EP2904051A1 - Metal-free reactive dyes, process for the production thereof and their use - Google Patents
Metal-free reactive dyes, process for the production thereof and their useInfo
- Publication number
- EP2904051A1 EP2904051A1 EP13729019.3A EP13729019A EP2904051A1 EP 2904051 A1 EP2904051 A1 EP 2904051A1 EP 13729019 A EP13729019 A EP 13729019A EP 2904051 A1 EP2904051 A1 EP 2904051A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- amino
- carbamoyl
- sulfamoyl
- monocycloalkyl
- monoalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000985 reactive dye Substances 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- -1 hydroxyl- Chemical group 0.000 claims abstract description 507
- 239000000463 material Substances 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 184
- 229910052736 halogen Inorganic materials 0.000 claims description 177
- 150000002367 halogens Chemical class 0.000 claims description 177
- 125000002252 acyl group Chemical group 0.000 claims description 174
- 125000003118 aryl group Chemical group 0.000 claims description 171
- 125000001072 heteroaryl group Chemical group 0.000 claims description 158
- 125000003441 thioacyl group Chemical group 0.000 claims description 154
- 125000003545 alkoxy group Chemical group 0.000 claims description 153
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 144
- 125000004423 acyloxy group Chemical group 0.000 claims description 140
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 140
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 139
- 125000004685 alkoxythiocarbonyl group Chemical group 0.000 claims description 136
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 136
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 136
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 130
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 126
- 125000001424 substituent group Chemical group 0.000 claims description 112
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 108
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 92
- 239000001257 hydrogen Substances 0.000 claims description 73
- 229910052739 hydrogen Inorganic materials 0.000 claims description 73
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 73
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 54
- 239000005864 Sulphur Chemical group 0.000 claims description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 54
- 125000005842 heteroatom Chemical group 0.000 claims description 54
- 239000001301 oxygen Substances 0.000 claims description 54
- 229910052760 oxygen Inorganic materials 0.000 claims description 54
- 239000000975 dye Substances 0.000 claims description 51
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 49
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 46
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 45
- 125000005281 alkyl ureido group Chemical group 0.000 claims description 42
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 42
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- 239000007864 aqueous solution Substances 0.000 claims 2
- 238000004043 dyeing Methods 0.000 abstract description 15
- 238000007639 printing Methods 0.000 abstract description 12
- 125000005518 carboxamido group Chemical group 0.000 abstract description 4
- 239000000976 ink Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004744 fabric Substances 0.000 description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004442 acylamino group Chemical group 0.000 description 4
- 125000004663 dialkyl amino group Chemical group 0.000 description 4
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
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- 239000004753 textile Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 2
- 229940015975 1,2-hexanediol Drugs 0.000 description 2
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
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- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- ZROILLPDIUNLSE-UHFFFAOYSA-N 1-phenyl-1h-pyrazole-4-carboxylic acid Chemical compound C1=C(C(=O)O)C=NN1C1=CC=CC=C1 ZROILLPDIUNLSE-UHFFFAOYSA-N 0.000 description 1
- 229940044613 1-propanol Drugs 0.000 description 1
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-UHFFFAOYSA-N 0.000 description 1
- PTQMVTWYHWFMEJ-UHFFFAOYSA-N 2-(2-anilinoethylsulfonyl)ethyl hydrogen sulfate Chemical compound OS(=O)(=O)OCCS(=O)(=O)CCNC1=CC=CC=C1 PTQMVTWYHWFMEJ-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- IALORYHODRVWKZ-UHFFFAOYSA-N 2-(4-aminophenyl)sulfonylethyl sulfate;hydron Chemical compound NC1=CC=C(S(=O)(=O)CCOS(O)(=O)=O)C=C1 IALORYHODRVWKZ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- JBDQVFGGGVTGDI-UHFFFAOYSA-N 2-[2-(2-propan-2-yloxypropoxy)propoxy]propan-1-ol Chemical compound CC(C)OC(C)COC(C)COC(C)CO JBDQVFGGGVTGDI-UHFFFAOYSA-N 0.000 description 1
- MXVMODFDROLTFD-UHFFFAOYSA-N 2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound CCCCOCCOCCOCCOCCO MXVMODFDROLTFD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- PVCJKHHOXFKFRP-UHFFFAOYSA-N N-acetylethanolamine Chemical compound CC(=O)NCCO PVCJKHHOXFKFRP-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- UEJWRQDKIBEMCR-UHFFFAOYSA-L calcium;sodium;carbonate Chemical compound [Na+].[Ca+2].[O-]C([O-])=O UEJWRQDKIBEMCR-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 238000010014 continuous dyeing Methods 0.000 description 1
- 238000005112 continuous flow technique Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 229940113120 dipropylene glycol Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- TUEYHEWXYWCDHA-UHFFFAOYSA-N ethyl 5-methylthiadiazole-4-carboxylate Chemical compound CCOC(=O)C=1N=NSC=1C TUEYHEWXYWCDHA-UHFFFAOYSA-N 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BAMUPQJDKBGDPU-UHFFFAOYSA-N n-(2-hydroxyethyl)formamide Chemical compound OCCNC=O BAMUPQJDKBGDPU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent 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
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
- C09B62/4411—Azo dyes
- C09B62/4415—Disazo or polyazo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
- D06P3/148—Wool using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/248—Polyamides; Polyurethanes using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
Definitions
- Metal-free reactive dyes process for the production thereof and their use
- the present invention relates to the technical field of reactive dyestuffs for dyeing and printing of hydroxyl-, amino-, and/or carboxamido-containing material.
- Metal free reactive dyes are known from prior art and can be used as colorants in different applications, see for example US 20030172476.
- the known dyes that are metal free have a number of technical disadvantages such as unsatisfactory light fastness and especially limitations in achieving darker shades such as dark violet, dark brown, navy and black shades of very good overall fastness level.
- dyes of the formula (I) as described below show highly advantageous properties over the known dyes. These include high build-up to darker shades with high fastness properties such as light fastness, wash and contact fastness on the materials mentioned above and on blends containing them. Most importantly, dyes of formula (I) are metal free and thus superior in ecological performance and provide dyeings that are of very good levelness.
- the present invention refers to dyes of the formula (I) and mixtures thereof
- A is a radical of diazo component as described below.
- B is a radical of middle component as described below.
