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AU2013279553A1 - Metal-free reactive dyes, process for the production thereof and their use - Google Patents

Metal-free reactive dyes, process for the production thereof and their use Download PDF

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Publication number
AU2013279553A1
AU2013279553A1 AU2013279553A AU2013279553A AU2013279553A1 AU 2013279553 A1 AU2013279553 A1 AU 2013279553A1 AU 2013279553 A AU2013279553 A AU 2013279553A AU 2013279553 A AU2013279553 A AU 2013279553A AU 2013279553 A1 AU2013279553 A1 AU 2013279553A1
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AU
Australia
Prior art keywords
amino
carbamoyl
sulfamoyl
monocycloalkyl
monoalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
AU2013279553A
Inventor
Roxana Barbieru
Hyeong Kyu Kim
Xiao Tien WONG
Han YUAN
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Dystar Colours Distribution GmbH
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Dystar Colours Distribution GmbH
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Publication date
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Publication of AU2013279553A1 publication Critical patent/AU2013279553A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
    • C09B62/006—Azodyes
    • C09B62/0061—Azodyes with coupling components containing an amino directing group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
    • C09B62/006—Azodyes
    • C09B62/0062—Azodyes with coupling components containing a hydroxyl directing group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
    • C09B62/006—Azodyes
    • C09B62/0064—Azodyes with coupling components containing both hydroxyl and amino groups as directing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/08—Azo dyes
    • C09B62/09—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4411—Azo dyes
    • C09B62/4415—Disazo or polyazo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/14—Wool
    • D06P3/148—Wool using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/248—Polyamides; Polyurethanes using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Metal-free reactive dyes, process for the production thereof and their use The present invention relates to reactive dyes of the formula (I), in which A, B, a and K are defined as given in claim, a process for preparing them, and their use for dyeing and printing hydroxyl-, amino-, and/or carboxamido-containing materials.

Description

WO 2013/189814 PCT/EP2013/062198 Metal-free reactive dyes, process for the production thereof and their use The present invention relates to the technical field of reactive dyestuffs for dyeing and 5 printing of hydroxyl-, amino-, and/or carboxamido-containing material. Metal free reactive dyes are known from prior art and can be used as colorants in different applications, see for example US 20030172476. 0 However, in the context of the dyeing and printing of hydroxyl-, amino- and/or carboxamido-containing material the known dyes that are metal free have a number of technical disadvantages such as unsatisfactory light fastness and especially limitations in achieving darker shades such as dark violet, dark brown, navy and black shades of very good overall fastness level. 5 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 build-up to darker shades with high fastness properties such as light fastness, wash and contact fastness on the materials mentioned above and on blends containing 20 them. Most importantly, dyes of formula (1) are metal free and thus superior in ecological performance and provide dyeings that are of very good levelness. The present invention refers to dyes of the formula (1) and mixtures thereof A,N 1n K N$B N N OH N N a MO S 03 g03 M (1) 25 wherein, WO 2013/189814 PCT/EP2013/062198 2 A is a radical of diazo component as described below; and B is a radical of middle component as described below; and K is a radical of coupling component as described below; and a is an integer of 0 or 1; and 5 with the general proviso that dyes of general formula (1) contain at least one reactive anchor; and this invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I), 10 A is a radical of general formula (1a) R1 R3 R2 (1a) wherein, each of R 1 to R 3 , independent of each other is hydrogen, halogen, alkyl, N 15 acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N 20 triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylammo nium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 25 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- WO 2013/189814 PCT/EP2013/062198 3 monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 5 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or is a group of general formula (2a), (2b) or (2c) RW N, R1
R
4 Rn R11 N'RG N N'R R12N\ bN C1 -c\2 RGd R5 R6 RO (2a) (2b) (2c) 10 wherein, each of R 4 and R 7, independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, 15 heterocycloalkyl, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, 20 heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, 25 COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and WO 2013/189814 PCT/EP2013/062198 4 each of R , R , R 8 and R , independent of each other is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of 5 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 10 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and 15 each of R 9 to R", independent of each other is hydrogen, halogen, alkyl, alkoxy or
SO
3 M; and b is an integer of 0 to 6; and 20 c is an integer of 1 to 6; and when each of b and c, independent of each other is > 2, R 4 and R 7 can have different meanings within the same rest as per meaning defined above; and 25 d isOorl; and RG is a reactive anchor of general formula (3a), (3b) or (3c); WO 2013/189814 PCT/EP2013/062198 5 R14 R17 R19 N N N N N N R13 R16 R18
R
15 (3a) (3b) (3c) wherein, 5 each of R 14 to R 1 9, independent of each other is halogen; and R14 can additionally be a rest of formula (8a) 0 + 0 N * (8a) 10 wherein,
R
96 is hydrogen, halogen, alkyl, alkoxy, thioalkoxy, hydroxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO 3 M or COOM; or 15 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or 20 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3
M,
WO 2013/189814 PCT/EP2013/062198 6 COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and
R
13 is one of the groups selected from general formula (4a) or (4b); 5 20 21 R 2023 R 2 R *-N 94 *-N R \< 95 R22R (4a) (4b) wherein, 10 each of R 20 , R 23 and R4, independent of each other is hydrogen, alkyl, cycloalkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, 15 COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of 20 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R , R 2 and R , independent of each other is hydrogen, halogen, alkyl, N 25 acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, sulfamoyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, S0 3 M or COOM; or WO 2013/189814 PCT/EP2013/062198 7 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or 5 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, 10 heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and R94 can additionally be -CH 2
CH
2
-SO
2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y where Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M,
OCOCH
3 , OPO 3 M or halogen; and 15 R95 can additionally be -S0 2 -X where X is the same as defined above. B is a radical of general formula (5a) * (5a) 20 wherein, each of R 24 to R 2 6 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, 25 alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or WO 2013/189814 PCT/EP2013/062198 8 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, 5 COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of 10 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 15 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or is a group of general formula (2a) or (2b) R4 R7 N NRG -RG -b l I - -C 1
R
5 R6 R 8 20(2a) (2b) where R 4 to R 8 , b, c and RG are the same as defined above, K is a radical of general formula (6a) or (6b) WO 2013/189814 PCT/EP2013/062198 9 31 30 N R29 DN OH 74 n1 R N R27L R2 |' 7 3
MO
3 S (6a) (6b) wherein, 5 D is a radical of general formula (1a) as defined above; and each of R 27 to R 29 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, ureido, alkylureido, phenylureido, sulfamoyl, acyl, thioacyl, 10 aryloyl, trifluoromethyl, acyloxy, aryloyloxy, carbamoyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N 15 triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N 20 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-monoarylsulfamoy or N 25 monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of WO 2013/189814 PCT/EP2013/062198 10 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkyl ammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, 5 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 10 monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; and each of R 3 , R , R'h and R4, independent of each other is hydrogen, alkyl, acyl, 15 thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is 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 20 monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, 25 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 30 monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or WO 2013/189814 PCT/EP2013/062198 11 is alkyl interrupted by one or more heteroatoms such as oxygen or 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 5 monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkyl ammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, 10 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 15 monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or 20 is a rest of the general formula (7a) RG, N - * R (7a) 25 wherein, RG is the same as defined above; and WO 2013/189814 PCT/EP2013/062198 12
R
32 is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, S0 3 M or COOM; or 5 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or 10 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and 15 R33 is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, 20 COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of 25 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and e is an integer of 1 to 6; and when e is > 2, R 32 can have different meanings within 30 the same rest, as per meaning defined above. Alkyl groups appearing in this application may be straight-chain or branched and are
(C
1
-C
1 2 )-alkyl groups, preferably (C 1
-C
8 )-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.
