ZA200106939B - Composition and method for bleaching a substrate. - Google Patents
Composition and method for bleaching a substrate. Download PDFInfo
- Publication number
- ZA200106939B ZA200106939B ZA200106939A ZA200106939A ZA200106939B ZA 200106939 B ZA200106939 B ZA 200106939B ZA 200106939 A ZA200106939 A ZA 200106939A ZA 200106939 A ZA200106939 A ZA 200106939A ZA 200106939 B ZA200106939 B ZA 200106939B
- Authority
- ZA
- South Africa
- Prior art keywords
- alkyl
- optionally substituted
- composition according
- bleaching composition
- pyridin
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 95
- 238000004061 bleaching Methods 0.000 title claims description 89
- 239000000758 substrate Substances 0.000 title claims description 36
- 238000000034 method Methods 0.000 title description 29
- -1 methoxy, hydroxy, nitro, amino, carboxyl Chemical group 0.000 claims description 72
- 239000003446 ligand Substances 0.000 claims description 63
- 229910052739 hydrogen Inorganic materials 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 33
- 239000007844 bleaching agent Substances 0.000 claims description 30
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 28
- 125000001072 heteroaryl group Chemical group 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 21
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 20
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 20
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 20
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 20
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 20
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 229910052723 transition metal Inorganic materials 0.000 claims description 19
- 150000003624 transition metals Chemical class 0.000 claims description 19
- 125000000623 heterocyclic group Chemical group 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 125000000524 functional group Chemical group 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000012736 aqueous medium Substances 0.000 claims description 13
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 11
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 10
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 10
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 10
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 10
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 10
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 10
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 10
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002609 medium Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 claims description 9
- 150000003852 triazoles Chemical class 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000005549 heteroarylene group Chemical group 0.000 claims description 5
- 239000003352 sequestering agent Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- SHODXMYKLLGZQP-UHFFFAOYSA-N n-methyl-1,1-dipyridin-2-yl-n-(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1C(C=1N=CC=CC=1)N(C)CC1=CC=CC=N1 SHODXMYKLLGZQP-UHFFFAOYSA-N 0.000 claims description 4
- 125000006588 heterocycloalkylene group Chemical group 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- QNPHFVFBJIYVAX-UHFFFAOYSA-N n,n-bis[(6-methylpyridin-2-yl)methyl]-1,1-dipyridin-2-ylmethanamine Chemical compound CC1=CC=CC(CN(CC=2N=C(C)C=CC=2)C(C=2N=CC=CC=2)C=2N=CC=CC=2)=N1 QNPHFVFBJIYVAX-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 125000004174 2-benzimidazolyl group Chemical group [H]N1C(*)=NC2=C([H])C([H])=C([H])C([H])=C12 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 2
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 claims description 2
- 125000002140 imidazol-4-yl group Chemical group [H]N1C([H])=NC([*])=C1[H] 0.000 claims description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 2
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 claims description 2
- 125000004159 quinolin-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C([H])C(*)=NC2=C1[H] 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 33
- 239000011734 sodium Substances 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 27
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- 239000004753 textile Substances 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000004744 fabric Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 239000011575 calcium Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 241000894007 species Species 0.000 description 12
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 11
- 239000003599 detergent Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 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 9
- 150000001412 amines Chemical class 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 5
- OURLZCSNCILFGO-UHFFFAOYSA-N 2-[chloro(pyridin-2-yl)methyl]pyridine Chemical compound C=1C=CC=NC=1C(Cl)C1=CC=CC=N1 OURLZCSNCILFGO-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- DADSTHZQYZQBQI-UHFFFAOYSA-N 2,6-bis[methoxy(dipyridin-2-yl)methyl]pyridine Chemical compound C=1C=CC=NC=1C(C=1N=C(C=CC=1)C(OC)(C=1N=CC=CC=1)C=1N=CC=CC=1)(OC)C1=CC=CC=N1 DADSTHZQYZQBQI-UHFFFAOYSA-N 0.000 description 3
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000000160 oxazolidinyl group Chemical group 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 125000003386 piperidinyl group Chemical group 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 2
- CCQZPBJVUOUHJN-UHFFFAOYSA-N 1,1-dipyridin-2-yl-n-(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1CNC(C=1N=CC=CC=1)C1=CC=CC=N1 CCQZPBJVUOUHJN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 2
- YKCVYVYCIXFHMD-UHFFFAOYSA-N 2-phenyl-1,1-dipyridin-2-yl-n,n-bis(pyridin-2-ylmethyl)ethanamine Chemical compound C=1C=CC=NC=1CN(C(CC=1C=CC=CC=1)(C=1N=CC=CC=1)C=1N=CC=CC=1)CC1=CC=CC=N1 YKCVYVYCIXFHMD-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N 4-Ethylbenzaldehyde Chemical class CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 101000679359 Homo sapiens Phosphatidylinositol 3,4,5-trisphosphate 3-phosphatase TPTE2 Proteins 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 241000227653 Lycopersicon Species 0.000 description 2
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 102100022577 Phosphatidylinositol 3,4,5-trisphosphate 3-phosphatase TPTE2 Human genes 0.000 description 2
- 241000206607 Porphyra umbilicalis Species 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126142 compound 16 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- WTWBUQJHJGUZCY-UHFFFAOYSA-N cuminaldehyde Chemical class CC(C)C1=CC=C(C=O)C=C1 WTWBUQJHJGUZCY-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 125000002757 morpholinyl group Chemical group 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000004076 pulp bleaching Methods 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 2
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 2
- 125000001425 triazolyl group Chemical group 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- VIMVCRQBXYUFMX-UHFFFAOYSA-N 1-(dipyridin-2-ylmethyl)-4,7-dimethyl-1,4,7-triazonane Chemical compound C1CN(C)CCN(C)CCN1C(C=1N=CC=CC=1)C1=CC=CC=N1 VIMVCRQBXYUFMX-UHFFFAOYSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-N 0.000 description 1
- AIEISGJPQVKLQI-UHFFFAOYSA-N 2-[6-[[[[5-(carboxymethyl)pyridin-2-yl]-dipyridin-2-ylmethyl]amino]methyl]pyridin-3-yl]acetic acid Chemical compound N1=C(C=CC=C1)C(NCC1=NC=C(C=C1)CC(=O)O)(C1=NC=CC=C1)C1=NC=C(C=C1)CC(=O)O AIEISGJPQVKLQI-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- WFIFHOWQEJADPH-UHFFFAOYSA-N 2-chloro-4-(2-oxo-4-phenylpyrrolidin-1-yl)benzenesulfonamide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC=C1N1C(=O)CC(C=2C=CC=CC=2)C1 WFIFHOWQEJADPH-UHFFFAOYSA-N 0.000 description 1
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 241001530105 Anax Species 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 206010010071 Coma Diseases 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- BVMWIXWOIGJRGE-UHFFFAOYSA-N NP(O)=O Chemical compound NP(O)=O BVMWIXWOIGJRGE-UHFFFAOYSA-N 0.000 description 1
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 125000002340 chlorooxy group Chemical group ClO[*] 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WHQWJVROPJNMEX-UHFFFAOYSA-N dipyridin-2-ylmethanamine Chemical compound C=1C=CC=NC=1C(N)C1=CC=CC=N1 WHQWJVROPJNMEX-UHFFFAOYSA-N 0.000 description 1
- XMKKDBULSAMYCJ-UHFFFAOYSA-N dipyridin-2-ylmethanol Chemical compound C=1C=CC=NC=1C(O)C1=CC=CC=N1 XMKKDBULSAMYCJ-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- UENYKSLRDITUNR-UHFFFAOYSA-L iron(2+) diperchlorate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O UENYKSLRDITUNR-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- DKVQBWOSMHXJEH-UHFFFAOYSA-N methyl 6-(chloromethyl)-1-oxidopyridin-1-ium-3-carboxylate Chemical compound COC(=O)C1=CC=C(CCl)[N+]([O-])=C1 DKVQBWOSMHXJEH-UHFFFAOYSA-N 0.000 description 1
- UAYKHVMBFFBZFI-UHFFFAOYSA-N methyl 6-(chloromethyl)pyridine-3-carboxylate Chemical compound COC(=O)C1=CC=C(CCl)N=C1 UAYKHVMBFFBZFI-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- AURBNAIBZFMGBT-UHFFFAOYSA-N n,n'-bis(dipyridin-2-ylmethyl)-n,n'-bis(pyridin-2-ylmethyl)propane-1,3-diamine Chemical compound C=1C=CC=NC=1CN(C(C=1N=CC=CC=1)C=1N=CC=CC=1)CCCN(C(C=1N=CC=CC=1)C=1N=CC=CC=1)CC1=CC=CC=N1 AURBNAIBZFMGBT-UHFFFAOYSA-N 0.000 description 1
- ZMIIJNKZTOCEME-UHFFFAOYSA-N n,n-bis(1h-benzimidazol-2-ylmethyl)-1,1-dipyridin-2-ylmethanamine Chemical compound N=1C2=CC=CC=C2NC=1CN(CC=1NC2=CC=CC=C2N=1)C(C=1N=CC=CC=1)C1=CC=CC=N1 ZMIIJNKZTOCEME-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000009896 oxidative bleaching Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Detergent Compositions (AREA)
Description
) t
COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE
This invention relates to compositions and methods for catalytically bleaching substrates with atmospheric oxygen, more particularly using a defined class of ligand or complex as catalyst, and further relates to ligands and complexes useful in such compositions and methods. This invention also relates to a method of treating textiles, such as laundry fabrics, using the defined class of ligand or complex as catalyst, more specifically to a method whereby bleaching by atmospheric oxygen is catalysed after the treatment.
Peroxygen bleaches are well known for their ability to remove stains from substrates.
Traditionally, the substrate is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals. such as inorganic or organic peroxides. Generally, these systems must be activated. One method of activation is to employ wash . temperatures of 60°C or higher. However. these high temperatures often lead to inefficient cleaning, and can also cause premature damage to the substrate. . 20
A preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United States laundry bleach products are typically based on sodium nonanoyloxybenzenesulfonate (SNOBS) as the organic precursor coupled with sodium perborate.
Precursor systems are generally effective but still exhibit several disadvantages. For example, organic precursors are moderately sophisticated molecules requiring multi-step manufacturing processes resulting in high capital costs. Also. precursor systems have large formulation space requirements so that a significant proportion of a laundry powder must be devoted to the bleach components. leaving less room for other active ingredients and complicating the development of concentrated powders. Moreover. precursor systems do not bleach very efficiently in countries where consumers have wash habits entailing low dosage. short wash times. cold temperatures and low wash liquor to substrate ratios.
Alternatively, or additionally, hydrogen peroxide and peroxy systems can be activated by bleach catalysts, such as by complexes of iron and the ligand N4Py (i.e. N. N- bis(pyridin-2-yi-methyl)-bis{pyridin-2-yl)methylamine) disclosed in W095/34628, or the ligand Tpen (i.e. N, N, N°, N'-tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in WO97/48787. According to these publications, molecular oxygen may be used as the oxidant as an alternative to peroxide generating systems. However. no role in catalysing bleaching by atmospheric oxygen in an aqueous medium is reported.
It has-long been thought desirable to be able to use atmospheric oxygen (air) as the source for a bleaching species, as this would avoid the need for costly hydroperoxyl generating systems. Unfortunately, air as such is kinetically inert towards bleaching . substrates and exhibits no bleaching ability. Recently some progress has been made in this area. For example, WO 97/38074 reports the use of air for oxidising stains on - fabrics by bubbling air through an aqueous solution containing an aldehyde and a radical initiator. A broad range of aliphatic, aromatic and heterocyclic aldehydes is reported to be useful, particularly para-substituted aldehydes such as 4-methyi-, 4-ethyl- and 4- isopropyl benzaldehyde, whereas the range of initiators disclosed includes N- hydroxysuccinimide, various peroxides and transition metal coordination complexes.
However, although this system employs molecular oxygen from the air, the aldehyde component and radical initiators such as peroxides are consumed during the bleaching process. These components must therefore be included in the composition in relatively high amounts so as not to become depleted before completion of the bleaching process in the wash cycle. Moreover. the spent components represent a waste of resources as they can no longer participate in the bleaching process.
Accordingly, it would be desirable to be able to provide a bleaching system based on atmospheric oxygen or air that does not rely primarily on hydrogen peroxide or a hydroperoxyl generating system. and that does not require the presence of organic components such as aldehydes that are consumed in the process. Moreover. it would be desirable to provide such a bleaching system that is effective in aqueous medium.
It may also be noted that the known art teaches a bleaching effect only as long as the substrate is being subjected 10 the bleaching treatment. Thus. there is no expectation : that hydrogen peroxide or peroxy bleach systems could continue to provide a bleaching effect on a treated substrate. such as a laundry fabric after washing and drying. since the bleaching species themselves or any activators necessary for the bleaching systems would be assumed to be removed from the substrate. or consumed or deactivated. on completing the wash cycle and drying.
It would be therefore also be desirable to be able to treat a textile such that, after the : treatment is completed, a bleaching effect is observed on the textile. Furthermore, it would be desirable to be able to provide a bleach treatment for textiles such as laundry : fabrics whereby residual bleaching occurs when the treated fabric has been treated and is dry.
