NZ713120B2 - Dye mixtures of reactive dyes, production and use - Google Patents

Dye mixtures of reactive dyes, production and use Download PDF

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Publication number
NZ713120B2
NZ713120B2 NZ713120A NZ71312014A NZ713120B2 NZ 713120 B2 NZ713120 B2 NZ 713120B2 NZ 713120 A NZ713120 A NZ 713120A NZ 71312014 A NZ71312014 A NZ 71312014A NZ 713120 B2 NZ713120 B2 NZ 713120B2
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New Zealand
Prior art keywords
hydrogen
phenyl
sulfatoethyl
sozx
soz
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NZ713120A
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NZ713120A (en
Inventor
Roxana Barbieru
Brian Connolly
Clemens Grund
Yuan Han
Adrian Murgatroyd
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Dystar Colours Distribution Gmbh
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Priority claimed from EP20130182245 external-priority patent/EP2862902A1/en
Application filed by Dystar Colours Distribution Gmbh filed Critical Dystar Colours Distribution Gmbh
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Publication of NZ713120B2 publication Critical patent/NZ713120B2/en

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Abstract

The present invention is directed to dye mixture(s) comprising at least one dye of general formula (I) and at least one dye selected from the group consisting of the dyes of formula (IIa)-(IIf) process for their production and their use for dying fibers and textiles.

Description

Dye mixtures of reactive dyes, production and use The present invention s to the technical field of reactive dyes.
Mixed reactive dyes and their use for dyeing and printing of hydroxyl-, amino-, and/or carboxamido-containing al in black and dark brown shades are known from prior art and can be used as colorants in different applications, see for example US ,445,654, US 5,611,821, KR 94-2560 and Sho 58—160362. However, they have a number of technical disadvantages such as unsatisfactory light fastness and insufficient or l color build-up.
The poor performance of the reactive dyes ned in the documents above is the reason for the fact that other dyes are still used instead for dyeing even though they have other disadvantages. For dyeing wool in dark shades and in black in particular C.|. Mordant Black 9 — based dyes are in use since 1902. Dyes based on this substance show a good build-up on the fibre and have good fastness properties.
However, they have a big disadvantage: For fixation on the textile fibre they need to be treated with Chromium. This causes an environmental issue, since the chromium in the ater of the dyeing process will mostly get into the environment. In case the dyeing process is not handled properly there may also be a direct health threat for the workers, since the Chromium III, which is used may be oxidized to the cancerogenic Chromium VI.
Accordingly there is a long felt need to avoid the Mordant Black — based dyes, but of course the good dyeing properties should be ined. CH 695 613 describes mono- functional dyes of a tris-azo type as well as bi-functional dyes of a bis-azo type. Both variants do not have sufficient fastness properties compared to Mordant Black. EP 0 870 807 also discloses bis-azo compounds. A couple of other documents including also EP 1 155 089 describe and claim mixtures bi-functional dyes, however, none of the es disclosed can match the dyeing ties of the Mordant Black dyes.
Consequently, there is a uous demand for novel reactive dyes or reactive dye mixtures having improved properties, such as deep color build—up coupled with good fastness properties. singly, it has now been found that the dye mixtures described in the present invention show these above-mentioned properties to a high degree. The novel dye es are remarkable for high build-up, excellent light fastness and good overall fastness properties on the materials mentioned above and on blends containing them. Most importantly, the dye mixtures described in the present invention are heavy metal free and also do not need to be treated using heavy metals during the dyeing process. Thus they are or in ecological and toxicological performance and provide dyeings that are of very good levelness.
The t invention accordingly provides dye mixtures comprising at least one dye ’IO of general formula (I) BNCN a NCN/DJBNCMC 803M and at least one dye selected from the group consisting of the dyes of formula (Ila)- (llf) sozx SO2X (Ilf) each ofA and C, independent of each other is a radical of general formula (1a) wherein each of R3 to R5, independent of each other is en, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, y, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, oromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, 803M or COOM, or is alkyl substituted by one or more substituents ed from the group consisting of y, aryl, cycloalkyl, alkoxy, thioalkoxy, N,N,N-trialkylammonium, N,N,N- ’IO triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylammoni- um, N-acylamino, N-cinnamoylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, thiocarbonyl, acyloxy and aryloyloxy, or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents ed 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, amino, N- cinnamoylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or is SO2—X, where X is vinyl or a radical —CH2CH2—Y and Y is a group removable under alkaline conditions such as OSOsM, SSOsM, OCOCHs, OPOsM or halogen, or is a group of general formula (2a) WO 28499 (28) R6 is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, 803M or COOM, or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, lkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SOsM, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, cycloalkyl, ’10 alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and 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, amino, halogen, cyano, 803M, COOM, nitro, acyl, ’I5 thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, R7 is en, alkyl, lkyl 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, SOsM, COOM, nitro, acyl, yl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and 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 ting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SOsM, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, aryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, c is an integer of 0 to 6, RG is a reactive anchor of general a (3a), (3b) or (30), R19 R21 w W W *MRzo *AN/ R15 *MRW (33) (3b) (30) wherein each of R16 to R“, independent of each other is halogen, R16 can also be a rest of formula (4a) (48) wherein ’IO R22 is hydrogen, halogen, alkyl, , thioalkoxy, y, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, 803M or COOM, or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, koxy, N-acylamino, halogen, cyano, SOsM, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, R15 is one of the groups selected from general formula (5a) or (5b), 2014/068151 each of R23, R24 and R26, independent of each other is hydrogen, alkyl, cycloalkyl or aryl, is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-alkylaminocarbonyl, N,N- dialkylaminocarbonyl, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, carbonyl, alkoxythiocarbonyl, acyloxy and 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, lkyl, alkoxy, thioalkoxy, N-acylamino, N-alkylaminocarbonyl, N,N- dialkylaminocarbonyl, halogen, cyano, 803M, COOM, nitro, acyl, yl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and loxy, each of R25, R27 and R28, independent of each other is hydrogen, halogen, alkyl, N- acylamino, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, l, sulfamoyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SOsM or COOM, or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-alkylaminocarbonyl, N,N- dialkylaminocarbonyl, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, y and aryloyloxy, or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and tuted by one or more tuents selected from the group consisting of hydroxy, aryl, cycloalkyl, , thioalkoxy, N-acylamino, N-alkylaminocarbonyl, N,N- dialkylaminocarbonyl, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, oromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, R24 can also be —CH20H2-SOz-X, where X is vinyl or a l —CH20H2—Y where Y is a group removable under alkaline conditions such as 0803M, SSOsM, OCOCH3, 0P03M or halogen, and R28 can also be -SOz-X where X is the same as defined above, each of B and D, independent of each other is a radical of general formula (6a) (68) wherein each of R29 to R31, independent of each other is hydrogen, halogen, alkyl, amino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, ’I5 thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, 803M 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, alkyl—N—monoarylammonium, N,N—diaryl—N— monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, oromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and loxy, or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and tuted 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-diaryI-N-monoalkylammonium, N-acylamino, N- oylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, 2014/068151 aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or is SO2—X, where X is vinyl or a radical —CH2CH2—Y and Y is a group removable under alkaline conditions such as OSOsM, SSOsM, , OPOsM or halogen, or is a group of general formula (2a) as defined above, each of a and b, independent of each other is an r of O or 1 whereby a + b is not ’IO 0 and dyes of general a (I) contain at least two reactive anchors, M is hydrogen, lithium, sodium, potassium, ammonium or mono-, di-, tri- or tetra-(C1- C4)-alkylammonium, one equivalent of an alkali earth metal, or a monovalent organic cation, each of R41 to R68, 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, 803M or COOM, or is alkyl substituted by one or more substituents ed from the group consisting of hydroxy, aryl, cycloalkyl, , 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, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and loxy, 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 ting of hydroxy, aryl, cycloalkyl, alkoxy, koxy, N,N,N—trialkylammonium, N,N,N—triarylammonium, N,N— dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, halogen, cyano, 803M, COOM, nitro, acyl, yl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, each of R69 and R70 independent of each other is Cl or F, each of d, e, fand g ndent of each other is an integer of O or 1, each of h and k independent of each other is an integer ofO to 6, each of Z1 to Z4, independent of each other is a group ofgeneral formula (2a), where (2a) is the same as defined above, each ofW1 and W2, independent of each other is a linking group of general formula (7a), (7b) or (70), * ’ ‘ \HEW“9c/ *—N N \ / _\_H R R \ (7a) (7b) (70) wherein each of R71, R72, R75, R76 and R77, independent of each other is hydrogen, halogen, alkyl, N-acylamino, N,N-dia|ky|amino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, 803M or COOM, or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, koxy, N-acylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, l, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, thiocarbonyl, acyloxy and 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 y, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, l, oromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, and each of R73, R74, R78 and R79, independent of each other is hydrogen, alkyl, cycloalkyl or aryl, or is alkyl substituted by one or more substituents selected from the group ting of hydroxy, aryl, cycloalkyl, , thioalkoxy, N-acylamino, N,N-dialkylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, l, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, ’IO 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, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, cycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, R71 or R72 can form rings with R73, m is an integer of 1 to 6, M and X are the same as defined above and means point of attachment.
This invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I) and (lla)—(llf).
Alkyl groups appearing in this invention may be straight—chain or branched and are (01' lkyl groups, preferably (C1-CB)—8|ky| groups, for example n-butyl, isobutyl, n- pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.
The same applies to alkoxy groups which accordingly are preferably (Ci-Cs)-alkoxy, for e methoxy and , to thioalkoxy groups, which are ably (C1-Cs)— thioalkoxy, for example —SCH3 or —SC2H5. 2014/068151 Cycloalkyl groups are preferably (C3-Cs)-cyc|oalkyl and especially preferably cyclopentyl and cyclohexyl. The term cyloalkyl 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 tuents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalky|)amino, bis-(hydroxyalkyl)amino, monoalkyI-mono- (hydroxyalky|)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
’IO Aryl groups in this invention are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprises unsubstituted as well as substituted phenyl and naphthyl.
Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalky|)- amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl or y.
Heteroaryl groups appearing in this invention are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1,2,4-thiadiazole, 1,2,4-triazole, ole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1,3,4- thiadiazole, furane, e, benzoxazole or isoxazole. The terms heteroayl 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, ydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and y.
Heterocycloalkyl groups are preferably pyrrolidine, dine, morpholine, tetrahydrofuran or piperazine. The term heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, , alkylthio, acyl, nitro, cyano, amino, monoalkylamino, lamino, mono(hydroxyalkyl)amino, bis xyalkyl)amino, monoalkyl—mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, ino, amino— carbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.
Halogen is preferably chlorine, bromine or fluorine.
M is preferably hydrogen, lithium, sodium, or potassium.
A group ble under alkaline conditions (Y) is a group, which will leave the molecule under alkaline conditions to yield the vinyl sulfone function. es of such groups are OSOsM, SSOsM, OCOCH3, OPOsM and halogen.
Preferred mixtures comprise at least one dye of general a (la) (la) and at least one dye of general formula (Ila) or (llb) sozx wherein each of R34 to R40, independent of each other is en, halogen, alkyl, N-acylamino, alkoxy, hydroxy, cyano, nitro, carbonyl, acyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, lkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, 803M or COOM, X and M are the same as defined above, in formula (la) ’IO each of R34 to R40, independent of each other is hydrogen, (C1-C4)alkyl, )alkoxy, n, acyl, N-acylamino or 803M, X is vinyl or B-sulfatoethyl, in formula (Ila) and (llb) each of R41 to R48 and R57, independent of each other is hydrogen, (Cl-C4)alkyl, (Cl- C4)alkoxy, halogen, acyl, N-acylamino or 803M, Z1 is d as above whereby c is 0 or ’I, R6 and R7 is hydrogen or alkyl, R16 to R21 independent of each other is halogen, R22 is hydrogen, each of R23, R24 and R26 independent of each other is hydrogen, alkyl, or aryl, each of R25, R27 and R28 independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, hydroxy, acyl, aryloyl, trifluoromethyl, acyloxy, cycloalkyl, aryl, heteroaryl, SOsM or COOM, R24 can also be —CH20H2-SOz—X, where X is vinyl or a radical —CH20H2—Y where Y is a group removable under alkaline conditions such as OSOsM, SSOaM, OCOCHs, OPOsM or halogen, and R28 can also be -SOz—X where X is the same as defined above, X is most preferred to be vinyl or B-sulfatoethyl.
Even more preferred is a dye mixture as described above, comprising at least one dye of general a (lb) (lb) wherein each of R34, R35, R39 and R40 ndent of each other is hydrogen, (C1-C4)alkyl, (C1- C4)a|koxy, 803M or COOM, ’IO M is the same as defined above and X is vinyl or B-sulfatoethyl.
Also highly preferred are dye mixtures as described above, comprising at least one dye of the general formula (Ila) or (llb) sozx 2014/068151 wherein, in the formula (Ila) or (Ilb), each of R41 to R48 and R57, independent of each other is hydrogen, (C1-C4)alkyl, (Cl- C4)alkoxy or 803M, Z1 is defined as above whereby c is 0 or 1, R6 and R7 are hydrogen, R16 to R“, independent of each other is halogen, R22 is hydrogen, each of R23, R24 and R26 independent of each other is hydrogen, (Ci-C4)alkyl, (Ci- C4)alkoxy, 803M or COOM or aryl, each of R25, R27 and R28 independent of each other is hydrogen, )alkyl, (Ci- C4)alkoxy, 803M or coom, R24 can also be —CH20H2-SOz-X, where X is vinyl or a radical —CH20H2—Y where Y is a group removable under alkaline conditions such as OSOsM, SSOsM, , OPOsM or halogen, and R28 can also be -SOz—X where X is the same as defined above, X is vinyl or B—sulfatoethyl.