WO 2013/189814 PCT/EP2013/062198 13 The same logic applies to alkoxy groups which accordingly are preferably (C1-C8) alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably
(C
1
-C
8 )-thioalkoxy, for example -SCH 3 or -SC 2
H
5 . 5 Cycloalkyl groups are preferably (C 3
-C
8 )-cycloalkyl and especially preferably cyclopentyl and cyclohexyl. The term cycloalkyl comprises for the purpose of the present application substituted cycloalklyl groups and unsatured cycloalkyl groups as well. A preferred group of this type is cyclopentenyl. Preferred substituents are alkyl, 10 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. 15 Aryl groups appearing in this application are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl 20 mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonyl amino, alkoxycarbonyl or acyloxy. Heteroaryl groups appearing in this application are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1,2,4-thiadiazole, 1,2,4-triazole, 25 tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1,3,4 thiadiazole, furane, oxazole, benzoxazole or isoxazole. The term 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 30 (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy. Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine. The terms heterocycloalkyl comprises the above WO 2013/189814 PCT/EP2013/062198 14 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 5 carbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy. Halogen is preferably chlorine, bromine or fluorine. M is preferably hydrogen, lithium, sodium, potassium, ammonium or mono-, di-, tri- or 10 tetra-(C-C 4 )-alkylammonium, one equivalent of an alkali earth metal, or a monovalent organic cation. Particular preferred embodiments of the present invention are dyes of the formula (la) and mixtures thereof 38 37 R sN-R RaeK Ras SOaM SN OH N N R34 MO 3S 3o S 3M 15 (Ia) wherein, each of R34 to R 36 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, 20 alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or WO 2013/189814 PCT/EP2013/062198 15 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, 5 halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 10 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 15 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or 20 is a group of general formula (2a), (2b) or (2c) as defined above; and each of R3 and R 38 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or 25 is 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-N-monocycloalkyl 30 amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, WO 2013/189814 PCT/EP2013/062198 16 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 5 monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 10 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-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N 15 triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N 20 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-monoarylsulfamoy or N 25 monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. 30 In especially preferred dyes of general formual (Ia), each of R34 to R 36 , independent of each other is hydrogen, (C 1
-C
4 )alkyl, (C1
C
4 )alkoxy, halogen, acyl or SO 3 M; or WO 2013/189814 PCT/EP2013/062198 17 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M; or 5 is -NH-RG, where RG is the same as defined above; or is -(CH 2 )f-NH-RG, where f is an integer of 1 to 3 and RG is the same as defined above; and 10 each of R3 and R 38 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or 15 is -(CH 2 )g-NH-RG, where g is an integer of 1 to 3 and RG is the same as defined above. Further preferred embodiments of this invention are dyes of general formula (Ib) and mixtures thereof 20 46 45 R41 N R40 R44 N M N OH N
R
39
R
4 3 ,
R
42
MO
3 S so 3 M (Ib) wherein, WO 2013/189814 PCT/EP2013/062198 18 each of R39 to R44, independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, 5 cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, S0 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 10 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 15 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, 20 halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under 25 alkaline conditions such as OS0 3 M, SS0 3 M, OCOCH 3 , OP0 3 M or halogen; or is a group of general formula (2a) or (2b) as defined above;and each of R3 to R 4 , independent of each other can additionally be a group of general 30 formula (2c) as defined above; and each of R45 and R 46 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or WO 2013/189814 PCT/EP2013/062198 19 is 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-N-monocycloalkyl 5 amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 10 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 15 sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of 20 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-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 25 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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 30 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-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or WO 2013/189814 PCT/EP2013/062198 20 is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. 5 In especially preferred dyes of general formual (Ib), each of R39 to R44, independent of each other is hydrogen, (C 1
-C
4 )alkyl, (C1
C
4 )alkoxy, halogen, acyl or SO 3 M; or 10 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M; or is -NH-RG, where RG is the same as defined above; or 15 is -(CH 2 )h-NH-RG, where h is an integer of 1 to 3 and RG is the same as defined above; and each of R45 and R 46 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, 20 acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )i-NH-RG, where i is an integer of 1 to 3 and RG is the same as defined 25 above. Further preferred embodiments of this invention are dyes of general formula (Ic) and mixtures thereof WO 2013/189814 PCT/EP2013/062198 21 R51 5 0 N
MO
3 S j R48 -4 HO N SO 3 M N OH N N R47
MO
3 S
S
3 M (Ic) wherein, 5 j isOorl;and each of R47 to R 49 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, 10 cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 15 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 20 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N- WO 2013/189814 PCT/EP2013/062198 22 triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, 5 acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or 10 is a group of general formula (2a), (2b) or (2c) as defined above; and each of R" and R , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or 15 is 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-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N 20 triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N 25 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-monoarylsulfamoy or N 30 monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or 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- WO 2013/189814 PCT/EP2013/062198 23 amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 5 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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 10 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-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or 15 is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. 20 In especially preferred dyes of general formual (Ic), each of R47 to R 49 , independent of each other is hydrogen, (C 1
-C
4 )alkyl, (C1
C
4 )alkoxy, halogen, acyl or SO 3 M; or 25 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M; or is -NH-RG, where RG is the same as defined above; or 30 is -(CH 2 )k-NH-RG, where k is an integer of 1 to 3 and RG is the same as defined above; and each of R 50 and R 51 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or WO 2013/189814 PCT/EP2013/062198 24 is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )m-NH-RG, where m is an integer of 1 to 3 and RG is the same as defined 5 above. Further preferred embodiments of this invention are dyes of general formula (Id) and mixtures thereof: 59 58 R N-R N
R
54 Mo 3 S 3n
R
53 R 5 7 N' HO
SO
3 M -N '' :' . N OH N'
R
52
R
56 l , N
R
55
MO
3 S 3 M 10 (Id) wherein, n is Oor 1; and 15 each of R 52 to R 57 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or 20 WO 2013/189814 PCT/EP2013/062198 25 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, 5 halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 10 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 15 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or 20 is a group of general formula (2a) or (2b) as defined above; and each of R 52 to R4, independent of each other can additionally be a group of general formula (2c) as defined above; and 25 each of R 58 and R , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of 30 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-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- WO 2013/189814 PCT/EP2013/062198 26 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N 5 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-monoarylsulfamoy or N 10 monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or 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 15 amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, 20 ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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, 25 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-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or 30 is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. In especially preferred dyes of general formual (Id), WO 2013/189814 PCT/EP2013/062198 27 each of R 52 to R 57 , independent of each other is hydrogen, (C 1
-C
4 )alky, (C1
C
4 )alkoxyl, halogen, acyl or SO 3 M; or 5 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M; or is -NH-RG, where RG is the same as defined above; or 10 is -(CH 2 )p-NH-RG, where p is an integer of 1 to 3 and RG is the same as defined above; and each of R 58 and R , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or 15 is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )q-NH-RG, where q is an integer of 1 to 3 and RG is the same as defined above. 20 Further preferred embodiments of this invention are dyes of general formula (le) and mixtures thereof: OH R64 R61, R6N Re63
MO
