EP1042265A2 - O-derivatives of halogenated diphenyl ether compounds - Google Patents
O-derivatives of halogenated diphenyl ether compoundsInfo
- Publication number
- EP1042265A2 EP1042265A2 EP98965241A EP98965241A EP1042265A2 EP 1042265 A2 EP1042265 A2 EP 1042265A2 EP 98965241 A EP98965241 A EP 98965241A EP 98965241 A EP98965241 A EP 98965241A EP 1042265 A2 EP1042265 A2 EP 1042265A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- compound
- radical
- compounds
- sulfo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title abstract description 18
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 25
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 87
- 239000000203 mixture Substances 0.000 claims description 50
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- -1 halogenated diphenyl ether compound Chemical class 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004659 sterilization and disinfection Methods 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 210000004209 hair Anatomy 0.000 claims description 2
- 210000004400 mucous membrane Anatomy 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 229920001817 Agar Polymers 0.000 description 13
- 239000008272 agar Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000000344 soap Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 4
- 239000001888 Peptone Substances 0.000 description 4
- 108010080698 Peptones Proteins 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000005018 casein Substances 0.000 description 4
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 4
- 235000021240 caseins Nutrition 0.000 description 4
- 239000007374 caso agar Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 235000019319 peptone Nutrition 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- 241000191967 Staphylococcus aureus Species 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
- 238000004140 cleaning Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002781 deodorant agent Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229930182478 glucoside Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000007799 cork Substances 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- GMMUMXYUVFRBFV-UHFFFAOYSA-N dodecane;2-methyloxirane;oxirane Chemical compound C1CO1.CC1CO1.CCCCCCCCCCCC GMMUMXYUVFRBFV-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000008131 glucosides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229940088640 ppg-25-laureth-25 Drugs 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229940080279 sodium cocoate Drugs 0.000 description 2
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 229940045990 sodium laureth-2 sulfate Drugs 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229940045905 sodium tallowate Drugs 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- GUQPDKHHVFLXHS-UHFFFAOYSA-M sodium;2-(2-dodecoxyethoxy)ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOS([O-])(=O)=O GUQPDKHHVFLXHS-UHFFFAOYSA-M 0.000 description 2
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000007762 w/o emulsion Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000194031 Enterococcus faecium Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 238000002768 Kirby-Bauer method Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241000607715 Serratia marcescens Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000004395 glucoside group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 description 1
- 229940048848 lauryl glucoside Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- MDSQKJDNWUMBQQ-UHFFFAOYSA-M sodium myreth sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O MDSQKJDNWUMBQQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
- A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/02—Monocyclic aromatic halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Definitions
- the present invention relates to O-derivatives of halogenated diphenyl ether compounds, to a process for the preparation of these compounds, to their use as antimicrobial active substance.
- halogenated diphenyl ether compounds have an excellent antimicrobial activity. These compounds are therefore widely used, for example as active substances for the antimicrobial finishing of medical items and household articles, as detergent additive and in the hygiene sector, for example in soaps or dental hygiene products.
- Polymeric materials can be antimicrobially finished by incorporating halogenated diphenyl ether compounds, the active substances being, as a result of their excellent migration properties, constantly conveyed to the surface of the corresponding material ("slow release"). For certain industrial applications, this effect is undesired since the long-term effect of antimicrobially finished materials such as textiles, paper, plastics, cellulose sponges etc. is reduced at the same time.
- the object of the present invention is thus to provide diphenyl ether compounds which have antimicrobial activity and which, at the same time, are stable to migration.
- the present invention thus provides O-derivatives of halogenated diphenyl ether compounds of the formula
- R, and R 2 independently of one another are F, CI or Br; is a radical of the formula (1 a) -(CH 2 ) — CH - 0-R 4 ; (1 b)
- R 3 is C C 22 alkyl; C.-C ⁇ alkoxy; phenyl; phenyl-C.-C ⁇ lkyl; — (CH 2 ) p - A + R 5 R 6 R 7 ;
- R 5 , R 6 , R 7 and R 8 independently of one another are hydrogen; C 1 -C 4 all yl; sulfo- C ⁇ C ⁇ Ikyl; or R 5 and R 6 together with A form a cyclic radical unsubstituted or substituted by sulfo groups; or R 7 and R 8 together with N form a cyclic radical unsubstituted or substituted by sulfo groups;
- A is N or P
- Z is fluorine, chlorine, the radical of the formula (1 g)
- Z 2 is fluorine, chlorine, d-Caaalkoxy, C C 22 alkylthio or CrC 22 -monoalkylamino or
- C C-aadialkylamino each of which is unsubstituted or substituted by OH, NH 2 or sulfo; C 6 -C 12 aryloxy, C 6 -C 12 arylthio or C 6 -C ⁇ 2 monoarylamino or C 6 -C 12 diarylamino, each of which is unsubstituted or substituted by OH, NH 2 or sulfo; m is from 1 to 3; n is 1 or 2; and p p 2 , p 3> p 4 and p 5 independently of one another are 1-4.