Most particulary preferred mixtures comprise at least one dye of the formula (lb) SOZX (lb) and at least one dye of the general formula (Ila) or (llb) SO2X SO2X wherein, each of R34, R35, R39 and R40, independent of each other is hydrogen, (C1-C4)alkyl, (Ci- C4)a|koxy, 803M or COOM, M is the same as defined above, X is vinyl or B-sulfatoethyl, in the formula (Ila) or (llb), ’IO each of R41 to R48 and R57 independent of each other is hydrogen, (Ci-C4)alkyl, (C1- C4)a|koxy or 803M, Z1 is d as above with c is 0 or 1, R6 and R7 are hydrogen, R16 to R21 independent of each other is halogen, R22 is hydrogen, each of R23, R24 and R26 independent of each other is hydrogen, (C1-C4)alkyl, (C1- oxy, 803M or COOM or aryl, each of R25, R27 and R28 independent of each other is hydrogen, (Ci-C4)alkyl, (C1- C4)a|koxy, 803M or COOM, R24 can also be 2—SOz-X, where X is vinyl or a radical —CH20H2—Y where Y is a group ble under alkaline conditions such as OSOsM, SSOsM, OCOCHs, OPOsM or halogen, R28 can also be -SOz-X where X is the same as defined above, X is vinyl or B-sulfatoethyl.
The dyes of the general formula (I) are obtainable via standard s of synthesis ’IO known to one skilled in the art. The dyes of the general formula (llf) can be prepared according to known procedures described e.g. in WC 568 A1.
Ranges of weight% of the components of the inventive dye mixtures are e.g.: Component(s) of formula (I): 5-95, preferably 25-80 Component(s) of formula (Ila) to (Ilf): 95-5, preferably 75-20 In each dye mixture the components (I) and (lla)—(llf) add up to 100 % in case the dye mixture consists of the dyes mentioned above or to less than 100 % in case additional dyes are added e.g. as shading components. In such a case the amount of shading components preferably is less than 10, more preferred less than 5 and most preferred less than 2 weight % based on the weight of all dyes of the dye mixture, with the ratio of component(s) of formula (I) to those offormula (lla-llf) being the same as in the case of a composition consisting of those components.
The dyes according to the invention can be present as a preparation in solid or liquid (dissolved) form. In solid form, they n, in general, the electrolyte salts customary in the case of water—soluble and especially fiber—reactive dyes, such as sodium chloride, potassium chloride and sodium sulphate, and may further contain the aries customary in commercial dyes, such as buffer substances capable of setting a pH in aqueous solution between 3 and 7, for example sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogenphosphate, sodium rate and disodium hydrogenphosphate, and small amounts of siccatives or when they are present in a liquid, aqueous solution (including a t ofthickeners of the type customary in print pastes), they may also contain substances which ensure a long life for these preparations, for example mold preventatives. ln solid form, the dye mixtures according to the ion are generally present as powders or grannules which contain electrolyte salt and which will hereinbelow generally be referred to as a preparation with or whithout one or more of the abovementioned auxiliaries. In the preparations, the dye mixture is t at 20 to 90% by weight, based on the preparation containing it. The buffer substances are generally t in a total amount of up to 5% by weight, based on the preparation.
When the dye mixtures according to the invention are present in an aqueous solution, the total dye content of these solutions is up to about 50% by weight, for example between 5 and 50% by weight, the electrolyte salt t preferably being below 10% by weight, based on the aqueous solution. The aqueous solutions (liquid preparations) can also contain buffer substances in an amount which is lly up to 5% by weight and preferably from 0.1 to 2% by wight.
The dye mixtures according to the ion are preparable in a conventional manner, for example by mechanically mixing the individual dyes, whether in the form of their dye powders or grannules or in the form of aqueous solutions, for example their as- synthesized solutions, which may additionally contain customary auxiliaries.
As an alternative, the dye mixtures according to the invention can be obtained by conventional diazotization and coupling reactions of le mixtures of diazo and coupling components in the desired amount ratios.
Dye mixtures contain vinylsulfonyl groups as reactive ls can be synthesized not only starting from riately substituted vinylsulfonyl-anilines or naphthylamines but also by reaction of a dye mixture with a vinylizable reaction group such as the B- sulfatoethylsulfonyl in ne medium at a temperature, for example, from 20 to 80 °C, at a pH of, for example, from 7 to 14. This conversion is effected in a manner ar to one skilled in the art.
The dyes ofthe dye mixtures in the present invention are reactive containing fiber- 2014/068151 reactive functional rests. 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.
The dye mixtures of the t invention are le for dyeing and printing of natural, manufactured, regenerated, mechanically or chemically ed, recycled 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.
The present invention thus also provides for the use of the dye mixtures of the present invention for dyeing or printing the above-mentioned fiber materials and their blends, or rather processes for dyeing or printing such materials in a conventional manner, by using a dye mixture of the present invention as a colorant. The dye mixtures of the present invention provide shades from deep browns to deep blacks having good technical performance on these materials. Technical performance includes build-up, fastness properties and ess.
Examples of natural fibre materials as described above are vegetable fibres such as seed fibres i.e. cotton, organic cotton, kapok, coir from coconut husk, bast fibers i.e. flax, hemp, jute, kenaf, ramie, rattan, leaf fibres i.e. sisal, en, banana, stalk fibres i.e. bamboo, and fibres from animals such as wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials.
Examples of manufactured and regenerated fibres are cellulosic fibres such as paper and cellulosic regenerated fibres such as viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers. es of synthetic fiber materials as bed above are nylon materials, like nylon—6, nylon—6.6 and aramid fibres.
The above-mentioned ates to be dyed can be t in various forms such as but not limited to yarn, woven fabric, loop—formingly knitted fabric or carpet.
The dye mixtures of the present invention can be applied to and fixed on the materials mentioned, in particular on the fiber materials mentioned, by the application techniques known for water-soluble dyes and particularly for fiber-reactive dyes.
On cellulose fibers, they produce by the t method from a short liquor as well from a long liquor, by using various acid-binding agents and ifappropriate l salts, such as sodium chloride or sodium sulfate, dyeings having good color yields. The liquor ratio can be selected within a wide range and is for example between 3:1 and 100:1 and preferably between 5:1 and 30:1. Applications are preferably from an aqueous batch at temperatures between 40 and 105 °C, if appropriate at a temperature of up to 130 °C under superatmospheric pressure, and if appropriate in the ce of customary dyeing auxiliaries. One possible ure here is to introduce the material into the warm batch and to gradually heat the batch to the desired ature and complete the dying operation. The neutral salts which accelerate the tion of the ’I5 dyes can also if desired only be added to the batch after the actual dyeing temperature has been reached.
Padding processes likewise provide excellent color yields and a very good color buildup on cellulose fibers, the dyes being fixable in a conventional manner by batching at room temperature or elevated temperature, for example at up to about 60 °C, or by ng or by means of dry heat.
Similarly, the customary printing processes for cellulise fibers, which can be carried out in one step, for e by printing with a print paste containing sodium bicarbonate or some other inding agent and by subsequent steaming at 100 to 130 °C, or in two steps, for example by printing with a neutral to weak acidic print color and then fixing either by passing the printed material through a hot electrolyte— containing alkaline batch or by overpadding with an alkaline electrolyte-containing padding liquor and uent batching or steming or dry heat treatment of the alkali- overpadded material, produce strong color prints with well—defined contours and a clear white ground. The outcome of the prints is affected little, if at all, by ions in the fixing conditions.
When fixing by means of dry heat in accordance with the customary thermofix processes, hot air at 120 to 200°C is used. In addition to the customary steam at 101 to 103 °C, it is also possible to use superheated steam and high-pressure steam at temperatures of up to 160 °C.
The inding agents which effect the fixation of the dyes on the cellulose fibers are for example water-soluble basic salts of alkali metals and se alkaline earth metals of inorganic or organic acids or compounds which liberate alkali in the heat. Especially suitable are the alkali metal hydroxides and alkali metal salts of weak to medium ’IO inorganic or organic acids, the preferred alkali metal nds being the sodium and potassium compounds. Such acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium onate, potassium carbonate, sodium formate, sodium ogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, lass or trisodium phosphate.
The dye mixtures of the present invention are notable for outstanding color strength and a steep course of the buildup curve on cellulose fiber materials when applied in the familiar dyeing and printing ses. The dyeings and prints obtainable with the dye mixtures of the t invention on cellulose fiber materials further have good lightfastness and, in particular, good tnesses, such as fastness to washing, water and acidic and alkaline perspiration.
The dyeings and prints obtained following the customary aftertreatment of rinsing to remove unfixed dye portions further exhibit good tnesses, in particular since unfixed dye portions are easily washed off because of their good solubility in cold water.
Furthermore, the dye mixtures according to the invention are also notable for outstanding color strength and very good buildup on wool fiber als when applied in the familiar dyeing and printing ses. The process of dyeing on wool is here carried out in a conventional manner from an acidic medium. For instance, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate can be added to the dyebatch to obtain the desired pH. To obtain a dyeing of acceptable levelness, it is advisable to add a customary leveling agent, for example a leveling agent based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzensulfonic acid and/or of an aminonaphthalene sulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide.
For instance, the dye mixture according to the invention is preferably subjuected to the t process initially form an acidic dyebatch having a pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end ofthe dyeing time, shifted into the neutral and optionally weakly ne range up to a pH of 8.5 to bring about, especially for very deep s, the full ve bond between the dyes of the dye mixtures according to the invention and the fiber. At the same time, the dye portion not vely ’IO bound is removed. The dyeings and prints obtainable with the dye mixtures of the present invention on wool fiber materials further have very good lightfastness and, in particular, good wetfastnesses, such as fastness to washing, crossdyeing, potting and acidic and alkaline perspiration.
The procedure described herein also applies to the production of s on fiber materials composed of other natural polyamides or of synthetic polyamides and polyurethanes. These materials can be dyed using the ary dyeing and printing processes described in the literature and known to one skilled in the art (see for example H.-K.Rouette, Handbuch der Textilveredlung, Deutscher rlag GmbH, Frankfurt/Main). In general, the material to be dyed is introduced into the batch at a temperature of about 40 °C, agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature n 60 and 98 °C. However, the dyeings can also be carried out at the boil or in sealed dyeing apparatus at temperatures of up to 106 °C. Since the water solubility of the dye mixtures ing to the ions is very good, they can also be used with advantage in customary continuous dyeing ses. The color strength of the dye mixtures according to the invention is very high. The dyeings obtainable with the dye mixtures of the present invention on polyamide fiber materials further have good lightfastness and, in particular, good wetfastnesses, such as fastness to washing, water and acidic and alkaline ration.
The dye mixtures 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 mixture of the present invention likewise form part of the subject matter of the present invention.
The inks of the present invention comprise a dye mixture of the present invention in amounts which preferably range from 0.1% by weight to 50% by weight, more ably from 1% by weight to 30% by weight and most preferably from 1% by weight to 15% by weight, based on the total weight of the ink.
The inks, as well as the dye mixtures of the t invention may, if desired, contain r dyes used in digital printing.
For the inks of the present invention to be used in the continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present ’I5 invention may include c solvents at a total level of 1-50% and preferably 5-30% by weight.
The inks of the present invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in a temperature range from 20 to 50°C. Preferred inks have a viscosity of 1.5 to 20 mPas and ularly preferred inks have a viscosity of 1.5 to 15 mPas.
Useful viscosity moderators include gical additives, for example: polyvinylcaprolactam, nylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose .
As further additives the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a function of the process used (thermal or piezo technology). Useful surface—active substances include for example all surfactants, preferably nonionic tants, butyldiglycol and 1,2—hexanediol.
The inks of the t invention may further include customary ves, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1% by weight based on the total weight of the ink.
The inks may be prepared in a conventional manner by mixing the components in water.
The inks of the present invention are particularly useful in inkjet printing processes for ng a wide variety of materials, in particular of wool and polyamide fibers.
’IO In contrast to conventional textile printing, where the printing ink already contains all the fixing chemicals and thickeners for a reactive dye, in inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step. The pretreatment of the textile ate, for example cellulose and regenerated cellulose fibers and also silk and wool, is effected with an aqueous alkaline liquor prior to printing.
To fix reactive dyes there is a need for alkali, for example sodium carbonate, sodium bicarbonate, sodium acetate, trisodium phosphate, sodium silicate, sodium hydroxide, alkali donors such as sodium chloroacetate, sodium formate, hydrotropic substances such as urea, ion tors such as sodium nitrobenzenesulfonates, and also thickeners to prevent flowing of the motives when the ng ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans. These pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3- roll pad, contactless spraying technologies, by means of foam application or using appropriately d inkjet technologies, and uently dried. After printing, the textile fiber material is dried at 120 to 150 °C and subseuqnetly fixed.
The fixing of the inkjet prints prepared with reactive dyes may be effected at room temperature or with saturated steam, with superheated steam, with hot air, with microwaves, with infrared radiation, with laser or elctron beams or with other suitable energy transfer techniques.
A distinction is made between one- and two- phase fixing ses. In ase fixing, the necessary fixing chemicals are y on the e substrate.
In two-phase fixing, this pretreatment is unnecessary. Fixing only requires alkali, which, following inkjet printing, is applied prior to the fixing process, without intermediate drying. There is no need for r additives such as urea or thickener. Fixing is followed by the print aftertreatment, which is the uisite for good fastness, high brilliance and an impeccable white groud.
The prints produced using the inks of the present ion have, in particular on polyamide, a high color strength and a high dye bond stability not only in the acidic region but also in the alkali region, also good lightfastness and good wetfastness ’IO properties, such as fastness to washing, water, crossdyeing, g and alkaline and acidic perspiration.
The examples hereinbelow serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to parts by volume as the kilogram relative to the liter. The compounds described in the examples in terms of a formula are indicated in the form of the sodium salts, since they are generally prepared and isolated in the form of their salts, preferably sodium or ium salts, and used for dyeing in the form of their salts. The starting compounds described in the examples hereinbelow can be used in the sis in the form of the free acid or likewise in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.
EXAMPLE ’I 29 parts of an electrolyte—containing dye powder containing the brown dye of the formula (la-1) 2014/068151 g/VosoSNa (la-1) and 71 parts of an electrolyte—containing dye powder containing the navy dye of the formula (Ila-1) \o o NaOSO\<.\/IS QWOSOsNa OH NH2 ‘0 /O o NaOS 803Na \ (Ila-1) are mechanically mixed with each other.
The resulting dye mixture according to the invention provides grey to black s on wool under the dyeing conditions customary for reactive dyes.