3 S N OH N N R60 M MO S SO 3 3 03s M (le) WO 2013/189814 PCT/EP2013/062198 28 wherein, each of R 60 , R 1 and R 2 , independent of each other is hydrogen, halogen, alkyl, N 5 acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, S0 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of 10 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, 15 acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N 20 triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 25 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OS0 3 M, SS0 3 M, OCOCH 3 , OP0 3 M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and 30 each of R 63 and R 64 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or WO 2013/189814 PCT/EP2013/062198 29 is 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-N-monocycloalkyl 5 amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 10 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 15 sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of 20 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-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 25 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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 30 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-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or WO 2013/189814 PCT/EP2013/062198 30 is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. 5 In especially preferred dyes of general formual (le), each of R 60 to R 62 , independent of each other is hydrogen, (C 1
-C
4 )alkyl, (C1
C
4 )alkoxy, halogen, acyl or SO 3 M; or 10 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M; or is -NH-RG, where RG is the same as defined above; or 15 is -(CH 2 )r-NH-RG, where r is an integer of 1 to 3 and RG is the same as defined above; and each of R 63 and R 64 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, 20 acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )s-NH-RG, where s is an integer of 1 to 3 and RG is the same as defined 25 above. Further preferred embodiments of this invention are dyes of general formula (If) and mixtures thereof: WO 2013/189814 PCT/EP2013/062198 31 R67 OH R72 R66 |R70 |I R 71 R N MO 3 S N N OH N
R
65
R
69
R
68 MO 3 S (If) wherein, 5 each of R 65 to R 70 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or 10 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 15 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of 20 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, WO 2013/189814 PCT/EP2013/062198 32 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under 5 alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or is a group of general formula (2a) or (2b) as defined above;and each of R 65 to R 67 , independent of each other can additionally be a group of general 10 formula (2c) as defined above; and each of R 71 and R 2 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or 15 is 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-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N 20 triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N 25 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-monoarylsulfamoy or N 30 monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or 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- WO 2013/189814 PCT/EP2013/062198 33 amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 5 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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 10 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-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or 15 is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. 20 In especially preferred dyes of general formual (If), each of R 65 to R 70 , independent of each other is hydrogen, (C 1
-C
4 )alkyl, (C1
C
4 )alkoxy, halogen, acyl or SO 3 M; or 25 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M; or is -NH-RG, where RG is the same as defined above; or 30 is -(CH 2 )t-NH-RG, where t is an integer of 1 to 3 and RG is the same as defined above; and each of R 71 and R 2 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or WO 2013/189814 PCT/EP2013/062198 34 is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )u-NH-RG, where u is an integer of 1 to 3 and RG is the same as defined 5 above. Further preferred embodiments of this invention are dyes of general formula (Ig) and mixtures thereof: R79 R78, N OH I82 R N R76, R7N R 8
MO
3 SR N OH N 11 N R75 MO SS 3 SO3 M 10 (Ig) wherein, each of R 7 to R 80 independent of each other is hydrogen, halogen, alkyl, N 15 acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of 20 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- WO 2013/189814 PCT/EP2013/062198 35 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 5 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 10 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 15 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and 20 each of R 1 and R 2 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is 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 25 amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, 30 ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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, WO 2013/189814 PCT/EP2013/062198 36 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-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or 5 is alkyl interrupted by one or more heteroatoms such as oxygen or 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 10 monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, 15 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 20 monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or 25 is a rest of the general formula (7a) as defined above. In especially preferred dyes of general formual (Ig), 30 each of R 7 to R 8 0, independent of each other is hydrogen, (C 1
-C
4 )alkyl, (C1
C
4 )alkoxy, halogen, acyl or SO 3 M; or is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M; or WO 2013/189814 PCT/EP2013/062198 37 is -NH-RG, where RG is the same as defined above; or is -(CH 2 )v-NH-RG, where v is an integer of 1 to 3 and RG is the same as defined 5 above; and each of R 1 and R 2 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or 10 is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )w-NH-RG, where w is an integer of 1 to 3 and RG is the same as defined above. 15 Further preferred embodiments of this invention are dyes of general formula (Ih) and mixtures thereof: R89 R90 R91, R85 N OH 11 93 N ~R R84 | R88 | N-9 N 92 MO S R N N OH NN
R
83
R
87 N N
MO
3 S S0 3 M (Ih) 20 wherein, WO 2013/189814 PCT/EP2013/062198 38 each of R 83 to R 9 1 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, S0 3 M or COOM; or 5 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, 10 halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 15 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 20 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OS0 3 M, SS0 3 M, OCOCH 3 , OP0 3 M or halogen; or 25 is a group of general formula (2a) or (2b) as defined above;and each of R 83 , R 8 4 , R 85 , R 89 , R 90 and R91, independent of each other can additionally be a group of general formula (2c) as defined above; and 30 each of R 92 and R 3 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or WO 2013/189814 PCT/EP2013/062198 39 is 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-N-monocycloalkyl 5 amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 10 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 15 sulfamoyl, N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of 20 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-N-monocycloalkyl-amino, N monoaryl-N-monocycloalkyl-amino, N,N,N-trialkylammonium, N,N,N-triarylammoni um, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acyl 25 amino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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 30 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-monoarylsulfamoy or N monoalkyl-N-monoarylsulfamoyl; or WO 2013/189814 PCT/EP2013/062198 40 is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. 5 In especially preferred dyes of general formual (Ih), each of R 83 to R91, independent of each other is hydrogen, (C 1
-C
4 )alkyl, (C1
C
4 )alkoxy, halogen, acyl or SO 3 M; or 10 is S0 2 -X, where X is vinyl or a radical -CH 2
CH
2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M; or is -NH-RG, where RG is the same as defined above; or 15 is -(CH 2 )x-NH-RG, where x is an integer of 1 to 3 and RG is the same as defined above; and each of R 92 and R 3 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, 20 acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )y-NH-RG, where y is an integer of 1 to 3 and RG is the same as defined 25 above. Examples of preferred dyes of the formulae (Ia) to (1h) are the compounds 11 to 1140 listed in the table 1 below and having the general formula (I'). 30 WO 2013/189814 PCT/EP2013/062198 41 A, N N OH N,
M
3 S SoM 03(3 ) WO 2013/189814 PCT/EP2013/062198 42 CV) (Y)(Y 0 0 0 U) Cl) Cl) LL-\z L- z _L z U- ZU Z U- Z 00 \o4I\O o 0 0 U) U) U) CY) (Y) (Y o 0 0 0-
)
0 o -0 ~ 0 0 0 0C) 00r 0 0-) 0 0 3E 0u U WO 2013/189814 PCT/EP2013/062198 43 60 0 60 U) l) Ul) z z z ZI: ZI: ZI: 0
()
o 0 0 U) U) U) CY)) CY) o 0 0 I: I:I 0 0)I 00 aU0 0Y 0- 0 U 0( WO 2013/189814 PCT/EP2013/062198 44 Cl) U) Ul) zI z T-z o 0 0 U) U) Ul) o 0 0 r T-c 0 0 Cl) 0 >00O=)= 00 0 0I- 0 0 0 0 w 0 0 0 N-2 WO 2013/189814 PCT/EP2013/062198 45 0 0 0 U) C) Cl) U- ZU Z U- Z LL- z LL-\z LL\z ZI ZI ZI o o 0 U) U) U) co) co c o 0 0 o - 0x~ 0OU) o 0 00) 0 0 0 0 0 0 0 WO 2013/189814 PCT/EP2013/062198 46 0 0 0 U) U) Ul) z z z o 0 0 )U) U) 000 0 0 0 C) o0 o ()O 0=(/) 0 d U 0 0 0 oz) 0I 0 C~~0 WO 2013/189814 PCT/EP2013/062198 47 60 0 60 U) U) U i
I
U-- Z UL- Z UL Z Z= Z ZI o 0 0 U) U) U) 60 60 0 :> 0 U)7) co 0 00 0 0 O'iUi)zzO I) I ? 0 (0 N0 WO 2013/189814 PCT/EP2013/062198 48 U() &) U Z Z- Z LL-(s Z L-s Z L-s Z z o z 0 O\ z z 0 o0 o0 0 0C 0 0 0 0 000 0C0OCZ o to O=o0 o o o 6 0~' 0 CN C WO 2013/189814 PCT/EP2013/062198 49 0 00 Iz I - ar -Zr L-Z LL< zL-< Co Co - Co C Z- Co C) Z -I 1 0 ' Z \ I 0 11 /0 0 / 0 0 00 0C~ 00 0 0=UC=0 0
=U=C/X'
0 o 6I cc 0I r
T)
WO 2013/189814 PCT/EP2013/062198 50 0 0 0 (I) CO) CO) LJA \/Z Mi LL-\/Z iLL-(/Z z- o co &- 0 ) Z- 0 Z-\- 0 110 0 0 0 0 0 / 0 0> 070 co OP C/C/) 00 00 0 00 0 I 0 (0 N- WO 2013/189814 PCT/EP2013/062198 51 Cl) C) 0z 0 - Z 0L Z 0L< Z Cl) \ Cl) / )-\ Cl) / C/)\- ) 10 0 0"110 0 0 o- _0o Qzzc/)z 0=(/)0-- 0(/)0 o 0 0 o0 0 I I I 00 CF 0 C L C LC2.- WO 2013/189814 PCT/EP2013/062198 52 0 0 0 z 60z 0z 6 I 0 11 0 11 0 0 0 0 0 0 0z0)O 0 0 0 O~CoO Oc0O 62-C.
WO 2013/189814 PCT/EP2013/062198 53 0l 0 0l Z- z Z LL-(z Z LL-(\ Z 0LL-( Z Z- 0 CY Z- 0 Y Z- Y Z O Z-\ O Z-\ O z 1'-0 z1 0 z1 0 00 00 00 000 O 0 o) U )I-co~~ o) _ -/ 6 O=)= rO 00 04' 0 0 0 o oO 0O 0 2 o2 o WO 2013/189814 PCT/EP2013/062198 54 0 0 0 (I) Cl) CO) Z-- -- *- ZL- C Z z ~ z LL LL LL .2 o-o o O =O o o o o o oon o 0 0 Ozco-O O=C/):O OU o0 0 C2.- C2.- C2.