- K is a radical of coupling component as described below.
- a is an integer of 0 or 1 ;
- dyes of general formula (I) contain at least one reactive anchor
- this invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I),
- A is a radical of general formula (1 a)
- each of R 1 to R 3 independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylamm
- each of R 4 and R 7 independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alk
- RG is a reactive anchor of general formula (3a), (3b) or (3c);
- each of R 14 to R 19 independent of each other is halogen; and R 14 can additionally be a rest of formula (8a)
- R 96 is hydrogen, halogen, alkyl, alkoxy, thioalkoxy, hydroxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, al
- R 13 is one of the groups selected from general formula (4a) or (4b);
- each of R 20 , R 23 and R 94 independent of each other is hydrogen, alkyl, cycloalkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acy
- R 94 can additionally be -CH 2 CH 2 -SO 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y where Y is a group removable under alkaline conditions such as OSO3M, SSO3M, OCOCH3, OPO3M or halogen; and
- R 95 can additionally be -SO 2 -X where X is the same as defined above.
- each of R to R independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium N,N-dialkyl-N-monoarylammonium N,N-diaryl-N- monoalkyl
- R 4 to R 8 , b, c and RG are the same as defined above
- K is a radical of general formula (6a) or (6b)
- D is a radical of general formula (1 a) as defined above; and each of R 27 to R 29 , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, ureido, alkylureido, phenylureido, sulfamoyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, carbamoyl, cycloalkyi, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy,
- RG is the same as defined above; and R 32 is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxy
- R 33 is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl
- Alkyl groups appearing in this application may be straight-chain or branched and are (Ci-Ci2)-alkyl groups, preferably (Ci-Cs)-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.
- alkoxy groups which accordingly are preferably (Ci-Cs)- alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (d-CsHhioalkoxy, for example -SCH 3 or -SC2H 5 .
- Cycloalkyi groups are preferably (C3-C8)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl.
- the term cycloalkyi comprises for the purpose of the present application substituted cycloalklyl groups and unsatured cycloalkyi groups as well.
- a preferred group of this type is cyclopentenyl.
- Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
- Aryl groups appearing in this application are preferably phenyl or naphthyl.
- phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl.
- Preferred substituents are alkyl, cycloalkyi, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl or acyloxy.
- Heteroaryl groups appearing in this application are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1 ,3,4- thiadiazole, furane, oxazole, benzoxazole or isoxazole.
- heteroaryl comprises the above groups in unsubstituted as well as in substituted form.
- Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
- Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine.
- the terms heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form.
- Preferred substituents are alkyl, hydroxyalkyi, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, amino- carbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.
- Halogen is preferably chlorine, bromine or fluorine.
- M is preferably hydrogen, lithium, sodium, potassium, ammonium or mono-, di-, tri- or tetra-(Ci-C 4 )-alkylammonium, one equivalent of an alkali earth metal, or a monovalent organic cation.
- Particular preferred embodiments of the present invention are dyes of the formula (la) and mixtures thereof
- each of R 34 to R 36 independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalky
- each of R 34 to R 36 independent of each other is hydrogen, (Ci-C 4 )alkyl, (Ci- C 4 )alkoxy, halogen, acyl or SO 3 M; or is SO 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH 2 ) f -NH-RG, where f is an integer of 1 to 3 and RG is the same as defined above; and each of R 37 and R 38 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 ) g -NH-RG, where g is an integer of 1 to 3 and
- each of R to R independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylam
- each of R 39 to R 44 independent of each other is hydrogen, (Ci-C 4 )alkyl, (Ci- C 4 )alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH 2 )h-NH-RG, where h is an integer of 1 to 3 and RG is the same as defined above; and each of R 45 and R 46 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )i-NH-RG, where i is an integer of 1 to 3 and RG is the same
- each of R to R independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-di
- each of R 47 to R 49 independent of each other is hydrogen, (Ci-C 4 )alkyl, (Ci- C 4 )alkoxy, halogen, acyl or SO 3 M; or is SO 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH 2 ) k -NH-RG, where k is an integer of 1 to 3 and RG is the same as defined above; and each of R 50 and R 51 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyi; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 ) m -NH-RG, where m is an integer of 1 to 3
- n is 0 or 1 ; and each of R 52 to R 57 , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N
- each of R to R independent of each other is hydrogen, (Ci-C 4 )alky, (Ci- C 4 )alkoxyl, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH 2 ) P -NH-RG, where p is an integer of 1 to 3 and RG is the same as defined above; and each of R 58 and R 59 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 ) q -NH-RG, where q is an integer of 1 to 3 and RG
- each of R , R and R 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, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoal
- each of R 60 to R 62 independent of each other is hydrogen, (CrC 4 )alkyl, (Ci- C 4 )alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH 2 ) r -NH-RG, where r is an integer of 1 to 3 and RG is the same as defined above; and each of R 63 and R 64 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )s-NH-RG, where s is an integer of 1 to 3 and RG is
- each of R 65 to R 70 independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO 3 M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-
- each of R 65 to R 70 independent of each other is hydrogen, (Ci-C 4 )alkyl, (Ci- C 4 )alkoxy, halogen, acyl or SO 3 M; or is SO 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH 2 )t-NH-RG, where t is an integer of 1 to 3 and RG is the same as defined above; and each of R 71 and R 72 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyi; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )u-NH-RG, where u is an integer of 1 to 3 and RG is
- each of R to R independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium
- each of R 75 to R 80 independent of each other is hydrogen, (Ci-C 4 )alkyl, (Ci- C 4 )alkoxy, halogen, acyl or SO 3 M; or is SO 2 -X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH 2 )v-NH-RG, where v is an integer of 1 to 3 and RG is the same as defined above; and each of R 81 and R 82 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 )w-NH-RG, where w is an integer of 1 to 3 and
- each of R 83 to R 91 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, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, ⁇ , ⁇ , ⁇ -trialkylammonium, ⁇ , ⁇ , ⁇ - triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- mono
- each of R 83 to R 91 independent of each other is hydrogen, (CrC 4 )alkyl, (Ci- C 4 )alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH 2 CH 2 -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH 2 )x-NH-RG, where x is an integer of 1 to 3 and RG is the same as defined above; and each of R 92 and R 93 , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH 2 ) y -NH-RG, where y is an integer of 1 to 3 and
- Examples of preferred dyes of the formulae (la) to (Ih) are the compounds I 1 to I 140 listed in the table 1 below and having the general formula ( ⁇ ). 41
- the present invention also provides a process for the preparation of the dyes of the formula (I).