EXAMPLE 2 31 parts of an electrolyte-containing dye powder containing the brown dye of the formula (la-2) iiNosoNa ”m8\ N033 N E:NH6' \SOaNa (Ia-2) and 69 parts of an electrolyte-containing dye powder containing the navy dye of the formula (Ila-1) NaOSSO\/\CS) i iNOSOSNa 0‘ OH NH \O / N N \ o o / Na038 803Na \ (Ila-’I) are mechanically mixed with each other.
The resulting dye mixture according to the invention es grey to black dyeings on wool under the dyeing conditions customary for ve dyes.
EXAMPLE 3 2014/068151 33 parts of an electrolyte-containing dye powder containing the brown dye of the formula (Ia-3) g<\\/osoym NH2 \0 NaO3S N\\ E] El 809w OK/l \O O OsNa (Ia-3) and 19 parts of an electrolyte-containing dye powder containing the brown dye of the formula (Ia-4) 2014/068151 QNOSOsNa NH2 \0 N8038 N\\ I I 803Na 803Na O / \ O OSOsNa (la-4) and 48 parts of an electrolyte-containing dye powder containing the navy dye of the formula (Ila—’I) NaOSO\/O\|SO|087:!“1N OH NH2 ME)jsoIOI/O\/0803Na NaOS SO3Na 0\ (Ila-1) are mechanically mixed with each other.
The resulting dye mixture according to the invention provides grey to black dyeings on wool under the dyeing conditions customary for reactive dyes.
All examples of the following tables are prepared as formulations as explained above and give black dyeings g from reddish black over neutral to sh, yellowish blacks.
In the following es 4-199, dyes of a (la’) are used in formulations.
A\ //N wherein, M is hydrogen, sodium, potassium and lithium and means a point of attachment.
All examples of the following table are prepared as formulations as explained above using dyes of formula (Ila-1) and (la’). o \o o NaO3SO\/\/g EWOSO3Na O’ OH NH2 ‘0 NaO3S SO3Na 0\ (Ila-1) Expl Compo- Component (la') Component (la') Ratio nent (II) (II) : (la') : (la') 4 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl W0 2015/028499 2014/068151 4-SOzX= 4—soz(rs- 4-SOzX= 4502(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f?>- 4-SOzX= 4-8020!)- oethyl) sulfatoethyl) (Ila-1) R34: Hydrogen R34: Hydrogen 51 : 31 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(3- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SO3M R40: 2-SOaM C = phenyl C = phenyl 4-SOzX= 4-SOz(f?>- = 4-8020!)- sulfatoethyl) sulfatoethyl) 6 (Ila-1) R34: Hydrogen R34: Hydrogen 5O : 30 : 20 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= L7>- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOz(L7>- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 7 ) R34: Hydrogen 52 :48 : -- R35: Hydrogen A = phenyl W0 2015/028499 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4-SOz(fS- sulfatoethyl) 8 (Ila-1) R34: Hydrogen 55 : -- : 45 R35: 2-SOsM A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4-8020!)- sulfatoethyl) 9 (Ila-1) R34: 2-Methoxy 52 :48 : -- R35: 5-Methoxy A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: 2—Methoxy R40: 5-Methoxy C = phenyl = 4-SOz(f$- sulfatoethyl) ) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOaM A = phenyl A = phenyl W0 2015/028499 2014/068151 4-SOzX= 4—soz(rs- 4-SOzX= 4502(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f?>- 4-SOzX= 4-8020!)- sulfatoethyl) sulfatoethyl) 11 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= f?>- 3-SOzX= 3-8020!)- oethyl) sulfatoethyl) 12 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(L7>- = 5802(3- sulfatoethyl) sulfatoethyl) 13 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOaM A = phenyl A = phenyl W0 2015/028499 4-SOzX= rs- 4-SOzX= 4502(3- oethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl = 4-SOz(fZ>- 4-SOzX= 4-8020!)- sulfatoethyl) sulfatoethyl) ”l4 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl = 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz(fZ>- 4-SOzX= 4-8020!)- sulfatoethyl) sulfatoethyl) (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4-SOz(fZ>- 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 16 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4-SOz(l3>- 3-SOzX= 3302(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l?>- 3-SOzX= 3-8020!)- sulfatoethyl) sulfatoethyl) ”l7 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- = !»- sulfatoethyl) oethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= lS- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of a (Ila-2) and (la’).
IO 00 0 NaO 8 80 Na Na0380 3 3 OSO3Na (Ila-2) Expl Compo- Component (la') Component (la') Ratio nent (II) (II) : (la') : (la') 18 (Ila-2) R34: Hydrogen R34: Hydrogen 55:31:14 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: en R40: Hydrogen R40: en C = phenyl C = phenyl 4-SO2X= 4-SOz(f$- 4-SOzX= - oethyl) sulfatoethyl) 19 (Ila-2) R34: Hydrogen R34: Hydrogen 56:29:15 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) (Ila-2) R34: Hydrogen R34: Hydrogen 55:30:15 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOZ(B- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 21 (Ila-2) R34: Hydrogen 54 :46 : -- R35: Hydrogen A = phenyl W0 2015/028499 2014/068151 4-SOzX= 4602(8- sulfatoethyl) R39: en R40: Hydrogen C = phenyl = 4602(8- sulfatoethyl) 22 (Ila-2) R34: Hydrogen 57 : -- : 43 R35: 2-SOsM A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 23 (Ila-2) R34: 2-methoxy 55 :45 : -- R35: 5-methyl A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: 2-SO3M C = phenyl 4-SOzX= 4602(3- sulfatoethyl) 24 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl W0 28499 = 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SOsM C = phenyl C = phenyl 4-SO2X= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- = 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 3-SOzX= 3602(8- sulfatoethyl) oethyl) 26 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: oxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOZ(B- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 27 (Ila-2) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SO2X= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 28 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 29 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: en A = phenyl A = phenyl 4-SOzX= 4-SOz(f3- 3-SOzX= 53-80202,- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: 2—SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= - oethyl) sulfatoethyl) (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4—soz(r3- 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= l3- 3-SOzX= 3602(8- oethyl) sulfatoethyl) 31 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- = 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: oxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4-SOz(l3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (Ila—3) and (la’).
Expl Compon Component (la') Component (la') Ratio ent (ll) (ll) : (la') : (la') 32 (Ila-3) R34: Hydrogen R34: Hydrogen 48 :20 :32 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl W0 2015/028499 = 4-SOz([?>- 4-SOzX= 4602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: en R40: en C = phenyl C = phenyl 4-SO2X= 4-SOz(f3- 4-SOzX= 4-SOz(f3- sulfatoethyl) sulfatoethyl) 33 (Ila-3) R34: Hydrogen R34: Hydrogen 5’I : 18 : 31 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4—soz(ts- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SO3M C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4-SOz(f3- sulfatoethyl) oethyl) 34 (Ila-3) R34: Hydrogen R34: Hydrogen 5O : 20:30 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—sozm- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOZ(B- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) ) R34: Hydrogen 52 : 48 : -- R35: Hydrogen A = phenyl W0 28499 4-SO2X= - sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 36 (Ila-3) R34: Hydrogen 55 : -- : 45 R35: 2-803M A = phenyl = 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4-SOz(f3- sulfatoethyl) 37 (Ila-3) R34: 2-Methoxy 52 : 48 : -- R35: Hydrogen A = phenyl -SO2X= - sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 3-SOzX= 3—SOZ(f$—sulfatoethyl) 38 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—SOzX= 4—8020!)— 4—SOzX= 4—8020!)— sulfatoethyl) sulfatoethyl) W0 2015/028499 2014/068151 R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—803M C = phenyl C = phenyl = 4—soz(ts- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 39 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4—80203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4—30203- 3-SOzX= 3602(8- sulfatoethyl) oethyl) 40 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4—80203- 4-sogx= 4602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl 4-SO2X= 4-SOz(B- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) 41 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—803M A = phenyl A = phenyl 4-SO2X= 4602(8- 4-SOzX= 4602(3- oethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy W0 2015/028499 R40: en R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4-SOz([3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 42 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 3- = 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz([3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 43 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4—30203- 3-SOzX= 3-SOz(fZ>- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 44 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4-SOz(fS- 3-SOzX= 3-SOz(fZ>- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen W0 2015/028499 C = phenyl C = phenyl 4-SO2X= 4-SOz(i$- 3-SOzX= 3-SOz(l$- sulfatoethyl) sulfatoethyl) 45 (Ila—3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= l3— 3-SOzX= 3-soz(rs- oethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SO2X= 4602(8- 5-SOzX= 5-SOz(lZ>- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of form ula ) and (la’).
O O N 0 808 ll II 080 Na 3 \/\//S SO3Na s\<\/ 3 o \@ OH NH2 0 o /N N\ N/ 00 ‘“ NaO3S 803Na (Ila-4) EXpl Compo- Component (la') Component (la') Ratio nent (II) (II) : (la') : (la') 46 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 10 : 32 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl = 4602(8- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen W0 2015/028499 C = phenyl C = phenyl 4—so2x= 4—80203- 4-SOzX= fS- sulfatoethyl) sulfatoethyl) 47 (Ila—4) R34: Hydrogen R34: Hydrogen 51 : 8 : 41 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4 4-SOzX= 4802(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-803M C = phenyl C = phenyl = 4—80203- 4-SOzX= 4802(3- oethyl) sulfatoethyl) 48 (Ila-4) R34: Hydrogen R34: Hydrogen 50 : 1O : 40 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl 4—SOzX= 4—sozus- 4—SOzX= 4802(3— sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 4-SOz(f3— 5-SO2X= 5602(3- sulfatoethyl) sulfatoethyl) 49 (Ila-4) R34: Hydrogen 62 : 38 : -- R35: Hydrogen A = phenyl = 4—8020!)— sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl W0 2015/028499 4-SO2X= 4602(8- sulfatoethyl) 50 (Ila-4) R34: Hydrogen 55 : -- : 45 R35: 2—SOaM A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) ) R34: Hydrogen 55 : 45 : -- R35: 2—SO3M A = phenyl 4-SO2X= - oethyl) R39: Hydrogen R40: 2-SO3M C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 52 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SO2X= 4602(8- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SO3M C = phenyl C = phenyl W0 2015/028499 4—so2x= [?>- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 53 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4-SOz([Z>- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4-SOz(f$- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 54 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4—soz(ts- 4-SOzX= 4-SOz(fZ>- sulfatoethyl) oethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SO2X= f3— 5-SO2X= - sulfatoethyl) sulfatoethyl) 55 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SO2X= 4602(8- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl W0 2015/028499 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 56 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4-SOz([Z>- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl 4—so2x= 3- = 4—soz(rs- sulfatoethyl) sulfatoethyl) 57 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(f$- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 58 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl = 4602(8- 3-sogx= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4—so2x= 4-SOz(l3— 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) 59 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4602(8- = 3-SOz(lZ~,- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: en C = phenyl C = phenyl 4-SO2X= - 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (Ila-5) and (la’). 8II<\/OSO3Na OH NH2 N\ /©/ \0 I I N NaO3S SO3Na (Ila-5) Expl Compo- Component (la') ent (la') Ratio nent (II) (II) : (la') : (la') 60 (lla- R34: Hydrogen R34: Hydrogen 45 : 1O : 35 ) R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(r3- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) 61 (”3- R34: en R34: Hydrogen 50 : 9 : 41 ) R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl 4—sogx= 4-SOzU3- 4-sogx= 4502(3- sulfatoethyl) sulfatoethyl) 62 (”3- R34: Hydrogen R34: Hydrogen 50 : 10 : 40 ) R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl = 4—soz(rs- 4-sogx= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 4-SOz(f3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 63 (”3- R34: Hydrogen 60 : 40 : -- ) R35: Hydrogen A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: en R40: Hydrogen C = phenyl W0 2015/028499 4-SOzX= - sulfatoethyl) 64 (”3- R34: Hydrogen 55 : -- : 45 ) R35: 2—SOsM A = phenyl 4-SOzX= - sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 65 (”3- R34: Hydrogen 55 : 45 : -- ) R35: en A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: 2-Methoxy R40: 5-Methyl C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 66 (lla- R34: Hydrogen R34: Hydrogen 48 : 34 : 18 ) R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SO3M C = phenyl C = phenyl W0 28499 4-SOzX= r3- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) 67 (”3- R34: en R34: Hydrogen 48 : 34 : 18 ) R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—sogx= 4-SOz(f3- 3-sogx= },- sulfatoethyl) sulfatoethyl) 68 (”8- R34: Hydrogen R34: Hydrogen 48 : 34 : 18 ) R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—sogx= 4—soz(rs- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SO2X= 4-SOz(f3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 69 (lla- R34: Hydrogen R34: Hydrogen 48 : 34 : 18 ) R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: en R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl W0 2015/028499 2014/068151 4-SOzX= r3- = 4—soz(r3- sulfatoethyl) sulfatoethyl) 70 (”3- R34: Hydrogen R34: en 48 : 34 : 18 ) R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4—sogx= 4-SOzU3- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) 71 (”3- R34: Hydrogen R34: Hydrogen 48 : 34 : 18 ) R35: en R35: Hydrogen A = phenyl A = phenyl 4—sogx= 3- 3-sogx= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4—sogx= 4—soz(rs- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) 72 (lla- R34: Hydrogen R34: Hydrogen 48 : 34 : 18 ) R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(3- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(r3- 3-SO2X= 3602(8- oethyl) sulfatoethyl) 73 (lla- R34: Hydrogen R34: Hydrogen 48 : 34 : 18 ) R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-SOzX= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SO2X= 4602(8- 5-SO2X= 5602(8- oethyl) sulfatoethyl) All examples of the following table are ed as formulations as explained above using dyes of formula (Ila-6) and (la’).
