-ethane 3 4 3 4

1aa ⁶³⁰ H SOsH H H SOsH H sulfonyl)-ethyl

1 aa ⁶³¹ H SOsH H H H SOsH

2-Hydroxy ethoxy

1aa ⁶³² H H SOsH H SOsH H CONH2 3 4 3 4 propyl

1 aa ⁶³³ H SOsH H H SOsH H

1aa ⁶³⁴ H SOsH H H H SOsH

1 aa ⁶³⁵ H H SOsH H SOsH H CONH2 2-Hydroxy 3 4 3 4 ethoxyethyl

1 aa ⁶³⁶ H SOsH H H SOsH H

1aa ⁶³⁷ H SOsH H H H SOsH

1 aa ⁶³⁸ H H SOsH H SOsH H CONH2 2-(Ethylsulfonyl)- 3 4 3 4 ethanol

1aa ⁶³⁹ H SOsH H H SOsH H

_{1 aa} 640 H SOsH H H H SOsH

1aa ⁶⁴¹ H H SOsH H SOsH H CONH2 3-(2-Phenoxy- 3 4 3 4 ethoxy)-propyl

1aa ⁶⁴² H SOsH H H SOsH H

1aa ⁶⁴³ H SOsH H H H SOsH

1aa ⁶⁴⁴ H H SOsH H SOsH H CONH2 3-lsopropoxy- 3 4 3 4 propyl

1aa ⁶⁴⁵ H SOsH H H SOsH H

1aa ⁶⁴⁶ H SOsH H H H SOsH

1aa ⁶⁴⁷ H H SOsH H SOsH H CONH2 3-Ethoxy-propyl 3 4 3 4

_{1 aa} 648 H SOsH H H SOsH H

1aa ⁶⁴⁹ H SOsH H H H SOsH

1aa ⁶⁵⁰ H H SOsH H SOsH H CN Ally I 3 3 3 3

1aa ⁶⁵¹ H SOsH H H SOsH H

1aa ⁶⁵² H SOsH H H H SOsH

1 aa ⁶⁵³ H H SOsH H SOsH H CN 2-Methoxy ethyl 3 3 3 3

1aa ⁶⁵⁴ H SOsH H H SOsH H

1 aa ⁶⁵⁵ H SOsH H H H SOsH

1 aa ⁶⁵⁶ H H SOsH H SOsH H CN 3-Methoxy propyl 3 3 3 3

1aa ⁶⁵⁷ H SOsH H H SOsH H

1aa ⁶⁵⁸ H SOsH H H H SOsH

1aa ⁶⁵⁹ H H SOsH H SOsH H CN 2-Methyl thioethyl 3 3 3 3

1aa ⁶⁶⁰ H SOsH H H SOsH H

1aa ⁶⁶¹ H SOsH H H H SOsH

1aa ⁶⁶² H H SOsH H SOsH H CN 2-Hydroxy ethyl 3 3 3 3

1 aa ⁶⁶³ H SOsH H H SOsH H

1aa ⁶⁶⁴ H SOsH H H H SOsH

1 aa ⁶⁶⁵ H H SOsH H SOsH H CN 2-Fluoro ethyl 3 3 3 3

1 aa ⁶⁶⁶ H SOsH H H SOsH H

1aa ⁶⁶⁷ H SOsH H H H SOsH

1 aa ⁶⁶⁸ H H SOsH H SOsH H CN 2-Chloro ethyl 3 3 3 3

_{1 aa} 669 H SOsH H H SOsH H

_{1 aa} 670 H SOsH H H H SOsH

1aa ⁶⁷¹ H H SOsH H SOsH H CN 3-Chloro propyl 3 3 3 3

1aa ⁶⁷² H SOsH H H SOsH H

1aa ⁶⁷³ H SOsH H H H SOsH

1aa ⁶⁷⁴ H H SOsH H SOsH H CN Tetrahydro 3 3 3 3 furfuryl

1aa ⁶⁷⁵ H SOsH H H SOsH H

1aa ⁶⁷⁶ H SOsH H H H SOsH

1aa ⁶⁷⁷ H H SOsH H SOsH H CN 2-Furan-2-yl-ethyl 3 3 3 3

1aa ⁶⁷⁸ H SOsH H H SOsH H

1aa ⁶⁷⁹ H SOsH H H H SOsH

6-Hydroxy-1-[2-

1aa ⁶⁸⁰ H H SOsH H SOsH H CN (2-hydroxy-ethyl 3 3 3 3

1aa ⁶⁸¹ H SOsH H H SOsH H sulfanyl)-ethyl]