- This process comprises diazotization of the compounds of the formula (II) and reacting the correspondingly obtained diazonium salts with a compound of the formula K to obtain the intermediate of general formula (III).
- the diazo component (A-NH 2 ) is diazotised and coupled onto the intermediate III to obtain the bisazo dye product of general formula (IV).
- the diazo component (A-NH 2 ) can be diazotised and coupled onto the compound (B-NH 2 ) to obtain intermediate (V). Further, the intermediate (V) is diazotised and coupled onto compound (III) to obtain the trisazo dye product of general formula (VI).
- the diazotization reactions in general, can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used.
- the coupling reactions in general can be performed by known methods.
- the end product can optionally also be subjected to a vinylization reaction.
- a vinylizable reaction group such as the ⁇ -sulfatoethylsulfonyl is converted into its vinyl form.
- Such reactions are known to a person skilled in the art. They are generally performed in a neutral to alkaline medium at a temperature, for example, from 20 to 80°C, at a pH of, for example, from 7 to 14.
- the dyes of formula (I) are fiber-reactive containing fiber-reactive functional rests.
- Fiber-reactive functional rests refer to rests capable of reacting with the hydroxyl groups of cellulosic materials, the amino, carboxyl, hydroxyl and thiol groups in the case of wool and silk, or with the amino and possibly carboxyl groups of synthetic polyamides to form covalent chemical bonds.
- the dyes of the present invention are suitable for dyeing and printing of natural, manufactured regenerated, modified or synthetic hydroxyl-, amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for reactive dyes. Therefore, the present invention also provides for a process for dyeing and printing of the above-mentioned fiber materials and their blends in which a dye or a dye mixture according to the present invention is used.
- Examples of natural fibre materials as described above are vegetable fibres such as seed fibres i.e. cotton, kapok, coir from coconut husk; bast fibers i.e. cotton, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres i.e. sisal, henequen, banana; stalk fibres i.e. bamboo; and fibres from animals such as wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials.
- seed fibres i.e. cotton, kapok, coir from coconut husk
- bast fibers i.e. cotton, flax, hemp, jute, kenaf, ramie, rattan
- leaf fibres i.e. sisal, henequen, banana
- stalk fibres i.e. bamboo
- fibres from animals such as wool, silk, cashmere wool, alpaca fiber, mo
- manufactured and manufactured regenerated fibres are cellulosic fibres such as paper and cellulosic regenerated fibres such as viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers.
- nylon materials like nylon-6, nylon-6.6 and aramid fibres.
- the above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet.
- the dyes of the present invention and their salts or mixtures can be used as a single dyeing product in dyeing or printing processes or it can be part of a di/tri or multi- component combination product in dyeing or in printing compositions.
- Dyes of this invention and their salts or mixtures are highly compatible with other known and/or commercially available dyes and they can be used together with such dyes to obtain specific hues of similarly good technical performance.
- Technical performance includes build-up, fastness properties and levelness.
- the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.
- the dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing.
- Aqueous inks for digital printing which comprise a dye of the present invention likewise form part of the subject matter of the present invention.
- the inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 % by weight to 50% by weight, more preferably from 1 % by weight to 30% by weight and most preferably from 1 % by weight to 15% by weight, based on the total weight of the ink.
- the inks, as well as the dyes of the present invention may, if desired, contain further dyes used in digital printing.
- a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte.
- Useful electrolytes include for example lithium nitrate and potassium nitrate.
- the inks of the present invention may include organic solvents at a total level of 1 -50% and preferably 5-30% by weight.
- Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5-pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6- hexanediol, 1 ,2,6-hexanetriol, 1 ,2-octanediol, polyalkylene
- the inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1 .5 to 40.0 mPas in a temperature range from 20 to 50°C.
- Preferred inks have a viscosity of 1 .5 to 20 mPas and particularly preferred inks have a viscosity of 1 .5 to 15 mPas.
- Useful viscosity moderators include rheological additives, for example: polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.
- rheological additives for example: polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.
- the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mlM/m, which are adapted if necessary as a function of the process used (thermal or piezo technology).
- Useful surface-active substances include for example all surfactants, preferably nonionic surfactants, butyldiglycol and 1 ,2-hexanediol.
- the inks of the present invention may further include customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.
- the inks may be prepared in a conventional manner by mixing the components in water.
- the inks of the present invention are particularly useful in inkjet printing processes for printing a wide variety of materials, in particular of wool and polyamide fibers.
- the examples below serve to illustrate the invention. Parts and percentages are by weigh unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.
- Example 1 i) 6.2 parts of sulfuric acid mono-[2-(2-phenylamino-ethanesulfonyl)-ethyl] ester was suspended in 70 parts of water. 14 parts of sodium bicarbonate was added. The reaction vessel was cooled to 0 ⁇ 5°C using ice. 3.8 parts of cyanuric chloride was added. The reaction was stirred at temperature of 0 ⁇ 5°C and pH of 4-4.5 for 3 hours. Thereafter, 4.8 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was added and the pH was adjusted to 6-6.5 using 15% soda solution. The reaction was stirred at ambient temperature and pH of 6-6.5 for 2 hours. The product (a) obtained was used in next ste without isolation.
- the diazonium salt was added slowly into the solution of (b) synthesized above while maintaining the pH to 5-6.5. The reaction was stirred until completion. The product was precipitated out, collected by filtration and dried to give 21 .8 parts of dye I 56 as black solid.
- 3 parts of the dye I 56 of this invention 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) 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, 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 and then spun and dried.
- 1 part of the dye I 56 of this invention 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 fabric.
- the temperature is raised to 1 10°C over the course of 50 minutes and then dyeing is carried out at this temperature for 60 minutes. This is followed by cooling to 60°C and removal of the dyed material.
- the polyamide fabric is washed with hot and cold water, soaped and then spun and dried.
- 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 low-viscosity 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 the dye I 56 of this invention, 20% of sulfolane, 0.01 % of Mergal K9N and 77.99% of water using a drop- on-demand (bubblejet) ink-jet printing head.