NaO3S 3 (Ila-6) Expl Compo- Component (la') Component (la') Ratio nent (II) (II) : (la') : (la') 74 (Ila-6) R34: Hydrogen R34: Hydrogen 50 : 30 : 20 R35: Hydrogen R35: 2—803M A = phenyl A = phenyl 4—so2x= 4302(3- 4-SO2X= 4602(3- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4—so2x= 4-SOz([?>- 4-SOzX= rs- sulfatoethyl) sulfatoethyl) 75 (Ila-6) R34: Hydrogen R34: Hydrogen 54 : 28 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4-SOz([Z>- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-803M C = phenyl C = phenyl 4—so2x= 4—soz(ts- 4-SOzX= rs- sulfatoethyl) sulfatoethyl) 76 (Ila-6) R34: Hydrogen R34: Hydrogen 56 : 26 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4—soz(ts- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 4-SOz(f3— 5-SO2X= - sulfatoethyl) sulfatoethyl) 77 (Ila-6) R34: Hydrogen 55 : 45 : -- R35: Hydrogen A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl W0 2015/028499 4-SO2X= 4602(8- sulfatoethyl) 78 ) R34: Hydrogen 58 : -- : 42 R35: 2—SO3M A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 79 (Ila-6) R34: Hydrogen 55 : 45 : -- R35: Hydrogen A = phenyl 3-so2x= 3602(3- sulfatoethyl) R39: en R40: Hydrogen A = phenyl 3-so2x= 3-8020!)- sulfatoethyl) 80 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SO2X= 4602(8- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: 2-SO3M C = phenyl C = phenyl W0 2015/028499 4—so2x= 4-SOz([?>- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 81 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl = 4-SOz([Z>- 4-SOzX= 4602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4-SOz(f$- 3-SOzX= - oethyl) sulfatoethyl) 82 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4—soz(ts- 4-SOzX= 4—soz(r3- sulfatoethyl) oethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SO2X= 4-SOz(f3— = 5602(8- sulfatoethyl) sulfatoethyl) 83 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SO2X= 4602(8- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl W0 2015/028499 = 4—30203- 4-SOzX= rs- sulfatoethyl) sulfatoethyl) 84 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4-SOz([Z>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: oxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 85 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(f$- 3-SOzX= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 86 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4602(8- 3-sogx= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4—so2x= 4-SOz(l3— 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 87 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(l3— 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SO2X= 4-SOz(l3— 5-SO2X= - sulfatoethyl) sulfatoethyl) All examples of the ing table are prepared as formulations as explained above using dyes of formula (Ila-7) and (la’).
O (ISDI<\/OSOBNa /@ \ OH NH2 g ‘o f0 00 NaO S 80 Na Na0380 3 3 (Ila-7) EXpl Compo- Component (la') Component (la') Ratio nent (II) (II) : (la') : (la') 88 (Ila-7) R34: Hydrogen R34: Hydrogen 55 : 3O : 15 R35: en R35: 2—SO3M A = phenyl A = phenyl 4-SO2X= 4-SOz(i$- 4-SOzX= i3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) 89 ) R34: Hydrogen R34: en 55 : 35 : 10 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) 90 (Ila-7) R34: Hydrogen R34: Hydrogen 56 : 32 : 12 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4-SOzX= 4—soz(r3- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: en C = phenyl C = naphthyl 4-SOzX= 4-SOz(f3>- 5-SO2X= 5602(8- sulfatoethyl) oethyl) 91 (Ila-7) R34: Hydrogen 56 : 44 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl W0 2015/028499 4-SOzX= 4602(8- sulfatoethyl) 92 (Ila-7) R34: Hydrogen 56 : -- : 44 R35: 2—SOsM A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 93 (Ila-7) R34: Hydrogen 54 : 46 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: 2-Methoxy R40: en C = phenyl -SOzX= 5602(8- sulfatoethyl) 94 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: 2—SO3M C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-SOzX= r3- sulfatoethyl) oethyl) 95 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= rs- 3-sogx= 3-3020},- sulfatoethyl) oethyl) 96 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4-SOzX= 4—soz(r3- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SOzX= f3>- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 97 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) 98 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) 99 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4-SOz(f3>- 3-sogx= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: 2-803M C = phenyl C = phenyl = 4-SOz(L7>- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) 100 ) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4-SOz(iZ>- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) 101 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4-SOz(i?>- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: en R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l3— 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of a (Ila-8) and (la’).
NaO3S SO3Na (Ila-8) Expl Compo- ent (la') Component (la') Ratio nent (II) (II) : (la') : (la') 102 ) R34: Hydrogen R34: Hydrogen 48 : 30 : 22 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SO2X= 4-SOz(i3- 4-802X= 4-SOz(i$- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 103 (Ila-8) R34: Hydrogen R34: Hydrogen 51 : 27 : 22 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4-SOz(fZ>- 4-SOzX= 4—soz(rs- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 104 (Ila-8) R34: Hydrogen R34: Hydrogen 50 : 26 : 24 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: en R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOz(f3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 105 (Ila-8) R34: en 55 : 45 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: en R40: Hydrogen C = phenyl W0 2015/028499 = 4602(8- sulfatoethyl) 106 (Ila-8) R34: Hydrogen 50 : -- : 50 R35: 2—SOsM A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 107 (Ila-8) R34: oxy 55 :45 : -- R35: 5—Methoxy A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 108 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- 4-802X= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl W0 28499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 109 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4-SOz(fZ>- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 110 (Ila-8) R34: en R34: Hydrogen 48 : 34 : 18 R35: en R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl 4-SOzX= f3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 111 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- = 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: en R40: 5-methyl C = phenyl C = phenyl W0 2015/028499 = 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) oethyl) 112 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4—soz(rs- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 113 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: Hydrogen A = phenyl A = phenyl 4-SOzX= B- 3-802X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SOsM C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(rs- oethyl) sulfatoethyl) 114 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-sogx= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(r3- = 3602(8- sulfatoethyl) oethyl) 115 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4—soz(rs- 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(i3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) All examples of the ing table are prepared as formulations as explained above using dyes of formula (llc-1) and (la’).
HNJQNANHIN 0 803Na NaOSS 0 OH NH2 @ SO3Na NaO s so Na 01 3 3 OSO3Na (llc-1) Expl Compo- ent (la') Component (la') Ratio nent (II) (II) : (la') : (la') 116 (IIc-1) R34: Hydrogen R34: Hydrogen 70 : 5 : 25 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SO2X= 4-SOz(l3- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen W0 2015/028499 R40: Hydrogen R40: en C = phenyl C = phenyl 4-SOzX= 4-SOz(13- 4-SOzX= 4602(8- sulfatoethyl) oethyl) 117 (IIc-1) R34: Hydrogen R34: Hydrogen 72 : 6 : 22 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4-SOz(1$- sulfatoethyl) sulfatoethyl) 118 (IIc-1) R34: en R34: Hydrogen 70 : 5 : 25 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SO2X= 4—soz(rs- 4-SOzX= 4—soz(rz.- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOz(B- 5-SOzX= 5602(3- sulfatoethyl) oethyl) 119 (IIc-1) R34: en 75 :25 : -- R35: Hydrogen A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen W0 2015/028499 C = phenyl 4-SOzX= 4302(8)- sulfatoethyl) 120 (llc—1) R34: Hydrogen 7O : —— : 30 R35: 2-SOsM A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: Hydrogen R40: en C = phenyl 4-802X= 4602(3- sulfatoethyl) 121 (llc-1) R34: Hydrogen 75 :25 : -- R35: Hydrogen A = phenyl 3—SOzX= 3602(8— sulfatoethyl) R39: 2-SO3M R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 122 (llc-1) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4—SOzX= 4—8020!)— 4—SOzX= !)— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SOsM C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 123 (IIc-1) R34: en R34: Hydrogen 48 : 34 : 18 R35: en R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4-SOz(fZ>- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 124 (IIc—1) R34: Hydrogen R34: Hydrogen 48 : 34 : “l8 R35: en R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: en R40: 3-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 125 (IIc—1) R34: Hydrogen R34: Hydrogen 48 : 34 : “l8 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl = 4602(8- 4-802X= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 126 (IIc-1) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4-SOz(fZ>- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= L7>- 4-SOzX= 4602(8- oethyl) sulfatoethyl) 127 (IIc—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl = 4-802(B- 3-802X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SOsM C = phenyl C = phenyl 4-SOzX= rs- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 128 (IIc—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- = 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(r3- 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) 129 (IIc-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4—soz(rs- 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: en R39: 2—methoxy R40: en R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4602(8- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as ations as explained above using dyes of formula (lib-1) and (la’). 80 N g OSO3Na a \ 3 OH NH2 ‘0 /N N \ HN t as ‘N / N Na038 SOSNa F N (lib-1) Expl Compo- ent (la') ent (la') Ratio nent (II) (II) : (la') : (la') 130 (lib-1) R34: Hydrogen R34: Hydrogen 60 : 1O : 30 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—SOzX= 4—8020!)— 4—SOzX= 4—8020!)— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen W0 2015/028499 C = phenyl C = phenyl 4-SO2X= 4-SOz([Z>- = 1$- sulfatoethyl) sulfatoethyl) 131 (llb—1) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(13- 4-SOzX= 4-SOz(1$- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SO3M C = phenyl C = phenyl 4-SO2X= 4-SOz([Z>- 4-SO2X= 4602(3- oethyl) sulfatoethyl) 132 (llb-1) R34: Hydrogen R34: Hydrogen 60 : 8 : 32 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl 4—SOzX= 4—SOz(1$— 4—SOzX= 4—SOz(1$— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 3- 5-SO2X= 5602(3- sulfatoethyl) sulfatoethyl) 133 (IIb-1) R34: Hydrogen 60 :40 : -- R35: en A = phenyl 4—SOzX= 4—SOz(l$—sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SO2X= 4-SOz(1$-sulfatoethyl) W0 2015/028499 134 (Ilb—1) R34: Hydrogen 65 : —— : 35 R35: 2-803M A = phenyl 4-SOzX= 4602(3- oethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- oethyl) 135 (IIb—1) R34: Hydrogen 62 :38 : —- R35: Hydrogen A = phenyl 3—SOzX= 3—SOz(l$—sulfatoethyl) R39: en R40: Hydrogen C = phenyl 4-SO2X= 4-SOz(13-sulfatoethyl) 136 (IIb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-SOsM A = phenyl A = phenyl 4—so2x= 4—sozm- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4-SOz(f3— sulfatoethyl) sulfatoethyl) 137 (IIb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SO3M W0 2015/028499 A = phenyl A = phenyl = 4—80203- = 4-SOz(fS- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 3- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 138 (llb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4—80203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl 4-SO2X= 4-SOz(B- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) 139 (Ilb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4—so2x= 4—soz(ts- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 140 (Ilb-1) R34: en R34: en 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl W0 2015/028499 4—so2x= [?>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: oxy C = phenyl C = phenyl 4-SO2X= 4-SOz([Z>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 141 (Ilb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(f$- 3-SOzX= 3-soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(1$- = 4602(8- sulfatoethyl) oethyl) 142 (IIb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(f3— 3-SOzX= rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(13— 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 143 (IIb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4602(8- 3-SOzX= i3— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: en C = phenyl C = phenyl 4-SO2X= 4-SOz(i3— 5-SOzX= - sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (lib—2) and (la’).
N g<\/0803Na /N N\ HN N/ \N 3 SO3Na F N F (lib-2) Expl Compo- Component (la') Component (la') Ratio nent (II) (II) : (la') : (la') 144 (lib—2) R34: en R34: en 60 : 10 : 30 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(l3— 4-SOzX= 4-SOz(l3— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(i$- 4-SOzX= 4-8020},- sulfatoethyl) sulfatoethyl) 145 (lib—2) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl W0 2015/028499 = 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SO3M R40: 2-SOsM C = phenyl C = phenyl 4-SO2X= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) oethyl) 146 ) R34: Hydrogen R34: Hydrogen 6O : 8 : 32 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SO2X= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= f3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 147 (IIb-2) R34: Hydrogen 6O :40 : -- R35: Hydrogen A = phenyl = 4-SOz(f3-su|fatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4—SOzX= 4—SOz(l$—su|fatoethyl) 148 (IIb-2) R34: Hydrogen 65 : -- : 35 R35: 2-SOsM A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen W0 2015/028499 R40: en C = phenyl = 4-SOz(f3— sulfatoethyl) 149 (IIb-2) R34: Hydrogen 62 :38 : -- R35: Hydrogen A = phenyl 3-SOzX= 3-SOz(f3-su|fatoethyl) R39: Hydrogen R40: 2-803M C = phenyl 4—SOzX= 4—SOz(l$—su|fatoethyl) 150 (IIb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rz- 4-SOzX= 4-8020},- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 151 (IIb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SO2X= 4602(8- 4-802X= 4602(3- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 28499 4-SOzX= 4—soz(r3- 3-SOzX= 3602(8- oethyl) sulfatoethyl) 152 (IIb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl = 4-SOz(fZ>- 4-SOzX= rs- sulfatoethyl) sulfatoethyl) R39: en R39: 2—methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 5-SO2X= 5602(8- sulfatoethyl) oethyl) 153 (IIb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 154 (IIb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- 4-802X= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl W0 28499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 155 (IIb-2) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4—soz(rs- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: 2—SOsM C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 156 (IIb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: en A = phenyl A = phenyl 4-SOzX= 4-802(B- 3-802X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 3-SOzX= 02,- sulfatoethyl) sulfatoethyl) 157 (IIb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-sogx= 3602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4602(8- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (lib-3) and (la’).
SOH Q80H m3 O“ 3 /N N\ HN N/ O0 \N N/XN Hogs sogH ”0&3Q N \NACI H0380 5 H (”b_3) Compo- Component (la') Component (la') Ratio Expl nent (II) (II) : (la') : (la') 158 (lib-3) R34: Hydrogen R34: Hydrogen 60 : 10 : 30 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4-SOzX= 4—80203- 4-SOzX= - sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—sogx= 4-SOzU3- = 4—3020},- sulfatoethyl) sulfatoethyl) 159 (lib-3) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2—803M A = phenyl A = phenyl 4-SOzX= 4602(8- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-803M R40: 2-803M C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(r3- 4-SOzX= 4—soz(r3- sulfatoethyl) oethyl) 160 (IIb-3) R34: en R34: Hydrogen 60 : 8 : 32 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = yl 4-SO2X= 4-802U3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 161 (IIb-3) R34: Hydrogen 60 :40 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 162 ) R34: Hydrogen 65 : -- : 35 R35: 2-SOsM A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl W0 2015/028499 4-SOzX= 4802(8- oethyl) 163 (IIb-3) R34: 2-Methoxy 62 :38 : -- R35: 5—Methyl A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: 2-Methoxy R40: 5-Methyl C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 164 (IIb-3) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl = 4—soz(rs- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4—sogx= 4—soz(rs- 4-sogx= 4602(8- oethyl) sulfatoethyl) 165 (Ilb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4602(3- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 = 4—soz(r3- = 3602(8- sulfatoethyl) sulfatoethyl) 166 (IIb-3) R34: en R34: en 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl = 4-802U3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 167 (IIb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—sogx= 4—soz(rs- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4—sogx= 4—soz(rs- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) 168 (IIb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(3- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: en R40: 2—methoxy C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(r3- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) 169 (IIb-3) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 3-SOzX= 3602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4—sogx= 4-SOzU3- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) 170 (IIb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl = 4-802U3- = 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—sogx= 4—soz(rs- 3-sogx= 3602(8- sulfatoethyl) sulfatoethyl) 171 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(3- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: oxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4-SOz(l3- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as ned above using dyes of formula (llf—1) and (la’).