- C.-C ⁇ alkyl and C ⁇ C ⁇ alkoxy are straight-chain or branched alkyl radicals, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl, and methoxy, ethoxy, propoxy, butyloxy, pentyloxy, amyloxy, isoamyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy
- Phenyl-C 1 -C 4 all ⁇ yl is, for example, phenylethyl, phenylpropyl, phenylbutyl or, preferably, benzyl.
- the derivatives according to the invention are ester, ether or glucoside derivatives of halogenated diphenyl compounds.
- Preferred ester derivatives are those of the formula
- R 1t R 2 , R 3 , m and n are as defined in formula (1).
- R 3 is C.,-C 12 alkyl; or phenyl; and, in particular, to those compounds of the formula (2) in which
- R, and R 2 are chlorine
- R 3 is C.-C ⁇ alkyl; m is 1 or 2; and n is 1;
- Illustrative ester derivatives of halogenated diphenyl compounds according to the invention are those of the formula
- R 3 is C ⁇ C ⁇ alkyl or phenyl.
- ester derivatives according to the invention are those of the formulae: o ⁇ n 8
- R v R 2 , m and n are as defined in formula (1); and R 8 , R 9 and R 10 independently of one another are hydrogen; or C.-C 4 alkyl.
- Preferred ether derivatives according to the invention are those of the formula
- R R 2 , R 4 , X, m, n, p, and p 2 are as defined in formula (1 )
- R 4 is C 1 -C22alkyl. or of the formula
- ether derivatives according to the invention are those of the formulae (12) v-0 — ,
- V is a radical of the formula (1 h), preferably (1 i) or (1 k); R 8 , R 9 and R 10 are hydrogen; or C ⁇ C ⁇ Ikyl; and Z, is -O-V; and Z 2 is CI; or N(CH 2 CH 2 OH) 2 .
- Preferred glucoside derivatives according to the invention are those of the formula
- V is a radical of the formula (1 h), or, preferably, (1 i) or (1 k).
- halogenated diphenyl ether derivatives according to the invention which have a phosphate, sulfate or glucoside group are hydrophilic compounds, which are readily obtainable synthetically in high yields.
- Y is a radical of the formula (1b);
- R 3 is -(CH 2 ) p4 -N + R 5 R6R 7 ; are obtained in good yields by reacting the chloroacetate of the compound of the formula
- Sulfobetaines i.e. compounds of the formula (1), in which
- Y is a radical of the formula (1 b); R 3 is -(CH 2 ) p4 -A-N + R 5 R 6 R 7 ;
- R 5 is sulfoalkyl; or R 5 and R 6 with A form a cyclic radical, are obtained by reacting corresponding N-dialkyl- or -monoalkylbetaine esters of the compound of the formula (15) with aqueous MSO 3 solution and a suitable catalyst system.
- Y is a radical of the formula (1f);
- chlorophosphate the compound of the formula • anc * corresponding amine.
- the glucoside derivatives are obtainable by reacting the phenolic OH group of the compound of the formula (15) with peracetylated glucose and subsequently hydrolyzing the ester protective groups.
- the hydrophilic derivatives are colourless, high-melting compounds having good solubility in water.
- Hydrophobic halogenated diphenyl ether derivatives for example compounds of the formulae (3a), (3b), (10a), (10b) and (11a) and (11b) are obtainable in a single-stage reaction by esterifying or etherifying the phenolic OH group of the compound of the formula (15). Solubility and melting point of the acylated derivatives can be varied within a wide range by the choice of reactant.
- the diphenyl ether derivatives according to the invention are thermally stable and antimicrobially effective compounds of low volatility and having a severely reduced tendency to migrate. They are therefore preferably suitable for the antimicrobial finishing of polymeric compounds, for example in plastics, rubbers, paints, surface coatings, (textile) fibres which are exposed to a microbially contaminated environment.