- the print is fully dried. It is fixed by means of saturated steam at 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.
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Abstract
Metal-free reactive dyes, process for the production thereof and their use The present invention relates to reactive dyes of the formula (I), in which A, B, a and K are defined as given in claim, a process for preparing them, and their use for dyeing and printing hydroxyl-, amino-, and/or carboxamido-containing materials.
Description
Metal-free reactive dyes, process for the production thereof and their use
The present invention relates to the technical field of reactive dyestuffs for dyeing and printing of hydroxyl-, amino-, and/or carboxamido-containing material.
Metal free reactive dyes are known from prior art and can be used as colorants in different applications, see for example US 20030172476. However, in the context of the dyeing and printing of hydroxyl-, amino- and/or carboxamido-containing material the known dyes that are metal free have a number of technical disadvantages such as unsatisfactory light fastness and especially limitations in achieving darker shades such as dark violet, dark brown, navy and black shades of very good overall fastness level.
Surprisingly, it has now been found that the dyes of the formula (I) as described below show highly advantageous properties over the known dyes. These include high build-up to darker shades with high fastness properties such as light fastness, wash and contact fastness on the materials mentioned above and on blends containing them. Most importantly, dyes of formula (I) are metal free and thus superior in ecological performance and provide dyeings that are of very good levelness.
The present invention refers to dyes of the formula (I) and mixtures thereof
wherein,
A is a radical of diazo component as described below; and
B is a radical of middle component as described below; and
K is a radical of coupling component as described below; and
a is an integer of 0 or 1 ; and
with the general proviso that dyes of general formula (I) contain at least one reactive anchor; and
this invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I), A is a radical of general formula (1 a)
wherein,
each of R1 to R3, 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, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylammo- nium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-
monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c)
wherein,
each of R4 and R7, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and
each of R5, R6, R8 and R12, independent of each other is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R9 to R11, independent of each other is hydrogen, halogen, alkyl, alkoxy or
b is an integer of 0 to 6; and c is an integer of 1 to 6; and when each of b and c, independent of each other is > 2, R4 and R7 can have different meanings within the same rest as per meaning defined above; and d is 0 or 1 ; and
RG is a reactive anchor of general formula (3a), (3b) or (3c);
wherein, each of R14 to R19, independent of each other is halogen; and R14 can additionally be a rest of formula (8a)
(8a) wherein,
R96 is hydrogen, halogen, alkyl, alkoxy, thioalkoxy, hydroxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M,
COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and
R13 is one of the groups selected from general formula (4a) or (4b);
(4a) (4b) wherein, each of R20, R23 and R94, independent of each other is hydrogen, alkyl, cycloalkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R , R and R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, sulfamoyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and
R94 can additionally be -CH2CH2-SO2-X, where X is vinyl or a radical -CH2CH2-Y where Y is a group removable under alkaline conditions such as OSO3M, SSO3M, OCOCH3, OPO3M or halogen; and
R95 can additionally be -SO2-X where X is the same as defined above.
B is a radical of general formula (5a)
(5a) wherein, each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium N,N-dialkyl-N-monoarylammonium N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula 2a) or (2b)
(2a)
where R4 to R8, b, c and RG are the same as defined above
K is a radical of general formula (6a) or (6b)
(6a) (6b) wherein, D is a radical of general formula (1 a) as defined above; and each of R27 to R29, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, ureido, alkylureido, phenylureido, sulfamoyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, carbamoyl, cycloalkyi, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of
hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylamnnoniunn, Ν,Ν,Ν- triarylamnnoniunn, N,N-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N-monoalkyl- ammoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; and each of R30, R31, R73 and R74, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or
is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkyl- ammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a)
(7a) wherein,
RG is the same as defined above; and
R32 is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and
R33 is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and e is an integer of 1 to 6; and when e is > 2, R32 can have different meanings within the same rest, as per meaning defined above.
Alkyl groups appearing in this application may be straight-chain or branched and are (Ci-Ci2)-alkyl groups, preferably (Ci-Cs)-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.
The same logic applies to alkoxy groups which accordingly are preferably (Ci-Cs)- alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (d-CsHhioalkoxy, for example -SCH3 or -SC2H5.
Cycloalkyi groups are preferably (C3-C8)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl. The term cycloalkyi comprises for the purpose of the present application substituted cycloalklyl groups and unsatured cycloalkyi groups as well. A preferred group of this type is cyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy. Aryl groups appearing in this application are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyi, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl or acyloxy.
Heteroaryl groups appearing in this application are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1 ,3,4- thiadiazole, furane, oxazole, benzoxazole or isoxazole. The term heteroaryl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine. The terms heterocycloalkyl comprises the above
groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyi, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, amino- carbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.
Halogen is preferably chlorine, bromine or fluorine.
M is preferably hydrogen, lithium, sodium, potassium, ammonium or mono-, di-, tri- or tetra-(Ci-C4)-alkylammonium, one equivalent of an alkali earth metal, or a monovalent organic cation.
Particular preferred embodiments of the present invention are dyes of the formula (la) and mixtures thereof
(la)
wherein, each of R34 to R36, 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, SO3M or COOM; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and each of R37 and R38, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl,
alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.
In especially preferred dyes of general formual (la), each of R34 to R36, independent of each other is hydrogen, (Ci-C4)alkyl, (Ci- C4)alkoxy, halogen, acyl or SO3M; or
is SO2-X, where X is vinyl or a radical -CH2CH2-Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH2)f-NH-RG, where f is an integer of 1 to 3 and RG is the same as defined above; and each of R37 and R38, independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH2)g-NH-RG, where g is an integer of 1 to 3 and RG is the same as defined above.
Further preferred embodiments of this invention are dyes of general formula (lb) and mixtures thereof
wherein,
each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined above;and each of R39 to R41, independent of each other can additionally be a group of general formula (2c) as defined above; and each of R45 and R46, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or
is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.
In especially preferred dyes of general formual (lb), each of R39 to R44, independent of each other is hydrogen, (Ci-C4)alkyl, (Ci- C4)alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH2CH2-Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH2)h-NH-RG, where h is an integer of 1 to 3 and RG is the same as defined above; and each of R45 and R46, independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH2)i-NH-RG, where i is an integer of 1 to 3 and RG is the same as defined above.