N2\|N HN/* HN)\\N O * H SO3H H038 0 OH NH2 N”N N“ J? [N] N N 803H 1 H038 SO3H (IIf—1) Compo- Component (la') Component (la') Ratio EXpI nent (II) (II) : (la') : (la') R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl 4—so2x= 4-SOz(lZ>- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 173 (Hf-1) R34: en R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl W0 28499 4-SO2X= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SO3M R40: 2-803M C = phenyl C = phenyl 4-SO2X= [Z>- 4-SOzX= 4-SOz(f3— sulfatoethyl) sulfatoethyl) 174 (Hf-1) R34: en R34: Hydrogen 6O : 8 : 32 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SO2X= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 175 (Hf-1) R34: Hydrogen 6O :40 : -- R35: Hydrogen A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 176 (Hf-1) R34: Hydrogen 65 : -- : 35 R35: 2-803M A = phenyl W0 2015/028499 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 177 (Ilf—1) R34: Hydrogen 62 : 38 : -- R35: en A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: 2-Methoxy R40: oxy C = phenyl 4-SOzX= - sulfatoethyl) 178 (IIf—1) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(13— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 179 (IIf—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 28499 4—so2x= 4-SOz([?>- 4-SOzX= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SO2X= 13— 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 180 (Ilf—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4—soz(ts- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SOzX= 4-SOZU3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 181 (IIf—1) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: oxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4-SOz(13— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 182 (IIf—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 28499 4—so2x= 4-SOz([?>- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl 4-SO2X= 4-SOz([Z>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 183 (Ilf—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(f$- 3-SOzX= 3-soz(rs- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(1$- 4-SOzX= 4602(8- sulfatoethyl) oethyl) 184 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(f3— 3-SOzX= 3-soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(13— 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 185 (IIf—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl WO 28499 4-SO2X= - 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SO2X= 4-SOz(l3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (lid—1) and (la’).
CI N NH HN N CI OH NH2 / N N \ 80 H 3 30 H038 303H 3 (IId-1) Expl Compo- Component (la') Component (la') Ratio nent (II) (II) : (la') : (la') 186 (lid-1) R34: Hydrogen R34: Hydrogen 60 : 10 : 30 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SO2X= 4-SOz(i$- = - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-so2x= 4602(8- sulfatoethyl) sulfatoethyl) 187 (IId-1) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-so2x= 4-8020},- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-so2x= 4602(3- sulfatoethyl) sulfatoethyl) 188 (IId-1) R34: en R34: Hydrogen 60 : 8 : 32 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4-SOzX= 4—soz(r3- 4-so2x= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOz(f3>- 5-SO2X= - sulfatoethyl) oethyl) 189 ) R34: Hydrogen 60 :40 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl W0 28499 4-SOzX= 4602(8- sulfatoethyl) 190 (IId-1) R34: Hydrogen 65 : -- : 35 R35: 2—SOsM A = phenyl 4-SO2X= - sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 191 (IId-1) R34: 2—Meth0xy 62 :38 : -- R35: Hydrogen A = phenyl -SOzX= 4602(8- sulfatoethyl) R39: 2-Methoxy R40: Hydrogen C = phenyl = 4602(8- sulfatoethyl) 192 (IId-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- 4-SO2X= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SO3M C = phenyl C = phenyl W0 2015/028499 = 4—soz(rs- 4-so2x= - sulfatoethyl) sulfatoethyl) 193 (IId-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-so2x= 4-8020},- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 3-so2x= 3602(3- sulfatoethyl) sulfatoethyl) 194 (IId-1) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4-SOzX= 4—soz(r3- 4-so2x= 4602(3- oethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: en R40: 3-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(fZ>- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 195 (IId-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl = 4602(8- 4-SO2X= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-so2x= 4602(8- sulfatoethyl) sulfatoethyl) 196 (IId-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-so2x= 4-8020},- sulfatoethyl) oethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-so2x= 4602(8- sulfatoethyl) sulfatoethyl) 197 (IId-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4-SOz(fZ>- 3-so2x= 3602(3- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= L7>- 4-so2x= 4-8020!)- oethyl) sulfatoethyl) 198 (IId-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- = },- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4-SOz(lS- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) 199 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: en A = phenyl A = phenyl 4-SOzX= 4-SOz(l$- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4602(8- 5-SO2X= - sulfatoethyl) sulfatoethyl) Furthermore, in the following examples 200-395, dyes of formula (la”) are used in formulations. wherein M is hydrogen, sodium, ium and lithium, means point of attachment.
All examples of the following table are prepared as ations as ned above using dyes of formula (Ila-1) and (la”) NaO3SO\/O\|SOI08¢“)! OH NH2 rum/$80ISOI/O\/OSO3Na NaO3:“:3880Na 0\ (Ila-1) Expl Compo- Component (la") Component (la") Ratio nent (II) (II) : (la") : (la") 200 (Ila-1) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(l3— 4-SOzX= 4602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—SOzX= 4-SOz(l$— 4—SOzX= 4602(8— sulfatoethyl) sulfatoethyl) 201 (Ila-1) R34: Hydrogen R34: Hydrogen 51 :31 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl 4—SOzX= 4—8020!)— 4—SOzX= 4—8020!)— sulfatoethyl) sulfatoethyl) W0 2015/028499 202 (Ila-1) R34: Hydrogen R34: Hydrogen 50 : 3O : 20 R35: Hydrogen R35: 2—803M A = phenyl A = phenyl 4—sogx= 4—soz(rs- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= f3- 5-SO2X= - sulfatoethyl) sulfatoethyl) 203 (Ila-1) R34: Hydrogen 52 :48 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 204 (Ila-1) R34: Hydrogen 55 : -- : 45 R35: 2-SOsM A = phenyl 4-SOzX= 4802(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= - sulfatoethyl) 205 (Ila-1) R34: 2-Methoxy 52 :48 : -- W0 2015/028499 R35: 5-Methoxy A = phenyl 4-SOzX= 4-8020!)- sulfatoethyl) R39: 2—Methoxy R40: 5-Methoxy C = phenyl 4—SOzX= 4602(8— oethyl) 208 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4 4-SOzX= 4-8020!)- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: 2-SOsM C = phenyl C = phenyl 4—SOzX= 4—soz(r$- 4—SOzX= 4-8020},— sulfatoethyl) sulfatoethyl) 207 ) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4-8020!)- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4—80203- 3-SOzX= },- sulfatoethyl) sulfatoethyl) 208 (Ila—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM W0 2015/028499 A = phenyl A = phenyl 4-SOzX= 4-SOz(fZ>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3—803M C = phenyl C = phenyl 4-SOzX= 4-SOz(B- 5-SO2X= - sulfatoethyl) sulfatoethyl) 209 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4—80203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4—soz(r3- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) 210 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl = 3- 4-SO2X= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: en R40: oxy C = phenyl C = phenyl = 4-SOzU3- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) 211 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 2014/068151 4-SOzX= 4—soz(r3- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(l3- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) 212 (Ila-1) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—sogx= 4-SOz(l3- = 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l3- 3-SOzX= 3-SOz(l3— sulfatoethyl) sulfatoethyl) 213 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4602(8- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: oxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= l3— 5-SOzX= 5-802“- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of a (Ila—2) and (la”) NaOSS SOsNa Na0380 OSOsNa (Ila-2) Expl Compo- Component (la") Component (|a") Ratio nent (II) (II) : (|a") : (Ia") 214 (Ila—2) R34: Hydrogen R34: Hydrogen 55:31 :14 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl 4-SOzX= 4-SOz(l$— 4-SOzX= f$— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SO2X= 4-SOz(l$- 4-SOzX= 4-SOz(f$- sulfatoethyl) sulfatoethyl) 215 (Ila-2) R34: Hydrogen R34: Hydrogen 56:29:15 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(l$— 4-SOzX= 4—SOz(f$— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-803M C = phenyl C = phenyl 4-SO2X= f$- 4-SO2X= 4602(3- sulfatoethyl) sulfatoethyl) 216 (Ila-2) R34: en R34: en 55:30:15 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl W0 2015/028499 4—so2x= 4—30203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 4-SOz(13- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 217 (Ila-2) R34: en 54 :46 : -- R35: Hydrogen A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4-8020!)- sulfatoethyl) 218 (Ila-2) R34: Hydrogen 57 : -- : 43 R35: 2-SO3M A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= f3— sulfatoethyl) 219 (Ila-2) R34: oxy 55 :45 : -- R35: 5-methyl A = phenyl W0 2015/028499 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: 2-SO3M C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 220 (Ila-2) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4—so2x= 4—soz(r3- 4-SOzX= 4—soz(rs- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 221 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—soz(r3- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: en C = phenyl C = phenyl = 4-SOz(f3— 3-SOzX= 3-SOz(f3— sulfatoethyl) sulfatoethyl) 222 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 2015/028499 1 1 O 4—so2x= 4—30203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: 2-methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SO2X= 13- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 223 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl = 4—30203- 4-SOzX= rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 224 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- = 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 225 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 1 1 1 4—so2x= 4-SOz(l3— 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOaM C = phenyl C = phenyl 4-SO2X= 4-SOz(l3— 4-SOzX= 4-SOz(lS- sulfatoethyl) sulfatoethyl) 226 (Ila-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(l3— 3-SOzX= rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l3— = 3-SOz(lS- sulfatoethyl) sulfatoethyl) 227 (Ila-2) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: en C = phenyl C = phenyl 4-SOzX= - 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (Ila—3) and (la”) W0 2015/028499 ’l 12 NaO3SO\/\PI PI/VOSOsNa 0‘SooSO3Na OH NH2 8*0 oo SO3Na NaO3S so3 a (Ila-3) Expl Compo- Component (Ia") Component (Ia") Ratio nent (II) (II) : (Ia") : (Ia") 228 (Ila-3) R34: Hydrogen R34: en 48 : 20 : 32 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4—80203- = 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 229 (Ila-3) R34: en R34: Hydrogen 51 : 18 : 31 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4-SOz([Z>- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: 2-SOsM R40: 2-803M C = phenyl C = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 230 (Ila-3) R34: Hydrogen R34: Hydrogen 50 : 20:30 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl W0 2015/028499 1 13 = 4—30203- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 4-SOz([3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 231 (Ila-3) R34: Hydrogen 52 : 48 : -- R35: Hydrogen A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: en C = phenyl 4-SOzX= 4-8020!)- sulfatoethyl) 232 (Ila-3) R34: Hydrogen 55 : -- : 45 R35: 2-SO3M A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl = 4-SOz(f3— sulfatoethyl) 233 (Ila-3) R34: 2-Methoxy 52 :48 : -- R35: Hydrogen A = phenyl W0 2015/028499 ’l 14 -SO2X= 5602(8- oethyl) R39: Hydrogen R40: Hydrogen C = phenyl 3-SOzX= 3-SO2(13-sulfatoethyl) 234 (Ila—3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-802X= 4-soz(rs- 4-SOzX= 4-SOz(f$- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4—so2x= 4—80203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 235 (Ila—3) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4—802X= 4—soz(rs- 4—SOzX= 4—soz(rs— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4—80203- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) 236 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl 4—802X= !)— 4—SOzX= 4—8020!)— sulfatoethyl) sulfatoethyl) W0 2015/028499 1 15 R39: en R39: oxy R40: Hydrogen R40: 3—803M C = phenyl C = phenyl 4-SO2X= 4-SOz(f3— 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) 237 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 3- = 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4—so2x= 4—soz(rs- = 4—soz(rs- sulfatoethyl) sulfatoethyl) 238 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4—so2x= 4-SOz(L7>- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 239 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen W0 2015/028499 1 16 R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(l$- 4-SOzX= 4-SOz(l3— sulfatoethyl) sulfatoethyl) 240 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= i3- 3-SOzX= rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l3— 3-SOzX= 3-SOz(l3— sulfatoethyl) sulfatoethyl) 241 (Ila-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4—soz(i3- 3-SOzX= 3-SOz(lZ>- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4602(8- 5-SOzX= 5602(3- sulfatoethyl) sulfatoethyl) All examples of the ing table are prepared as formulations as explained above using dyes of a (Ila-4) and (la”) II/\/OSO3Na Expl Compo— Component (la") Component (Ia") Ratio nent (II) (H) i ('3") 1 ('3") 242 (Ila-4) R34: en R34: Hydrogen 48 : 1O : 32 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl = 4—soz(rs- 4—SOzX= 4—soz(rs— sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SO2X= 4602(8- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 243 (Ila-4) R34: Hydrogen R34: Hydrogen 51:8:41 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SO2X= 4802(8- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2—SOsM C = phenyl C = phenyl 4-SO2X= 4602(8- 4-SOzX= 4602(8- oethyl) sulfatoethyl) 244 (Ila-4) R34: Hydrogen R34: Hydrogen 50:10:40 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl W0 2015/028499 1 18 4—so2x= 4—30203- = 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 4-SOz([3- 5-SOzX= - sulfatoethyl) sulfatoethyl) 245 (Ila-4) R34: en 62 : 38 : -- R35: Hydrogen A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4-8020!)