WO 2013/189814 PCT/EP2013/062198 55 0 0 CO) C) Cl) z ~z LL-\/CO IL /0C LL-\/C) z z z
CUD
0 0 C/) )= _=/=OU 0 0 0 0 l WO 2013/189814 PCT/EP2013/062198 56 0 00 Cl) CO) CO) IL C) LL-(\/CO LL-( / C z- z /z 0 C) -~ 0 _-) 0\ 00 a-0U -0 0 C)O0 00 0 Ir I O WO 2013/189814 PCT/EP2013/062198 57 0 0 0' Cl) CO) U) ZL- _-- ZL _) ZL _ z z LL LL LL 0 0 0 Orn'O oo 0=coU 000 o-/- =O O=U= o o (0 0- WO 2013/189814 PCT/EP2013/062198 58 0 0 0 0) CO U) LL-K\/C0 LL-(\/ C)( /0 C Z/ z z 0 0 CUD LO0 0C10 00 0 0 6 ~ 00 WO 2013/189814 PCT/EP2013/062198 59 000 CO) C) Cl) LL4 C) L- \z C)LL-(\ /) z z z 00 U-0 0 0 00 0 I 0 WO 2013/189814 PCT/EP2013/062198 60 000 CO) CO) CO 010 0p O z zz z-z z-z z -z 0 C/) 0 CO 0 Cl) I0 I0 I0 U)ooOU)OOU= 0 cozO O=CDO oc/)O 0(0 (0r WO 2013/189814 PCT/EP2013/062198 61 0 0 0 00 0 0 Op Op 00 zIJI Zz ZJz 0~0 0 00 I0 Io0Id W -0 0 0 06~ 0~ 0 r~
(
WO 2013/189814 PCT/EP2013/062198 62 Ccle O 1c, ocY Cl) U-<, C lNo Co zl 0 Z0
C
1 C) ClCO 0 0 0 0 ~~ 0 O-'co o 00 00 0 (0 (0 00 (0 WO 2013/189814 PCT/EP2013/062198 63 QLL LL/ LL/ zz- z C) zL< ZI: ZI ZI ZI ~CO) C) ~ CO) CO 0 0O 0o \ 0 0/~ 0 0 CO (I UC) CO) CO o 0 00 0 0 0 CO 0 0 (0 0 WO 2013/189814 PCT/EP2013/062198 64 C3 LL-\/ LL-(/ z xz z z \1 C/) \1 C/) 3c CO. CO M \1 co 1: \ C)m ) 0-- 0 0 0 oo Co) 0C/) ~0 C)-0 0 0 0 0 0 -0 O'7c o 0 0 )= 0 0 0 u 0 (0 r -N WO 2013/189814 PCT/EP2013/062198 65 Z LL-(<O CO U) CO CO Cv) c Y 0 0 0 0 o- o 0-C \< 0 _Co 0-)0-U-0 K)-::oO / 0 0- 0 0 0 0 0 0 I cr~) WO 2013/189814 PCT/EP2013/062198 66 zz z ml C0 (Y) 0 060 -o0 0-0 0- o~ 0-) 0 6 0
\
1 0\ r00 I 00CF WO 2013/189814 PCT/EP2013/062198 67 I75 z/ 0 C~U) 0 C/) 0 0 0 00 00 0 0C 00 WO 2013/189814 PCT/EP2013/062198 68 CY) (Y)(Y 0 60 0 Cl) l) U 0 0 0 cv)U 0~ COC 0U 0 0 0 0 0 0 U) ) U) 00 0 I I 0 C0 0 0 00 0 \ 60 Ir I O U= 0 0 1 WO 2013/189814 PCT/EP2013/062198 69 600 Cl) Ul) 0 0 -0 Z"z Cl) -0 Z"z Cl) 0 0 0 0 0 0 Cl) Ul) 0 0 r -o 0 -0o 0 06) 00 0 0- WO 2013/189814 PCT/EP2013/062198 70 0 00 ZI: ZI: ZI 0- 0- 0 -0 ZCZ U) -0 Z§Z U) -0 Z§:Z U 0 00 O 0U)0 O) 0 0-U)0 0 0 0 0 0 0 U1) 1) U1) co) co) co 0 0 0 :> 0 ~0 O00 0 0' o=U 0~0 0~ WO 2013/189814 PCT/EP2013/062198 71 0 Y Cl)0 0 0 CO) Z Z LL-\ Z 0- C)) Z 0 0 / _- 75 0 Cl) C) oo 00 &un Cl) 0 CD CDY 0U)0~ 0~ WO 2013/189814 PCT/EP2013/062198 72 CY) Ul) 0 Zr U- Z
Z
Z-r 00 5 CU) 0
U
z 7
U
0 C) WO 2013/189814 PCT/EP2013/062198 73 / L-\ LLEZ 05 L< O CO) 0 0 Cl) l) CO 0 0 0 Cl)O ClOa 0I 0 0 Z= 0Z 0
Z
Co Cz o ZI Z Zroun 0 0 0 Uo 0 0 0 ~0 \ 0~ WO 2013/189814 PCT/EP2013/062198 74 LL-<\Z CO, LL-<\ Z C L< ) 0 0- 0 0 0 0 *9m co) 'CC/ YC 000 Cl) CO) CO) 0 0 0 0 CO 0 0 00 0 \ 60 I- I =/= 0~ 0~ 0 WO 2013/189814 PCT/EP2013/062198 75 LL-CZ /), LL-( Z C-' L- Z /), ZIZ 6 ZI0 0 0 0 C/) CO) C) 00 0 0-0 c oC) C) co 0 0 0 U) C) C/) 0 0o -oo 00 /wo 00 0 0- 6)- 0) 0P 0 0 I I\ 00 0 WO 2013/189814 PCT/EP2013/062198 76 U- Z I), Zm 0 ZI 0-0 0 C/)- C/) Cl) (I) 0 _ 0 z- z- Z co) 0 75 Z- Z zZ zI Z= Cl) 0 cn)l (n ) o 0 0 0 0 0~K ;co 0 - 0000U-, -U(0$0i 0 0 00 WO 2013/189814 PCT/EP2013/062198 77 0000 _ z z z U-4 LL--/ /L z z z z ZJ Z1 Z C/) C/) CO) C/) (Y) (Y) m CV) o o 0 0 CO 0 coo -0 07 0 0 0 00 )O 0 0 00) O=C/)=O 0/) 0 0 WO 2013/189814 PCT/EP2013/062198 78 0 CO) Z 0l)0 C/)- C/) z- 0 z z 0 I z- z () C) o 60 0 Cl) 0 o 0 0' =J= 0 0 0 \/- 0 \I_
CC/)
WO 2013/189814 PCT/EP2013/062198 79 Cf) C) c) 0 0 0 I U)U) IU) 0 0 0 OU)C~ OU Z\ -\m 0 oZo\ 0 0 -- - 0 Z<0 Cfc o oc o 0(0 0- WO 2013/189814 PCT/EP2013/062198 80 C) C) C) 00 0 o0 U)> Ul> Ul 0 0 0 0 0 0j Z \ I II -- Z \ II (JY0Z- 0 C/)- 0 oV CV/CV Z- o 0 0 00 0 0-0 0 WO 2013/189814 PCT/EP2013/062198 81 60 0 0 0 Z-\ Z-\- I L <, z _L 0 11 0- 0
U)
1 U) 0
/)
00 0 0 0r I
I~
WO 2013/189814 PCT/EP2013/062198 82 0 0 0 cU) Clo Cl) 0 0 0 I I:I 0 0 0 U) U) U) o 0 0 - o UU:1 O z-U Z-U Z z- z-- z zJ-\, Zi L-\Z - Zi 0 0 0 oLo o 0 0 - U) -- U-: 0 : 0 0- 0 0/ -0 O=U)=O 00 r6 Ir IO WO 2013/189814 PCT/EP2013/062198 83 &Y 60 & 0 0 0 0 0 0 o 0 0 U- U U 0 0 0 0 0 0 0 0 Oco oc 0 Z- Z ZI 0 0 - WO 2013/189814 PCT/EP2013/062198 84 0 0& 75; ) l) U OCY) CY & U)\ U)\ U)\ &r r C) U) U) o 0 0 U) U O U)~3 o 0 0 - Z- Z- Z zZ z T-z U)U) U) Co ) :> 0 0 -U) O07 0O-'O ~~0 O ) 0 \)- 0 0 00 r~ 0 CF) 0~ WO 2013/189814 PCT/EP2013/062198 85 z /KZ cZ O 0= 0= -0 Z-zZ C/) -0 Z"'Z2 l -0 Z"'Z Cl) 0"cl) 0o 0"l)0 "c 0 0 0 o 0 0 Cl) l) Cl) (Y) CY) (Y) o 0 0 c) C) C) Z= ZI ZI l) Cl) Cl) cr) CY) CY) 0 0 0 0 C)0 07 0 Cfy:O 00 0 \ -- 0 0\~ C ) aC/) - 0O=)= WO 2013/189814 PCT/EP2013/062198 86 zz Z -Z Z 3Z *' 0 0 0 0"i0 0" 0 0CI 0 0 0 o o 0 Cl) C/) 0 0 00 Ir 0 06 ZI: ZIr 0 0 o o 0~ 0 C')) 6 00 rI LO)C~ ~ WO 2013/189814 PCT/EP2013/062198 87 Z zz Z Z Z 0 00 -0 Z-zZ C) -0 Z"'Z C/) -0 Z-zZ C) 0 0 0 o 0 0 Cl) C) C/) o 0 0 I I: I: .3c / U) <) U),, 00 0>0 o~ 0E~ 0 ~ 00_ 00 CF 0 C)3 C 2 a, co ~ WO 2013/189814 PCT/EP2013/062198 88 co 0 -Z E 0 Sao 0 0 c ' o Z=Z c,/ S-o 0 C0 co Ea, O o o 0 -4 0m 0 o a a E a, -0 Co o a, a, 0 0- ~' 0 0'(~ WO 2013/189814 PCT/EP2013/062198 89 0 0 LL-\ Z L- Z - Ir o/ C)C/ C) 6' 0-0 0 D C/ U)- U o o0 0 O 06
S.