Further preferred embodiments of this invention are dyes of general formula (Ic) and mixtures thereof
wherein, j is 0 or 1 ; and each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν-
triarylammonium, Ν,Ν-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylannnnoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and each of R50 and R51, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-
amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-annino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-nnonocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-annino, Ν,Ν,Ν-thalkylannnnoniunn, Ν,Ν,Ν- tharylamnnoniunn, N,N-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylammoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. In especially preferred dyes of general formual (lc), each of R47 to R49, independent of each other is hydrogen, (Ci-C4)alkyl, (Ci- C4)alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH2CH2-Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH2)k-NH-RG, where k is an integer of 1 to 3 and RG is the same as defined above; and each of R50 and R51, independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyi; or
is a reactive anchor RG, where RG is the same as defined above; or is -(CH2)m-NH-RG, where m is an integer of 1 to 3 and RG is the same as defined above.
Further preferred embodiments of this invention are dyes of general formula (Id) and mixtures thereof:
wherein, n is 0 or 1 ; and each of R52 to R57, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyi, N-cinnamoylamino, SO3M or COOM; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined above; and each of R52 to R54, independent of each other can additionally be a group of general formula (2c) as defined above; and each of R58 and R59, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-
monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.
In especially preferred dyes of general formual (Id),
each of R to R , independent of each other is hydrogen, (Ci-C4)alky, (Ci- C4)alkoxyl, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH2CH2-Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH2)P-NH-RG, where p is an integer of 1 to 3 and RG is the same as defined above; and each of R58 and R59, independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH2)q-NH-RG, where q is an integer of 1 to 3 and RG is the same as defined above.
Further preferred embodiments of this invention are dyes of general formula (le) and mixtures thereof:
wherein, each of R , R and R , 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, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and each of R63 and R64, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or
is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.
In especially preferred dyes of general formual (le), each of R60 to R62, independent of each other is hydrogen, (CrC4)alkyl, (Ci- C4)alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH2CH2-Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH2)r-NH-RG, where r is an integer of 1 to 3 and RG is the same as defined above; and each of R63 and R64, independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH2)s-NH-RG, where s is an integer of 1 to 3 and RG is the same as defined above.
Further preferred embodiments of this invention are dyes of general formula (If) and mixtures thereof:
(if) wherein, each of R65 to R70, 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, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl,
trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined above;and each of R65 to R67, independent of each other can additionally be a group of general formula (2c) as defined above; and each of R71 and R72, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-
amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-annino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-nnonocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-annino, Ν,Ν,Ν-thalkylannnnoniunn, Ν,Ν,Ν- tharylamnnoniunn, N,N-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylamnnoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. In especially preferred dyes of general formual (If), each of R65 to R70, independent of each other is hydrogen, (Ci-C4)alkyl, (Ci- C4)alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH2CH2-Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH2)t-NH-RG, where t is an integer of 1 to 3 and RG is the same as defined above; and each of R71 and R72, independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyi; or
is a reactive anchor RG, where RG is the same as defined above; or is -(CH2)u-NH-RG, where u is an integer of 1 to 3 and RG is the same as defined above.
Further preferred embodiments of this invention are dyes of general formula (Ig) and mixtures thereof:
wherein, each of R to R independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-
monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and each of R81 and R82, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl,
N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfannoyl, Ν,Ν-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfannoyl or N- monoalkyl-N-monoarylsulfannoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.
In especially preferred dyes of general formual (Ig), each of R75 to R80, independent of each other is hydrogen, (Ci-C4)alkyl, (Ci- C4)alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH2CH2-Y and Y is a group removable under alkaline conditions such as OSO3M; or
is -NH-RG, where RG is the same as defined above; or is -(CH2)v-NH-RG, where v is an integer of 1 to 3 and RG is the same as defined above; and each of R81 and R82, independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH2)w-NH-RG, where w is an integer of 1 to 3 and RG is the same as defined above. Further preferred embodiments of this invention are dyes of general formula (Ih) and mixtures thereof:
wherein,
each of R83 to R91, 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, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined above;and each of R83, R84, R85, R89, R90 and R91, independent of each other can additionally be a group of general formula (2c) as defined above; and each of R92 and R93, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo- alkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl-amino, N- monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν-triarylammoni- um, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acyl- amino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl- carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl- carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N- monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or
is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.
In especially preferred dyes of general formual (Ih), each of R83 to R91 , independent of each other is hydrogen, (CrC4)alkyl, (Ci- C4)alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH2CH2-Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH2)x-NH-RG, where x is an integer of 1 to 3 and RG is the same as defined above; and each of R92 and R93, independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH2)y-NH-RG, where y is an integer of 1 to 3 and RG is the same as defined above.
Examples of preferred dyes of the formulae (la) to (Ih) are the compounds I1 to I140 listed in the table 1 below and having the general formula (Γ).
41
Table 1
43
55
60
61
62
64
65
66
72
73
80
81
85
86
* refers to the attachment point of A and of K;
* also refers to the attachment point of B with A when a is 1 ;
refers to the other attachment point of B when a is 1 . Further examples of preferred dyes of the formulae (la) to (Ih) are th compounds I141 to I280 listed in the table 2 below ' aarnd having the general formula (I").
Table 2
91
92
93
103
104
106
107
109
111
112
114
117
118
120
ı32
* refers to the attachment point of A and of K;
* also refers to the attachment point of B with A when a is 1 ** refers to the other attachment point of B when a is 1 .
The present invention also provides a process for the preparation of the dyes of the formula (I). This process comprises diazotization of the compounds of the formula (II) and reacting the correspondingly obtained diazonium salts with a compound of the formula K to obtain the intermediate of general formula (III).
In a further step the diazo component (A-NH2) is diazotised and coupled onto the intermediate III to obtain the bisazo dye product of general formula (IV).
(III) (IV)
Alternatively, the diazo component (A-NH2) can be diazotised and coupled onto the compound (B-NH2) to obtain intermediate (V). Further, the intermediate (V) is diazotised and coupled onto compound (III) to obtain the trisazo dye product of general formula (VI).
A.NH2 + B.NH2
A'^N^NH.
(V)
The diazotization reactions, in general, can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used.
The coupling reactions in general can be performed by known methods.
