NZ713120B2 - Dye mixtures of reactive dyes, production and use - Google Patents
Dye mixtures of reactive dyes, production and use Download PDFInfo
- 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
- Authority
- NZ
- New Zealand
- Prior art keywords
- hydrogen
- phenyl
- sulfatoethyl
- sozx
- soz
- Prior art date
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- 239000000975 dye Substances 0.000 title claims abstract description 137
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 239000000985 reactive dye Substances 0.000 title description 15
- 239000001257 hydrogen Substances 0.000 claims description 1986
- 229910052739 hydrogen Inorganic materials 0.000 claims description 1986
- 150000002431 hydrogen Chemical group 0.000 claims description 1127
- -1 N- ino Chemical group 0.000 claims description 116
- 125000000217 alkyl group Chemical group 0.000 claims description 76
- 229910052736 halogen Inorganic materials 0.000 claims description 76
- 150000002367 halogens Chemical class 0.000 claims description 76
- 125000003118 aryl group Chemical group 0.000 claims description 70
- 125000002252 acyl group Chemical group 0.000 claims description 62
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 62
- 125000003545 alkoxy group Chemical group 0.000 claims description 57
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 56
- 125000001072 heteroaryl group Chemical group 0.000 claims description 54
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 52
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 52
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 50
- 125000004423 acyloxy group Chemical group 0.000 claims description 49
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 49
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 47
- 125000003441 thioacyl group Chemical group 0.000 claims description 45
- 125000004685 alkoxythiocarbonyl group Chemical group 0.000 claims description 44
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 44
- 125000001424 substituent group Chemical group 0.000 claims description 39
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 37
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 125000005842 heteroatoms Chemical group 0.000 claims description 17
- 239000011734 sodium Chemical group 0.000 claims description 15
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 13
- 150000003254 radicals Chemical group 0.000 claims description 13
- 239000005864 Sulphur Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 125000003277 amino group Chemical compound 0.000 claims description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 6
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 6
- 229940035295 Ting Drugs 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Chemical group 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000002892 organic cations Chemical class 0.000 claims description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 3
- VMJNTFXCTXAXTC-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-5-carbonitrile Chemical group C1=C(C#N)C=C2OC(F)(F)OC2=C1 VMJNTFXCTXAXTC-UHFFFAOYSA-N 0.000 claims 2
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims 1
- 125000004429 atoms Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 239000000835 fiber Substances 0.000 abstract description 11
- 239000004753 textile Substances 0.000 abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1340
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 846
- 229910006080 SO2X Inorganic materials 0.000 description 178
- 235000013350 formula milk Nutrition 0.000 description 57
- 125000001624 naphthyl group Chemical group 0.000 description 30
- 238000004043 dyeing Methods 0.000 description 25
- 238000007639 printing Methods 0.000 description 18
- 239000000976 ink Substances 0.000 description 17
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 13
- 235000002639 sodium chloride Nutrition 0.000 description 13
- 210000002268 Wool Anatomy 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating Effects 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M buffer Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 9
- 239000002657 fibrous material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 229920003043 Cellulose fiber Polymers 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910006069 SO3H Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000001049 brown dye Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 101700010476 lid-1 Proteins 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 101700000038 mpas Proteins 0.000 description 3
- 150000002926 oxygen Chemical compound 0.000 description 3
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- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000036633 rest Effects 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