1aa ⁶⁸² H SOsH H H H SOsH

2-(2-tert-Butyl

1 aa ⁶⁸³ H H SOsH H SOsH H CN sulfanyl-ethane 3 3 3 3

1aa ⁶⁸⁴ H SOsH H H SOsH H sulfonyl)-ethyl

1aa ⁶⁸⁵ H SOsH H H H SOsH

1 aa ⁶⁸⁶ H H SOsH H SOsH H CN 2-Hydroxy ethoxy 3 3 3 3 propyl

1aa ⁶⁸⁷ H SOsH H H SOsH H

1 aa ⁶⁸⁸ H SOsH H H H SOsH

1aa ⁶⁸⁹ H H SOsH H SOsH H CN 2-Hydroxy 3 3 3 3 ethoxyethyl

_{1 aa} 690 H SOsH H H SOsH H

1 aa ⁶⁹¹ H SOsH H H H SOsH

1aa ⁶⁹² H H SOsH H SOsH H CN 2-(Ethylsulfonyl)- 3 3 3 3 ethanol

1aa ⁶⁹³ H SOsH H H SOsH H

1aa ⁶⁹⁴ H SOsH H H H SOsH

1aa ⁶⁹⁵ H H SOsH H SOsH H CN 3-(2-Phenoxy- 3 3 3 3 ethoxy)-propyl

1aa ⁶⁹⁶ H SOsH H H SOsH H

1aa ⁶⁹⁷ H SOsH H H H SOsH

1aa ⁶⁹⁸ H H SOsH H SOsH H CN 3-lsopropoxy- 3 3 3 3 propyl

1aa ⁶⁹⁹ H SOsH H H SOsH H

_{1 aa} 700 H SOsH H H H SOsH

1aa ⁷⁰¹ H H SOsH H SOsH H CN 3-Ethoxy propyl 3 3 3 3

1aa ⁷⁰² H SOsH H H SOsH H

1aa ⁷⁰³ H SOsH H H H SOsH

1aa ⁷⁰⁴ H H SOsH H SOsH H CONH2 Ally I 3 3 3 3

1aa ⁷⁰⁵ H SOsH H H SOsH H

1aa ⁷⁰⁶ H SOsH H H H SOsH

1aa ⁷⁰⁷ H H SOsH H SOsH H CONH2 2-Methoxy ethyl 3 3 3 3

1aa ⁷⁰⁸ H SOsH H H SOsH H

_{1 aa} 709 H SOsH H H H SOsH

1aa ⁷¹⁰ H H SOsH H SOsH H CONH2 3-Methoxy propyl 3 3 3 3

1aa ⁷¹¹ H SOsH H H SOsH H

1aa ⁷¹² H SOsH H H H SOsH

1aa ⁷¹³ H H SOsH H SOsH H CONH2 2-Methyl thioethyl 3 3 3 3

1aa ⁷¹⁴ H SOsH H H SOsH H

1aa ⁷¹⁵ H SOsH H H H SOsH

1aa ⁷¹⁶ H H SOsH H SOsH H CONH2 2-Hydroxy ethyl 3 3 3 3

1aa ⁷¹⁷ H SOsH H H SOsH H

1aa ⁷¹⁸ H SOsH H H H SOsH

1aa ⁷¹⁹ H H SOsH H SOsH H CONH2 2-Fluoro ethyl 3 3 3 3

1aa ⁷²⁰ H SOsH H H SOsH H

1aa ⁷²¹ H SOsH H H H SOsH

1aa ⁷²² H H SOsH H SOsH H CONH2 2-Chloro ethyl 3 3 3 3

1aa ⁷²³ H SOsH H H SOsH H

1aa ⁷²⁴ H SOsH H H H SOsH

1aa ⁷²⁵ H H SOsH H SOsH H CONH2 3-Chloro propyl 3 3 3 3

1aa ⁷²⁶ H SOsH H H SOsH H

1aa ⁷²⁷ H SOsH H H H SOsH

1aa ⁷²⁸ H H SOsH H SOsH H CONH2 Tetrahydro 3 3 3 3 furfuryl

1aa ⁷²⁹ H SOsH H H SOsH H

_{1 aa} 730 H SOsH H H H SOsH

1aa ⁷³¹ H H SOsH H SOsH H CONH2 2-Furan-2-yl ethyl 3 3 3 3

1aa ⁷³² H SOsH H H SOsH H

1aa ⁷³³ H SOsH H H H SOsH

6-Hydroxy-1-[2-

1aa ⁷³⁴ H H SOsH H SOsH H CONH2 (2-hydroxy-ethyl 3 3 3 3