The compounds of the formula A-NH2, B-NH2, K are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art.
The end product can optionally also be subjected to a vinylization reaction. For example, a vinylizable reaction group such as the β-sulfatoethylsulfonyl is converted into its vinyl form. Such reactions are known to a person skilled in the art. They are
generally performed in a neutral to alkaline medium at a temperature, for example, from 20 to 80°C, at a pH of, for example, from 7 to 14.
The dyes of formula (I) are fiber-reactive containing fiber-reactive functional rests. Fiber-reactive functional rests refer to rests capable of reacting with the hydroxyl groups of cellulosic materials, the amino, carboxyl, hydroxyl and thiol groups in the case of wool and silk, or with the amino and possibly carboxyl groups of synthetic polyamides to form covalent chemical bonds. The dyes of the present invention are suitable for dyeing and printing of natural, manufactured regenerated, modified or synthetic hydroxyl-, amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for reactive dyes. Therefore, the present invention also provides for a process for dyeing and printing of the above-mentioned fiber materials and their blends in which a dye or a dye mixture according to the present invention is used.
Examples of natural fibre materials as described above are vegetable fibres such as seed fibres i.e. cotton, kapok, coir from coconut husk; bast fibers i.e. cotton, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres i.e. sisal, henequen, banana; stalk fibres i.e. bamboo; and fibres from animals such as wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials.
Examples of manufactured and manufactured regenerated fibres are cellulosic fibres such as paper and cellulosic regenerated fibres such as viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers.
Examples of synthetic fiber materials as described above are nylon materials, like nylon-6, nylon-6.6 and aramid fibres.
The above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet.
The dyes of the present invention and their salts or mixtures can be used as a single
dyeing product in dyeing or printing processes or it can be part of a di/tri or multi- component combination product in dyeing or in printing compositions.
Dyes of this invention and their salts or mixtures are highly compatible with other known and/or commercially available dyes and they can be used together with such dyes to obtain specific hues of similarly good technical performance. Technical performance includes build-up, fastness properties and levelness.
Since the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.
The dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing. Aqueous inks for digital printing which comprise a dye of the present invention likewise form part of the subject matter of the present invention.
The inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 % by weight to 50% by weight, more preferably from 1 % by weight to 30% by weight and most preferably from 1 % by weight to 15% by weight, based on the total weight of the ink.
The inks, as well as the dyes of the present invention may, if desired, contain further dyes used in digital printing.
For the inks of the present invention to be used in the continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present invention may include organic solvents at a total level of 1 -50% and preferably 5-30% by weight. Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5-pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6- hexanediol, 1 ,2,6-hexanetriol, 1 ,2-octanediol, polyalkylene glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols having 1 to 8 alkylene
groups, for example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydric alcohols, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers, such as for example: polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as for example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-acetylethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives, such as for example: urea, thiourea, N-methylurea, Ν,Ν'-epsilon dimethylurea, ethyleneurea, 1 ,1 ,3,3-tetramethylurea, amides, such as for example: dimethylformamide, dimethylacetamide, acetamide, ketones or keto alcohols, such as for example: acetone, diacetone alcohol, cyclic ethers, such as for example: tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma butyrolactone, epsilon-caprolactam, further sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide, N-cyclohexyl pyrrol idone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone,
1 - (2-hydroxyethyl)-2-pyrrolidone, 1 -(3-hydroxypropyl)-2-pyrrolidone, 1 ,3-dimethyl-
2- imidazolidinone, 1 ,3-dimethyl-2-imidazolinone, 1 ,3-bismethoxymethylimidazolidine, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, trimethylpropane, 1 ,2-dimethoxypropane, dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether, 1 ,2-dimethoxypropane and trimethylpropane.
The inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1 .5 to 40.0 mPas in a
temperature range from 20 to 50°C. Preferred inks have a viscosity of 1 .5 to 20 mPas and particularly preferred inks have a viscosity of 1 .5 to 15 mPas.
Useful viscosity moderators include rheological additives, for example: polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.
As further additives the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mlM/m, which are adapted if necessary as a function of the process used (thermal or piezo technology). Useful surface-active substances include for example all surfactants, preferably nonionic surfactants, butyldiglycol and 1 ,2-hexanediol. The inks of the present invention may further include customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.
The inks may be prepared in a conventional manner by mixing the components in water.
The inks of the present invention are particularly useful in inkjet printing processes for printing a wide variety of materials, in particular of wool and polyamide fibers. The examples below serve to illustrate the invention. Parts and percentages are by weigh unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.
Example 1 : i) 6.2 parts of sulfuric acid mono-[2-(2-phenylamino-ethanesulfonyl)-ethyl] ester was suspended in 70 parts of water. 14 parts of sodium bicarbonate was added. The reaction vessel was cooled to 0~5°C using ice. 3.8 parts of cyanuric chloride was added. The reaction was stirred at temperature of 0~5°C and pH of 4-4.5 for 3 hours.
Thereafter, 4.8 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was added and the pH was adjusted to 6-6.5 using 15% soda solution. The reaction was stirred at ambient temperature and pH of 6-6.5 for 2 hours. The product (a) obtained was used in next ste without isolation.
ii) 6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid was added into 70 parts of water. The pH was adjusted to 5-6 using 15% soda solution. The reaction vessel was cooled to 0~5°C using ice. 4.3 milliliters of 5M sodium nitrite solution was added into the reaction mixture. After stirring for 10 min, 20.7 parts of 37% hydrochloric acid was added. The reaction was stirred at 0~5°C for 0.5 h and then 0.2 parts of sulfamic acid was added.
The solution of product (a) obtained above was cooled to 0~5°C using ice. The diazonium salt was added into this coupler solution slowly while maintaining the pH to 5-6.5. The reaction was stirred until completion to yield the intermediate (b).
iii) 5.9 parts of {2-[(4-aminobenzene)sulfonyl]ethoxy}sulfonic acid was suspended in 50 parts of water. The reaction vessel was cooled to 0~5°C using ice. 6.2 parts of 37% hydrochloric acid was added into the reaction mixture. After stirring for 10 min, 4.3 milliliters of 5M sodium nitrite solution was added. The reaction was stirred at 0~5°C for 1 h and then 0.2 parts of sulfamic acid was added.