We have found that a selected class of ligand or complex is surprisingly effective in catalysing the bleaching of substrates using atmospheric oxygen or air. Furthermore, we have found certain novel ligands which are useful in the bleaching of substrates using atmospheric oxygen or air.
Accordingly, in a first aspect, the present invention provides a bleaching composition comprising, in an aqueous medium, atmospheric oxygen and a ligand which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by the
' atmospheric oxygen. wherein the aqueous medium is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system. The medium 1s therefore preferably insensitive or stable to catalase. which acts on peroxy species.
Ina second aspect. the present invention provides a method of bleaching a substrate comprising applying to the substrate, in an aqueous medium. a ligand which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by atmospheric oxygen.
Furthermore. in a third aspect. the present invention provides the use of a ligand which forms a complex with a transition metal as a catalytic bleaching agent for a substrate in an aqueous medium substantially devoid of peroxygen bleach or a peroxy-based or - generating bleach system. the complex catalysing bleaching of the substrate by the atmospheric oxygen.
We have also found that certain ligands or complexes of this class are surprisingly effective in catalysing bleaching of the substrate by atmospheric oxygen after treatment of the substrate.
Accordingly, in a fourth aspect, the present invention provides a method of treating a textile by contacting the textile with a ligand which forms a complex with a transition : metal, whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment.
In a fifth aspect, the present invention provides a dry textile having a ligand as defined above applied or deposited thereon, whereby bleaching by atmospheric oxygen is catalysed on the textile.
In further aspects, the present invention provides ligands and complexes, as defined further below.
N
Advantageously, the method according to the present invention permits all or the majority of the bleaching species in the medium (on an equivalent weight basis) to be derived from atmospheric oxygen. Thus, the medium can be made wholly or substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach 5 system. Furthermore, the complex is a catalyst for the bleaching process and. as such. is not consumed but can continue to participate in the bleaching process. The catalytically activated bleaching system of the type in accordance with the present invention. which is based on atmospheric oxygen. is therefore both cost-effective and environmentally friendly. Moreover. the bleaching system is operable under unfavourable wash conditions which include low temperatures. short contact times and low dosage requirements. Furthermore, the method is effective in an aqueous medium and is therefore particularly applicable to bleaching of laundry fabrics. Therefore. whilst the composition and method according to the present invention may be used for bleaching any suitable substrate, the preferred substrate is a laundry fabric. The bleaching method may be carried out by simply leaving the substrate in contact with the medium for a sufficient period of time. Preferably, however, the aqueous medium on or containing the substrate is agitated. : An advantage of the method according to the fourth aspect of the invention is that. by enabling a bleaching effect even after the textile has been treated. the benefits of : bleaching can be prolonged on the textile. Furthermore. since a bleaching effect is conferred to the textile after the treatment, the treatment itself, such as a laundry wash cycle, may for example be shortened. Moreover, since a bleaching effect is achieved by atmospheric oxygen after treatment of the textile. hydrogen peroxide or peroxy-based bleach systems can be omitted from the treatment substance.
The ligand may be present as a preformed complex of a ligand and a transition metal.
Alternatively, the composition may comprise a free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate. The composition may also be formulated as a composition of a free ligand or a transition metal-substitutable metal-ligand complex. and a source of transition metal, whereby the complex is formed in situ in the medium.
The ligand forms a complex with one or more transition metals. in the latter case for example as a dinuclear complex. Suitable transition metals include for example: manganese in oxidation states II-V, iron II-V. copper I-111. cobalt I-11]. titanium II-1V, tungsten [V-VI. vanadium II-V and molybdenum II-VI.
The ligand forms a complex of the general formula (Al):
MaLiXn) Ym (AD) in which:
M represents a metal selected from Mn(I1)-(IID-(IV)-(V). Cu(D)-(ID)-(III). Fe(I)- dI)-(AV)-(V). Co(D)-(AN)-(111), Ti(I)-(UI)-AV), VID-(I)-(IV)-(V). Mo(ID)-(II1)-(IV)-(V)- (VI) and W(IV)-(V)-(VI), preferably selected from Fe(I)-(lII)-(IV)-(V);
L represents a ligand as herein defined, or its protonated or deprotonated analogue;
X represents a coordinating species selected from any mono. bi or tri charged . anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner, preferably selected from 0%, RBO,*, RCOO", RCONR", OH", NOy’, NO, S¥, :
RS’, PO,>, PO;OR”, H,0, CO;*, HCO5', ROH, N(R), ROO". 0,%. 07, RCN, CI". Br,
OCN/’, SCN’, CN, Ny, F', I', RO’, C104, and CF3S03’, and more preferably selected from 0%, RBO,*, RCOO’, OH’, NO", §*, RS’, PO;*, H,0. CO”, HCO5’, ROH, N(R);
CI',Br,OCN, SCN, RCN, N;', F, I, RO’, CIOs, and CF;SO5’;
Y represents any non-coordinated counter ion, preferably selected from ClOq’,
BRs , [MX4] , [MX4]*, PFs, RCOO’, NO, RO", N*(R)s, ROO", 0,7, 05, CI’, Br, F,
I', CF3S05, $,06% , OCN', SCN", H,0, RBO,”. BF, and BPhy’, and more preferably selected from C104, BRy™, [FeCly]~, PFs. RCOO", NO;y', RO", N*(R),. Ct, Br, F, I,
CF;805, S;0¢* , OCN, SCN’, H,0 and BFs; a represents an integer from 1 to 10, preferably from 1 to 4;
k represents an integer from 1 to 10: n represents an integer from 1 to 10. preferably from 1 to 4: m represents zero or an integer from 1 to 20, preferably from 1 to 8: and each R independently represents a group selected from hydrogen. hydroxyl. -R’ and -OR'. wherein R'= alkyl. alkenyl. cycloalkyl. heterocycloalkyl. aryl. heteroaryl or a carbonyl derivative group, R’ being optionally substituted by one or more functional groups E, wherein E independently represents a functional group selected from -F. -Cl. -
Br, -1, -OH, -OR’, -NH,, -NHR’, -N(R"),, -N(R");". -C(O)R’, -OC(O)R'. -COOH. -COO’ (Na*, K*), -COOR', -C(O)NH,, -C(O)NHR', -C(O)N(R’),, heteroaryl. -R’. -SR'. -SH, - *P(R)a -P(O)R')3, -P(O)(OH),, -P(O)(OR"), -NO,, -SO;H, -SO3’ (Na", K"). -S(O).R’, -
NHC(O)R'. and -N(R")C(O)R'. wherein R’ represents cycloalkyl, aryl. arylalkyl. or alkyl optionally substituted by -F, -Cl, -Br. -I, -NH;". -SO3H, -SOy(Na", K"), -COOH. -COO (Na, K"), -P(O)(OH),, or -P(O)(O'(Na", K)),. and preferably each R independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl. more preferably hydrogen or optionally substituted phenyl, naphthyl or C;_s-alkyl.
The ligand L is of the general formula (I): 21—@h
TC (Q3)—u : Z1—@Qn | a1 wherein : Z1 groups independently represent a coordinating group selected from hydroxy, amino, -NHR or -N(R); (wherein R=C, ¢-alkyl), carboxylate, amido, -NH-C(NH)NH,, hydroxyphenyl, a heterocyclic ring optionally substituted by one or more functional groups E or a heteroaromatic ring optionally substituted by one or more functional groups E, the heteroaromatic ring being selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole;
Q! and Q3 independently represent a group of the formula:
RS if - | - le hey te EE
R6 R8 3 wherein > atb+c > 1; a=0-5; b=0-5; ¢=0-5, n=0 or 1 (preferably n=0);
Y independently represents a group selected from -O-. -S-. -SO-. -SO»-. -C(0)-. arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-. -P(0)- and -(G)N-, wherein G is selected from hydrogen, alkyl, aryl. arylalkyl. cycloalkyl. each except hydrogen being optionally substituted by one or more functional groups E;
R35, R6, R7, R8 independently represent a group selected from hydrogen. } hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl. heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or RS together with R6, or R7 together with R8, or both. represent oxygen, or RS together with R7 and/or independently R6 together with R8, or R35 together with R8 and/or independently R6 together with R7, represent C,¢-alkylene optionally substituted by C,4-alkyl, -F, -Cl, -Br or -I;
T represents a non-coordinated group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl or a carbonyl derivative group, R being optionally substituted
{ .
AY 00/60044 PCT/EP00/02590 by one or more functional groups E (preferably T= -H. -OH. methyl. methoxy or benzyl);
U represents either a non-coordinated group T independently defined as above or a coordinating group of the general formula (II), (III) or (IV):
AQ
—N \
QH)—2z4 (IT) ~~ @- EN
N, 2 {2-73} (III)
Q)—2l —Q—(@C—T
QH)—2zi (Vv) wherein
Q2 and Q4 are independently defined as for Q1 and Q3;
Q represents -N(T)- (wherein T is independently defined as above), or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole;
Z2 is independently defined as for Z1;
Z3 groups independently represent -N(T)- (wherein T is independently defined as above); 74 represents a coordinating or non-coordinating group selected from hydrogen. hydroxyl, halogen, -NH-C(NH)NH,. -R and -OR. wherein R= alkyl, alkenyl. cycloalkyl. heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group. R being optionally substituted by one or more functional groups E. or Z4 represents a group of the general formula (Ila): o— Qh—z1
MN —(@B) CC T
Qh—21 (lla) and 1<j<4.
Preferably, Z1, Z2 and Z4 independently represent an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, : pyrazine, pyrazole, imidazole. benzimidazole. quinoline, quinoxaline. triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole. More preferably, Z1, . 72 and Z4 independently represent groups selected from optionally substituted pyridin- 2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-1-yl. and optionally substituted quinolin-2-yl. Most preferred is that Z1, Z2 and Z4 each represent optionally substituted pyridin-2-yl.
The groups Z1, Z2 and Z4 if substituted, are preferably substituted by a group selected from C,4-alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl. Preferred is that Z1, Z2 and Z4 are each substituted by a methyl group. Also, we prefer that the Z1 groups represent identical groups.
¥
The groups R3, R6, R7. R8 preferably independently represent a group selected from -
H. hydroxy-Co-Cjo-alkyl. halo-Co-Cag-alkyl. nitroso. formyl-Co-Cag-alkyl. carboxyl-Co-
Cap-alkyl and esters and salts thereof. carbamoyl-Co-Cag-alkyl. sulfo-Cy-Cap-alkyl and esters and salts thereof. sulfamoyl-Co-Cag-alkvl. amino-Co-Cap-alkyl. aryl-Cy-Cap-alkyl.
Cg-Cyo-alkyl, alkoxy-Co-Cg-alkyl, carbonyl-Co-Cg-alkoxy. and Co-Cag-alkylamide.
Each QI preferably represents a covalent bond or C1-C4-alkylene. more preferably a covalent bond. methylene or ethylene, most preferably a covalent bond.
Group Q3 preferably represents a covalent bond or C1-C4-alkylene, more preferably a covalent bond. -
Non-coordinated group T preferably represents hydrogen. hydroxy. methyl. ethyl. benzyl, or methoxy. 13
In one aspect of the present invention. the group U in formula (I) represents a coordinating group of the general formula (II):
JOE
\ : Q@)—z4 (Im
According to this aspect, it is preferred that Z2 represents an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole. benzimidazole. quinoline. quinoxaline, azole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole, more preferably optionally substituted pyridin-2-yl or optionally substituted benzimidazol-2- yl
It is also preferred, in this aspect, that Z4 represents an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine,
AMENDED SHEET 2002 -06- 10 pyrimidine, pyrazine, pyrazole. imidazole. benzimidazole. quinoline. quinoxaline. triazole, isoquinoline, carbazole. indole. 1soindole. oxazole and thiazole. more preferably optionally substituted pyridin-2-yl. or an non-coordinating group selected from hvdrogen. hydroxy. alkoxy. alkyl. alkenyl. cycloalkyl. aryl. or benzyl.
In preferred embodiments of this aspect, the ligand L is selected from: ~~ 1,1-bis(pyridin-2-yl)-N-methyl-N-(pyridin-2-ylmethyl)methylamine 1,1-bis(pyridin-2-y1)-N,N-bis(6-methyl-pyridin-2-ylmethyl)methylamine 1,1-bis(pyridin-2-y1)-N.N-bis(5-carboxymethyl-pyridin-2-ylmethyl)methylamine 1,1-bis(pyridin-2-yl)-1-benzyl-N,N-bis(pyridin-2-ylmethyl)methylamine 1.1-bis(pyridin-2yl)-N.N-bis(benzimidazol-2-ylmethyl)methylamine
In a variant of this aspect, the group Z4 in formula (II) represents a group of the general formula (Ila): 2 @ ,Qh~ 71
N — (QB) C T
QHh—zi (Ila) }
In this variant, Q4 preferably represents optionally substituted alkylene, preferably - }
CH,-CHOH-CH,- or -CH;,-CH,-CH,-. In a preferred embodiment of this variant, L represents the ligand:
Py Py ~~
Py So
Nd oo n= C— Nos << H
Py Py wherein -Py represents pyridin-2-yl.