- sulfatoethyl) 246 (Ila-4) R34: Hydrogen 55 : -- : 45 R35: 2-SO3M A = phenyl = 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4-SOz(f3— sulfatoethyl) 247 (Ila-4) R34: Hydrogen 55 : 45 : -- R35: 2-SO3M A = phenyl W0 2015/028499 1 19 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: 2-SO3M C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 248 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4—soz(r3- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 249 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—soz(r3- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— = 3-SOz(f3— oethyl) sulfatoethyl) 250 (Ila-4) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 2015/028499 = 4—30203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SO2X= 4-SOz([3- = 5802(3- oethyl) sulfatoethyl) ’I (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-SOsM A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 252 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: oxy C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 253 (Ila-4) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 4—so2x= 4-SOz(l3— 3-SOzX= 3602(3- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SO2X= l3— 4-SOzX= 4-SOz(lS- sulfatoethyl) sulfatoethyl) 254 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= l3— 3-SOzX= 3-soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4-SOz(l3— 3-SOzX= 3-SOz(lS- sulfatoethyl) sulfatoethyl) 255 (Ila-4) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SO2X= - 3-SOzX= 3602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l3— 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (Ila—5) and (la”) 1 22 II /\/OSOSNa /S S\ 0/ \©\ OH NH2 //N DO N\ /©/ \0 N \N Na038 SO3Na (Ila-5) Expl Compo- Component (|a") Component (Ia") Ratio nent (II) (II) : (Ia") : (Ia") R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SO2X= 4-SOz([3— 4-SOzX= 4-SOz(fS- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—SOzX= 4-SOz(l3— 4—SOzX= 4—SOz(fS— sulfatoethyl) sulfatoethyl) 257 (Ila-5) R34: Hydrogen R34: Hydrogen 50 : 9 : 41 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4-SOz([3— 4-SOzX= 4-SOz(fS- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SO3M R40: 2-SO3M C = phenyl C = phenyl 4—SOzX= 4-SOz(l$— 4—SOzX= 4—SOz(fS— sulfatoethyl) sulfatoethyl) 258 (Ila-5) R34: en R34: en 50 : 1O : 40 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 2015/028499 4—so2x= 4—30203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 4-SOz([3- 5-SOzX= 5802(3- sulfatoethyl) oethyl) 259 (Ila-5) R34: Hydrogen 6O : 40 : -- R35: Hydrogen A = phenyl 4-SO2X= - oethyl) R39: Hydrogen R40: Hydrogen C = phenyl = 4-8020!)- sulfatoethyl) 260 (Ila-5) R34: Hydrogen 55 : -- : 45 R35: 2-SO3M A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4-SOz(f3— sulfatoethyl) 261 (Ila-5) R34: Hydrogen 55 : 45 : -- R35: Hydrogen A = phenyl W0 2015/028499 4-SO2X= 4602(8- sulfatoethyl) R39: 2-Methoxy R40: 5-Methyl C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 282 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4—so2x= 4—soz(ts- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— = 4602(8- sulfatoethyl) sulfatoethyl) 263 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—sozm- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 3-SOzX= 3-SOz(f3— sulfatoethyl) sulfatoethyl) 264 (Ila-5) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 2015/028499 4—so2x= 4—30203- = - sulfatoethyl) oethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SO2X= 4-SOz([3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 265 (Ila-5) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4—30203- = 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl = 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 266 (Ila-5) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: en R39: 2—methoxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 267 (Ila-5) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 2014/068151 4—so2x= 4-SOz(l3— 3-SOzX= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: 2-803M C = phenyl C = phenyl 4-SO2X= 4-SOz(l$- = 4-SOz(l3— sulfatoethyl) sulfatoethyl) 268 (Ila-5) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(l3— 3-SOzX= 3-soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l$- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 269 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= l3— 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (Ila—6) and (la”) W0 2015/028499 NaOBSO\/\Iq Iq/\/OSO‘3Na 033 COOH OH NHZ S\‘o 00 COOH NaOSS 803Na (Ila-6) Expl Compo- Component (|a") Component (|a") Ratio nent (II) (II) : (Ia") : (|a") 270 (Ila-6) R34: Hydrogen R34: en 50 : 30 : 20 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4-SOz(f3- 4-SO2X= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 271 (Ila-6) R34: Hydrogen R34: Hydrogen 54 : 28 : 18 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl = 4-SOz(f3- 4-SO2X= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SO3M C = phenyl C = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) 272 (Ila-6) R34: Hydrogen R34: Hydrogen 56 : 26 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOz(f3- = 5802(3- sulfatoethyl) sulfatoethyl) 273 (Ila-6) R34: Hydrogen 55 : 45 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: en R40: Hydrogen C = phenyl = 4602(8- sulfatoethyl) 274 (Ila-6) R34: Hydrogen 58 : -- : 42 R35: 2-SO3M A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= - sulfatoethyl) 275 (Ila-6) R34: Hydrogen 55 : 45 : -- R35: Hydrogen A = phenyl W0 2015/028499 = 3302(3- sulfatoethyl) R39: Hydrogen R40: Hydrogen A = phenyl 3-SOzX= 3-8020!)- oethyl) 276 (Ila-6) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—sog(rs- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 277 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4—sog(rs- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 278 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) R39: en R39: 2—methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 279 (Ila-6) R34: en R34: en 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—sog(rs- 4-sogx= },- sulfatoethyl) sulfatoethyl) R39: en R39: 2—methoxy R40: Hydrogen R40: yl C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 280 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4—sog(rs- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 281 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4—soz(r3- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(l3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 282 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: Hydrogen A = phenyl A = phenyl 4-SOzX= l3- 3-sogx= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: en C = phenyl C = phenyl 4-SOzX= 4-SOz(l3- 3-SOzX= 3602(8- oethyl) sulfatoethyl) 283 (Ila-6) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(3- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4602(8- 5-SOzX= 5-802“- sulfatoethyl) sulfatoethyl) All examples of the following table are ed as formulations as explained above using dyes of formula (Ila—7) and (la”) W0 2015/028499 O\ (ISDI\ OSO3Na /@ OH NH2 0 \o f0 0o NaO 8 80 Na Na0380 3 3 (Ila-7) Expl Compo- Component (|a") Component (|a") Ratio nent (II) (II) : (la") : (la") 284 (Ila-7) R34: Hydrogen R34: Hydrogen 55 : 30 : 15 R35: en R35: 2-SO3M A = phenyl A = phenyl 4-SOzX= f$- 4-SO2X= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= f$- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) 285 (Ila-7) R34: Hydrogen R34: Hydrogen 55 : 35 : 10 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4-SOz(f3>- = 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 286 (Ila-7) R34: Hydrogen R34: Hydrogen 56 : 32 : 12 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-SOzX= r3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOZ(L7>- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 287 (Ila-7) R34: Hydrogen 56 : 44 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl = 4602(8- sulfatoethyl) 288 (Ila-7) R34: Hydrogen 56 : -- : 44 R35: 2-SO3M A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- oethyl) 289 (Ila-7) R34: Hydrogen 54 : 46 : -- R35: Hydrogen A = phenyl W0 2015/028499 4-SOzX= 4602(8- sulfatoethyl) R39: 2—Methoxy R40: en C = phenyl = 5802(3- sulfatoethyl) 290 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(fS- 4-SOzX= 4602(8- sulfatoethyl) oethyl) 291 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4-SOz(f3— 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 292 (Ila-7) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: oxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl 4-SOzX= L7>- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 293 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: oxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4-SOz(f?>- 4-SOzX= 4602(8- oethyl) sulfatoethyl) 294 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 295 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 28499 4-SOzX= 4-SOz(l3>- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= lS- = - sulfatoethyl) sulfatoethyl) 296 ) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 3-sogx= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(lS- 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) 297 (Ila-7) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-8020!»- 5-SOzX= 5-802“- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (Ila—8) and (la”) W0 2015/028499 N30 80 PI 3 \/\/S 080 Na O S(\/II 3 0/m \ OH NH2 \O /©/ \0 Na038 803Na (Ila-8) Expl Compo- Component (|a") Component (Ia") Ratio nent (II) (II) : (Ia") : (Ia") 298 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 30 : 22 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SO2X= 4-SOz(f3— 4-SOzX= 4-SOz(f3— oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(I3— 4-SOzX= 4—SOz(f$— sulfatoethyl) sulfatoethyl) 299 (Ila-8) R34: Hydrogen R34: Hydrogen 51 : 27 : 22 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4-SOz(f3— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SO3M R40: 2-SO3M C = phenyl C = phenyl 4-SOzX= I$— = 4—SOz(f$— sulfatoethyl) sulfatoethyl) 300 (Ila-8) R34: Hydrogen R34: Hydrogen 50 : 26 : 24 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl W0 2015/028499 4—so2x= 4—30203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: Hydrogen C = phenyl C = naphthyl 4-SO2X= 4-SOz([3- 5-SOzX= 5802(3- sulfatoethyl) oethyl) 301 (Ila-8) R34: Hydrogen 55 : 45 : -- R35: en A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 302 (Ila-8) R34: Hydrogen 5O : -- : 50 R35: 2-SO3M A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(3- sulfatoethyl) 303 ) R34: 2—Methoxy 55 : 45 : -- R35: 5-Methoxy A = phenyl W0 2015/028499 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl sulfatoethyl) 304 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4—so2x= 4—soz(r3- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(13- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 305 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—soz(r3- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 13- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 306 (Ila-8) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl W0 2015/028499 2014/068151 4—so2x= 4—30203- 4-SOzX= 4602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SO2X= 4-SOz([3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 307 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: en R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= },- sulfatoethyl) sulfatoethyl) 308 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2—methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4-8020!)- sulfatoethyl) sulfatoethyl) 309 ) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 4—so2x= 4-SOz(l3— 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: 2-803M C = phenyl C = phenyl 4-SO2X= 4-SOz(l$- 4-SOzX= 4-SOz(l3— sulfatoethyl) sulfatoethyl) 310 (Ila-8) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: en A = phenyl A = phenyl 4—so2x= 4-SOz(l3— 3-SOzX= 3-soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l$- 3-SOzX= 3-SOz(l3— sulfatoethyl) sulfatoethyl) 311 (Ila-8) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SO2X= 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l3— 5-SOzX= - sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as ations as explained above using dyes of formula (llc—1) and (la“) NJQNXNH| NaO38%:ZON OH NH i iIZNi:80 Na NaO3S 303Na 3 51 OSOsNa (IIc-1) Expl Compo- Component (Ia") Component (Ia") Ratio nent (II) (II) : (Ia") : (Ia") R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(I3- 4-SOzX= 4-SOz(f$- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4-SOz(f$- 4-SOzX= 4-SOz(fS- sulfatoethyl) sulfatoethyl) 313 (llc—1) R34: Hydrogen R34: Hydrogen 72 : 6 : 22 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(I3- = 4-SOz(f$- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-SO3M C = phenyl C = phenyl 4-SO2X= 4-SOz(f$- 4-SOzX= f$- sulfatoethyl) sulfatoethyl) 314 ) R34: Hydrogen R34: Hydrogen 70 : 5 : 25 W0 2015/028499 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4-SOz(1$- 4-SOzX= 4-SOz(f3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: Hydrogen C = phenyl C = naphthyl 4—SOzX= 4—SOzU3— 5—SOzX= 5—SOz(f$— sulfatoethyl) oethyl) 315 ) R34: Hydrogen 75 :25 : -- R35: Hydrogen A = phenyl 4-SOzX= 4-8020!)- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4—SOzX= 4602(8— sulfatoethyl) 316 (llc—1) R34: Hydrogen 70 : —— : 30 R35: 2-SO3M A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl = 4602(8- sulfatoethyl) 317 (llc—1) R34: Hydrogen 75 :25 : —— R35: Hydrogen W0 2015/028499 A = phenyl 3-so2x= 3602(3- sulfatoethyl) R39: 2-SOsM R40: Hydrogen C = phenyl 4-SO2X= 4602(8- oethyl) 318 (”C-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl = 4—80203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl = 4—30203- 4-SOzX= 4602(8- oethyl) sulfatoethyl) 319 (IIc-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4—80203- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4—30203- 3-SOzX= - sulfatoethyl) sulfatoethyl) 320 (IIc-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl W0 2015/028499 4—so2x= 4—30203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SO2X= [3- 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) 32’I (IIc-1) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: en R39: 2-methoxy R40: Hydrogen R40: yl C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) oethyl) 322 (IIc-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 323 (IIc-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 4—so2x= 4-SOz(l3— 3-SOzX= 3602(3- sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SO2X= 4-SOz(l3— 4-SOzX= 4-SOz(lS- sulfatoethyl) oethyl) 324 (llc-1) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—so2x= 4-SOz(l3— 3-SOzX= 3-soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= l3— 3-SOzX= 3-SOz(lS- sulfatoethyl) sulfatoethyl) 325 (llc-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl = 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: en C = phenyl C = phenyl 4-SOzX= 4-SOz(l3— 5-SOzX= 5802(3- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (lib—1) and (la”) W0 2015/028499 ICI)/\/OSO Na 803Na 3 /@ \\ OH NH2 g o / 00 IN NaOSS 803Na F N (IIb-1) Expl Compo- Component (|a") Component (|a") Ratio nent (II) (II) : (|a") : (|a") 326 (Ilb—’|) R34: Hydrogen R34: Hydrogen 60 : 1O : 30 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= fZ>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4-SOz(f?>- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) 327 (Ilb—1) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= fS— 4—SOzX= 4602(8— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SOsM R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(f?>- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) 328 (Ilb-1) R34: Hydrogen R34: Hydrogen 60 : 8 : 32 R35: Hydrogen R35: 2-803M W0 2015/028499 2014/068151 A = phenyl A = phenyl = 4-SOz(fS- 4-SOzX= 4-SOz(f3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOz(f3>- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 329 (IIb-1) R34: Hydrogen 60 : 40 : -- R35: Hydrogen A = phenyl = 4-SOz(f?