- polymers and other substrates which can be antimicrobially finished in this way are:
- polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other, and precursors thereof, - polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams,
- polyureas polyimides, polyamide-imides. poiyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles,
- - natural polymers such as cellulose, natural rubber, gelatine, and derivatives thereof modified chemically in a polymer-homologous manner, such as cellulose acetates, cellulose propionates cellulose butyrates, or the cellulose ethers, such as methylcellulose; and also rosins and derivatives.
- the invention thus also provides a composition
- a composition comprising
- the invention also relates to a process for the antimicrobial finishing of an organic material, which comprises adding at least one compound of the formula (1 ) thereto, and to the use of the compound of the formula (1) for the antimicrobial finishing of polymeric materials.
- the amount of antimicrobial active substance to be used depends on the organic material to be antimicrobially finished and on the intended use of the material finished in this way.
- the composition according to the invention generally comprises, per 100 parts by weight of component (A), from 0.01 to 15 parts by weight, in particular from 0.05 to 10 parts by weight, and especially from 0.1 to 5 parts by weight of the antimicrobial active substance (component (B)).
- the antimicrobial active substance (component (B)) can also be a mixture of two or more compounds of the formula (1).
- the compositions according to the invention can, in addition to the compounds according to the invention, also comprise other additives, for example antioxidants or light protection agents.
- Incorporation into the organic polymers can take place by adding the halogenated diphenyl ether compound according to the invention and, if desired, other additives by the methods customary in the art. Incorporation can expediently take place before or during shaping, for example by mixing the pulverulent components or by adding the antimicrobial active substance to the melt or solution of the polymer, or by applying the dissolved or dispersed compounds to the polymer, if desired with subsequent evaporation of the solvent.
- Another method of incorporating the mixtures according to the invention into polymers involves adding the former before or during polymerization of the corresponding monomers or before crosslinking.
- the mixtures according to the invention can also be added to the organic polymers to be finished in the form of a masterbatch which comprises these compounds, for example, in a concentration of from 2.5 to 25% by weight.
- the resulting antimicrobially finished polymer compositions can be converted into shaped articles, for example fibres, films, tapes, sheets, multi-wall sheets, containers, tubes and other profiles, by conventional methods, for example by hot pressing, spinning, extrusion or injection moulding.
- the diphenyl ether derivatives of the formula (1 ) are also suitable for the antimicrobial finishing of undyed and dyed or printed fibre materials made, for example, of silk, wool, polyamide or polyurethane, and in particular of cellulosic fibre materials of all types.
- Such fibre materials are the natural cellulose fibres, such as cotton, linen, jute and hemp, and also pulp and regenerated cellulose. Preference is given to textile fibre materials made of cotton.
- the diphenyl ether derivatives according to the invention are also suitable for the antimicrobial finishing of hydroxyl-group-containing fibres which are present in mixed fabrics, for example, of mixtures of cotton with polyester fibres or polyamide fibres.
- one or more compounds of the formula (1) are advantageously applied to the textile fibre material in an amount of from 0.01 to 5% by weight, preferably 0.1-3% by weight, and in particular from 0.25 to 2% by weight, based on the weight of the fibre material, in a process analogous to dyeing.
- the diphenyl ether derivatives according to the invention can be applied to the fibre material and fixed to the fibre in different ways, in particular in the form of aqueous dispersions or printing pastes.
- the textile fibre materials finished using the compounds of the formula (1 ) according to the invention have an excellent and long-lasting antimicrobial protection.
- the diphenyl ether derivatives according to the invention are also useful for the disinfection of the skin, mucous membrane and hair, preferably for the disinfection of hands and wounds.
- these compounds are suitable as an antimicrobial active substance in personal care products as shampoos, bath- and shower additives, hair-care products, liquid and bar soaps, lotions and cremes, deodorants, other aqueous or alcoholic solutions, for example cleaning solutions for the skin, moist cleaning sheets, oils and powders.
- a further subject of the present invention is therefore a personal care composition
- a personal care composition comprising at least one compound of the formula (1) and cosmetically tolerable carriers or auxiliaries.
- the personal care composition according to the present invention comprises 0.01 to 15, preferably 0.5 to 10 % b.w. of the diphenyl ether derivative of formula (1) and cosmetically tolerable carriers or auxiliaries.