In another aspect of the present invention. the group U in formula (I) represents a coordinating group of the general formula (III):
TE a [2-723 (11D) wherein j is 1 or 2, preferably 1.
According to this aspect, each Q2 preferably represents -(CHz),- (n=2-4). and each Z3 preferably represents -N(R)- wherein R = -H or C,4-alkyl, preferably methyl.
In preferred embodiments of this aspect. L represents a ligand selected from:
Py Py \ / Nn. Me \ / NN Me
H—C—N N Me—C—N N py _ J) py \_ \
N —
Me Me . 15 wherein -Py represents pyridin-2-yl.
In yet another aspect of the present invention, the group U in formula (I) represents a coordinating group of the general formula (IV):
Q)—2zi
QC T
Q)—2i (Iv)
In this aspect, Q preferably represents -N(T)- (wherein T= -H, methyl, or benzyl) or pyridin-diyl.
In preferred embodiments of this aspect. L represents a ligand selected from: no HR Pr Py
Me—C—N—C—Me MeO—C—Q —C— OMe
Py Py Py Py
Py Py \ /
HO—C—Q —C—OH
PY Py wherein -Py represents pyridin-2-yl. and -Q- represents pyridin-2.6-divl.
In a further aspect, the present invention provides a ligand L as defined above. with the proviso that T in formula (I) is not benzyl.
In a further aspect, the present invention provides a complex (Al) as defined above, with the proviso that T in formula (I) is not benzyl.
In a further aspect, the present invention provides a ligand as defined above, with the proviso that U represents a non-coordinated group T or a coordinated group of the } formula (IT) or (IIT), and if U represents a coordinating group of formula (II) and
Z1=72=Z4=unsubstituted pyridin-2-yl, T is not hydrogen, methyl or benzyl.
In preferred embodiments of this aspect, the ligand is selected from: 1,1-bis(pyridin-2-yl)-N-methyl-N(pyridin-2-yimethyl)methylamine; 1,1-bis(pyridin-2-yl)-N,N-bis(6-methyl-pyridin-2-ylmethyl)methylamine; 1,1-bis(pyridin-2-yl)-N,N-bis(5-carboxymethyl-pyridin-2-yl)methylamine; 1,1-bis(pyridin-2yl)-N,N-bis(benzimidazol-2-ylmethyl)methylamine; 2,6-bis(pyridin-2ylmethyl)-1,1,7,7-tetrakis(pyridin-2-yl)-2,6-diazaheptane; or a ligand selected from:
ie WEI WL
PY / RC ; \_ LL \ —
Me Me wherein -Py represents pyridin-2-yl.
In a further aspect. the present invention provides a transition-metal complex of the general formula (Al):
MaLiXn] Ym (Al) in which:
M represents a metal selected from Mn(ID-(IID-AV)-(V). Cu(D)-(1D)-(111). Fe(D)- (IID)-(IV)-(V). Co(1)~(I1)-(111), Ti(ID)-(1)-(IV), VAD-AUD-IV)-(V). Mo(ID)-(IIN)-(IV)-(V)- (VI) and W(IV)-(V)-(VD);
X represents a coordinating species selected from any mono. bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono. bi or tridentate manner;
Y represents any non-coordinated counter ion: a represents an integer from 1 to 10; k represents an integer from 1 t0 10; n represents an integer from 1 to 10; m represents zero or an integer from 1 to 20; and
L represents a ligand (or its protonated or deprotonated analogue) as defined above, with the proviso that U represents a non-coordinated group T or a coordinated group of the formula (II) or (III), and if U represents a coordinating group of formula (II) and Z1=Z2=Z4=unsubstituted pyridin-2-yl, T is not hydrogen, methyl or benzyl.
In preferred embodiments of this aspect, the ligand L is selected from: 1,1 -bis(pyridin-2-yl)-N-methyl-N(pyridin-2-yimethyl)methylamine; 1,1 -bis(pyridin-2-yl)-N,N-bis(6-methyl-pyridin-2-ylmethyl)methylamine;
1.1-bis(pyridin-2-y1)-N.N -bis(5-carboxymethyvi-pyridin-2-yvi)methylamine: 1.1 -bis(pyridin-2yl)-N.N-bis(benzimidazol-2-vimethyl ymethylamine: 2.6-bis(pyridin-2ylmethyl)-1.1 .7.7-tetrakis(pyridin-2-v1)-2.6-diazaheptane: or a ligand selected from:
STN a TN p/ 4 ) ~ N k —y ep
Me Me wherein -Py represents pyridin-2-yl.
Preferably. the metal ion in the complex of this aspect is selected from Fe(I1)-(1I1)-(IV).
Mn(1D)-(1I)-(1V)-(V), Cu(D)-(I1)-(I11) and Co(T)-(11)-(I1I). more preferably Fe(ID-(I1) or
Mn(ID-A)-(IV).
The counter ions Y in formula (A1) balance the charge z on the complex formed by the ligand L. metal M and coordinating species X. Thus. if the charge z is positive, Y may be an anion such as RCOO", BPhs', C104, BF. PF. RSO;3". RSO4’. SO>. NO; . FCI,
Br. orI, with R being hydrogen. optionally substituted alkyl or optionally substituted aryl. If z is negative, Y may be a common cation such as an alkali metal. alkaline earth metal or (alkyl)ammonium cation.
Suitable counter ions Y include those which give rise to the formation of storage-stable solids. Preferred counter ions for the preferred metal complexes are selected from
R’COO, ClO, BF4, PF¢, RSO5 (in particular CF;SO37), RSO4 SO4* ,NOy F,
CI, Br, and I, wherein R represents hydrogen or optionally substituted phenyl, naphthyl or C;-C, alkyl.
It will be appreciated that the complex (Al) can be formed by any appropriate means, including in situ formation whereby precursors of the complex are transformed into the active complex of general formula (A1) under conditions of storage or use. Preferably, the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species. Alternatively. the catalyst may be formed in situ from suitable precursors for the complex. for example in a solution or dispersion containing the precursor materials. In one such example. the active catalyst may be formed in situ in a mixture comprising a salt of the metal M and the ligand L. or a ligand L-generating species. in a suitable solvent. Thus. for example. if M is iron, an iron salt such as FeSO4 can be mixed in solution with the ligand L. or a ligand L-generating species, to form the active complex. Thus, for example. the composition may formed from a mixture of the ligand L and a metal salt MX, in which : preferably n=1-5, more preferably 1-3. In another such example, the ligand L. or a ligand L-generating species. can be mixed with metal M ions present in the substrate or wash liquor to form the active catalyst in situ. Suitable ligand L-generating species include metal-free compounds or metal coordination complexes that comprise the ligand
L and can be substituted by metal M ions to form the active complex according the formula (Al).
The bleaching compositions according to the present invention may be used for laundry cleaning. hard surface cleaning (including cleaning of lavatories. kitchen work surfaces, floors, mechanical ware washing etc.). As is generally known in the art. bleaching compositions are also employed in waste-water treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food processing, : starch bleaching, sterilisation, whitening in oral hygiene preparations and/or contact lens disinfection. :
In the context of the present invention bleaching should be understood as relating generally to the decolourisation of stains or of other materials attached to or associated with a substrate. However, it is envisaged that the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to or otherwise associated with a substrate. Furthermore, in the context of the present invention bleaching is to be understood as being restricted to any bleaching mechanism or process that does not require the presence of light or activation by light. Thus, photobleaching compositions and processes relying on the use of photobleach catalysts or photobleach activators and the presence of light are excluded from the present invention.
In typical washing compositions the level of the catalyst is such that the in-use level 1s from 0.05uM to 50mM. with preferred in-use levels for domestic laundry operations falling in the range 0.5 pM to 100 uM, more preferably from 1 pM to 10 uM. Higher levels may be desired and applied in industrial bleaching processes. such as textile and paper pulp bleaching.
Preferably. the aqueous medium has a pH in the range from pH 6 to 13. more preferably from pH 6 to 11. still more preferably from pH 8 to 11. and most preferably trom pH 8 to 10, in particular from pH 9 to 10.
The bleaching composition of the present invention has particular application in detergent formulations, especially for laundry cleaning. Accordingly. in another preferred embodiment, the present invention provides a detergent bieach composition comprising a bleaching composition as defined above and additionally a surface-active material, optionally together with detergency builder.
The bleach composition according to the present invention may for example contain a surface-active material in an amount of from 10 to 50% by weight. The surface-active : material may be naturally derived, such as soap. or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof.
Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents". Volumes I and II, by
Schwartz, Perry and Berch.
Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher aryl groups. Examples of suitable synthetic anionic detergent compounds are sodium and
+ WO 00/60044 PCT/EP00/02590 ammonium alkyl sulfates. especially those obtained by sulfating higher (Cs-Cis) alcohols produced. for example. from tallow or coconut oil: sodium and ammonium alkyl (Co-C30) benzene sulfonates, particularly sodium linear secondary alkyl (C;o-Cis) benzene sulfonates: sodium alkyl glyceryl ether sulfates. especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium and ammonium salts of sulfuric acid esters of higher (Co-C)3) fatty alcohol alkylene oxide, particularly ethylene oxide. reaction products: the reaction : products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide: sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulfonates such as those derived by reacting alpha-olefins (Cs-Ca0) with sodium bisulfite and those derived by reacting paraffins with SO» and Cl» and then hvdrolysing with a base to produce a random sulfonate; sodium and ammonium (C»-C;) dialkyl sulfosuccinates; and olefin sulfonates. which term is used to describe material made by reacting olefins. particularly (C,o-C30) alpha-olefins. with
SO; and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C,o-C,5) alkylbenzene sulfonates. and sodium (C¢-
C3) alkyl ether sulfates.
Examples of suitable nonionic surface-active compounds which may be used, preferably together with the anionic surface-active compounds. include. in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (Ce-C22) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (Cs-C\s) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO. Other so-called nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides. long-chain tertiary phosphine oxides and dialkyl sulfoxides.
Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
The detergent bleach composition of the invention will preferably comprise from 1 to 15 9 wt of anionic surfactant and from 10 to 40 % by weight of nonionic surfactant. Ina further preferred embodiment. the detergent active system is free from C;¢-C2 fanty acid soaps.
The bleach composition of the present invention may also contains a detergency builder. for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 %o by weight.
Builder materials may be selected from 1) calcium sequestrant materials. 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
Examples of calcium sequestrant builder materials include alkali metal polyphosphates. such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts: the alkali metal salts of carboxymethyloxy succinic acid. ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids. citric acid: and } polyacetal carboxylates as disclosed in US-A-4,144,226 and US-A-4,146.495.
Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
Examples of calcium ion-exchange builder materials include the various types of water- insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384.070.
In particular, the compositions of the invention may contain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts. Typical builders usable in the present invention are, for example. sodium carbonate. calcite/carbonate. the sodium salt of nitrilotriacetic acid. sodium citrate. carboxvmethyloxy malonate. carboxymethyloxy succinate and water-insoluble crystalline or amorphous aluminosilicate builder materials. each of which can be used as the main builder. either alone or in admixture with minor amounts of other builders or polymers as co-builder.
It is preferred that the composition contains not more than 5% by weight of a carbonate builder, expressed as sodium carbonate, more preferably not more than 2.5 % by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
Apart from the components already mentioned, the bleach composition of the present invention can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions. Examples of these additives include buffers such as carbonates, lather boosters. such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids; lather depressants. such as alkyl phosphates and silicones; anti- redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted : alkyl cellulose ethers; stabilisers, such as phosphonic acid derivatives (i.e. Dequest® types); fabric softening agents; inorganic salts and alkaline buffering agents. such as : sodium sulfate and sodium silicate; and. usually in very small amounts. fluorescent agents; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants.
Transition metal sequestrants such as EDTA, and phosphonic acid derivatives such as
EDTMP (ethylene diamine tetra(methylene phosphonate)) may also be included, in addition to the ligand specified, for example to improve the stability sensitive ingredients such as enzymes, fluorescent agents and perfumes, but provided the composition remains bleaching effective. However, the composition according to the present invention containing the ligand, is preferably substantially, and more preferably completely, devoid of transition metal sequestrants (other than the ligand).
PCT/EP00/02590
Whilst the present invention is based on the catalytic bleaching of a substrate by atmospheric oxygen or air. it will be appreciated that small amounts of hydrogen peroxide or peroxy-based or -generating systems may be included in the composition. 1f desired. Therefore. by “substantially devoid of peroxygen bleach or peroxy-based or - generating bleach systems” is meant that the composition contains from 0 to 50 %. preferably from 0 to 10 %. more preferably from 010 5 %. and optimally from 0 to 2 % by molar weight on an oxygen basis, of peroxygen bleach or peroxv-based or - generating bleach systems. Preferably. however. the composition will be wholly devoid of peroxvgen bleach or peroxy-based or -generating bleach systems.
Thus, at least 10 %, preferably at least 50 % and optimally at least 90 % of any bleaching of the substrate is effected by oxygen sourced from the air.
According to the fourth aspect, the catalyst may be contacted to the textile fabric in any suitable manner. For example. it may be applied in dry form. such as in powder form. or in a liquor that is then dried, for example as an aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning. or a non-aqueous dry cleaning fluid or spray- on aerosol fluid. Other suitable means of contacting the catalyst to the textile may be used. as further explained below.