The diazonium salt was added slowly into the solution of (b) synthesized above while maintaining the pH to 5-6.5. The reaction was stirred until completion. The product was precipitated out, collected by filtration and dried to give 21 .8 parts of dye I56 as black solid.
Through analogy, all the dyes of fornnulae (l1-1280) can be synthesized according to the method described above in the example 1 .
Dyeing example 1
3 parts of the dye I56 of this invention 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) 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, 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 and then spun and dried.
Dyeing example 2
2 parts of the dye I56 of this invention and 60 parts of sodium chloride are dissolved in 1000 parts of water, and 12 parts of sodium carbonate and 0.5 part of a wetting agent are added. This dyebath is entered with 100 parts of bleached cotton knitted fabric. The temperature of the dye bath is raised to 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 initially 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 40~50°C for 20 minutes and dried.
Dyeing example 3
1 part of the dye I56 of this invention 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 fabric. The temperature is raised to 1 10°C over the course of 50 minutes and then dyeing is carried out at this
temperature for 60 minutes. This is followed by cooling to 60°C and removal of the dyed material. The polyamide fabric is washed with hot and cold water, soaped and then spun and dried. Dyeing 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 low-viscosity 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 the dye I56 of this invention, 20% of sulfolane, 0.01 % of Mergal K9N and 77.99% of water using a drop- on-demand (bubblejet) ink-jet printing head. The print is fully dried. It is fixed by means of saturated steam at 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.
Claims
Claims: Chemical compound of formula (I) and mixtures thereof
(I)
wherein,
A is a radical of diazo component as described below; and
B is a radical of middle component as described below; and
K is a radical of coupling component as described below; and
a is an integer of 0 or 1 ; and
with the general proviso that dyes of general formula (I) contain at least one reactive anchor; and
this invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I).
A is a radical of general formula (1 a)
(1 a) wherein,
each of R1 to R3, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c)
wherein
each of R4 and R7, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyi, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R5, R6, R8 and R12, independent of each other is hydrogen, alkyl or aryl; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R9 to R11, independent of each other is hydrogen, halogen, alkyl, alkoxy or SO3M; and b is an integer of 0 to 6; and c is an integer of 1 to 6; and when each of b and c, independent of each other is > 2, R4 and R7 can have different meanings within the same rest as per meaning above defined; and d is 0 or 1 ; and
RG is a reactive anchor of general formula (3a), (3b) or (3c);
(3a) (3b) (3c)
wherein, each of R14 to R19, independent of each other is halogen; and
R14 can additionally be a rest of formula (8a)
(8a) wherein,
R96 is hydrogen, halogen, alkyl, alkoxy, thioalkoxy, hydroxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyi, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and
R13 is one of the groups selected from general formula (4a) or (4b);
(4a) (4b) wherein each of R , R and R , independent of each other is hydrogen, alkyl, cycloalkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R21, R22 and R95, independent of each other is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyi, sulfamoyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyi, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi,
trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and
R94 can additionally be -CH2CH2-SO2-X, where X is vinyl or a radical - CH2CH2-Y where Y is a group removable under alkaline conditions such as OSO3M, SSO3M, OCOCH3, OPO3M or halogen; and
R95 can additionally be -SO2-X where X is the same as defined above.
B is a radical of general formula (5a)
(5a) wherein, each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b)
where R to R , b, c and RG are the same as defined above.
K is a radical of general formula (6a) or (6b)
(6a) (6b) wherein,
D is a radical of general formula (1 a) as defined above; and each of R27 to R29, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, ureido, alkylureido, phenylureido, sulfamoyi, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, carbamoyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyi, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or
is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl- carbamoyl, N, N -d ia I kyl -carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl- sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; and each of R30, R31, R73 and R74, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocydoalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-
monocycloalkyl-sulfamoyi, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a)
(7a) wherein,
RG is the same as defined above; and
R is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyi, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and
R33 is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl,
heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and e is an integer of 1 to 6; and when e is > 2, R can have different meanings within the same rest, as per meaning defined above.
Chemical compound according to claim 1 having formula (la):
wherein, each of R34 to R36, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or
is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined in claim 1 ; and each of R37 and R38, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl,
Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- nnonocycloalkyl-N-nnonoarylsulfannoyl or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1 ; or is a rest of the general formula (7a) as defined in claim 1 .
Chemical compound according to claim 1 having formula (lb):
(l b) wherein, each of R39 to R44, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi,
trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined in claim 1 ;and each of R39 to R41, independent of each other can additionally be a group of general formula (2c) as defined in claim 1 ; and each of R45 and R46, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocydoalkyl-sulfamoyi, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl,
Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or
is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1 ; or is a rest of the general formula (7a) as defined in claim 1 .
Chemical compound according to claim 1 having formula (lc):
(Ic) wherein, j is 0 or 1 ; and each of R47 to R49, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of
hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylamnnoniunn, N,N-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylamnnoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined in claim 1 ; and each of R50 and R51, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or
is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1 ; or is a rest of the general formula (7a) as defined in claim 1 .
Chemical compound according to claim 1 having formula (Id):
wherein, n is 0 or 1 ; and each of R52 to R57, independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of
hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylamnnoniunn, N,N-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylamnnoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined in claim 1 ; and each of R52 to R54, independent of each other can additionally be a group of general formula (2c) as defined in claim 1 ; and each of R58 and R59, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl,
Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- nnonocycloalkyl-N-nnonoarylsulfannoyl or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1 ; or is a rest of the general formula (7a) as defined in claim 1 .
Chemical compound according to claim 1 having formula (le):
(le) wherein, each of R60, R61 and R62, independent of each other is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi,
trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined in claim 1 ; and each of R63 and R64, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-
monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-annino, N-monoaryl-N-monocycloalkyl-annino, Ν,Ν,Ν- trialkylammoniunn, Ν,Ν,Ν-triarylannnnoniunn, N,N-dialkyl-N- nnonoarylannnnoniunn, N,N-diaryl-N-monoalkylannnnoniunn, N-acylamino, N- cinnamoylannino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbannoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfannoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1 ; or is a rest of the general formula (7a) as defined in claim 1 .