- the personal care composition according to the invention can be formulated as a water-in-oil or oil-in-water emulsion, as an oil-in-alcohol lotion, as a vesicular dispersion of an ionic or non-ionic amphiphilic lipid, as a gel, solid stick or as an aerosol formulation.
- the cosmetically compatible auxiliary preferably contains 5 to 50% of an oil phase, 5 to 20% of an emulsifier and 30 to 90% of water.
- the oil phase can in this case contain any oil suitable for cosmetic formulations, e.g.
- hydrocarbon oils one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol.
- Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
- diphenyl ether derivatives according to the invention are useful as household cleaners for the cleaning and disinfection of hard surfaces.
- Example 8 Determination of the antimicrobial activity of the compound of the formula
- Test bacteria Staphylococcus aureus ATCC 9144 Escherichia coli NCTC 8196
- wells having a diameter of 1 cm are cut out using a cork borer (a maximum of 4 wells per plate).
- 100 ⁇ i of the compound of the formula (102) are poured into each well, and the plates are incubated at 37°C (E. coli and S. aureus for 24 hours). Dilutions of the compound of the formula (102) are prepared in 96% analytical grade ethanol.
- Example 9 Determination of the antimicrobial activity of the compound of the formula (103) An agar well test corresponding to method CG 126 is carried out with the following modifications:
- Test bacteria Staphylococcus aureus ATCC 9144 Escherichia coli NCTC 8196
- Example 10 Determination of the minimum inhibitory concentration (MIC) of the compound of the formula (101):
- test substances are dissolved in methyl Cellosolve, and a dilution series of the compound of the formula (101) in agar are prepared.
- the cells are floated out using NaCI solution and adjusted to a density of about 10 6 CFU/ml (live bacterial count).
- each bacterial suspension 1 ⁇ l of each bacterial suspension is dropped onto the agar plates containing the test substance, and the plates are then incubated at 37°C for 2 days.
- the bacterial suspensions are applied to agar plates without test substances.
- the bacterial suspensions are applied to agar plates containing methyl Cellosolve, but without test substance. After the plates have been incubated, the growth of the bacteria on the test-substance-containing plates is compared with that on the control plates.
- the minimum inhibitory concentration (MIC) is given as the lowest concentration which shows clear inhibition compared with the control.
- the MIC values are given in the table below.
- composition (100% active ingredients) % w/w A Compound of formula (102) 1% B Sodium Laureth-2 Sulfate 10.0%
- (C) is added by stirring to 50% of the calculated amount of the formulation.
- the suspension is heated up to about 60°C and stirred until (C) is dissolved completely.
- composition (100% active ingredients) % w/w
- (C) is added by stirring to 50% of the calculated amount of the formulation.
- the suspension is heated up to about 60°C and stirred until (C) is dissolved completely.
- composition (100% active inqredients) % w/w
- composition (100% active inqredients) % w/w
- composition (100% active inqredients) % w/w
- Solution (2) is added to (1) and stirred at maximum speed. Then slowly cool down under continuos stirring. G is added at ⁇ 40°C.
- composition (100% active ingredients) % w/w
- Solution (2) is added to (1 ) and stirred at maximum speed. Then slowly cool down under continuos stirring. (G) is added at ⁇ 40°C.
- Example 17 Preparation of a liguid laundry detergent
- composition (100% active ingredients) % w/w
- composition (100% active inqredients) % w/w
- composition (100% active ingredients) % w/w
- Non-ionic surfactants 2.9%
- Example 20 Preparation of a laundry detergent powder
- composition (100% active ingredients) % w/w
- Non-ionic surfactants 2.9%
- composition (100% active ingredients) % w/w
- Example 22 10 grams of the compound of formula (102) is added into 45 grams of low density polyethylene (Escorene LL6301 XR, from Exxon) and 45 grams of low density polyethylene (Escorene LL6301 RQ, from Exxon). The mixture is tumble mixed for 10 minutes followed by addition into a 29mm twin-extruder to produce a master batch. The extrusion temperature is set at 180°C.
- Example 23 10 gram of the resulting master batch (contains 10% of compound of formula 102) in Example 22 is added into 90 grams of low density polyethylene pellets (Escorene LL6301 XR, from Exxon) and well mixed. The mixture is then charged into an injection moulding machine to produce low density polyethylene plates (10 x 20 cm, thickness 2mm). The resulting low density polyethylene plates contain 1% of compound of formula (102). The plates are then cut into discs of 2 cm in diameter and tested for antimicrobial efficacy in agar diffusion test by using the same procedures as described in Example 8.