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- HLBBKKJFGFRGMU-UHFFFAOYSA-M Sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- 159000000000 sodium salts Chemical class 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical compound C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- UOVHNSMBKKMHHP-UHFFFAOYSA-L potassium;sodium;sulfate Chemical compound [Na+].[K+].[O-]S([O-])(=O)=O UOVHNSMBKKMHHP-UHFFFAOYSA-L 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- KYQCOXFCLRTKLS-UHFFFAOYSA-N pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 235000013533 rum Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- LIBWRRJGKWQFSD-UHFFFAOYSA-M sodium;2-nitrobenzenesulfonate Chemical class [Na+].[O-][N+](=O)C1=CC=CC=C1S([O-])(=O)=O LIBWRRJGKWQFSD-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N stearylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 230000002110 toxicologic Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-M triacetate(1-) Chemical compound CC(=O)CC(=O)CC([O-])=O ILJSQTXMGCGYMG-UHFFFAOYSA-M 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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$-
sulfatoethyl)
) R34: en R34: Hydrogen 48 : 34 : 18
R35: Hydrogen R35: 2—SOaM
A = phenyl A = phenyl
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4-SOzX= 4—soz(rs- 4-SOzX= 4502(3-
sulfatoethyl) sulfatoethyl)
R39: Hydrogen R39: en
R40: Hydrogen R40: 2-SOsM
C = phenyl C = phenyl
4-SOzX= 4-SOz(f?>- 4-SOzX= 4-8020!)-
sulfatoethyl) sulfatoethyl)
11 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18
R35: Hydrogen R35: 2—SOsM
A = phenyl A = phenyl
4-SOzX= 4—soz(rs- 4-SOzX= 4602(3-
sulfatoethyl) sulfatoethyl)
R39: Hydrogen R39: Hydrogen
R40: Hydrogen R40: Hydrogen
C = phenyl C = phenyl
4-SOzX= f?>- 3-SOzX= 3-8020!)-
oethyl) sulfatoethyl)
12 ) R34: Hydrogen R34: Hydrogen 48 : 34 : 18
R35: Hydrogen R35: 2-SOsM
A = phenyl A = phenyl
4-SOzX= 4-SOz(L7>- 4-SOzX= 4602(3-
sulfatoethyl) sulfatoethyl)
R39: Hydrogen R39: 2—methoxy
R40: Hydrogen R40: 3-SOsM
C = phenyl C = phenyl
4-SOzX= 4-SOz(L7>- = 5802(3-
sulfatoethyl) sulfatoethyl)
13 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18
R35: Hydrogen R35: 2—SOaM
A = phenyl A = phenyl
W0 2015/028499
4-SOzX= rs- 4-SOzX= 4502(3-
oethyl) sulfatoethyl)
R39: Hydrogen R39: 2-methoxy
R40: Hydrogen R40: 5-methyl
C = phenyl C = phenyl
= 4-SOz(fZ>- 4-SOzX= 4-8020!)-
sulfatoethyl) sulfatoethyl)
”l4 (Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18
R35: Hydrogen R35: 2—SOsM
A = phenyl A = phenyl
= 4—soz(rs- 4-SOzX= 4602(8-
sulfatoethyl) sulfatoethyl)
R39: Hydrogen R39: 2-methoxy
R40: Hydrogen R40: 2-methoxy
C = phenyl C = phenyl
4-SOzX= 4-SOz(fZ>- 4-SOzX= 4-8020!)-
sulfatoethyl) sulfatoethyl)
(Ila-1) R34: Hydrogen R34: Hydrogen 48 : 34 : 18
R35: en R35: Hydrogen
A = phenyl A = phenyl
4-SOzX= 4-SOz(fZ>- 3-SOzX= 3602(3-
sulfatoethyl) sulfatoethyl)
R39: Hydrogen R39: Hydrogen
R40: Hydrogen R40: 2-SOsM
C = phenyl C = phenyl
4-SOzX= 4-SOz(f$- 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
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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
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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)
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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
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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
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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
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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
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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
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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
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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
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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
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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 : --
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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
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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
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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
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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
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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
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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
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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
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’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)
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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
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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
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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)
- 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
- * 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. 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. Dye mixture(s) acoording to any one of claims 1 to 3, comprising at least one dye of the general formula (Ila) or (llb)
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 |
Publications (2)
Publication Number | Publication Date |
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NZ713120A NZ713120A (en) | 2021-02-26 |
NZ713120B2 true NZ713120B2 (en) | 2021-05-27 |
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