>-sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4-SOz(f?>-sulfatoethyl) 330 (IIb-1) R34: Hydrogen 65 : -- : 35 R35: 2-SOsM A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4—SOzX= 4602(3— sulfatoethyl) 331 (IIb-’|) R34: en 62 : 38 : -- R35: Hydrogen A = phenyl 3-SOzX= 3-SOz(f3-sulfatoethyl) R39: Hydrogen W0 2015/028499 R40: Hydrogen C = phenyl 4-SOzX= 4-SOz(fS-sulfatoethy|) 332 (IIb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SOsM C = phenyl C = phenyl 4—SOzX= 4—soz(rs- 4—SOzX= — sulfatoethyl) sulfatoethyl) 333 (Ilb—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(f$- = 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(L7>- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 334 (Ilb—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= - 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4-SOz(f3- 5-SOzX= 5602(8- sulfatoethyl) oethyl) 335 (Ilb-1) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-sogx= 4—3020},- sulfatoethyl) sulfatoethyl) 336 (Ilb-1) R34: Hydrogen R34: Hydrogen 48 : 34 : “l8 R35: en R35: 2—SO3M A = phenyl A = phenyl 4-SOzX= 4—soz(r3- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl = 4-SOz(L7>- 4-sogx= 4602(8- sulfatoethyl) oethyl) 337 ) R34: Hydrogen R34: Hydrogen 48 : 34 : “l8 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SO3M C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-SOzX= 4502(3- sulfatoethyl) sulfatoethyl) 338 (lib-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4-SOz(i?>- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: en C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 3-sogx= },- sulfatoethyl) sulfatoethyl) 339 (lib-1) R34: Hydrogen R34: Hydrogen 48 : 34 : “l8 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl = 4602(8- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4602(8- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (lib-2) and (la”) W0 2015/028499 Iq OSOBNa CI 00 / IN NaOSS 803Na F N F (IIb-2) Expl Compo- Component (|a") Component (la") Ratio nent (II) (II) : (Ia") : (|a") 340 (Ilb-2) R34: Hydrogen R34: Hydrogen 60 : 10 : 30 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(fS- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f$- 4-SO2X= 4602(8- oethyl) sulfatoethyl) 341 (Ilb-2) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(fS- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: 2-SOsM R40: 2-SOsM C = phenyl C = phenyl = 4-SOz(f$- 4-SO2X= 4602(8- sulfatoethyl) oethyl) 342 (Ilb-2) R34: Hydrogen R34: Hydrogen 60 : 8 : 32 R35: Hydrogen R35: 2—SOsM W0 2015/028499 A = phenyl A = phenyl 4-SOzX= 4-SOz(fS- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOz(f3>- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 343 (IIb-2) R34: Hydrogen 60 : 40 : -- R35: Hydrogen A = phenyl = 4-SOz(f?>-sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl = 4-SOz(f?>-sulfatoethyl) 344 (IIb-2) R34: Hydrogen 65 : -- : 35 R35: 2-SOsM A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4—SOzX= 4602(3— sulfatoethyl) 345 (IIb-2) R34: en 62 : 38 : -- R35: Hydrogen A = phenyl 3-SOzX= 3-SOz(f3-sulfatoethyl) R39: Hydrogen W0 2015/028499 R40: 2-SO3M C = phenyl 4-SOzX= 4-SOz(fS-sulfatoethy|) 346 (Ilb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: 2—SOsM C = phenyl C = phenyl 4—SOzX= rs- 4—SOzX= 4602(3— sulfatoethyl) sulfatoethyl) 347 (Ilb—2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(L7>- 3-SOzX= 3602(8- sulfatoethyl) oethyl) 348 (Ilb—2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4602(3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4-SOz(f3- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) 349 (Ilb-2) R34: en R34: Hydrogen 48 : 34 : 18 R35: en R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 4-sogx= 4—3020},- sulfatoethyl) oethyl) 350 (Ilb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4-SOzX= 4—soz(r3- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= 4-SOz(L7>- 4-sogx= 4602(8- sulfatoethyl) sulfatoethyl) 351 (Ilb-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-SOzX= - oethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: 2—SO3M C = phenyl C = phenyl W0 2015/028499 4-SOzX= 4—soz(rs- 4-SOzX= 4502(3- sulfatoethyl) sulfatoethyl) 352 (lib-2) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4-SOz(i?>- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4—soz(rs- 3-sogx= 3602(8- oethyl) sulfatoethyl) 353 (lib-2) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4602(8- = - oethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (lib-3) and (la”) OH NH2 g 3 CC \” SO3H W0 2015/028499 Epr Compo- Component (la") Component (la") Ratio nent (II) (II) : (la") : (la") 354 (IIb—3) R34: Hydrogen R34: Hydrogen 60 : 1O : 30 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4-SOz(f3- 4-SO2X= - sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SO2X= - sulfatoethyl) sulfatoethyl) 355 (llb-3) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2—803M A = phenyl A = phenyl 4-SOzX= 4-SOz(f$- 4-SOzX= 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2—SOsM R40: 2—SOsM C = phenyl C = phenyl 4-SOzX= f$- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 356 (llb-3) R34: Hydrogen R34: Hydrogen 60 : 8 : 32 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4—SOzX= 4602(8)— 4—SOzX= 4602(8)— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen W0 2015/028499 R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOZ(B- = 5-802“- sulfatoethyl) sulfatoethyl) 357 (IIb-3) R34: Hydrogen 6O : 4O : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(3- sulfatoethyl) R39: en R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 358 (IIb-3) R34: Hydrogen 65 : -- : 35 R35: 2—SOsM A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 359 (Ilb-3) R34: 2-Methoxy 62 : 38 : -- R35: 5-Methyl A = phenyl 4—SOzX= 4—8020!)— sulfatoethyl) W0 2015/028499 R39: 2-Methoxy R40: 5-Methyl C = phenyl 4—SOzX= — sulfatoethyl) 360 (llb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 361 (IIb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl = 4—sog(rs- 4-sogx= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl = 4-SOz(f3- 3-sogx= },- sulfatoethyl) sulfatoethyl) 362 (Ilb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl W0 2015/028499 2014/068151 4-SOzX= 4-SOz(L7>- 4-SOzX= 4302(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 3—803M C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 5-SO2X= 5602(8- sulfatoethyl) sulfatoethyl) 363 (llb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4-SOzX= 4—sog(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl 4-SOzX= 4-SOz(fZ>- 4-SOzX= 4602(8- sulfatoethyl) oethyl) 364 (llb—3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-SOsM A = phenyl A = phenyl = 4—soz(rs- 4—SOzX= 4802(3— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: oxy C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- oethyl) sulfatoethyl) 365 (IIb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 W0 2015/028499 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl = 4-SOz(f$- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: 2-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 366 (llb-3) R34: Hydrogen R34: en 48 : 34 : 18 R35: en R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4-SOz(B- 3-SO2X= 3-soz(r3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SO2X= rs- 3-SO2X= 3602(8- sulfatoethyl) sulfatoethyl) 367 (llb-3) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4602(3- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) 2014/068151 ’l 62 All examples of the following table are prepared as formulations as explained above using dyes of formula (llf-1) and (la”) N / N HN/* O HN N 80 H H038 ’ 3 OH NH2 / N N \ [N] N / \ N [\‘1 SO3H * H038 SO3H (Hf-1) Expl Compo- Component (la") Component (la") Ratio nent (II) (II) : (la") : (la") 368 (llf-1) R34: Hydrogen R34: Hydrogen 60 : 1O : 30 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4—SOzX= 4-SOz(l$— 4—SOzX= 4-8020!)— sulfatoethyl) oethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: en C = phenyl C = phenyl 4—SOzX= 4-SOz(lS— 4—SOzX= 4-SOz(lS— sulfatoethyl) sulfatoethyl) 369 (llf—1) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl W0 2015/028499 4-SOzX= 4-SOz(L7>- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2—SOsM R40: 2—SO3M C = phenyl C = phenyl 4-SO2X= 4—soz(rs- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) 370 (Hf-1) R34: Hydrogen R34: Hydrogen 60 : 8 : 32 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4—sog(rs- = 4602(8- oethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl 4-SOzX= 4-SOz(f3>- 5-SOzX= 5602(8)- oethyl) sulfatoethyl) 371 (Hf—1) R34: Hydrogen 60 :40 : —— R35: Hydrogen A = phenyl 4—SOzX= 4602(8— oethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(3- sulfatoethyl) 372 (IIf—1) R34: Hydrogen 65 : -- : 35 W0 2015/028499 R35: 2-SOsM A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SOzX= 4602(8- sulfatoethyl) 373 (Hf-1) R34: Hydrogen 62 : 38 : -- R35: Hydrogen A = phenyl 4-SOzX= 4602(8- sulfatoethyl) R39: 2-Methoxy R40: 5-Methoxy C = phenyl 4-SOzX= 4602(3- sulfatoethyl) 374 (Hf-1) R34: Hydrogen R34: en 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- = 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2—SOsM C = phenyl C = phenyl 4-SOzX= 4602(3- 4-SOzX= 4802(3- oethyl) sulfatoethyl) W0 2015/028499 375 (Hf—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: en R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4-soz(r3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) 376 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl 4-SOzX= 4-SOz(f3- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: en R39: 2-methoxy R40: Hydrogen R40: 3-803M C = phenyl C = phenyl 4-SOzX= 4-SOz(f3- 5-SO2X= 5602(8- oethyl) sulfatoethyl) 377 (Hf-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(3- 4-SOzX= 4602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 5—methyl C = phenyl C = phenyl W0 2015/028499 = L7>- 4-SOzX= 4—soz(r3- sulfatoethyl) sulfatoethyl) 378 (Hf-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SOsM A = phenyl A = phenyl 4-SOzX= 4—soz(rs- 4-SOzX= 4602(8- sulfatoethyl) oethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4-SOzX= 4—sog(rs- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 379 (IIf—1) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—SOzX= 4—SOz(f$- 3-SOzX= 3602(8— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: 2-SOsM C = phenyl C = phenyl 4—SOzX= 4—soz(rs- 4—SOzX= 4—soz(rs— sulfatoethyl) sulfatoethyl) 380 (IIf—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(8- 3-SOzX= 3602(8- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen W0 2015/028499 2014/068151 R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4-SOz(l3- 3-SOzX= 3602(8- oethyl) sulfatoethyl) 381 (llf—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4-SOzX= 4602(3- 3-SO2X= 3602(8- oethyl) sulfatoethyl) R39: en R39: 2-methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4602(8- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) All examples of the following table are prepared as formulations as explained above using dyes of formula (lid-1) and (la”) H 9H3 \ HN /CH3 ANH OM\ HN N Cl OH NH2 , N\ 303“ SOH H038 sogH (lid-1) Expl Compo- Component (la") Component (la") Ratio nent (ll) (II) : (la") : (la") W0 2015/028499 382 (Ild-’|) R34: Hydrogen R34: Hydrogen 60 : 1O : 30 R35: Hydrogen R35: 2—803M A = phenyl A = phenyl 4—so2x= 4—80203- 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4—80203- 4-sogx= 4602(3- sulfatoethyl) sulfatoethyl) 383 (lld-1) R34: Hydrogen R34: Hydrogen 62 : 8 : 30 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—SOzX= 4—soz(rs- = 4—soz(rs— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: 2-SO3M R40: 2-SO3M C = phenyl C = phenyl = 4—sozus- 4—SOzX= 4602(3— sulfatoethyl) sulfatoethyl) 384 ) R34: Hydrogen R34: Hydrogen 60 : 8 : 32 R35: Hydrogen R35: 2-SOsM A = phenyl A = phenyl 4-SOzX= 4602(8- 4-SOzX= 4-SOz(f5- sulfatoethyl) sulfatoethyl) R39: en R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = naphthyl W0 2015/028499 = 4-SOz(B- 5-SOzX= 5602(8- sulfatoethyl) sulfatoethyl) 385 (lld-1) R34: Hydrogen 60 :40 : -- R35: Hydrogen A = phenyl 4-SO2X= 4602(8- sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4-SO2X= 4602(8- sulfatoethyl) 386 ) R34: Hydrogen 65 : -- : 35 R35: 2-803M A = phenyl 4—SOzX= 4—SOz(f$— sulfatoethyl) R39: Hydrogen R40: Hydrogen C = phenyl 4—SOzX= 4—SOz(f$— sulfatoethyl) 387 (Ild-1) R34: 2-Methoxy 62 : 38 : -- R35: Hydrogen A = phenyl -SO2X= 4602(8- oethyl) R39: 2-Methoxy W0 2015/028499 R40: Hydrogen C = phenyl -SOzX= 4602(8- sulfatoethyl) 388 (IId-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: en R40: 2-SOsM C = phenyl C = phenyl 4—so2x= 4—soz(r3- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 389 (Ild-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2—SO3M A = phenyl A = phenyl 4—so2x= 4-SOz([Z>- 4-SOzX= - sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4—80203- 3-SO2X= - sulfatoethyl) sulfatoethyl) 390 (lld-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-SO3M A = phenyl A = phenyl 4—SOzX= 4—8020!)— 4—SOzX= !)— sulfatoethyl) sulfatoethyl) W0 2015/028499 R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 3-SOsM C = phenyl C = phenyl = 4—SOzU3— 5—SOzX= 5—SOz(f$— sulfatoethyl) sulfatoethyl) 391 (lld-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl = 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: 5-methyl C = phenyl C = phenyl = 4-SOz(f3— 4-SOzX= 4602(8- sulfatoethyl) sulfatoethyl) 392 (IId-1) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: 2-803M A = phenyl A = phenyl 4—so2x= 4—30203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2-methoxy R40: Hydrogen R40: 2-methoxy C = phenyl C = phenyl 4—so2x= 3- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 393 (Ild-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl W0 2015/028499 = 4—30203- 3-SOzX= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: en R40: Hydrogen R40: 2—803M C = phenyl C = phenyl 4—so2x= 4—80203- 4-SOzX= 4—soz(rs- sulfatoethyl) sulfatoethyl) 394 (lld-1) R34: en R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl = 4—80203- 3-SO2X= 3602(3- sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: Hydrogen R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4—so2x= 4—80203- 3-SO2X= 3-SOz(fS- sulfatoethyl) sulfatoethyl) 395 (lld—1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18 R35: Hydrogen R35: Hydrogen A = phenyl A = phenyl 4—SOzX= 4—sozus- 3-SOzX= 3—soz(rs— sulfatoethyl) sulfatoethyl) R39: Hydrogen R39: 2—methoxy R40: Hydrogen R40: Hydrogen C = phenyl C = phenyl 4-SOzX= 4602(8- 5-SOzX= 5602(3- sulfatoethyl) sulfatoethyl) 1 73 USE EXAMPLE 1 3 parts of a dye mixture obtained according to example 1-3 are dissolved in 2000 parts of water and 1 part of levelling assistant (based on sation t of a higher aliphatic amine and ne 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 40°C over the course of 30 minutes, ined at this temperature for 15 minutes and then increased to 98°C over the course of 58 minutes and dyeing is carried out at this temperature for 90 minutes. This is followed by cooling to 90°C and removal of the dyed material. The wool fabric is washed with hot and cold water, alkaline-treated and then spun and dried. The grey to dark black dyeings obtained show superior fastness properties over commercially available products such as ve black 5.