- low density polyethylene pellets Escorene LL6301 XR, from Exxon
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Abstract
The invention describes O-derivatives of halogenated diphenyl ether compounds of formula (1), in which R1 and R2 independently of one another are F, Cl or Br; Y is a radical of formula (1a); (1b); (1c); (1d); (1e) or (1f); R3 is C1-C22alkyl; C1-C22alkoxy; phenyl; phenyl-C1-C4alkyl; --(CH2)p4-A+R5R6R7; the radical of formula (I); R4 C1-C22alkyl; R5, R6, R7 and R8 independently of one another are hydrogen; C1-C4alkyl; sulfo-C1-C4alkyl; or R5 and R6 together with A form a cyclic radical unsubstituted or substituted by sulfo groups; or R7 and R8 together with N form a cyclic radical unsubstituted or substituted by sulfo groups; A is N or P; Z1 is fluorine, chlorine, the radical of formula (1g); Z2 is fluorine, chlorine, C1-C22alkoxy, C1-C22alkylthio or C1-C22-monoalkylamino or C1-C22dialkylamino; each of which is unsubstituted or substituted by OH, NH2 or sulfo; C6-C12aryloxy, C6-C12arylthio or C6-C12monoarylamino or C6-C12diarylamino, each of which is unsubstituted or substituted by OH, NH2 or sulfo; m is from 1 to 3; n is 1 or 2; and p1, p2, p3, p4 and p5 independently of one another are 1-4. The diphenyl ether derivatives according to the invention have excellent antimicrobial properties and are stable to migration.
Description
O-Derivatives of halogenated diphenyl ether compounds
The present invention relates to O-derivatives of halogenated diphenyl ether compounds, to a process for the preparation of these compounds, to their use as antimicrobial active substance.
It is known that certain halogenated diphenyl ether compounds have an excellent antimicrobial activity. These compounds are therefore widely used, for example as active substances for the antimicrobial finishing of medical items and household articles, as detergent additive and in the hygiene sector, for example in soaps or dental hygiene products. Polymeric materials can be antimicrobially finished by incorporating halogenated diphenyl ether compounds, the active substances being, as a result of their excellent migration properties, constantly conveyed to the surface of the corresponding material ("slow release"). For certain industrial applications, this effect is undesired since the long-term effect of antimicrobially finished materials such as textiles, paper, plastics, cellulose sponges etc. is reduced at the same time.
The object of the present invention is thus to provide diphenyl ether compounds which have antimicrobial activity and which, at the same time, are stable to migration.
Surprisingly, it has been found that certain derivatives of halogenated diphenyl ether compounds satisfy this requirement.
The present invention thus provides O-derivatives of halogenated diphenyl ether compounds of the formula
in which
R, and R2 independently of one another are F, CI or Br;
is a radical of the formula (1 a) -(CH2) — CH - 0-R4 ; (1 b)
(1 c) -(CH2)
O R5 or (1 f) _ p _ o - (CH2) - N - R6 • O R7
R3 is C C22alkyl; C.-C^ alkoxy; phenyl; phenyl-C.-C^lkyl; — (CH2)p - A+R5R6R7 ;
4
. the radical of the formula ;
I
COO'
R4 0,-022311^1;
R5, R6, R7 and R8 independently of one another are hydrogen; C1-C4all yl; sulfo- C^C^Ikyl; or R5 and R6 together with A form a cyclic radical unsubstituted or substituted by sulfo groups; or R7 and R8 together with N form a cyclic radical unsubstituted or substituted by sulfo groups;
A is N or P;
Z, is fluorine, chlorine, the radical of the formula (1 g)
(R2)n
Z2 is fluorine, chlorine, d-Caaalkoxy, C C22alkylthio or CrC22-monoalkylamino or
C C-aadialkylamino; each of which is unsubstituted or substituted by OH, NH2 or sulfo; C6-C12aryloxy, C6-C12arylthio or C6-Cι2monoarylamino or C6-C12diarylamino, each of which is unsubstituted or substituted by OH, NH2 or sulfo; m is from 1 to 3; n is 1 or 2; and
p p2, p3> p4 and p5 independently of one another are 1-4.
C.-C^alkyl and C^C^alkoxy are straight-chain or branched alkyl radicals, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl, and methoxy, ethoxy, propoxy, butyloxy, pentyloxy, amyloxy, isoamyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy or eicosyloxy respectively.