0 0 F-0 WO 2013/189814 PCT/EP2013/062198 90 0 0 0 UO CO CO LL-(\ Z LL-(s Z LL-(s Z z z - z I OM OM O M Co U CO Co)- CO 6' 0 0 __ 0 0, 0 0 00 OO
O
O)-:o -0 0 0 O=Co=O ~co~ 0 66 0~o I cr~)LC WO 2013/189814 PCT/EP2013/062198 91 o co o LL-\ z z 14 z ZI ZI ZI \/,p * o o o C o co /0 co 0 o 0 0 _o 0 0I 0 o 10 0 0)7 0 o l0 0 ( - o c) -O ' 0 ~C/) 0 00 0 (00 WO 2013/189814 PCT/EP2013/062198 92 60 60 60 C) Cl) CO) z LL-(\ ,Z ZI: ZI: ZI: 00 6'0 co ) I) 06 0 I 0 Cl ) = 0 0- ) 0 0 Coil0 00 CF) 0 WO 2013/189814 PCT/EP2013/062198 93 000 U) U) Ul) Z _ Z9 _ c Z U-- Z UL Z UL- Z o 0 0\ U) U) U) o 0 0 0 0 U) U) U) co Y)(Y o 0 0 00 00 0 OO=U)=O 6~ 0~) I ~ l WO 2013/189814 PCT/EP2013/062198 94 0)0 Cl) C) Cl) z- U ZU- Z z z z o 0 0 Cl) U) U) o 0 0 0 0 0 Cl) cU oy' 00 0 0 00 0 0)7 0 \
(D-
WO 2013/189814 PCT/EP2013/062198 95 0 0 0 zJ Cl) UZz U Z z-\ 0 Z\ 0 U)) Cl 0 0 0 0 0 0 Ul) 0 r 0 0 0 0 C/) 0 I)= I r 0 WO 2013/189814 PCT/EP2013/062198 96 & 60) 0 0 0 _- _- Z _ L-\Z I L- Z 1 L< Z-\ 0 z-\060 Z\0 0 0 0 060 0 -cm 0 :I cmO 0 -0 0 0 0 o=)O ooo 66 0 I~ l WO 2013/189814 PCT/EP2013/062198 97 z _- Z-z z LL-\Z z L- ZL Z Z- 0 of z- 0 () z- 0 Y -C/) N-C/) C - -l I 1 0 00 0 0 0 00 0 07 0o 0 0/) ol 0 0 D C/)ocC 0 0 0 ((0(0 WO 2013/189814 PCT/EP2013/062198 98 0 0 0 U) U)/) Z60 0co Z-0 6' 0 c 0 0 0 0 0 C l)- 0 ClYo O0- \U 0 0 0 0 (0 0 (0 WO 2013/189814 PCT/EP2013/062198 99 000 CO) CO CO) LL-\Z i LL-{ i LL-{Z Z 0 Z 0 Z 0 z-\ 0 0 11 0 Co -\Co C Co / Co -\Co 0 0 0 o 0 0 \-0 O=Co=O O=C)O 0 6 6 0 I o N-l WO 2013/189814 PCT/EP2013/062198 100 z 0 z 0 z 0 U)o Co/ C CO CO C I 0 o-- 0 0 0"0 00 00 0 0) 1r)0 0) 00 0 0 oOC) 0 0 0 il IO WO 2013/189814 PCT/EP2013/062198 101 0 0I 0 Cl) o CooL 11 0 0 0 - 22:N WO 2013/189814 PCT/EP2013/062198 102 oe o of 0 60 0' Cl) C) Cl) zZ9 z Z9 z Z_* LL4 C\ LL CO LL-<\0 O zL z zL 0 K0 0O O0 00 O~c-oO O 0 0 O~O=o= O\ o 0 WO 2013/189814 PCT/EP2013/062198 103 CoY o 0 0 U) CO U) LL-(\/z0C LL-\z0C LL-(\ z/C z z zLL 0 0 0 0- 0 0~ ~ cO\C/01:3111 00 0 r WO 2013/189814 PCT/EP2013/062198 104 C) cl) co 0 (\ 0 IL0 z -- z z- -r IY) 0 (f)) 00 0 0(0 -0 0 r0( WO 2013/189814 PCT/EP2013/062198 105 0 00 CO CO CO zZ9 z Z9 z Z-9 LL- LL-( LL O O -0 O U):o /-: 0 O 0 0 ~ 0 WO 2013/189814 PCT/EP2013/062198 106 0 0 0 Cl) CO CO LL-(\/C0 LL-( / C LL-(\ /0C z /z z 00 00 cr) 0 0 0\ 0 00 01111() 111 0~ 0 0 WO 2013/189814 PCT/EP2013/062198 107 000 Cl) U) U) 0 0 0 0 0 0 zo z zo I ,-z z z z z
U
0 Ul) 0 C/) 0 C/) 0 /\ 0 00 U)l 0 0 \ 0::I Ozzzc)zO Cl) 0Cl) 00 0 0 0 ~00 WO 2013/189814 PCT/EP2013/062198 108 00 0 0 0 0 U Cl) U 00 010 00 0 0 bIlU)I j Cl ) JOC1,- ) ci , z ~ ~ "Lz Z- IZ - zl " -z z : " f-" z z -- -o T- m o~1 0 0 ~ 0l ~l 0 0 Cl)0 Cl) co- 0P 0- 10 0 0 0(00\ 0 0 60 0~ 00 oo ~ CF) 00 WO 2013/189814 PCT/EP2013/062198 109 CYII 00 Uo) U LL 0 0 0 0 z U) U) LL- Q C)-\/ Z -1,Z ZI:zT Z Z z - z Co CO 0- :zZ- 0 - 0 0 C o) 00l I0 0 075 00 0 0 0(O=)=0 0% 0\0 0 000 0 WO 2013/189814 PCT/EP2013/062198 110 H -\/C LL\/ z- z z z Z- zI z1 zi () = co = C) co o-_ 0 O/\O O\ 0o 0_ (Y ) ~ c o) C) c o) 0 000 075 00 o 0K oIo 0 0O 0 6 0 I 0 (0 0 0 WO 2013/189814 PCT/EP2013/062198 III U~z~ z z zZ4z / z LL< /0 -<4 /0C LL- 0 CzzJ z z z ZI ZI zJr . U () CO U) 0= Z0 C) co r Y o 0 0 l) 0l oY co (Y 00 0
CYO
0 :> ) 000 -'~ 0 0 0 -)b o 0 -0 0C) 1/) 0 ~ 0 0 0 0 0 0 0) WO 2013/189814 PCT/EP2013/062198 112 LL\/ LL-(/ LLL/ z z z z CO) U) Co CO 0 0 00 0 0 0 0O 0 0 0-o~ OCYoO 0- 6 0 C L L CL C I WO 2013/189814 PCT/EP2013/062198 113 LL LL LL &Y z 0 4~ _L zzzI zIzz 0 CO) Cl) 0l 00 0 0 0 C/ 0 0 0-L 0 r) - OP0(1 0 0' 0 00 0 r WO 2013/189814 PCT/EP2013/062198 114 0 0 0 C/)-\ C/)\ Cl)\ ZI: z T zI: _- 0 _-/ 0 _ -o0 C) (Y coz 0 0 0 Oz= 0 0"Cl) 0 0::U 00 0 0 0 0 0 0 0 0 0 0 \ 60 C.) OU WO 2013/189814 PCT/EP2013/062198 115 (Y) 0 0 (1)0 C/)-\ () z ZCO 6z U) z U) 0 Y 0 - 0 o co 0 07 0 0 00 0 0 CI) 0 CO O 0/ 0 0K)) 0)c 0 co0 r00 0 0 0 WO 2013/189814 PCT/EP2013/062198 116 _ 0 0 00 00 0 0 0 00 U) )Q ZY C/) 0/ 0 0 O( z 0~U) 0 0 Cv) CF) 0 WO 2013/189814 PCT/EP2013/062198 117 IY 0 0 CU () CO) 0 0 o 0 CO) 0 -- J c//0 -9Z z z L- Z Z I~ZZ- -- -(\ z 0 0 co 75 0 co) 0 / (I) Z z Y -zI: z~ /Z zz C/) C~(Y) CZ)Cr WO 2013/189814 PCT/EP2013/062198 118
U
LL/ z ZI 0 00 COO 0 c0 0 C'CO 0-0 06 00 zzC) 0 O{ 0 ) Z\/C)\ U) z 0 01 0 zI> 0 (Cl.) Cl.) WO 2013/189814 PCT/EP2013/062198 119 Z\/ 0 Z\0 LL-LL-(Z Z 0 0 0 C/) CO) CO CY) cy) 0 0 0 U ) C/) UC) o 0 0 0 0_ 0 9- o 00 00 0CF)0 Cl~) Cl) Cl) WO 2013/189814 PCT/EP2013/062198 120 1:-Q 0 LL0\ Cl) zQ 0 z~~ =zi o0 0 U) ) C/) 00 0 0- 0 l) ) cl) Y ) ( Y) 0 0 0 U) U) )0 0co 0~i 0 6 00 WO 2013/189814 PCT/EP2013/062198 121 ZQ /0 LL-\/ Z U)0 LL<\Z )0 0 0 (I) (I) 0-0 0 I: I U) 0 0 co 0o 0 0 0 0 0 0\ cr~) WO 2013/189814 PCT/EP2013/062198 122 C) C) C) C/) U)- Cl) 0 0 0-0 Z 0- -0 0O 0 0- WO 2013/189814 PCT/EP2013/062198 123 C) C) C)
U)U
z 5 0U, S LL L L CC/) 00 OCO Lt 0O 0 00 6 ~ 0 WO 2013/189814 PCT/EP2013/062198 124 CY) C) LL LL LLLLL Zq 0 Z 0 z 0 Z ) Zt cl) Z- a) :> 0 0 a) 0 7a 0 cr )o 0 0)= O'iua'rn 0 0 I I I WO 2013/189814 PCT/EP2013/062198 125 C) ml 00 0 CU) CO 0 0 -)Z Co z 0) z 0O 0 0 00\ -0
IU
WO 2013/189814 PCT/EP2013/062198 126 00 00 0 0 Iz 0 0 __ CO z U 0 0 0(/)0 0C co 6 6 I (.0 LO LO WO 2013/189814 PCT/EP2013/062198 127 0 00 0 0 0 - f~ Co - C Iz z 0 z 0 0 z 0 O-0 O 0 ol0 0 0 0 0 0 rI 00 CF) WO 2013/189814 PCT/EP2013/062198 128 Cl)) 0 00 0 0 0 COZZ z 0~ >-Z z 0 0 O CO U 0- 0 - z x ~0 o 0)- W 0-UY 0 00 (0 WO 2013/189814 PCT/EP2013/062198 129 Cl) 0 0 z 0 Cf) 0 0 Col C0 WO 2013/189814 PCT/EP2013/062198 130 0 0 o o) COU CO) co) Cl) Cl 0 0 0 0 / I- -9 I-9 i i II 0" 0" 0 0" Cl) CO) CO) CO o o 0 0 z- z- Z- Z LL-{Z LL-\ Z LL-\ Z O CO CO CO oy' oy' oy m o 0 0 o 0 0 oLo _ oo 0 00 0 0 -0 o0 o oc0 0 6 (0.0 1.0 ( WO 2013/189814 PCT/EP2013/062198 131 75CO CO U) CO CYv) ce 0 0 0 0 0 0c 0& CO CO CO CO o o 0 0 L-\Z L -\Z LL-\ Z LL-\ Z CO CO CO CO Cv) Cv) cC') o o 0 0 0-0 0 0 0-0 ooj 0 C & D U) 0 0 0\ 0\ 0 0 0 (.0 C. - WO 2013/189814 PCT/EP2013/062198 132 cl) CO-\ Z-9 I C 0 ZI LL-1' \ Z C c(I) 0 U) 0 0
CNL
WO 2013/189814 PCT/EP2013/062198 133 0 0 0 Z z -0 ZzZ 0) -0 ZzZ U) -0 Z"Z Ul) 0 0 0 0 0 0 0 0 0 0 000 C/) /) C/) C) C) mo 0 00 0 0 0 _0 0\ U- 0-
N-)=
WO 2013/189814 PCT/EP2013/062198 134 o 0 0 zz z Iz 00- 0 -0 Z"Z U) -0 ZzZ /D -0 Z Z C/) 0 00 O-co) 0Cl)W0- 0l) 0 0 0 0 o o 0 U) U) Cl) CV) CY) Y o o 0 C) C) 01 0 CO) CO CO) C 0 0 0 00 0(00Y- 0-~/ 0 0 0 (=)O 0 U a - \ N-\ WO 2013/189814 PCT/EP2013/062198 135 0 0 0 z z z z 0- 0- 0 -0 ZzZ Cl -0 Z"Z U) -0 Z-Z U) (Y) Y) (Y) 0 0 0 0-)0 - -)0- oOU 0 0 0 0 0o 0 0 0 U) U) C) 0 0 0 00 0 -0-0 -0 0 07 Cl)< 0 0 0 0 _30 0-0 01~~ zi0 E 0 0 0 co 0 U,) I- 1- 0U C L C C L () WO 2013/189814 PCT/EP2013/062198 136 C,) <a E co oo c~ -4, 0 oj -- WO 2013/189814 PCT/EP2013/062198 137 The present invention also provides a process for the preparation of the dyes of the formula (I). This process comprises diazotization of the compounds of the formula (II) and reacting the correspondingly 5 obtained diazonium salts with a compound of the formula K to obtain the intermediate of general formula (111). K OH NH2 OH NN | + K:|
HO
3 S (11) SO 3 H
HO
3 S (
SO