1aa ⁷³⁵ H SOsH H H SOsH H sulfanyl)-ethyl]

1aa ⁷³⁶ H SOsH H H H SOsH

2-(2-tert-Butyl

1aa ⁷³⁷ H H SOsH H SOsH H CONH2 sulfanyl-ethane 3 3 3 3

1aa ⁷³⁸ H SOsH H H SOsH H sulfonyl)-ethyl

_{1 aa} 739 H SOsH H H H SOsH

1aa ⁷⁴⁰ H H SOsH H SOsH H CONH2 2-Hydroxy ethoxy 3 3 3 3 propyl

1aa ⁷⁴¹ H SOsH H H SOsH H

1aa ⁷⁴² H SOsH H H H SOsH

1aa ⁷⁴³ H H SOsH H SOsH H CONH2 2-Hydroxy 3 3 3 3 ethoxyethyl

1aa ⁷⁴⁴ H SOsH H H SOsH H

1aa ⁷⁴⁵ H SOsH H H H SOsH

1aa ⁷⁴⁶ H H SOsH H SOsH H CONH2 2-(Ethylsulfonyl)- 3 3 3 3 ethanol

1aa ⁷⁴⁷ H SOsH H H SOsH H

1aa ⁷⁴⁸ H SOsH H H H SOsH

1aa ⁷⁴⁹ H H SOsH H SOsH H CONH2 3-(2-Phenoxy- 3 3 3 3 ethoxy)-propyl

_{1 aa} 750 H SOsH H H SOsH H

1aa ⁷⁵¹ H SOsH H H H SOsH

1aa ⁷⁵² H H SOsH H SOsH H CONH2 3-lsopropoxy- 3 3 3 3 propyl

_{1 aa} 753 H SOsH H H SOsH H

1aa ⁷⁵⁴ H SOsH H H H SOsH

1aa ⁷⁵⁵ H H SOsH H SOsH H CONH2 3-Ethoxypropyl 3 3 3 3

_{1 aa} 756 H SOsH H H SOsH H

Further particularly preferred embodiments of the present invention are the dyes of formula (1 ab)

(1 ab) wherein X is O,

_R iab _{j R} 2ab _{j R} 3ab _j ρ>4 ₃ ^ _R 7ab _{a nd R} 8ab independent of each other is SO ₃ M, hydrogen, alkyl or alkoxy, whereby at least two of them are SO3M,

_R 9ab _{a nc} | _R i8ab independent of each other is cyano or carbamoyl,

_R 10ab _{a nd R} 19ab j _{s me} thyl , m, n, o and p independent of each other is an integer of 2, 3 or 4, p13ab p14ab p15ab p16ab p22ab p23ab p24ab p25ab p1 1ab p17ab p26ab _{g nc} | p20ab jg hydrogen,

R ^12ab and R ^21ab 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 -ethyl propyl, 1 ,2-dimethyl- propyl, tert-butyl, 3-methyl butyl, 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-hy- droxy-1 -[2-(2-hydroxyethylsulfanyl)-ethyl], 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(ethylsulfonyl)ethanol, 2-hydroxyethoxypropyl, 2-hydroxyethoxyethyl, 2-(ethyl sulfo- nyl)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 formula (1 ab) are the compounds of the formulae (1 ab ¹ to 1 ab ⁷⁵⁶ ), wherein R ^2ab and R ^5ab is hydrogen:

DYS2012/S00

1ab ¹⁰⁴ H H SOsH H SOsH H cyclohexyl

_{1 ab} 105 H SOsH H H SOsH H

_1ab ioe H SO3H H H H SOsH

1ab ¹⁰⁷ H H SOsH H SOsH H CONH2 3-Methyl 2 2 2 2 cyclohexyl

_{1 ab} 108 H SOsH H H SOsH H

_{1 ab} 109 H SOsH H H H SOsH

1ab ¹¹⁰ H H SOsH H SOsH H CONH2 Isopropyl 2 2 2 2

1ab ¹¹¹ H SOsH H H SOsH H

1ab ¹¹² H SOsH H H H SOsH

1ab ¹¹³ H H SOsH H SOsH H CONH2 Sec-butyl 2 2 2 2

1ab ¹¹⁴ H SOsH H H SOsH H

1ab ¹¹⁵ H SOsH H H H SOsH

1ab ¹¹⁶ H H SOsH H SOsH H CONH2 2-Methyl butyl 2 2 2 2

1ab ¹¹⁷ H SOsH H H SOsH H

1ab ¹¹⁸ H SOsH H H H SOsH

1ab ¹¹⁹ H H SOsH H SOsH H CONH2 1 -Ethyl propyl 2 2 2 2

1ab ¹²⁰ H SOsH H H SOsH H

1ab ¹²¹ H SOsH H H H SOsH

1ab ¹²² H H SOsH H SOsH H CONH2 1 ,2-Dimethyl 2 2 2 2 propyl

1ab ¹²³ H SOsH H H SOsH H

1ab ¹²⁴ H SOsH H H H SOsH CONH2 Tert-butyl 2 2 2 2

The present invention also provides a process for the production of the dyes of formula (1 ) comprising steps:

a) diazotization of a compound of formula (2)

wherein R ¹ to R ⁸ are defined as above and

b) reacting the diazonium salt obtained in step a) with the compounds of formulae (3), (4), (5) and (6)

wherein R ⁹ to R ²⁶ are as defined above.

The diazotization of the compound of the 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 be used advantageously. 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 DE 140613 C.

The pyridines of formula (3), (4), (5) and (6) in which R ⁹ and R ¹⁸ represent cyano are commercially available or can be synthesized via methods disclosed in the literature such as DE 2230392. Through analogy, all the diamino pyridines that are used in this invention can be synthesized according to the protocol. The obtained pyridines can be further derivatized by reactions known to persons skilled in the art, such as hydrolysis to form pyridines in which R ⁹ and R ¹⁸ , represent carbonamide or by hydrolysis and further esterification to form pyridines in which R ⁹ and R ¹⁸ , represent alkoxycarbonyl.

The above-mentioned derivatization reactions can be carried out in alkaline or acidic media, preferably in acidic media using strong inorganic acids such as sulfuric acid or hydrochloric acid gaseous or solution, acidic resins or chlorotrimethylsilane or other suitable acid catalyst in the presence of the corresponding alkohol. The reactions are advantageously carried out under inert atmosphere at temperatures in the range from 40 to 150 °C. Alternatively, the above mentioned derivatization reactions can be undertaken as a final step after the synthesis of the corresponding dyes with pyridone nitriles.

The dyes of the present invention are suitable for dyeing and printing of natural, manufactured, regenerated, modified or synthetic hydroxyl- amino-, and/or carbox- amido-containing fiber materials and their blends by the application methods numerously described in the art for acid dyes.

Therefore, the present invention also provides a process for dyeing and printing of the above-mentioned fiber materials and their blends in which a dye or a dye mixture according to the present invention is used.

Examples of natural fibre materials as described above are vegetable fibres such as seed fibres i.e. cotton, kapok, coir from coconut husk; bast fibers i.e. cotton, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres i.e. sisal, henequen, banana; stalk fibres i.e. bamboo; and fibres from animals such as wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials.

Examples of manufactured and regenerated fibres are cellulosic fibres such as paper and cellulosic regenerated fibres such as viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers.

Examples of synthetic fiber materials as described above are e.g. nylon materials, like nylon-6 and nylon-6.6 and aramid fibres.

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.