Any suitable textile that is susceptible to bleaching or one that one might wish to subject to bleaching may be used. Preferably the textile is a laundry fabric or garment.
The bleaching method of the fourth aspect may be carried out by simply leaving the substrate in contact with the catalyst for a sufficient period of time. Preferably. however, the catalyst is in an aqueous medium, and the aqueous medium on or containing the substrate is agitated.
In a preferred embodiment, the treated textile is dried, by allowing it to dry under ambient temperature or at elevated temperatures.
In a particularly preferred embodiment the method according to the fourth aspect 1s carried out on a laundry fabric using aqueous treatment liquor. In particular the treatment may be effected in. or as an adjunct to. an essentially conventional wash cycle for cleaning laundry. More preferably. the treatment is carried out in an aqueous detergent wash liquor. The catalyst can be delivered into the wash liquor from a powder. granule. pellet. tablet. block. bar or other such solid form. The solid form can comprise a carrier. which can be particulate. sheet-like or comprise a three-dimensional object. The carrier can be dispersible or soluble in the wash liquor or may remain substantially - intact. In other embodiments. the catalyst can be delivered into the wash liquor from a paste, gel or liquid concentrate. . It is particularly advantageous that the catalyst used in the method of the fourth aspect makes use of atmospheric oxygen in its bleaching activity. This avoids the requirement that peroxygen bleaches and/or other relatively large quantities of reactive substances need be used in the treatment process. Consequently. only a relatively small quantity of bleach active substance need be employed and this allows dosage routes to be exploited which could previously not be used. Thus. while it is preferable to include the catalyst in a composition that is normally used in a washing process. such as a pre-treatment. main- : wash, conditioning composition or ironing aid. other means for ensuring that the catalyst is present in the wash liquor may be envisaged.
For example. it is envisaged that the catalyst can be presented in the form of a body from which it is slowly released during the whole or part of the laundry process. Such release can occur over the course of a single wash or over the course of a plurality of 75 washes. In the latter case it is envisaged that the catalyst can be released from a carrier substrate used in association with the wash process, e.g. from a body placed in the dispenser drawer of a washing machine, elsewhere in the delivery system or in the drum of the washing machine. When used in the drum of the washing machine the carrier can be freely moving or fixed relative to the drum. Such fixing can be achieved by mechanical means, for example by barbs that interact with the drum wall, or employ other forces, for example a magnetic force. The modification of a washing machine to provide for means to hold and retain such a carrer is envisaged similar means being known from the analogous art of toilet block manufacture. Freely moving carriers such as shuttles for dosage of surfactant materials and/or other detergent ingredients into the wash can comprise means for the release of the catalyst into the wash.
In the alternative, the catalyst can be presented in the form of a wash additive that preferably is soluble. The additive can take any of the physical forms used for wash additives. including powder. granule, pellet. sheet. tablet. block. bar or other such solid form or take the form of a paste, gel or liquid. Dosage of the additive can be unitary or in a quantity determined by the user. While it is envisaged that such additives can be used in the main washing cycle, the use of them in the conditioning or drying cycle is not hereby excluded.
The present invention is not limited to those circumstances in which a washing machine is employed, but can be applied where washing is performed in some alternative vessel.
In these circumstances it is envisaged that the catalyst can be delivered by means of slow release from the bowl, bucket or other vessel which is being employed. or from any implement which is being employed, such as a brush, bat or dolly. or from any suitable applicator.
Suitable pre-treatment means for application of the catalyst to the textile material prior : to the main wash include sprays, pens, roller-ball-devices, bars. soft solid applicator sticks and impregnated cloths or cloths containing microcapsules. Such means are well known in the analogous art of deodorant application and/or in spot treatment of textiles.
Similar means for application are employed in those embodiments where the catalyst is applied after the main washing and/or conditioning steps have been performed, e.g. prior to or after ironing or drying of the cloth. For example, the catalyst may be applied using tapes, sheets or sticking plasters coated or impregnated with the substance, or containing microcapsules of the substance. The catalyst may for example be incorporated into a drier sheet so as to be activated or released during a tumble-drier cycle, or the substance can be provided in an impregnated or microcapsule-containing sheet so as to be delivered to the textile when ironed.
Throughout the description and claims generic groups have been used. for example alkyl, alkoxy. arvl. Unless otherwise specified the following are preferred group restrictions that may be applied to generic groups found within compounds disclosed herein: alkyl: linear and branched C1-C8-alkyl. 10- © alkenyl: C2-Cé6-alkenyl. cycloalkyl: ~~ C3-C8-cycloalkyl. alkoxy: C1-Cé6-alkoxy, alkylene: selected from the group consisting of: methylene: 1.1-ethylene: 1.2- ethylene; 1,1-propylidene; 1.2-propylene; 1.3-propylene; 2.2-propylidene; butan-2-ol- 1.4-diyl; propan-2-ol-1,3-diyl; 1,4-butylene: cyclohexane-1.1-diyl; cyclohexan-1.2-diyl; cyclohexan-1,3-diyl; cyclohexan-1.4-diyl; cyclopentane-1.1 -diyl: cyclopentan-1.2-diyl: : and cyclopentan-1,3-diyl, aryl: selected from homoaromatic compounds having a molecular weight under 300, : arylene: selected from the group consisting of: 1,2-phenylene; 1.3-phenylene; 1 .4- phenylene; 1,2-naphtalenylene; 1,3-naphtalenylene; 1,4-naphtalenylene; 2,3- naphtalenylene; 1-hydroxy-2,3-phenylene; 1-hydroxy-2,4-phenylene; 1-hydroxy-2,5- phenylene; and 1-hydroxy-2,6-phenylene,
heteroarvl: selected from the group consisting of: pyridinyl: pyrimidinyl: pyrazinyl: triazolyl: pyridazinyl: 1.3.5-triazinyl: quinolinyl: isoquinolinyl: quinoxalinyi: imidazolyl; pyrazolyl: benzimidazolyl: thiazolyl: oxazolidinyl: pyrrolyl: carbazolyl: indolyl; and isoindolyl. wherein the heteroaryl may be connected to the compound via
S any atom in the ring of the selected heteroaryl. heteroarvlene: selected from the group consisting of: pyridindiyl: quinolindiyl: pyrazodiyl; pyrazoldiyl; triazolediyl: pyrazindiyl: and imidazolediyl. wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene. more specifically preferred are: pyridin-2.3-diyl; pyridin-2.4-divl; pyridin-2.5-diyl; pyrndin-2.6-diyl; pyndin-3.4-diyi: pyridin-3.3~diyi: quinoiin-2.3-diyl, quinolin-2.4-divl; quinolin-2.8-diyl; isoquinolin-1.3-diy}; isoquinolin-1 4-diyl: pyrazol- 1.3-diyl: pyrazol-3,5-diyl; triazole-3.5-diyl: triazole-1.3-diyl; pyrazin-2.5-divl: and imidazole-2.4-diyl, heterocycloalkyl: selected from the group consisting of: pyrrolinyl; pyrrolidinyl: morpholinyl; piperidinyl; piperazinyl: hexamethylene imine; 1.4-piperazinyl: tetrahydrothiophenyl; tetrahydrofuranyl; 1.4.7-triazacyclononanyl; 1.4.8.11- tetraazacyclotetradecanyl; 1,4,7.,10,13-pentaazacyclopentadecanyl: 1.4-diaza-7-thia- cyclononanyl; 1,4-diaza-7-oxa-cyclononanyl. 1.4.7.10-tetraazacyclododecanyl; 1.4- dioxanyl; 1,4,7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl. wherein the . heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of: piperidin-1.2-ylene; piperidin-2,6-ylene; piperidin-4,4-ylidene; 1.4-piperazin-1 ,4-ylene; 1.4-piperazin-2.3- ylene; 1,4-piperazin-2,5-ylene; 1,4-piperazin-2,6-ylene; 1,4-piperazin-1.2-ylene; 1,4- piperazin-1,3-ylene; 1,4-piperazin-1,4-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrothiophen-2,3-ylene; tetrahydrofuran-2,5-ylene; tetrahydrofuran-3,4-ylene; tetrahydrofuran-2,3-ylene; pyrrolidin-2,5-ylene; pyrrolidin- 3,4-ylene; pyrrolidin-2,3-ylene; pyrrolidin-1,2-ylene; pyrrolidin-1,3-ylene; pyrrolidin-
2.2-ylidene: 1.4.7-triazacvclonon-1.4-vlene: 1.4.7-tnazacyvclonon-2.3-vlene: 1.4.7- triazacyclonon-2,9-ylene; 1.4.7-triazacyclonon-3.8-vlene: 1.4.7-triazacvclonon-2.2- ylidene; 1.4.8.11-tetraazacyclotetradec-1.4-vlene: 1.4.8.11 -tetraazacvclotetradec-1.8- ylene: 1.4.8.11-tetraazacyclotetradec-2.3-ylene: 1.4.8.11 -tetraazacvclotetradec-2.5- ylene: 1.4.8.11-tetraazacyclotetradec-1.2-ylene: 1.4.8.11-tetraazacyclotetradec-2.2- ylidene: 1.4.7.10-tetraazacyclododec-1.4-ylene: 1.4.7.10-tetraazacyclododec-1 .7-vlene: 1,4,7.10-tetraazacyclododec-1,2-ylene; 1.4,7.10-tetraazacyclododec-2.3-ylene: 1 4.7.10- tetraazacyclododec-2.2-ylidene: 1,4,7,10.13-pentaazacyclopentadec-1.4-vlene: 1.4,7.10.13-pentaazacyvclopentadec-1.7-ylene: 1,4.7.10.1 3-pentaazacyvclopentadec-2.3- ylene: 1.4.7.10.13-pentaazacyclopentadec-1.2-ylene: 1.4,7.10.13- pentaazacvclopentadec-2.2-vlidene; 1.4-diaza-7-thia-cyclonon-1.4-ylene: 1 4-diaza-7- thia-cyclonon-1.2-ylene; 1.4-diaza-7-thia-cyclonon-2.3-ylene; 1 .4-diaza-7-thia- cyclonon-6.8-ylene; 1,4-diaza-7-thia-cyclonon-2.2-ylidene; 1.4-diaza-7-oxa-cyclonon- 1.4-ylene; 1.4-diaza-7-oxa-cyclonon-1.2-ylene: 1 .4-diaza-7-oxa-cyclonon-2.3-vlene: 1.4-diaza-7-oxa-cyclonon-6.8-ylene; 1.4-diaza-7-oxa-cycionon-2.2-ylidene: 1 .4-dioxan- 2.3-ylene; 1.4-dioxan-2.6-ylene; 1,4-dioxan-2.2-ylidene: tetrahydropyran-2.3-ylene: tetrahydropyran-2,6-ylene; tetrahydropyran-2.5-ylene: tetrahydropyran-2.2-ylidene: 1,4,7-trithia-cyclonon-2.3-ylene; 1,4.7-trithia-cyclonon-2.9-ylene; and 1.4.7-trithia- cyclonon-2,2-ylidene, : amine: the group -N(R), wherein each R is independently selected from: hydrogen; C1-Cé6-alkyl, C1-Cé6-alkyl-C6HS5; and phenyl, wherein when both R are C1-
C6-alkyl both R together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring. halogen: selected from the group consisting of: F; Cl; Brand I, sulfonate: the group -S(0),OR, wherein R is selected from: hydrogen: C1-Cé-alkyl; phenyl; C1-C6-alkyl-C6HS; Li; Na; K; Cs; Mg; and Ca,
sulfate: the group -OS(0)20R. wherein R is selected from: hydrogen: C1-Cé6-alk:L. phenyl; C1-C6-alkyl-C6H5: Li: Na: K: Cs: Mg: and Ca. sulfone: the group -S(O);R. wherein R is selected from: hydrogen: C1-Cé6-alkyl: phenyl: C1-Cé-alkyl-C6H5 and amine (to give sulfonamide) selected from the group: -
NR'2, wherein each R' is independently selected from: hydrogen: C1-C6-alkyl: C1-C6- alkyl-C6HS: and phenyl, wherein when both R' are C1-Cé6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring. carboxylate derivative: the group —C(O)OR. wherein R is sclected from: hydrogen: C1-C6-alkyl; phenyl; C1-C6-alkyl-C6HS; Li; Na; K: Cs: Mg: and Ca. carbonyl derivative: the group -C(O)R, wherein R is selected from: hydrogen: C1-C6- alkyl; phenyl; C1-C6-alkyl-C6H5 and amine (to give amide) selected from the group: -
NR'2. wherein each R' is independently selected from: hydrogen: C1-Cé-alkyl: C1-C6- alkyl-C6HS5; and phenyl, wherein when both R' are C1-C6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring. phosphonate: the group ~P(O)(OR),, wherein each R is independently selected . from: hydrogen; C1-Cé-alkyl; phenyl; C1-Cé6-alkyl-C6HS; Li: Na: K; Cs; Mg: and Ca, phosphate: the group —-OP(O)(OR),, wherein each R is independently selected from: hydrogen; C1-C6-alkyl; phenyl; C1-Cé-alkyl-C6H5: Li: Na; K; Cs; Mg; and Ca, phosphine: the group -P(R),, wherein each R is independently selected from: hydrogen; C1-Cé6-alkyl; phenyl; and C1-C6-alkyl-C6H5,
phosphine oxide: the group -P(O)R,. wherein R is independently selected from: hydrogen: C1-C6-alkyl: phenyl: and C1-C6-alkyl-C6HS: and amine (to give phosphonamidate) selected from the group: -NR'2. wherein each R'is independently selected from: hydrogen; C1-C6-alkyl: C1-C6-alkvl-C6HS5: and phenyl. wherein when both R' are C1-Cé6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring.