3 H In a further step the diazo component (A-NH 2 ) is diazotised and coupled onto the 10 intermediate III to obtain the bisazo dye product of general formula (IV). K K IN A, -N OH N A'N OH NN N A'NH2 +
HO
3 S
SO
3 H HO 3 S
SO
3 H (111) (IV) Alternatively, the diazo component (A-NH 2 ) can be diazotised and coupled onto the compound (B-NH 2 ) to obtain intermediate (V). Further, the intermediate (V) is 15 diazotised and coupled onto compound (111) to obtain the trisazo dye product of general formula (VI).
WO 2013/189814 PCT/EP2013/062198 138 NH NH N, B, A 2 + B' 2 A' N NH 2 (V) K N OH NN A
N
HO
3 S N K 3SO3H II (111) 'N OH N' N N
HO
3 S
SO
3 H (VI) The diazotization reactions, in general, can be performed by means of diazotization 5 methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used. 10 The coupling reactions in general can be performed by known methods. The compounds of the formula A-NH 2 , B-NH 2 , K are known and commercially available or can be synthesised by means of common chemical reactions known to a 15 person skilled in the art. The end product can optionally also be subjected to a vinylization reaction. For example, a vinylizable reaction group such as the p-sulfatoethylsulfonyl is converted into its vinyl form. Such reactions are known to a person skilled in the art. They are WO 2013/189814 PCT/EP2013/062198 139 generally performed in a neutral to alkaline medium at a temperature, for example, from 20 to 800C, at a pH of, for example, from 7 to 14. The dyes of formula (1) are fiber-reactive containing fiber-reactive functional rests. 5 Fiber-reactive functional rests refer to rests capable of reacting with the hydroxyl groups of cellulosic materials, the amino, carboxyl, hydroxyl and thiol groups in the case of wool and silk, or with the amino and possibly carboxyl groups of synthetic polyamides to form covalent chemical bonds. 10 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 reactive dyes. Therefore, the present invention also provides for a process for dyeing and printing of the above-mentioned fiber 15 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, 20 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 manufactured regenerated fibres are cellulosic fibres 25 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 nylon materials, like nylon-6, nylon-6.6 and aramid fibres. 30 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 WO 2013/189814 PCT/EP2013/062198 140 dyeing product in dyeing or printing processes or it can be part of a di/tri or multi component combination product in dyeing or in printing compositions. Dyes of this invention and their salts or mixtures are highly compatible with other 5 known and/or commercially available dyes and they can be used together with such dyes to obtain specific hues of similarly good technical performance. Technical performance includes build-up, fastness properties and levelness. Since the water solubility of the dyes according to the invention is very good, they 10 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. Aqueous inks for digital printing which comprise a dye of the present invention likewise form part of the subject matter of the present invention. 15 The inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 30% by weight and most preferably from 1% by weight to 15% by weight, based on the total weight of the ink. 20 The inks, as well as the dyes of the present invention may, if desired, contain further dyes used in digital printing. For the inks of the present invention to be used in the continuous flow process, a 25 conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present invention may include organic solvents at a total level of 1-50% and preferably 5-30% by weight. Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butanol, pentyl 30 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 WO 2013/189814 PCT/EP2013/062198 141 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, 5 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 10 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, 15 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 20 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, 25 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, 30 1,2-dimethoxypropane, dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether, 1,2-dimethoxypropane and trimethylpropane. The inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in a WO 2013/189814 PCT/EP2013/062198 142 temperature range from 20 to 500C. 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: 5 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 10 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 and 1,2-hexanediol. 15 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 20 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. 25 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: 30 i) 6.2 parts of sulfuric acid mono-[2-(2-phenylamino-ethanesulfonyl)-ethyl] ester was suspended in 70 parts of water. 14 parts of sodium bicarbonate was added. The reaction vessel was cooled to 0~50C using ice. 3.8 parts of cyanuric chloride was added. The reaction was stirred at temperature of 0~50C and pH of 4-4.5 for 3 hours.
WO 2013/189814 PCT/EP2013/062198 143 Thereafter, 4.8 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was added and the pH was adjusted to 6-6.5 using 15% soda solution. The reaction was stirred at ambient temperature and pH of 6-6.5 for 2 hours. The product (a) obtained was used in next step without isolation. CI NH OH N N + + 0 CI N CI S S NH 2 0 HO'\ HOO OSO HO 0 / \H O -SOH SN 0 0 N 'N S 0 N N 0 HO C N 5 (a) ii) 6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid was added into 70 parts of water. The pH was adjusted to 5-6 using 15% soda solution. The reaction vessel was cooled to 0~50C using ice. 4.3 milliliters of 5M sodium nitrite solution was 10 added into the reaction mixture. After stirring for 10 min, 20.7 parts of 37% hydrochloric acid was added. The reaction was stirred at 0~50C for 0.5 h and then 0.2 parts of sulfamic acid was added. The solution of product (a) obtained above was cooled to 0~50C using ice. The diazonium salt was added into this coupler solution slowly while maintaining the pH to 15 5-6.5. The reaction was stirred until completion to yield the intermediate (b).
WO 2013/189814 PCT/EP2013/062198 144 Os OH Oq OH NH 2 0 -0 N~ H I +HO / N N 0 0 / N-N O:.O CI HO (a) 9 OH SO s HO O / OH H 0S ZO HON, / / N N N N O=S- O=S- CI /-0 /-O HO HO (b) iii) 5.9 parts of {2-[(4-aminobenzene)sulfonyl]ethoxy}sulfonic acid was suspended in 5 50 parts of water. The reaction vessel was cooled to 0~50C using ice. 6.2 parts of 37% hydrochloric acid was added into the reaction mixture. After stirring for 10 min, 4.3 milliliters of 5M sodium nitrite solution was added. The reaction was stirred at 0~50C for 1 h and then 0.2 parts of sulfamic acid was added. The diazonium salt was added slowly into the solution of (b) synthesized above while 10 maintaining the pH to 5-6.5. The reaction was stirred until completion. The product was precipitated out, collected by filtration and dried to give 21.8 parts of dye 156 as black solid.