The dyes of the present invention and their salts or mixtures can be used as a single dyeing colorant in dyeing or printing processes or it 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 this 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 of the present invention can also be used in digital printing processes, in particular in digital textile printing. Aqueous inks for digital printing which comprise a dye of the present invention likewise are another aspect of the present invention. The inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 to 50 % by weight, more preferably from 0.5 to 30 % by weight and most preferably from 1 to 15 % by weight, based on the total weight of the ink.

The inks, as well as the dye of the present invention, may contain further dyes used in digital printing if desired.

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 % and preferably 5 to 30 % by weight. Suitable organic solvents are inter alia 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, urea deriva- tives, such as: thiourea, N-methylurea, Ν,Ν'-epsilon dimethylurea, ethyleneurea, 1 ,1 ,3,3-tetramethylurea, amides, such as for example: dimethylformamide, dimethylacetamide, acetamide, ketones or keto alcohols, such as for example: acetone, diacetone alcohol, cyclic ethers, such as for example: tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxy- ethanol, gamma butyrolactone, epsilon-caprolactam, further sulfolane, dimethylsulfo- lane, 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-hydroxy- propyl)-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 galacto- mannans, 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 mlM/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 and 1 ,2-hexanediol.

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

The inks may be prepared in a conventional manner by mixing the components in water.

The inks of the present invention are particularly useful in inkjet printing processes for printing a wide variety of materials, in particular of wool and polyamide fibers.

The production and dyeing 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.

Production-Example 1 12.06 g of 3-Amino-6-[3-(4-amino-2-sulfo-phenyl)-ureido]-benzene-1 ,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 the temperature reached 10 to 15 °C, 10.6 ml of 5N sodium nitrite solution were added dropwise into the 3-Amino-6-[3-(4-amino-2-sulfo- phenyl)-ureido]-benzene-1 ,2-disulfonic acid solution. The reaction mixture was further cooled down to 0 to 8 °C using an ice-salt-water bath. When the temperature reached 0 to 8 °C, the mixture was added dropwise into 12.38 g of concentrated HCI with 12 g of ice. A yellow suspension formed and reaction mixture was completed within an hour. 13.21 g of a mixture containing 2-Amino-6-[3-(4-hydroxy-butoxy)-propylamino]-4- methyl-nicotinonitrile, 6-Amino-2-[3-(4-hydroxy-butoxy)-propylamino]-4-methyl-nico- tinonitrile, 2-Amino-6-[2-(2-hydroxy-ethoxy)-ethylamino]-4-methyl-nicotin onitrile and 6-Amino-2-[2-(2-hydroxy-ethoxy)-ethylamino]-4-methyl-nicotin onitrile) was stirred in acidic water and added dropwise into the diazonium salt solution and stir. 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 1 aa ¹⁵⁴ , 1 ab ¹⁵⁴ , 1 aa ² and 1 ab ² . The analytic data are consistent with the assigned structure for the obtained product. The obtained product dyes the targeted fibre materials in brilliant yellow shades. Through analogy, all the dyes of formulae (1 aa ¹ -1 aa ⁷⁵⁶ ) and (1 ab ¹ -1 ab ⁷⁵⁶ ) can be synthesized according to the method described above. Dyeing example 1

1 part of the yellow product of Production-Example 1 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 was added. The pH was then adjusted to 5 using acetic acid (80 %). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98 °C over the course of 50 minutes and 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 yellow product of Production-Example 1 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 consisted of 40 parts of the yellow product of Production-Example 1 , 100 parts of urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 815 parts of water. The material was rolled up and placed into a steaming chamber at 85 to 98 °C for 3 to 6 hours. After fixation, the fabric was washed with hot and cold water, soaped and then spun and dried. The 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 yellow product of Production-Example 1 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 yellow product of Production-Example 1 was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate, and 1 part of a wetting agent (anionic) were added. 100 parts of bleached cotton knitted fabric were added to this solution. The dye bath was then heated up to 98 °C with a gradient of 2 °C/min then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling down to 80 °C. At 80 °C the dyeing was continued for another 20 minutes. The dyed material was then removed and was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained 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 yellow product of Production-Example 1 were dissolved in 82 parts of deionized water and 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 yellow product of Production-Example 1 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.