Chemical compound according to claim 1 having formula (If):
wherein,
each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or
COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined in claim 1 ; and each of R65 to R67, independent of each other can additionally be a group of general formula (2c) as defined above; and
each of R71 and R72, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl-
carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbannoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfannoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1 ; or is a rest of the general formula (7a) as defined in claim 1 .
Chemical compound according to claim 1 having formula (Ig):
wherein, each of R to R independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or
is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined in claim 1 ; and each of R81 and R82, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,
halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1 ; or is a rest of the general formula (7a) as defined in claim 1 .
Chemical compound according to claim 1 formula (Ih):
wherein, each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, cydoalkyi, aryl, heteroaryl, heterocydoalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocydoalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cydoalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν-
triarylammonium, Ν,Ν-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylannnnoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, 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 OSO3M, SSO3M, OCOCH3, OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined in claim 1 ;and each of R83, R84, R85, R89, R90 and R91, independent of each other can additionally be a group of general formula (2c) as defined in claim 1 ; and each of R92 and R93, independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl- amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N- aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl,
Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- nnonocycloalkyl-N-nnonoarylsulfannoyl or N-monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N- dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N- monocycloalkyl-amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν- trialkylammonium, Ν,Ν,Ν-triarylammonium, N,N-dialkyl-N- monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acylamino, N- cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, Ν,Ν-dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl- N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N- monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N- monocycloalkyl-N-monoarylsulfamoyl or N-monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined in claim 1 ; or is a rest of the general formula (7a) as defined in claim 1 .
Chemical composition consisting of two or more chemical compounds according to any one of claims 1 to 9.
Chemical composition comprising one or more chemical compounds according to any one of claims 1 to 9.
Aqueous solution for dying comprising one or more chemical compounds according to any one of claims 1 to 9.
Process for producing chemical compounds according to claim 1 comprising the steps: a) diazotizing compounds of formula (II),
b) reacting the diazonium salts obtained in step a) with a compound of
formula K to obtain an intermediate of formula (III)
H
diazotizing component (A-NH2),
optionally coupling the diazotized product of step c) onto the compound (B- NH2) and
diazotizing the coupling product of step cx1 )
coupling the diazotized product of step c) onto the intermediate III to obtain the bisazo-product of general formula (IV) in case of step c)
or coupling the diazotized coupling product of cx2) onto the intermediate III to obtain the trisazo-product of general formula (VI),
„NH2 + R.NH2 A^NT^NH,
(V)
H
Use of a chemical compound according to any one of claims 1 to 9, a chemical composition according to claim 10 or 1 1 or of an aqueous solution according to claim 12 for dying fibers, as well as blends of such fibres selected from the group consisting of: vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers; and synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres.
Fiber and blends containing such fiber selected from the group consisting of: vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal,
henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers; and synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres comprising one or more chemical compounds according to any one of claims 1 to 9 etither in chemically and/or physically bound form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13729019.3A EP2904051A1 (en) | 2012-06-18 | 2013-06-13 | Metal-free reactive dyes, process for the production thereof and their use |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12004554 | 2012-06-18 | ||
| EP13729019.3A EP2904051A1 (en) | 2012-06-18 | 2013-06-13 | Metal-free reactive dyes, process for the production thereof and their use |
| PCT/EP2013/062198 WO2013189814A1 (en) | 2012-06-18 | 2013-06-13 | Metal-free reactive dyes, process for the production thereof and their use |
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| Publication Number | Publication Date |
|---|---|
| EP2904051A1 true EP2904051A1 (en) | 2015-08-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP13729019.3A Withdrawn EP2904051A1 (en) | 2012-06-18 | 2013-06-13 | Metal-free reactive dyes, process for the production thereof and their use |
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| Country | Link |
|---|---|
| EP (1) | EP2904051A1 (en) |
| JP (1) | JP2015523436A (en) |
| KR (1) | KR20150033612A (en) |
| CN (1) | CN104508052A (en) |
| AU (1) | AU2013279553A1 (en) |
| MX (1) | MX2014015540A (en) |
| WO (1) | WO2013189814A1 (en) |
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| US9882142B2 (en) | 2012-07-23 | 2018-01-30 | Merck Patent Gmbh | Compounds and organic electronic devices |
| CN104478850A (en) * | 2014-12-08 | 2015-04-01 | 上海应用技术学院 | Preparation method of derivatives of 2-aminothiophene-3 formamide |
| JP2018199722A (en) * | 2018-09-14 | 2018-12-20 | 株式会社半導体エネルギー研究所 | Organic compound and light-emitting device |
| CN109651839B (en) * | 2019-01-22 | 2020-09-01 | 浙江劲光实业股份有限公司 | Preparation method of orange reactive printing dye |
| CN114628784B (en) * | 2021-10-28 | 2024-04-30 | 浙江超威创元实业有限公司 | High-low temperature general electrolyte and lithium ion battery containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6585782B2 (en) | 2001-02-27 | 2003-07-01 | Everlight Usa, Inc. | Mixtures of reactive dyes and their use |
| CN101323710B (en) * | 2007-06-11 | 2011-05-04 | 上海雅运纺织化工有限公司 | Red reactive dye composition and dyeing application thereof |
| EP2468822B1 (en) * | 2010-12-22 | 2015-06-10 | Rex-Tone Industries Ltd | Black trisazo dyes, their preparation and their use |
-
2013
- 2013-06-13 EP EP13729019.3A patent/EP2904051A1/en not_active Withdrawn
- 2013-06-13 CN CN201380032386.8A patent/CN104508052A/en active Pending
- 2013-06-13 AU AU2013279553A patent/AU2013279553A1/en not_active Abandoned
- 2013-06-13 JP JP2015517684A patent/JP2015523436A/en active Pending
- 2013-06-13 WO PCT/EP2013/062198 patent/WO2013189814A1/en not_active Ceased
- 2013-06-13 MX MX2014015540A patent/MX2014015540A/en unknown
- 2013-06-13 KR KR20147035527A patent/KR20150033612A/en not_active Withdrawn
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| Publication number | Publication date |
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| JP2015523436A (en) | 2015-08-13 |
| AU2013279553A1 (en) | 2014-11-06 |
| MX2014015540A (en) | 2015-06-23 |
| KR20150033612A (en) | 2015-04-01 |
| WO2013189814A1 (en) | 2013-12-27 |
| CN104508052A (en) | 2015-04-08 |
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