WO 2013/189814 PCT/EP2013/062198 145 0 -S O O H O-S 0 ,
NH
2 H ON ON HO HO\ N'- N 0s5,-O" 0 /SOH 00 0 NZN7C OHH OH (b) 0 11 O-S-OH 00 O 0 S=O HO 0 OOH O HO H O0 N\\ N S=O NN - N N HO O
O
0 CI)--N (156) Through analogy, all the dyes of formulae (11-1280) can be synthesized according to 5 the method described above in the example 1.
WO 2013/189814 PCT/EP2013/062198 146 Dyeing example 1 3 parts of the dye 156 of this invention is dissolved in 2000 parts of water and 1 part of 5 levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) is added. The pH is then adjusted to 3.8-4.2 using acetic acid (60%). The dyebath is entered with 100 parts of a woven wool fabric. The temperature is raised to 400C over the course of 30 minutes, maintained at this temperature for 15 minutes and then increased to 980C over the course of 58 minutes and dyeing is 10 carried out at this temperature for 90 minutes. This is followed by cooling to 900C and removal of the dyed material. The wool fabric is washed with hot and cold water, alkaline-treated and then spun and dried. Dyeing example 2 15 2 parts of the dye 156 of this invention and 60 parts of sodium chloride are dissolved in 1000 parts of water, and 12 parts of sodium carbonate and 0.5 part of a wetting agent are added. This dyebath is entered with 100 parts of bleached cotton knitted fabric. The temperature of the dye bath is raised to 300C at a gradient of 20 0.5 0 C/minute and held at this temperature for 30 minutes, and then increased to 600C over 30 minutes, this temperature being maintained for a further 60 minutes. Thereafter the dyed goods are initially rinsed with tapwater for 5 minutes. The dyed goods are neutralized at 500C using 60% strength acetic acid for 30-40 minutes. The goods are rinsed with tapwater at boil for 30-40 minutes followed by a final rinse at 25 40~500C for 20 minutes and dried. Dyeing example 3 1 part of the dye 156 of this invention is dissolved in 2000 parts of water and 1 part of 30 levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate are added. The pH is then adjusted to 4.5 using acetic acid (80%). The dyebath is heated to 500C for 10 minutes and then entered with 100 parts of a woven polyamide fabric. The temperature is raised to 1100C over the course of 50 minutes and then dyeing is carried out at this WO 2013/189814 PCT/EP2013/062198 147 temperature for 60 minutes. This is followed by cooling to 600C and removal of the dyed material. The polyamide fabric is washed with hot and cold water, soaped and then spun and dried. 5 Dyeing example 4 A textile fabric consisting of mercerized cotton is padded with liquor containing 35 g/I of calcium sodium carbonate, 100 g/I of urea and 150 g/I of a low-viscosity sodium alginate solution (6%), and then dried. The liquor pickup is 70%. The textile thus 10 pretreated is printed with an aqueous ink containing 2% of the dye 156 of this invention, 20% of sulfolane, 0.01 % of Mergal K9N and 77.99% of water using a drop on-demand (bubblejet) ink-jet printing head. The print is fully dried. It is fixed by means of saturated steam at 1020C for 8 minutes. The print is then rinsed warm, subject to a fastness wash with hot water at 950C, rinsed warm and then dried. 15

Claims (15)

1. Chemical compound of formula (I) and mixtures thereof A,N n K N I 'N OH N I I N a MO S 03s 3SOM (1) 5 wherein, A is a radical of diazo component as described below; and B is a radical of middle component as described below; and K is a radical of coupling component as described below; and 10 a is an integer of 0 or 1; and with the general proviso that dyes of general formula (I) contain at least one reactive anchor; and this invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I). 15 A is a radical of general formula (1a) R2 (1a) wherein, WO 2013/189814 PCT/EP2013/062198 149 each of R 1 to R 3 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or 5 COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N 10 cinnamoylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 15 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, 20 heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OS0 3 M, SS0 3 M, OCOCH 3 , OP0 3 M or 25 halogen; or is a group of general formula (2a), (2b) or (2c) WO 2013/189814 PCT/EP2013/062198 150 N R 11 * NRG N N RGN bI \ / . _cI R12 sRG R 5 R6 Rd (2a) (2b) (2c) wherein, 5 each of R 4 and R , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, S0 3 M or COOM; or 10 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or 15 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, 20 heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R , R , R 8 and R , independent of each other is hydrogen, alkyl or aryl; or 25 WO 2013/189814 PCT/EP2013/062198 151 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 5 alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, 10 SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R 9 to R", independent of each other is hydrogen, halogen, alkyl, 15 alkoxy or SO 3 M; and b is an integer of 0 to 6; and c is an integer of 1 to 6; and 20 when each of b and c, independent of each other is > 2, R 4 and R 7 can have different meanings within the same rest as per meaning above defined; and d is Oor 1; and 25 RG is a reactive anchor of general formula (3a), (3b) or (3c); R17 R14 N"-R19 N N N N | N N * N R13 R 15 R R 18 (3a) (3b) (3c) WO 2013/189814 PCT/EP2013/062198 152 wherein, each of R 1 4 to R 19 , independent of each other is halogen; and 5 R14 can additionally be a rest of formula (8a) +1 0 N * (8a) 10 wherein, R 96 is hydrogen, halogen, alkyl, alkoxy, thioalkoxy, hydroxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group 15 consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or 20 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or 25 aryloyloxy; and R 1 3 is one of the groups selected from general formula (4a) or (4b); WO 2013/189814 PCT/EP2013/062198 153 20 2 3 R2 *-N \ 94 *-N R i< R95 R22R (4a) (4b) wherein, 5 each of R 20 , R 23 and R4, independent of each other is hydrogen, alkyl, cycloalkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, 10 halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 15 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and 20 each of R , R 22 and R , independent of each other is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, sulfamoyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO 3 M or COOM; or 25 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, WO 2013/189814 PCT/EP2013/062198 154 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 5 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and 10 R94 can additionally be -CH 2 CH 2 -SO 2 -X, where X is vinyl or a radical CH 2 CH 2 -Y where Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; and 15 R95 can additionally be -S0 2 -X where X is the same as defined above. B is a radical of general formula (5a) FR24 R26 * (5a) 20 wherein, each of R 24 to R 26 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, 25 cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or WO 2013/189814 PCT/EP2013/062198 155 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N 5 cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 10 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, 15 heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or 20 halogen; or is a group of general formula (2a) or (2b) R4 R7 INRG N cN'RG bi / R5R6 R (2a) (2b) where R 4 to R 8 , b, c and RG are the same as defined above. 25 K is a radical of general formula (6a) or (6b) WO 2013/189814 PCT/EP2013/062198 156 31 30 N R29 DN OH 74 n1 R N / N R 2 7 R28 \73 MO 3 SR (6a) (6b) wherein, 5 D is a radical of general formula (1a) as defined above; and each of R 27 to R 29 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, ureido, alkylureido, phenylureido, sulfamoyl, acyl, thioacyl, 10 aryloyl, trifluoromethyl, acyloxy, aryloyloxy, carbamoyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N 15 trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 20 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, 25 N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or WO 2013/189814 PCT/EP2013/062198 157 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 5 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl 10 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-monoarylsulfamoy or N 15 monoalkyl-N-monoarylsulfamoyl; and each of R 3 , R , R'h and R4, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or 20 is 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-N 25 monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 30 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- WO 2013/189814 PCT/EP2013/062198 158 monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or 5 is alkyl interrupted by one or more heteroatoms such as oxygen or 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-N 10 monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 15 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 20 monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or 25 is a rest of the general formula (7a) R 3 RG' N e 1 33 _ R (7a) 30 wherein, WO 2013/189814 PCT/EP2013/062198 159 RG is the same as defined above; and R 32 is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, 5 cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, S0 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group 10 consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or 15 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or 20 aryloyloxy; and R33 is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group 25 consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or 30 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, WO 2013/189814 PCT/EP2013/062198 160 heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and e is an integer of 1 to 6; and when e is > 2, R 32 can have different meanings 5 within the same rest, as per meaning defined above.
2. Chemical compound according to claim 1 having formula (la): 38 37 R NN R R35,R |SO3 M - ,N S 3 M OH N N R34 MO SS 3 M (la) wherein, 10 each of R4 to R 36 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or 15 COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N 20 monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or WO 2013/189814 PCT/EP2013/062198 161 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 5 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifl uoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 10 is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined in claim 1; and 15 each of R3 and R 38 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group 20 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-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N 25 monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl 30 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, WO 2013/189814 PCT/EP2013/062198 162 N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 5 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-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N 10 trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 15 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, 20 N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1; or 25 is a rest of the general formula (7a) as defined in claim 1.