USE EXAMPLE 2 ’I5 2 parts of a dye mixture obtained according to example 1-3 and 60 parts of sodium chloride are dissolved in 1000 parts of water, and 12 parts of sodium carbonate and 0.5 part ofa g agent are added. This dyebath is entered with 100 parts ofa cotton fabric. The temperature of the dye bath is raised to 30°C at a gradient of 0.5°C/minute and held at this temperature for 30 minutes, and then increased to 60°C over 30 minutes, this temperature being maintained for a further 60 minutes. Thereafter the dyed goods are lly rinsed with tapwater for 5 minutes. The dyed goods are neutralized at 50°C 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 C for minutes and dried. The strong dark brown to black dyeings obtained have good overall fastness properties.
USE EXAMPLE 3 1 part of a dye mixture obtained according to example 1-3 is dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate are added. The pH is then adjusted to 4.5 using acetic acid (80%). The dyebath is heated to 50°C for 10 minutes and then entered with 100 parts of a woven polyamide . The temperature is raised to 110°C over the course of 50 minutes and then dyeing is d out at this temperature for 60 minutes. This is followed by g to 60°C and removal of the 2014/068151 ’l 74 dyed material. The polyamide fabric is washed with hot and cold water, soaped and then spun and dried. The strong dark brown to black dyeings obtained have good overall fastness properties and good levelness in the fibre.
USE EXAMPLE 4 A textile fabric consisting of mercerized cotton is padded with liquor containing 35 g/l of calcium sodium carbonate, 100 g/l of urea and 150 g/l of a scosity sodium alginate solution (6%), and then dried. The liquor pickup is 70%. The textile thus pretreated is printed with an aqueous ink containing 2% of a dye mixture obtained according to example 1-3, 20% of sulfolane, 0.01 % of Mergal K9N and 77.99% r using a n-demand ejet) ink-jet printing head. The print is fully dried. It is fixed by means of saturated steam at 102°C for 8 minutes. The print is then rinsed warm, subject to a fastness wash with hot water at 95°C, rinsed warm and then dried.
The obtained print has good overall fastness properties.
USE EXAMPLE 5 3 parts of a dye mixture obtained according to example 3 are dissolved in 2000 parts of water and 1 part of levelling assistant (based on sation 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 dye bath is d with 100 parts of a woven wool fabric. The temperature is raised to 40°C over the course of 30 minutes, maintained at this temperature for 15 minutes and then increased to 98°C over the course of 58 minutes and dyeing is carried out at this temperature for 90 minutes. This is followed by cooling to 90°C and removal of the dyed material. The wool fabric is washed with hot and cold water, alkaline-treated at 80 °C and then spun and dried. The black dyeing’s obtained show similar fastness properties compared to the tly used high fast After—chrom Mordant dyes, in particular Mordant Black 9, in Light fastness > 5 (EN ISO 105 802) and g fastness 4-5 (EN ISO 105 E09) without using Heavy metals (Cr3+).
COMPARATIVE EXAMPLE 1 according to EP1155089 9.34 parts of an electrolyte-containing dye powder containing the orange dye of the formula (B) ’l 75 H0380 II \/\/S 0/ OH CI //N k N N/ N \ J\ Hogs N N NHCN and 9.34 parts of an electrolyte-containing dye powder containing the orange dye of the formula (8-8) O HO3SO\/\/g O’ OH Cl ,/N x N N / N H038 N N NHCN ‘5 sogH H (B-8) and 81.32 parts of an electrolyte-containing dye powder containing the navy dye of the formula(A OH NH2 @0 H03S 803H are mechanically mixed with each other. 3 parts of this dye mixture obtained are dissolved in 2000 parts of water and 1 part of 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 40°C in 30 minutes, maintained at this temperature for 15 s and then increased to 98°C in 58 s and dyeing is carried out at this temperature for 90 minutes. This is followed by cooling to 90°C and l of the dyed material. The 1 76 wool fabric is washed with hot and cold water, alkaline-treated at 80 °C and then spun and dried.
The black ’s obtained using the e according to EP1155089 show inferior properties compared to inventive USE EXAMPLE 5 in Light fastness: Light fastness of COMPARATIVE E 1: 4 (EN ISO 105 802) Light fastness of inventive USE EXAMPLE 5: > 5 (EN ISO 105 802).
Thus it can be summarized that the inventive dye mixtures shows fastness properties, which are as good as the ones obtained using the After-Chrome dyes and surpass all other known combinations, which also do not need a chromium after- treatment.
Also it was noted that the inventive Black mixture does not only show good build-up, but also shows superior metamerism compared to a Black 5 based mixture. This behaviour in en light has been a long-standing weakness of Black 5 based products. ’l 77

Claims (4)

    Claims: Dye mixture(s) sing at least one dye of general formula (I) A/NCN/lBN/“N a NCN/DJBNCMC 803M and at least one dye selected from the group consisting of the dyes of formula (IIa)-(|If) 1 78 wherein each ofA and C, ndent of each other is a radical of general formula (1 a) (18) wherein each of R3 to R5, independent of each other is hydrogen, halogen, alkyl, N- ino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, ’IO alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, 803M or COOM, or 1 79 is alkyl substituted by one or more substituents ed 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, 5 cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, oromethyl, heteroaryl, heterocycloalkyl, carbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or is alkyl interrupted by one or more heteroatoms and substituted by one or more 10 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- oylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, ’l5 alkoxythiocarbonyl, acyloxy and aryloyloxy, or is SOz-X, where X is vinyl or a radical —CH20H2—Y and Y is a group removable under alkaline conditions, or 20 is a group of general formula (2a) *flN/RG (28) wherein R6 is hydrogen, halogen, alkyl, N—acylamino, , thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, 25 aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, 803M or COOM, or is alkyl substituted by one or more substituents selected from the group ting of y, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, halogen, cyano, 803M, COOM, nitro, acyl, yl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, 30 heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or 1 80 is alkyl interrupted by one or more atoms 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, SOsM, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, 5 cycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, R7 is hydrogen, alkyl, cycloalkyl or aryl, or is alkyl substituted by one or more substituents selected from the group ting 10 of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, aryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or is alkyl interrupted by one or more heteroatoms and substituted by one or more 15 substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, , thioalkoxy, N-acylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, y and aryloyloxy, 20 c is an integer of 0 to 6, RG is a ve anchor of general formula (3a), (3b) or (30), R1 9 R16 E1 \ N \ N N \ N
  1. A A 15 *MRZONI * N R *MR18NI (33) (3b) (30) wherein each of R16 to R21, independent of each other is halogen, R16 can also be a rest of formula (4a) WO 28499 (4a) wherein R22 is hydrogen, halogen, alkyl, alkoxy, thioalkoxy, hydroxy, lkyl, aryl, heteroaryl, heterocycloalkyl, 803M or COOM, or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, , thioalkoxy, N-acylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, R15 is one of the groups selected from general formula (5a) or (5b), R23 F5 *—N‘R24 *—N (5a) (5b) wherein each of R23, R24 and R26, independent of each other is hydrogen, alkyl, lkyl ’I5 or aryl, or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, 20 ulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, y and aryloyloxy, or is alkyl interrupted by one or more heteroatoms and substituted by one or more tuents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, 25 thioalkoxy, N-acylamino, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, halogen, cyano, 803M, COOM, nitro, acyl, yl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, each of R25, R27 and R28, independent of each other is en, halogen, alkyl, N-acylamino, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, sulfamoyl, oromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, 80M or COOM, or is alkyl substituted by one or more substituents ed from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, koxy, N-acylamino, N-alkylaminocarbonyl, alkylaminocarbonyl, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, aryl, heterocycloalkyl, alkoxycarbonyl, 15 alkoxythiocarbonyl, acyloxy and aryloyloxy, or is alkyl interrupted by one or more heteroatoms and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl, 20 n, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, y and aryloyloxy, R24 can also be —CH20H2—SOz—X, where X is vinyl or a radical —CH20H2—Y where 25 Y is a group removable under alkaline conditions, and R28 can also be -SOz-X where X is the same as defined above, each of B and D, independent of each other is a radical of general formula (6a) WO 28499 2014/068151 1 83 wherein each of R29 to R31, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, carbonyl, thiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, y, aryloyloxy, 5 lkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, 803M or COOM, 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- ’|0 triarylammonium, N,N-dialkyI-N-monoarylammonium, N,N-diaryI-N- monoalkylammonium, amino, N-cinnamoylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or 15 is alkyl interrupted by one or more heteroatoms 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, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, 20 alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or is SOz-X, where X is vinyl or a radical —CH20H2—Y and Y is a group removable under alkaline conditions such as 0803M, SSOsM, OCOCHs, OPOsM or halogen, 25 or is a group of l formula (2a) as defined above, each of a and b, independent of each other is an r of 0 or 1 whereby a + 30 b is not 0 and dyes of general formula (I) contain at least two reactive anchors, M is hydrogen, lithium, sodium, potassium, ammonium or mono-, di-, tri- or tetra—(C1—C4)—alkylammonium, one lent of an alkali earth metal, or a monovalent organic cation, 1 84 each of R41 to R58, 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, 803M or COOM, 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- ’|0 triarylammonium, alkyI-N-monoarylammonium, N,N-diaryI-N- monoalkylammonium, amino, N-cinnamoylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or 15 is alkyl interrupted by one or more heteroatoms and substituted by one or more substituents selected from the group consisting of y, 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, 803M, COOM, nitro, acyl, thioacyl, 20 alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, cycloalkyl, alkoxycarbonyl, thiocarbonyl, y and aryloyloxy, each of R69 and R70 independent of each other is Cl or F, 25 each of d, e, fand g ndent of each other is an integer of 0 or 1, each of h and k independent of each other is an integer of 0 to 6, each of Z1 to Z4, independent of each other is a group of general formula (2a), 30 where (2a) is the same as defined above, each of W1 and W2, independent of each other is a g group of general formula (7a), (7b) or (70), R71 R R
  2. * A R79 K w/* \N fixjyfli’i / N l74 :4; *iN N l73 R78/ /*i:'!~‘ N\ \ / X“ R R * \ R * (7a) (7b) (70) wherein each of R71, R72, R75, R76 and R77, independent of each other is hydrogen, halogen, alkyl, N-acylamino, N,N-dialkylamino, alkoxy, thioalkoxy, hydroxy, 5 cyano, alkoxycarbonyl, thiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, 80M or COOM, is alkyl tuted by one or more substituents selected from the group consisting 10 of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and loxy, or 15 is alkyl interrupted by one or more heteroatoms and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, l, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, thiocarbonyl, y and aryloyloxy, and each of R73, R74, R78 and R79, independent of each other is hydrogen, alkyl, lkyl or aryl, or is alkyl substituted by one or more substituents selected from the group consisting 25 of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N,N-dia|ky|amino, n, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, or WO 28499 1 86 is alkyl interrupted by one or more heteroatoms and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, , thioalkoxy, N-acylamino, halogen, cyano, 803M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy and aryloyloxy, R71 or R72 can form rings with R73, m is an integer of 1 to 6, M and X are the same as defined above and means point of attachment. 15 2. Mixture(s) ing to claim 1, comprising at least one dye of general formula ('8) (Ia) and at least one dye ofgeneral formula (Ila) or (llb) ’l 87 wherein each of R34 to R40, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, acyl, aryloyl, trifluoro- 5 methyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, cycloalkyl, N— cinnamoylamino, 803M or COOM, X and M are the same as in claim 1, 10 in a (la) each of R34 to R40, independent of each other is hydrogen, (C1-C4)alkyl, (C1- C4)alkoxy, halogen, acyl, N-acylamino or 803M, 15 X is vinyl or B-sulfatoethyl, in formula (Ila) and (llb) each of R41 to R48 and R57, ndent of each other is hydrogen, (Cl- 20 yl, (C1-C4)alkoxy, halogen, acyl, N—acylamino or SOsM, Z1 is defined as in claim 1 whereby c is 0 or 1, R6 and R7 is hydrogen or alkyl, 25 R18 to R21 independent of each other is halogen, R22 is hydrogen, each of R23, R24 and R26 independent of each other is hydrogen, alkyl, or aryl, WO 28499 1 88 each of R25, R27 and R28 independent of each other is hydrogen, halogen, alkyl, N-acylamino, alkoxy, hydroxy, acyl, aryloyl, trifluoromethyl, acyloxy, cycloalkyl, aryl, heteroaryl, 803M or COOM, 5 R24 can also be —CH20H2—SOz-X, where X is vinyl or a radical —CH2CH2—Y where Y is a group removable under alkaline conditions, and R28 can also be -SOz-X where X is the same as defined above, 10 X is most preferred to be vinyl or B-sulfatoethyl.
  3. 3. Dye e acoording to claim 1 or 2, comprising at least one dye of general formula (lb) (lb) 15 wherein each of R34, R35, R39 and R40 ndent of each other is hydrogen, (C1-C4)alkyl, (C1-C4)alkoxy, 803M or COOM, M is the same as defined in claim 1 and X is vinyl or B-sulfatoethyl.
  4. 4. Dye mixture(s) acoording to any one of claims 1 to 3, comprising at least one dye of the general formula (Ila) or (llb)
NZ713120A 2013-08-29 2014-08-27 Dye mixtures of reactive dyes, production and use NZ713120B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP20130182245 EP2862902A1 (en) 2013-08-29 2013-08-29 Dye mixtures of metal free reactive dyes, production and use
EP13182245.4 2013-08-29
PCT/EP2014/068151 WO2015028499A1 (en) 2013-08-29 2014-08-27 Dye mixtures of reactive dyes, production and use

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NZ713120B2 true NZ713120B2 (en) 2021-05-27

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