Unless otherwise specified the following are more preferred group restrictions that may be applied to groups found within compounds disclosed herein: alkyl: linear and branched C1-C6-alkyl, alkenyl: C3-Cé6-alkenyl. cycloalkyl: C6-C8-cycloalkyl, alkoxy: C1-C4-alkoxy, : alkylene: selected trom the group consisting of: methylene: 1.2-ethylene: 1.3- propylene; butan-2-ol-1,4-diyl; 1.4-butylene; cyclohexane-1.1-diyl; cyclohexan-1.2-diyl; : cyclohexan-1,4-diyl; cyclopentane-1.1-diyl: and cyclopentan-1.2-diyl, aryl: selected from group consisting of: phenyl; biphenyl; naphthalenyl. anthracenyl; and phenanthrenyl, arylene: selected from the group consisting of: 1.2-phenylene; 1,3-phenylene; 1,4- phenylene; 1,2-naphtalenylene; 1,4-naphtalenylene; 2,3-naphtalenylene and 1-hydroxy- 2,6-phenylene,
heteroarvl: selected from the group consisting of: pyridinyl: pyrimidinyl: quinolinyl: pyrazolyl: triazolyl; isoquinolinyl: imidazolyl: and oxazolidinyl. wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl.
heteroarylene: selected from the group consisting of: pyridin-2.3-diyl: pyridin-2.4-diyl: pyridin-2.6-diyl; pyridin-3.3-diyl; quinolin-2.3-divl: quinolin-2.4-divl: isoquinolin-1.3- diyl; isoquinolin-1.4-diyl; pyrazol-3.5-diyl; and imidazole-2,4-diyl. heterocycloalkyl: selected from the group consisting of: pyrrolidinyl: morpholinyl:
piperidinyl; piperidinyl; 1,4-piperazinyl: tetrahydrofuranyl; 1.4.7-triazacyclononanyl: 1.4.8.11-tetraazacyciotetradecanyi; 1.4.7.10.13-pentaazacyciopentadecanyi: 1.4.7.10- tetraazacvclododecanyl: and piperazinyi. wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl.
heterocvcloalkylene: selected from the group consisting of: piperidin-2.6-ylene: piperidin-4,4-ylidene; 1.4-piperazin-1,4-ylene; 1.4-piperazin-2.3-ylene; 1.4-piperazin- 2.6-ylene: tetrahydrothiophen-2,5-ylene: tetrahydrothiophen-3.4-ylene: tetrahydrofuran- 2,5-ylene; tetrahydrofuran-3,4-ylene; pyrrolidin-2.5-ylene; pyrrolidin-2.2-ylidene: 1.4,7- triazacyclonon-1,4-ylene; 1,4,7-triazacyclonon-2.3-ylene: 1 4.7-triazacyclonon-2,2- :
ylidene; 1,4.8,11-tetraazacyclotetradec-1,4-ylene; 1.4.8.1 1-tetraazacyclotetradec-1.8- ylene;
1,4,8.11-tetraazacyclotetradec-2.3-ylene; 1.4.8,1 1-tetraazacyclotetradec-2.2-ylidene; 1,4,7,10-tetraazacyclododec-1,4-ylene; 1,4,7,10-tetraazacyclododec- 1.7-ylene; 1,4,7,10-tetraazacyclododec-2.3-ylene: 1,4.7,1 0O-tetraazacyclododec-2.2-ylidene;
1,4,7,10,13-pentaazacyclopentadec-1,4-ylene; 1,4,7,10.1 3-pentaazacyclopentadec-1,7- ylene; 1,4-diaza-7-thia-cyclonon-1,4-ylene; 1.4-diaza-7-thia-cyclonon-2,3-ylene; 1,4-
diaza-7-thia-cyclonon-2,2-ylidene; 1,4-diaza-7-oxa-cyclonon-1,4-ylene; 1,4-diaza-7-
oxa-cyclonon-2,3-ylene;1,4-diaza-7-oxa-cyclonon-2.2-ylidene: 1 ,4-dioxan-2.6-ylene;
1,4-dioxan-2,2-ylidene; tetrahydropyran-2,6-ylene; tetrahydropyran-2,5-ylene; and tetrahydropyran-2,2-ylidene,
amine: the group -N(R),. wherein each R is independently selected from: hydrogen; C1-Cé6-alkyl: and benzyl. halogen: selected from the group consisting of: F and CL. 5 . sulfonate: the group -S(0),0R, wherein R is selected from: hydrogen: C1-Cé6-alkyl:
Na; K; Mg: and Ca, sulfate: the group -OS(O);OR. wherein R is selected from: hydrogen: C1-Cé-alkyl; Na: 10K; Mg: and Ca. sulfone: the group -S(O);R. wherein R is selected from: hydrogen: C1-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-Cé6-alkyl: and benzyl. carboxylate derivative: the group —C(O)OR. wherein R is selected from hydrogen; Na; K; Mg; Ca; C1-C6-alkyl: and benzyl. carbonyl derivative: the group: -C(O)R. wherein R is selected from: hydrogen; C1-C6- alkyl; benzyl and amine selected from the group: -NR'2. wherein each R'is : independently selected from: hydrogen; C1-Cé6-alkyl; and benzyl. phosphonate: the group —P(O)(OR),. wherein each R is independently selected from: hydrogen; C1-C6-alkyl; benzyl; Na; K; Mg: and Ca. phosphate: the group —OP(O)(OR),, wherein each R is independently selected from: hydrogen; C1-Cé-alkyl; benzyl: Na; K; Mg: and Ca, phosphine: the group -P(R),, wherein each R is independently selected from: hydrogen; C1-Cé6-alkyl; and benzyl,
phosphine oxide: the group -P(O)R,. wherein R is independently selected from: hydrogen; C1-C6-alkyl; benzyl and amine selected from the group: -NR'2. wherein each
R' is independently selected from: hydrogen: C1-Cé6-alkyl: and benzyl.
The invention will now be further illustrated by way of the following non-limiting examples:
The following compounds were prepared and tested for catalytic bleaching activity using air:
Compound 1: [Fe(L')(CH3CN)}(Cl104)-
L'= 1.1-bis(pyridin-2-y})-N-methyl-N-(pyridin-2-ylmethyl)methylamine
Compound 2: [Fe(L)(CH3CN)}(ClOs):
L*= 1,1-bis(pyridin-2-yl)-N,N-bis(6-methyl-pyridin-2-yimethyl)methylamine
Compound 3: [Fex(L*)(CH3CN);)(C1O4)4 L*= 2.6-bis(pyridin-2-ylmethyl)-1.1 ,7.7-tetrakis(pyridin-2-vl)-2.6-diazaheptane
Compound 4: [Fe(L*)(CH;CN))(C104), :
L*= 1,1-bis(pyridin-2-yl)-1-benzyl-N,N-bis(pyridin-2-ylmethyl)methylamine
Compound 5: [Fe(L’)(CH;CN)]CIOs),
L’=1,1 -bis(pyridin-2-y1)-N.N-bis(5-methoxycarbonyl-pyridin-2-ylmethyl)methylamine
Compound 6: [Fe(L®)(CH;CN),}(ClO4),
Lt= 1-(a,0-bis(pyridin-2-yl))methyl-4,7-dimethyl-1,4,7-triazacyclononane
Compound 7: [Fe(L’)(CH;CN);)(ClO4);
L’= 1-(o.a-bis(pyridin-2-yl))ethvl-4.7-dimethyl-1.4.7-triazacyclononane
Compound 8: 2.2.4 4-tetrakis(pyridin-2-yl)-3-azapentane (= L%) + Fe(ClO.):
Compound 9: L® + Mn(Cl10;),.6H,0
Compound 10: L? + Co(Cl04).6H,0
Compound 11: 1.1-bis(pyridin-2yl)-N.N-bis(benzimidazol-2-yl-methyl)methylamine (= L%)
Compound 12: LY + Fe(Cl04),.6H-0
Compound 13: L® + Mn(Cl0O;)2.6H,;0
Compound 14: L? + Co(Cl04)1.6H,0 :
Compound 15: L® + Cu(Cl04),.6H,0
Compound 16: 2,6-bis(methoxy-bis(pyridin-2-yl)methyl)pyridin (= L'%) +
Co(Cl04),.6H,O
Compound 17: 2,6-bis(hydroxy-bis-pyridin-2-yl)-methyl)pyridin (= L'Y +
Co(Cl04),.6H,0 .
Syntheses of compounds:
Compound 1 1,1-bis(pyridin-2-yl)-N-methyl-N-(pyridin-2-ylmethyl)methylamine (L1]) (= N-[di(2-pyridinyl)methyl]-N-methyl-N-(2-pyridinylmethyl)amine)
To di-2-pvridyl methyl amine (1.5 g. 8.1 mmol) was added freshly distilled pyridine-2- carboxaldehyde (900 mg. 8.4 mmol). After shaking the flask. the mixture was allowed to stand for approximately 2 hours. The white solid was collected and washed with cyclohexane to remove traces of unreacted starting material to give pure A-[di(2- pyridinyl)methyl]-N-[(Z)-2-pyridinyimethylidene]amine (2.02 2.91 %). "H-NMR (CDCls. 300 MHz) 8 6.0 (s. 1H). 7.16 (m. 2H). 7.31 (m. 1H). 7.39 (m. 5H). &.18 (m. 1H), 8.61 (m, 3H), 8.65 (s, 1H): MS (CI): m/z 275 (M+1).
To a solution of N-[di(2-pyridinyl)methyl]-A-{(Z)-2-pyridinylmethylidenejamine (1.5 g. 5.5 mmol) in methanol (20 ml) was added NaBH, (0.45 g. 11.8 mmol) in small portions.
After stirring at room temperature for 2 hours HCl (aq) is added unti! the pH<2. After stirring for 30 min 5 N NaOH (aq) is added until the pH>9. The methanol is removed through evaporation and the aqueous layer is extracted with ethyl acetate (3 x30 ml).
The combined ethyl acetate layers are washed with brine (30 ml) and dried (Na;SOs).
Evaporation of the solvent gave N-[di(2-pyridinvl)methyl]-N-(2-pyridinylmethyl)amine (N3Py) (1.35 g. 89 %) as a yellow oil. ‘H-NMR (CDCl;. 300 MHz) 8 3.85 (s. 2H), 5.10 (s. 1 H). 7.03 (m, 3H). 7.41 (m, 6H). 8.46 (m. 3H): 3C NMR (CDCl. 50 MHz) 6 53.1 (1), 68.9 (d), 121.8 (d), 122.1 (d), 122.2 (d). 122.3 (d). 136.3 (d). 136.5 (d). 149.2 (d), 159.6 (s), 161.2 (s); MS (CI): m/z 277 (M+1).
To a solution of N-{di(2-pyridinyl)methyl}-N-(2-pyridinylmethyl)amine (1.262 g. 4.59 mmol) in 1,2-dichloroethane (35 ml) was added formaldehyde (37 % solution in water, 0.45 ml, 6.0 mmol). NaBH(OAc); (3.92 g, 18.5 mmol) was added in small portions.
After stirring for 7 h at room temperature saturated NaHCOj35q) (35 ml) was added and the 1,2-dichloroethane layer was separated. The aqueous layer is extracted with CHCl, (3x 20 ml). The combined organic layers were washed with IN NaOH (20 m}) and brine (20 ml), dried (Na;SOs) and the solvent removed in vacuo to give N-[di(2- pyridinyl)methyl]-N-methyl-N-(2-pyridinylmethyl)amine (1.235 g, 4.27 mmol, 93 %) as a slightly yellow oil. 'H NMR (CDCl, 300 MHz) 3 2.19 (s, 3H), 3.72 (s, 2H), 4.96 (s, 1H), 7.14 (m, 3H), 7.71 (m, 6H), 8.56 (m, 3H); BC NMR (CDCl, 50 MHz) 6 40.32 (q),
61.04 (1). 77.87 (d). 121.76 (d). 122.10 (d). 122.92 (d). 123.21 (d). 136.29 (d). 136.43 (d). 148.86 (d), 149.22 (d). 159.37 (s). 160.59 (s). MS (CI): m/z 291 (M+1). [(L1)Fe(CH3CN):](ClOy)>
To a solution of N-[di(2-pyridinyl)methyl}-A-methyl-N-(2-pyridinylmethyl)amine (198 mg, 0.68 mmol) in acetonitrile (3 ml) was added a solution of Fe(Cl04)»'6H>0 (250 mg. 0.69 mmol) in methanol (3 ml). The solution was placed in an ethyl acetate bath and after 2 days [(L1)Fe(CH3;CN),)(C10s); (344 mg. 0.55 mmol, 81 %) was obtained as dark red crystals. '"H NMR (CD3CN. 300 MHz) 8 3.81 (br). 5.17 (br). 6.96 (br). 7.40 (1. I= 7.7 Hz). 7.64 (t. J = 7.7 Hz). 8.04 (1, J = 7.7 Hz). 8.59 (br). 8.70 (br). 8.87 (br). 9.02 (br). . 11.26 (br). 11.40 (br): Anal. Caled. for CyHasClyFeNgOs: C 42.13. H 3.86. N 13.40: found: C 41.98. H 3.78. N 13.27.