3. Chemical compound according to claim 1 having formula (Ib): WO 2013/189814 PCT/EP2013/062198 163 46 45 R 4 1 N R40 R44 S 3 M N N OH N' R 39 R 43 N R 42 MO 3 S S 3 M (Ib) wherein, 5 each of R3 to R4, independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or 10 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N 15 cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 20 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, WO 2013/189814 PCT/EP2013/062198 164 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable 5 under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or is a group of general formula (2a) or (2b) as defined in claim 1;and 10 each of R3 to R 4 , independent of each other can additionally be a group of general formula (2c) as defined in claim 1; and each of R45 and R 46 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or 15 is 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-N 20 monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 25 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 30 monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or WO 2013/189814 PCT/EP2013/062198 165 is alkyl interrupted by one or more heteroatoms such as oxygen or 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 5 monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, 10 halogen, cyano, SO 3 M, 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 15 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-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or 20 is a reactive anchor RG, where RG is the same as defined in claim 1; or is a rest of the general formula (7a) as defined in claim 1.
4. Chemical compound according to claim 1 having formula (Ic): 25 WO 2013/189814 PCT/EP2013/062198 166 51 50 N [MO 3 S R48, R4 HO SO M OH N N R47 MO 3 S S 3 M (Ic) wherein, 5 j isOorl; and each of R47 to R 49 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, 10 cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N 15 trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 20 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of WO 2013/189814 PCT/EP2013/062198 167 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 5 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or 10 halogen; or is a group of general formula (2a), (2b) or (2c) as defined in claim 1; and each of R 0 and R , independent of each other is hydrogen, alkyl, acyl, 15 thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is 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 20 aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, 25 halogen, cyano, SO 3 M, 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 30 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-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or WO 2013/189814 PCT/EP2013/062198 168 is alkyl interrupted by one or more heteroatoms such as oxygen or 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 5 monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, 10 halogen, cyano, SO 3 M, 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 15 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-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or 20 is a reactive anchor RG, where RG is the same as defined in claim 1; or is a rest of the general formula (7a) as defined in claim 1.
5. Chemical compound according to claim 1 having formula (Id): 25 WO 2013/189814 PCT/EP2013/062198 169 59 58 R -R N 3R54 [Mo 3 s n Rs3 R57 HO SO3M N N OH N R 52 R 56 ,N N MO 3 S SO 3 M (Id) wherein, 5 n isOorl; and each of R 52 to R 57 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, 10 cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N 15 trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 20 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of WO 2013/189814 PCT/EP2013/062198 170 hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 5 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or 10 halogen; or is a group of general formula (2a) or (2b) as defined in claim 1; and each of R 52 to R4, independent of each other can additionally be a group of 15 general formula (2c) as defined in claim 1; and each of R 58 and R , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or 20 is 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-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N 25 trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 30 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, WO 2013/189814 PCT/EP2013/062198 171 N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 5 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-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N 10 trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 15 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, 20 N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1; or 25 is a rest of the general formula (7a) as defined in claim 1.
6. Chemical compound according to claim 1 having formula (le): WO 2013/189814 PCT/EP2013/062198 172 OH R64 R 6 1 R62 \ R63 MO 3 S N N OH N 11 N R60 MO SS 3 S03 M (le) wherein, 5 each of R 60 , R 6 and R 2 , independent of each other is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or 10 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N 15 cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 20 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, WO 2013/189814 PCT/EP2013/062198 173 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable 5 under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined in claim 1; and 10 each of R 63 and R 64 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl 15 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-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N 20 cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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 25 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-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or 30 is alkyl interrupted by one or more heteroatoms such as oxygen or 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- WO 2013/189814 PCT/EP2013/062198 174 monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N 5 cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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 10 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-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or 15 is a reactive anchor RG, where RG is the same as defined in claim 1; or is a rest of the general formula (7a) as defined in claim 1. 20
7. Chemical compound according to claim 1 having formula (If): R67 OH R72 R6 R MO S N OH N R65 R69,N N R68 MO 3 S (If) wherein, WO 2013/189814 PCT/EP2013/062198 175 each of R 65 to R , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, 5 cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, S0 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N 10 trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 15 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N 20 monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, S0 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 25 is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OS0 3 M, SS0 3 M, OCOCH 3 , OP0 3 M or halogen; or is a group of general formula (2a) or (2b) as defined in claim 1; and 30 each of R 65 to R 67 , independent of each other can additionally be a group of general formula (2c) as defined above; and WO 2013/189814 PCT/EP2013/062198 176 each of R 71 and R 2 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group 5 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-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N 10 monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl 15 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 20 monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or 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 25 dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N 30 cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, 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- WO 2013/189814 PCT/EP2013/062198 177 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 5 monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1; or is a rest of the general formula (7a) as defined in claim 1. 10
8. Chemical compound according to claim 1 having formula (Ig): R78,1 -7 II R80 N OH 82 R N R761 R7N\ R 8 MO 3 S N OH N' N R75 MO Sso 3 M (19) 15 wherein, each of R 7 to R 80 independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, 20 cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or WO 2013/189814 PCT/EP2013/062198 178 is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N 5 cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 10 substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, 15 trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or 20 halogen; or is a group of general formula (2a), (2b) or (2c) as defined in claim 1; and each of R 1 and R 2 , independent of each other is hydrogen, alkyl, acyl, 25 thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is 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 30 aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, WO 2013/189814 PCT/EP2013/062198 179 halogen, cyano, SO 3 M, 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 5 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-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or 10 is alkyl interrupted by one or more heteroatoms such as oxygen or 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 15 monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, 20 halogen, cyano, SO 3 M, 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 25 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-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or 30 is a reactive anchor RG, where RG is the same as defined in claim 1; or is a rest of the general formula (7a) as defined in claim 1.
9. Chemical compound according to claim 1 formula (Ih): WO 2013/189814 PCT/EP2013/062198 180 R 90 R 91 , OH R85 93 N R R 8 4 R88 |O N/ N? OH N R83 R87,N MO 3 S so 3 M (Ih) wherein, 5 each of R 83 to R 9 1 , independent of each other is hydrogen, halogen, alkyl, N acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or 10 COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N 15 monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or 20 is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N- WO 2013/189814 PCT/EP2013/062198 181 triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 5 alkoxythiocarbonyl, acyloxy, aryloyloxy; or is S0 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; or 10 is a group of general formula (2a) or (2b) as defined in claim 1;and each of R 83 , R 8 4 , R 85 , R 89 , R 90 and R91, independent of each other can additionally be a group of general formula (2c) as defined in claim 1; and 15 each of R 92 and R 3 , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group 20 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-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N 25 monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl 30 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, WO 2013/189814 PCT/EP2013/062198 182 N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and 5 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-N monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, N,N,N 10 trialkylammonium, N,N,N-triarylammonium, N,N-dialkyl-N monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO 3 M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, 15 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, 20 N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl, N monocycloalkyl-N-monoarylsulfamoy or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1; or 25 is a rest of the general formula (7a) as defined in claim 1.
10. Chemical composition consisting of two or more chemical compounds according to any one of claims 1 to 9. 30
11. Chemical composition comprising one or more chemical compounds according to any one of claims 1 to 9.
12. Aqueous solution for dying comprising one or more chemical compounds according to any one of claims 1 to 9. WO 2013/189814 PCT/EP2013/062198 183
13. Process for producing chemical compounds according to claim 1 comprising the steps: 5 a) diazotizing compounds of formula (II), b) reacting the diazonium salts obtained in step a) with a compound of formula K to obtain an intermediate of formula (111) K -N OH NH 2 OH N | + K:| HO 3 SO 3 H HO 3 S SO 3 H (11) (III) c) diazotizing component (A-NH 2 ), 10 cxl) optionally coupling the diazotized product of step c) onto the compound (B NH 2 ) and cx2) diazotizing the coupling product of step cxl) d) coupling the diazotized product of step c) onto the intermediate III to obtain the bisazo-product of general formula (IV) in case of step c) KK I K -N A OHNN OH N ANH2 + --- 3W- N HO 3 S SO 3 H HO 3 S SO 3 H 15(1) (IV) or coupling the diazotized coupling product of cx2) onto the intermediate III to obtain the trisazo-product of general formula (VI), WO 2013/189814 PCT/EP2013/062198 184 A'NH 2 - B 'NH 2 : A'N N'B'NH 2 (V) K OH N A HO S N,,'N K 3 S HI N HO 3 S S0 3 H (VI) 5
14. Use of a chemical compound according to any one of claims 1 to 9, a chemical composition according to claim 10 or 11 or of an aqueous solution according to claim 12 for dying fibers, as well as blends of such fibres selected from the group consisting of: vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, 10 rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers; and 15 synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres.
15. Fiber and blends containing such fiber selected from the group consisting of: vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, WO 2013/189814 PCT/EP2013/062198 185 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 5 and triacetate fibers and Lyocell fibers; and synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres comprising one or more chemical compounds according to any one of claims 1 to 9 etither in chemically and/or physically bound form.
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