Compound 2 1. 1-bis(pyridin-2-yl)-N.N-bis(6-methyl-pyridin-2-ylmethyl) methylamine. 2HC1O,
To di-2-pyridyl methyl amine (1.8 g, 10 mmol) was mixed with 5 ml of SN NaOH in water. To 2.83 g (20 mmol) of 2-picolylchloride (synthesised according to W. Mattes et : al.. Angew Chem., 75. 235 (1963)) was mixed with 5 ml of SN NaOH in water. Both mixtures were colled in an ice bath and added together under stirring. Stirring was continued for 4 days at 20 °C. The reaction mixture was colled in an ice bath and under stirring 3 ml of 70% HCIO, was added. The salt seperated as a liquid which became solid after scratching with a spatula. The yellow precipitate was washed 2 times 10 ml of water and 2 times of 5 ml of methanol. The compound was recrystallised from hot water and dried under vacuum over siccapent. Yield 3.1g (52.%); m.p. 168.5 °C. 'H NMR (CD;CN, 200 MHz) 5 2.88 (s) 6H; 4.21 (s) 4H; 5.91 (s) 1H; 7.33 (d) 2H; 7.43 (d) 2H; 7.63 (m) 4H; 7.99 (t) 2H; 8.15 (t) 2H; 8.82 (d) 2H. C-NMR: 25.80; 58.34; 75.00; 122.60; 129.00; 129.74; 130.82; 132.00; 145.00; 150.80; 153.80.
Anal. Calcd. for C23H23CILNsOg: C 48.6, H4.1, N 12.3, Cl 12.5%; found: C 48.5, H4.7,
N11.5Cl11.5%.
The corresponding iron complex was synthesised as described for the non-methyvlated analogue (reference M. Lubben et al.. 34. 1512 (1995)).
Compound 3 2.6-bis(pyridin-2-ylmethyl)-1.1.7, 7 -tetrakis(pyridin-2-yl}-2.6-diazaheptane (L3)
Dipyridyl-methylchloride
To a solution of 9.2¢g of dipyridylketone in 200m! methanol was added 1g sodium borohvdride in small portions over 0.5h. The reaction was exothermic. After completion of the addition the mix was stirred 15’. TLC analysis showed the conversion to be quantitive. To the mix was added 10mi of cencentrated hydrochioric acid and the acid solution was concentrated by evaporation in vacuo. Water was added and the acidic water phase 1s washed with dichloromethane. Now 100ml of 2N NaOH was added and the resulting alkaline mixture was extracted 3x with dichloromethane. The combined organic layers were dried over sodium sulfate. fiitered and evaporated giving 9g of the dipyridylcarbinol. It was found that the compound degraded slowly and CDCls, samples were prepared just before measurement. 'H NMR (CDCl;) (ppm): 5.86 (s, 1H, Py2C-H); 7.15 (m, 2H, Py-H): 7.50 (m. 2H. Py-
H); 7.62 (m, 2H, Py-H); 8.53 (m, 2H, Py-H) 3C NMR (CDCI3) (ppm): 76.3, 122.2, 123.6, 137.9. 149.1. 161.9
N,N'-(Di-pyrid-2-yl methyl)-1,3-diaminopropane: 2-Pyridine carboxaldehyde (9.0g, 84mmol) was added dropwise to a solution of 1.3- diaminopropane (3.0g, 40mmol) in methanol (100ml). The mixture became hot. After stirring for 30 min. NaBH; (4.0g, 105mmol) was added in portions. After addition of the first 0.9g, sodium tetraborate.10aq (7.0g, 18mmol) was added. When the addition was complete it was stirred at ambient temperature for 45 min then evaporated to approx. 50ml, water added (250ml) and extracted (x4) with CHCI3. The extracts were washed with saturated NaCl then dried and evaporated to leave a pale yellow oil (9.52g). This was short path distilled to give a forerun of 140mg, b.p. up to 160°C/1mm (discarded) and a main fraction 7.33g b.p. 160-215°C/Imm.
'H NMR (CDCl3) (ppm) 1.78 (m. 2H). 2.2 (br s. 2NH). 2.76 (m. 4H). 3.9 (s. 4H). 6.96 (m. 2H). 7.15 (d. 2H). 7.45 (m. 2H). 8.37 (d. 2H) 'C NMR (CDCl3) 30.19.47.77.55.11. 121.59. 121.97. 136.12. 148.97. 159.81. 2.6-bis(pvridin-2-vimethyl)-1.1.~. 7-tetrakis(pyridin-2-yl)- 2. 6-diazaheptane (N,N'-Bis(Dipyrid-2-ylmethyl)-N.N'-bis(pvrid-2-yimethyl)- 1. 3-diamino-propane)
A mixture of 1.7g dipyridyl-methylchloride (14). 1 g N.N'-bis(pyrid-2-vlmethyl)-1.3- diamino-propane (15) and 0.5g potassium carbonate in 20 ml acetonitrile was stirred and refluxed under argon for 48h. TLC (silica/ eluent CH2C12/MeOH(7N NH3) 90/10) indicated the reaction to be almost complete. The mixture was filtered and evaporated.
The residue was chromatographed on silica using dichloromethane with increasing methanol concentration (up to 5%) to give 1.5g pure product as a yellow/brown glassy gum. 'H NMR (CDCl5) 8 (ppm): 1.75 (m. 2H), 2.42 ppm (m. 4H). 3.75 (s. 4H). 5.16 (s. 2H), 7.02 (m. 6H), 7.4-7.6 (multiplets, 12H), 8.38 (m. 2H), 8.46 (m. 4H): 13C NMR (CDCl3) (ppm): 23.5,49.5.57.1.73.0, 121.6. 121.9. 122.7. 123.6. 136.1. 136.2, 148.8. 149.0, 160.4; ESP-Mass m/z: 615.3 (M+Na)™*. 593.4 (M+H)*. 502.3 (M+H-
CH2C5H4N). 425.2 (502.3+H-C5H4N). Fe-complex
To a solution of 0.11g of the ligand (see above) in 2ml MeOH and 2 ml acetonitrile was added 0.1g iron(II) perchlorate hexahydrate and 0.2g of sodium perchlorate. Ethyl acetate was allowed to diffuse into the mixture for over three days. Dark brown crystals were isolated from the mixture by filtration giving 20mg of the product after drying.
UV/Vis (CH3CN) Anax (€ a.u.): 695 nm (0.038), 493 nm (0.259). 471 nm (0.271), 334 nm (2.95). LR. (Kbr, cm-1): 3421, 1607, 1447, 1112, 1088, 792, 628.
Compound 4: [Fe(L*)(CH3CN)](ClOy), 1,1-bis(pyridin-2-yl)-1-benzyl-N, N-bis(pyridin-2-ylmethyljmethylamine (L4)
Compound 4 was synthesised as described elsewhere (EP 0909 809 A2)
Compound 5 1,1-bis(pvridin-2vl)-N. N-bis(3-carboxymethvi-pyridin-2-yvimethylymethviamine (L3)
Methyl 6-methylnicotinate (10 g. 66.2 mmol) was dissolved in dichloromethane (150 ml). 3-Chloroperoxybenzoic acid (17 g. 112 mmol) was added and the mixture was stirred for 3 hours at room temperature. Saturated NaHCOj solution (200 ml) was added and the mixture was stirred for an additional hour. The dichloromethane laver was separated and the aqueous layer was extracted with dichloromethane (2 x 100 ml). The combined dichloromethane layers were washed with saturated NaHCO; (aq) (100 ml). brine (100 ml) and dried (Na,SOy). After evaporation of the solvent methyl 6- (chloromethyl)nicotinate N-oxide (7.8 g. 51.0 mmol) was obtained as a creme colored solid. mp 90.4 — 90.8 °C, which was combined with p-toluenesulfonyl chloride (10.7 g. 56.1 mmol) and dioxane (100 ml) under an Argon atmosphere. The reaction mixture was heated under reflux for 1 night. After cooling to room temperature the solvent was evaporated and the residue dissolved in dichloromethane (200 ml). The solution was washed with saturated NayCOs (aq) (2 x 100 ml). brine (50 ml) and dried (Na,SO;).
After evaporation of the solvent the product was purified by column chromatography (S102, using hexane/ethyl acetate 10:2.5 as an eluens) to give methyl 6- (chloromethyl)nicotinate (5.71 g, 46 % overall yield) as a slightly yellow solid. An analytically pure sample could be obtained by recrystallization from n-hexane. mp 63.5 - 63.8 °C; "H-NMR (CDCl;) & 3.94 (s. 3H). 4.70 (s. 2H). 7.58 (d. 1H. J = 8.4 Hz). 8.30 (dd, 1H, J = 8.1 Hz, J = 2.2 Hz). 9.08 (d, 1H. J = 1.5 Hz); Anal. Calcd. for CgHsCINO;:
C 51.77, H 4.34, N 7.55; found: C 51.50, H 4.23. N 7.46.
A solution of di(2-pyridinyl)methylamine (555 mg, 3.0 mmol), methyl} 6- (chloromethyl)nicotinate (1.7 g, 9.2 mmol) and N,N-diisopropylethylamine (1.6 ml, 9.2 mmol) was placed under argon and heated under reflux for 1 night. After evaporation of the solvent water (10 ml) was added and the product was extracted with ethyl acetate (3x15 ml).
The combined organic layers were washed with brine (10 ml), dried (Na;SO4) and the solvent removed in vacuo. Column chromotagraphy (Alox akt. I, ethyl acetate/hexane/triethylamine 10:5:1) afforded 1,1-bis(pyridin-2yl)-N,N-bis(5-
+ WO 00/60044 PCT/EP00/02590 carboxvmethyl-pyridin-2-vimethyl)methylamine (548 mg. 1.2 mmol. 40 %) as a slightly vellow oil. "H NMR (CDCl;. 300 MHz) 3.90 (s. 6H). 4.04 (s. 4H). 5.32 (s. 1H). 7.13 (m. 2H). 7.60 (m. 2H). 8.16 (dd. 2H. J = 8.05 Hz. J = 2.2 Hz). 8.56 (d. 2 H. J = 4.8 Hz) 9.06 (d. 2H. J = 1.8 Hz): *C NMR (CDCl;. 50 MHz) 8 52.03 (g). 57.28 (t). 72.32 (d). 122.16 (d). 122.39(d). 123.82 (d), 124.10 (s). 136.24 (d), 137.22 (d).149.25 (d). 150.15 (d). 159.48 (s). 164.33 (s), 165.69 (s): MS (CI): m/z 484 (M+1). [(L3)Fe(CH;CN)](CIO >
To a solution of 1,1-bis(pyridin-2yl)-N.N-bis(5-carboxymethyl-pyridin-2- vimethyl)methylamine (72 mg. 0.15 mmol) in acetonitrile (1.5 ml) was added a solution of
Fe(Cl0s);-6H-0 (55 mg. 0.15 mmol) in methanol (1.5 ml). The solution was placed in an ~ ethyl acetate bath and after 3 days [(L5)Fe(CH;CN))(ClO4); (96 mg, 0.12 mmol. 82 %) was obtained as dark red crystals. 'H NMR (CD;CN. 300 MHz) 8 3.94 (s. 6H). 4.39 (d. 2H.) = 18.7 Hz). 4.51 (d. 2H. J = 19.0 Hz). 6.40 (s. 1H). 7.21 (d. 2H. J = 8.1 Hz). (t. 2H. } = 6.2 Hz). 7.91 (m, 4H). 8.14 (d. 2H. 8.1 Hz). 8.91 (d. 2H. J = 4.8 Hz). 9.48 (s. 2H): Anal. calcd for
CaoH25CloFeNgO12: C 44.69. H 3.62. N 10.78: found: C 44.28. H 3.69. N 10.65.
Compound 6 1-[di(2-pyridin-2-yl)methyl]-4,7-dimethyl-1.4. 7-triazacyclonane (L6) : To a solution of 80 mL n-BuLi in hexanes (2.5 M, 0.2 mol) was added 2- pyridylbromide (31.6 gram 0.2 mol) in 100 ‘mL of ether at - 80°C - -60°C. The suspension was stirred for 1 h. and the temperature was allowed to rise to -45° C.
Subsequently 2-pyridinecarboxaldehyde (21.42 gram 0.2 mol) in of ether (100 mL) was added during 30 min. To the thick slurry was added additional THF (200 mL) and the mixture was stirred for 1.5 h at -40° C - -30° C and then the mixture was allowed to warm up to -10 ° C. The mixture was poured into water (200 ml) and acidified with 2 M
HCI to pH = 1-2 and the layers were separated. The aqueous layer was extracted twice with ether (100 mL) and neutralized with saturated Na;CO3aq to pH = 8. The aqueous layer was extracted CHCl, (3x100 ml). Drying (Na;SO4) and evaporation of the solvent yielded a brown oil. Vacuum distillation (118 ° C, 0.2 mmHg) afforded di(2-
pyridinyl)methanol (19.42 gram. 104.4 mmol. 52 %) as a vellow oil. "H-NMR (200
MHz. CDCl;3) & 5.88 (s. 2H). 7.11 - 7.19 (m. 2H). 7.47 - 7.67 (m. 4H). 8.50 - 8.54 (m. 2H). C-NMR (50.3 MHz. CDCl3) 8 75.0 (d). 121.0 (d). 122.5 (d). 136.8 (d). 1448.1 (d). 160.7 (s).
To di(2-pyridinyl)methanol (8.73 g. 46.94 mmol) in CH;CN (100 ml) at 0 °C was added a solution of PPh; (14.77 gram, 56.32 mmol) in of CCl; (80 mL) in 1.5 h. The solution was left standing overnight. After addition of MeOH (10 ml) and stirring for 13 min the mixture was concentrated in vacuum to ca 50 ml. To the residue was added of water (100 ml) and the mixture was acidified with 2M HCl to pH = 1. and washed twice with 100 mi of CHCl; the aqueous layer was neutralized with K>CO; and extracted 4 times with 75 ml of ether. Drying and evaporation of the solvent yielded 2- [chloro(2-pyridinyl)methyl}pyridine (5.41 gram. 36 %) as a pale brown solid.
Analytically pure material was obtained by column chromatography on silica (ether). 'H-NMR (200 MHz, CDCl;) & 6.20 (s.1H). 7.14 - 7.20 (m, 2H), 7.60 - 7.73 (m, 4H). 8.51 - 8.54 (m, 2H). *C-NMR (50.3 MHz. CDCl3) & 62.84 (d). 121.3 (d). 121.5 (d). 135.7 (d). 147.7 (d). 156.9 (s). Anal. Cald. for C,;HoCIN,:C 64.56. H 4.43. C1 17.32, N 13.69; Found: C 64.48, H 4.45. C1 17.29. N 13.49.
A solution of bis(2-pyridyl)methyl chloride (170 mg. 0.83 mmol). 1.4-dimethyl-1.4.7- triazacyclonane (155 mg, 0.99 mmol) (ref. Koek et al, J.Chem.Soc., Dalton. Trans. 353 : (1996)) and K,CO; (136 mg, 0.99 mmol) in acetonitrile (10 ml) was placed under Ar and heated under reflux during 16 h. The reaction mixture was poored out in water (20 ml) and brought to pH>10 with NaOH. The aqueous solution was extracted with ethyl acetate (3 x 15 ml). The combined organic layers were dried (K-CO5) and the solvent was removed in vacuo to give 1-{di(2-pyridinyl)methyl]-4,7-dimethyl-1.4,7-triazonane (250 mg, 0.77 mmol, 93 %) as a slightly yellow oil. 'H NMR (CDCl;, 300 MHz) § 2.28 (s, 6H), 2.60 (m, 4H), 2.79 (s, 4H), 2.81 (m, 4H), 5.07 (s, 1H), 7.06 (dt, 2H, J = 5.1 Hz, J = 3.3 Hz), 7.57 (m. 4H), 8.47 (d, 2H, J = 4.8 Hz); *C NMR (CDCl;, 50 MHz) 8 46.40 (q), 53.96 (1), 56.93 (1), 56.97 (1), 77.70 (d), 121.67 (d), 123.48 (d), 135.96 (d), 148.79 (d), 161.22 (s); HRMS calcd. for CioH27Ns 325.227, found 325.227.
[(L6)Fe(CH;CN)J(CIOy)-
To a solution of 1-[di(2-pyridinyl)methyl]-4.7-dimethyl-1.4.7-triazacyclonane (78 mg. 0.24 mmol) in acetonitrile (2 ml) was added a solution of Fe(C104)»-6H-0 (95 mg. 0.26 mmol) in methanol (2 ml). The solution was placed in an ethyl acetate bath and after night [(L6)Fe(CH3CN)}(CIO4)2 (0.2 mmol. 85 %) was obtained as dark red crystals. ‘H
NMR (CD;CN. 300 MHz) 2.73 (s, 6H), 2.86 (m. 6H). 2.96 (m. 6H). 6.09 (s. 1H). 7.33 (m, 2H), 7.79 (d, 2H, J = 7.7 Hz), 7.88 (dt. 2H. J = 7.7 Hz. J = 1.1 Hz). 8.99 (d. 2H. J = 5.5 Hz): Anal. calcd for Cy H30ClaFeNOg: C 40.60. H 4.87. N 13.53; found: C 40.56. H 4.85,N 1343.
Compound 7 1-[1,1-di(2-pyridinyl)ethyl]-4, 7-dimethyl-1.4.7-triazacyclonane (L7)
A solution of 1-[di(2-pyridinyl)methyl]-4.7-dimethyl-1.4.7-triazacyclononane (300 mg. 0.92 mmol) in ether/THF 1:1 (30 ml) was cooled to ~80 °C and t-butyllithium (1.5 Min pentane. 0.65 ml, 0.97 mmol) was added. After for stirring for 20 min at —80 °C Mel (60 nL, 0.96 mmol) and the solution was allowed to warm up to room temperature ) overnight. After removal of the solvent CHCl3 (30 ml) was added and the solution was washed with saturated NaHCO3 (4) (20 ml) and brine (20 ml). and dried (Na,S04).
Evaporation of the solvent afforded 1-[1 .1-di(2-pyridinyl)ethyl}-4.7-dimethyl-1.4.7- triazacyclonane (300 mg, 0.88 mmol. 96 %) as a slightly orange solid. which was used without further purification. >*C NMR (CDCl3, 50 MHz) & 14.1 (q). 45.4 (q). 50.0 (1), 55.3 (1), 56.6 (1), 60.3 (s), 122.6 (d), 123.8 (d), 136.8 (d), 148.8 (d), 162.6 (3); MS(EI): 339M"). [(L7)Fe(CH;CN)] (ClO):
To a solution of 1-[1,1-di(2-pyridin-2-yl)ethyl]-4.7-dimethyl-1.4,7-triazacyclonane (112 mg, 0.33 mmol) in acetonitrile (6 ml) was added Fe(ClO4)2-6H,0 (143 mg, 0.39 mmol),
The solution was placed in an ethyl acetate bath and after 1 night [(L7)Fe(CH3CN)](C104); (90 mg, 0.14 mmol, 43 %) was obtained as red microcrystals.
'"H NMR (CD;CN. 300 MHz) 8 2.24 (s. 3H). 2.67 (m. 6H). 2.70 (s. 6H). 2.97 (m. 6H). 7.33 (m. 2H). 7.63 (m. 2H). 7.90 (m. 2H). 9.01 (d. 2H. J = 5.5 Hz).
Compound 8 2.2.4 4-tetrakis(pyridin-2-vlj-3-azapentane (LS)
Under vigorous stirring and N,-atmosphere. 1 mL of a 3 M solution of MeMgBr in Et,0 was added dropwise to a solution of 300 mg (0.749 mmol) of 1.3.3-tris(2-pyridyl)-3H- imidazo[1.5-a]pyridin-4-ium (TPIP) in 20 mL of dry toluene (ref TPIP: M.Renz. et al..
J Chem. Soc.. Chem. Commun. 1998. 1635.). After 2 h. 2 mL of a saturated NH,Cl solution was added and the solvent evaporated. The residue was dissolved in 10 mL
CH,C}, and washed with 10 mL of a 2 N NaOH solution. After drying with MgSO. the solvent was evaporated, the residue dissolved in | mL CH,CI, and exposed to a pentane atmosphere overnight. 209 mg (73%) of L® were obtained as colorless crystals. H NMR (300 MHz. CDCl,, 25 °C): d = 1.48 (s, 6 H). 5.96 (brs. 1 H. N-H). 7.08 (ddd. J = 1.7. 4.8. 6.6 Hz, 4 H, 2-H), 7.56 (dt, J = 1.8, 8.1 Hz. 4 H. 3-H). 7.61 (ddd. J = 1.1. 1.7, 8.1
Hz, 4 H, 4-H). 8.55 (ddd, J= 1.1. 1.7, 4.8 Hz. 4 H. 1-H). - 13C NMR (75 MHz. CDCl3. 25°C): d = 26.3 (g, C-7), 65.6 (s, C-6), 121.5 (d. C-2). 122.3 (d. C-4). 136.4 (d, C-3), . 148.5 (d, C-1), 168.7 (s. C-5). - FAB-MS. m/z (%): 382 (57) [M+1]. 303 (16) [M-py], 183 [dipyridylethyl].
Compound 11 1.1 bis-[pyridyl-2yl]-N, N-bis-[benzimidazol-2yl-methylenyl ]-methyl amine (L9)
Preparation Dipyridyl-methylamine
Dipyridy! ketone (25.5g, 0.138mol, from Aldrich) and hydroxylamine hydrochloride (20g) were added to pyridine (120ml). The mixture was stirred and refluxed for 4h. allowed to cool to 20°C and concentrated by evaporation in vacuo. The residue was poored into 1 1 of ice water and after stirring a precipitate formed. After 15min the precipitate was isolated by filtration and dried in vacuo at 60°C (drying is not strictly necessary as it can be used wet in the next step). This product was used without further purification in the next step.
In a 2] flask the product was dissolved in ethanol (250ml) and concentrated ammonia (400ml). water (250ml) and ammonium acetate (10 g) were added. The mixture was heated to 90°C while stirring with a mechanical stirrer. Zinc powder (37.5g) was added in small portions to the stirred mixture over a 1h period. After the addition was complete stirring was contnued for 3h. TLC (silica. eluent ammonia/butanol 70/30) showed conversion to be complete and the mix was allowed to cool to 20°C. filtered over celite and concentrated. Sodium hydroxide solution (20%. 100ml) was added to the concentrate and the mixture was extracted three times with ether. (The aqueous layer should be strongly alkaline, in some cases more extractions were needed to obtain a good yield. The use of CH»Cl; instead of ether is preferred as extraction is more efficient)
The ether lavers were combined and washed with saturated sodium chloride solution. dried over sodium sulfate, filtered and evaporated to give 21g (81.9% if pure) of a light yellow oil 'H NMR (CDCls) (ppm): 2.50 (bs, 2H. NH2): 5.30 (s. 1H. Py2C-H): 7.05 (m. 2H. Py-
H); 7.37 (m, 2H. Py-H); 7.58 (m. 2H. Py-H): 8.51 (m. 2H, Py-H).
BC NMR (CDCl) (ppm): 62.6. 122.0, 122.3, 136.9. 149.4 and 163.0
N2Py-diacetate
To a cooled solution of sodium hydroxide (3.5 g in 3 ml water) was added 4.2 chloroacetic acid. Subsequently 3.7 g (20 mmol) of dipyrridylmethane in 6 ml water was added. The reaction was stirred and monitored by TLC (30% ammonia / 70% MeOH).
After 5 days still starting product was observed and again chloroacetic acid prenuetralized in alkaline was added in a couple of portions over time till TLC indicate that all starting material was converted. After workup a mixture of product, triethylamine (needed to extract the produuct into an organic phase) and glycolate was obtained. The product was used without further purification. 1,1 bis-[pyridyl-2yl]-N,N"-bis-[benzimidazol-2yl-methylenyl ]-methyl amine
To 2.5 g of the mixture obtained as described above. was added 1.4 g o-phenylene diamine and placed in a 195C oil bath. After 25 minutes the mixture was allowed to cool, taken up in dichloromethane and washed with ammonia. The dichloromethane layer was evaporated giving a dark red oil. Chromatography (S102. with CH2CI2/MeOH gradient) gave 0.56 g product. 'H NMR (CDCls) (ppm): 4.0 (s. 4H. CH2): 5.30 (s. 1H. Py2C-H): 7.06 (m. 2H. Py-H): 7.21 (m. 4H, Ar-CH), 7.39 (m. 2H, Py-H); 7.50 (m. 2H. Py-H): 7.60 (m. 4H. Ar-CH). 8.48 (m, 2H, Py-H). 3C NMR (CDCl3) (ppm): 49.3. 72.5, 115.2, 115.6. 122.6, 122.7. 123.0. 124.5. 137.3. 137.9,138.3. 141.1, 149.1 152.2 and 158.7
Compounds 16 and 17 2,6-bis(methoxy-bis(pyridin-2-yl)methyl)pyridin (L10) and 2.6-bis(hydroxy-bis-pyridin- 2-yl)-methyl)pyridin (L11) were synthesised as published elsewhere (M.E. de Vries, B.L. Feringa, et al, Chem Comm, 1549 (1997).
Experimental:
In an aqueous solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g/1
Na-LAS (linear alkylbenzene sulfonate) or containing 10 mM borate buffer (pH 8) without and with 0.6 g/l NaLAS, tomato-soya oil stained cloths (6x6 cm) were added and stirred for 30 minutes at 30 °C (blanks). In a second series of experiments, the same tests were done in : the presence of 10 uM of compound 1-7 or 20 uM of ligand L9, L10. or L11 in combination with Mn, Fe, Co or Cu perchlorate salt
The cloths were measured immediately after the wash (Table 1) or after 24 h storage in a dark room under ambient conditions (Table 2).
After the wash, the cloths were rinsed with water and subsequently dried at 30 °C and the change in colour was measured immediately after drying with a Linotype-Hell scanner (ex Linotype). The change in colour (including bleaching) is expressed as the
AE value. The measured colour difference (AE) between the washed cloth and the unwashed cloth is defined as follows:
AE = (AL) +(8a)’ +(ab) 1"? wherein AL is a measure for the difference in darkness between the washed and unwashed test cloth; Aa and Ab are measures for the difference in redness and yellowness respectively between both cloths. With regard to this colour measurement technique. reference is made to Commission International de I'Eclairage (CIE):
Recommendation on Uniform Colour Spaces. colour difference equations. psychometric colour terms, supplement no 2 to CIE Publication. no 15, Colormetry. Bureau Central de la CIE. Paris 1978.
The results are shown in Tables 1 and 2 below:
Table 1 Bleach values expressed as AE obtained for the tomato stains for the various compounds
OE 2 2 CL A
SL LA LA LE CO
Got [72 [Ti
Ec CO LS CA
Ear LI LCN LO
Gopunds [6 [on
Ear EN CA LE LA
Cc A LR CA LI
Car A LS CA LA
Coma pp 5 a EL CIN LAN
EE CI LA CAN LL
Table 2 Bleach values expressed as AE obtained for the tomato stains afier storage for 24 h in the dark [WEL [ETA DRIOLAS [PHI0CLAS
Compound 16 | 2 15 3 15
Claims (28)
1. A bleaching composition comprising. in an aqueous medium. atmospheric oxygen and a ligand which forms a complex with a transition metal. the complex catalysing bleaching of a substrate by the atmospheric oxygen. wherein the aqueous medium is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system. wherein the ligand forms a complex of the general formula (Al): [MLiXa] Ym (AD) in which: M represents a metal selected from Mn(1I)-(111)-(1V)-(V). Cu(1)-(ID-(IID. Fe(ID)- (IID-(IV)-(V), Co(D)-(I1)-(I11), Ti(N~(IIN-(IV), VI1)-(I)-(IV)-(V). Mo(ID-(ITH-(1V)-(V)- (VI) and WIV)-(V)-(VI); X represents a coordinating species selected from any mono. bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono. bi or tridentate manner; Y represents any non-coordinated counter 1on: a represents an integer from 1 to 10; k represents an integer from 1 to 10; n represents an integer from | to 10; : m represents zero or an integer from 1 to 20; and L represents a ligand of the general formula (1). or its protonated or deprotonated analogue: 2a CON Pr (Q3)—u Z1—(@Qn) 69) wherein AMENDED SHEET ~~ 2002 -06- 10
Z1 groups independently represent a coordinating group selected from hydroxy. amino, -NHR or -N(R), (wherein R=C¢-alkyl). carboxylate. amido. -NH-C(NH)NH.. hydroxyphenyl, a heterocyclic ring optionally substituted by one or more functional groups E or a heteroaromatic ring optionally substituted by one or more functional groups E. the heteroaromatic ring being selected from pyridine. pyrimidine. pyrazine. pyrazole. imidazole. benzimidazole, quinoline. quinoxaline. triazole. isoquinoline. carbazole, indole, isoindole. oxazole and thiazole;
Q! and Q3 independently represent a group of the formula:
C b | Y C c R6 R8 wherein : S > a+b+c > 1; a=0-5; b=0-3; ¢=0-5; n=0orl;
Y independently represents a group selected from -O-, -S-. -SO-, -SOz-, -C(0)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(0)- and -(G)N-, wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E;
RS, R6, R7, R8 independently represent a group selected from hydrogen. hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or RS together with R6, or R7 together with R8, or both, represent oxygen, AMENDED SHEET 2002 -06- 1g or R5 together with R7 and/or independently R6 together with R8. or R3 together with R8 and/or independently R6 together with R7. represent C,¢-alkvlene optionally substituted by C,4-alkyl. -F. -Cl. -Br or -I:
E independently represents a functional group selected from -F. -Cl. -Br. -1. -OH.. -OR’, -NH3, -NHR', -N(R"), -N(R");". -C(O)R’, -OC(O)R’, -COOH, -COO'(Na". K"). - COOR', -C(O)NHj;. -C(O)NHR', -C(O)N(R'),, heteroaryl. -R’, -SR’, -SH. -P(R')a. -
P(O)R')z, -P(O)OH)z, -P(O)(OR’);. -NOa:. -SO;H. -SO;°(Na". K*). -S(O):R". - NHC(O)R’, and -N(R")C(O)R'. wherein R’ represents cycloalkyl. aryl. arvlalkyl. or alkyl optionally substituted by -F. -Cl, -Br, -1, -NH3", -SO;H. -SO;’'(Na". K*). -COOH. -COO" (Na", K7). -P(O)(OH)a. or -P(O)(O"(Na*, K))2; T represents a non-coordinated group selected from hydrogen. hydroxyl. halogen, -R and -OR, wherein R represents alkyl. alkenyl, cycloalkyl, heterocycloalkyl. aryl, arylalkyl heteroaryl or a carbonyl derivative group.
R being optionally substituted by one or more functional groups E; U represents either a non-coordinated group T independently defined as above or a coordinating group of the general formula (II), (111) or (IV):
\ Q@—2z4 (11) vd @- 8, N - [2-23 (Ih AMENDED SHEET 2002 -06- 10
Qh—2Z1 QC —T Qh—2l (Iv) wherein Q2 and Q4 are independently defined as for Ql and Q3; Q represents -N(T)- (wherein T is independently defined as above). or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole. quinoline. quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole. oxazole and thiazole; Z2 is independently defined as for Z1; Z3 groups independently represent -N(T)- (wherein T is independently defined as above); Z4 represents a coordinating or non-coordinating group selected from hydrogen. hydroxyl, halogen, -NH-C(NH)NHj, -R and -OR, wherein R= alkyl, alkenyl. cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or Z4 represents a group of the general formula (Ila): o—@ ,Q)=21 a —@-C—T Qh—21 (Ila) and 1 <j<4
2. A bleaching composition according to claim 1, wherein n=0. AMENDED SHEET2002 -06- 10
3. A bleaching composition according to claim 1 or claim 2, wherein the medium has a pH value in the range from pH 6 to 11.
4. A bleaching composition according to claim 3, wherein the medium has a pH value in the range from pH8 to 10.
5. A bleaching composition according to any one of claims 1 to 4, wherein the : medium is substantially devoid of a transition metal sequestrant.
6. A bleaching composition according to any of claims 1 to 5, wherein the medium further comprises a surfactant.
7." A bleaching composition according to any of claims 1 to 6, wherein the medium further comprises a builder.
8. A bleaching composition according to any of claims 1 to 7, wherein the composition comprises a preformed complex of the ligand and a transition metal.
i 9. A bleaching composition according to any of claims 1 to 7, wherein the ligand is present as a free ligand that complexes with a transition metal present in the water.
10. A bleaching composition according to any of claims 1 to 7, wherein the ligand is present as a free ligand that complexes with a transition metal present in the substrate.
11.. A bleaching composition according to any of claims 1 to 7, wherein the composition comprises the ligand present as a free ligand or a transition metal- substitutable metal-ligand complex, and a source of transition metal.
12. A bleaching composition according to any preceding claim, wherein Z1, Z2 and Z4 independently represent an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole. AMENDED SHEET 2002 -06- 10
: 13. A bleaching composition according to any preceding claim. wherein the Z1, Z2 and Z4 independently represent groups selected from optionally substituted pyridin-2-yl. optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-1-yl, and optionally substituted quinolin-2-yl.
14. A bleaching composition according to any preceding claim, wherein Z1, Z2 and Z4 each represent optionally substituted pyridin-2-yl.
15. A bleaching composition according to any preceding claim, wherein Z1, Z2 and Z4 are optionally substituted by a group selected from C,4-alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl.
16. A bleaching composition according to any preceding claim, wherein one or more of Z1, Z2 and Z4 are substituted by a methyl group.
17. A bleaching composition according to any preceding claim, wherein the Z1 © groups represent identical groups.
18. A bleaching composition according to any preceding claim, wherein RS, R6, R7, R8 independently represent a group selected from -H, hydroxy-Cy-Cao-alkyl, halo-Co- / Cjo-alkyl, nitroso, formyl-Cs-Cyo-alkyl, carboxyl-Cgo-Cyo-alkyl and esters and salts thereof, carbamoyl-Co-Cyo-alkyl, sulfo-Cg-Cao-alky] and esters and salts thereof, sulfamoyl-Co-Cyo-alkyl, amino-Cq-Caq-alkyl, aryl-Co-Cyp-alkyl, Cq-Cyo-alkyl, alkoxy-Co- Cg-alkyl, carbonyl-Cy-Cg-alkoxy, and Co-Cyp-alkylamide.
19. A bleaching composition according to any preceding claim, wherein each Q1 represents a covalent bond or C1-C4-alkylene.
20. A bleaching composition according to claim 19, wherein each Q1 represents a covalent bond, methylene or ethylene.
21. A bleaching composition according to claim 20, wherein each Q1 represents a covalent bond. : AMENDED SHEET 2002 -06- 10
A
22. A bleaching composition according to any preceding claim, wherein each Q3 represents a covalent bond or C1-C4-alkylene.
23. A bleaching composition according to claim 22, wherein each Q3 represents a covalent bond.
24. A bleaching composition according to any preceding claim, wherein T represents hydrogen, hydroxy, methyl, ethyl, benzyl, or methoxy.
25. A bleaching composition according to any of claims 1 to 24,iwherein U represents a coordinating group of the general formula (II): S@—2 —N ()— 24 (11)
26. A bleaching composition according to claim 25, wherein Z2 represents an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole, and wherein Z4 represents an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole, or an non-coordinating group selected from hydrogen, hydroxy, alkoxy, alkyl, alkenyl, cycloalkyl, aryl, or benzyl.
27. A bleaching composition according to claim 26 wherein Z2 represents an optionally substituted pyridin-2-yl or an optionally substituted benzimidazol-2-yl, and wherein Z4 represents an optionally substituted pyridin-2-yl.
28. A bleaching composition according to claim 26 or claim 27, wherein L represents a ligand selected from: 1,1-bis(pyridin-2-yl)-N-methyl-N-(pyridin-2-ylmethyl)methylamine; 1,1-bis(pyridin-2-yl)-N,N-bis(6-methyl-pyridin-2-ylmethyl)methylamine; 1,1-bis(pyridin-2-y1)-N,N-bis(5-carboxymethyl-pyridin-2-ylmethyl)methylamine; 1,1-bis(pyridin-2-yl)-1-benzyl-N,N-bis(pyrdin-2-ylmethyl)methylamine; and AMENDED SHEET 2002 -06- 1 0
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9907714.1A GB9907714D0 (en) | 1999-04-01 | 1999-04-01 | Composition and method for bleaching a substrate |
Publications (1)
Publication Number | Publication Date |
---|---|
ZA200106939B true ZA200106939B (en) | 2002-08-22 |
Family
ID=10850946
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200106939A ZA200106939B (en) | 1999-04-01 | 2001-08-22 | Composition and method for bleaching a substrate. |
Country Status (3)
Country | Link |
---|---|
GB (1) | GB9907714D0 (en) |
RU (1) | RU2235125C2 (en) |
ZA (1) | ZA200106939B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2377614A1 (en) * | 2010-04-16 | 2011-10-19 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Bleaching of substrates |
-
1999
- 1999-04-01 GB GBGB9907714.1A patent/GB9907714D0/en not_active Ceased
- 1999-09-01 RU RU2001108585/04A patent/RU2235125C2/en not_active IP Right Cessation
-
2001
- 2001-08-22 ZA ZA200106939A patent/ZA200106939B/en unknown
Also Published As
Publication number | Publication date |
---|---|
GB9907714D0 (en) | 1999-05-26 |
RU2235125C2 (en) | 2004-08-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1109884B1 (en) | Composition and method for bleaching a substrate | |
US6245115B1 (en) | Method of treating a textile | |
US6610641B2 (en) | Composition and method for bleaching a substrate | |
WO2001016271A1 (en) | Composition and method for bleaching a substrate | |
US6537959B2 (en) | Bleach catalyst and composition and method for bleaching a substrate | |
WO2000060043A1 (en) | Composition and method for bleaching a substrate | |
EP1165738B1 (en) | Composition and method for bleaching a substrate | |
US6432900B1 (en) | Ligand and complex for catalytically bleaching a substrate | |
US6617299B1 (en) | Composition and method for bleaching a substrate | |
AU757351B2 (en) | Composition and method for bleaching a substrate | |
ZA200106939B (en) | Composition and method for bleaching a substrate. | |
CA2383935A1 (en) | Composition and method for bleaching a substrate | |
WO2001016272A2 (en) | Ligand and complex for catalytically bleaching a substrate | |
AU6571600A (en) | Composition and method for bleaching a substrate | |
AU7410400A (en) | Composition and method for bleaching a substrate | |
CA2401651A1 (en) | Method for reducing dye fading of fabrics in laundry bleaching compositions |