Phenyl-C1-C4all<yl is, for example, phenylethyl, phenylpropyl, phenylbutyl or, preferably, benzyl.
The derivatives according to the invention are ester, ether or glucoside derivatives of halogenated diphenyl compounds.
Preferred ester derivatives are those of the formula
in which R1t R2, R3, m and n are as defined in formula (1).
Particular preference is given to compounds of the formula (2) in which
R3 is C.,-C12alkyl; or phenyl; and, in particular, to those compounds of the formula (2) in which
R, and R2 are chlorine;
R3 is C.-C^alkyl; m is 1 or 2; and n is 1;
Illustrative ester derivatives of halogenated diphenyl compounds according to the invention are those of the formula
in which R3 is C^C^alkyl or phenyl.
Other suitable ester derivatives according to the invention are those of the formulae: o β n 8
(4) A_ 0j^ _ Rg ; (5) A_0_^ _ R
CH R CH-
10 10
(6) ■
in which
is the radical of the formula (1 h) ; or, preferably,
Rv R2, m and n are as defined in formula (1); and R8, R9 and R10 independently of one another are hydrogen; or C.-C4alkyl.
Preferred ether derivatives according to the invention are those of the formula
CH
in which
R R2, R4, X, m, n, p, and p2 are as defined in formula (1 )
Very particularly preferred ether derivatives are those of the formula
in which
R4 is C1-C22alkyl. or of the formula
Other ether derivatives according to the invention are those of the formulae
(12) v-0 — ,
in which
V is a radical of the formula (1 h), preferably (1 i) or (1 k); R8, R9 and R10 are hydrogen; or C^C^Ikyl; and Z, is -O-V; and Z2 is CI; or N(CH2CH2OH)2.
Preferred glucoside derivatives according to the invention are those of the formula
in which
V is a radical of the formula (1 h), or, preferably, (1 i) or (1 k).
The halogenated diphenyl ether derivatives according to the invention which have a phosphate, sulfate or glucoside group are hydrophilic compounds, which are readily obtainable synthetically in high yields.
Compounds of the formula (1 ) in which
Y is a radical of the formula (1b);
R3 is -(CH2)p4-N+R5R6R7; are obtained in good yields by reacting the chloroacetate of the compound of the formula
with primary, secondary and tertiary amines.
The preparation of these compounds when R3 is -(CH2)p4-P+R5R6R is analogous.
Sulfobetaines, i.e. compounds of the formula (1), in which
Y is a radical of the formula (1 b); R3 is -(CH2)p4-A-N+R5R6R7;
R5 is sulfoalkyl; or R5and R6 with A form a cyclic radical, are obtained by reacting corresponding N-dialkyl- or -monoalkylbetaine esters of the compound of the formula (15) with aqueous MSO3 solution and a suitable catalyst system.
Compounds of the formula (1) in which
Y is a radical of the formula (1f); and
are obtainable, for example, by reacting the compound of the formula (15) with ethylene
chlorophosphate, the compound of the formula • anc* corresponding amine.
The glucoside derivatives (compounds of the formula (14)) are obtainable by reacting the phenolic OH group of the compound of the formula (15) with peracetylated glucose and subsequently hydrolyzing the ester protective groups.
The hydrophilic derivatives are colourless, high-melting compounds having good solubility in water.
Hydrophobic halogenated diphenyl ether derivatives, for example compounds of the formulae (3a), (3b), (10a), (10b) and (11a) and (11b) are obtainable in a single-stage reaction by esterifying or etherifying the phenolic OH group of the compound of the formula (15). Solubility and melting point of the acylated derivatives can be varied within a wide range by the choice of reactant.
Compounds of the formula (1), in which Y is a radical of the formula (1 a) or (1 c);
R R2, m and n are as defined in formula(1), can be obtained by etherification of the phenolic OH group of the compound of the formula
with the corresponding halide compound.
The diphenyl ether derivatives according to the invention are thermally stable and antimicrobially effective compounds of low volatility and having a severely reduced tendency to migrate. They are therefore preferably suitable for the antimicrobial finishing of polymeric compounds, for example in plastics, rubbers, paints, surface coatings, (textile) fibres which are exposed to a microbially contaminated environment.
Examples of polymers and other substrates which can be antimicrobially finished in this way are:
- polymers of mono- and diolefins,
- polyolefins,
- copolymers of mono- and diolefins with one another or with other vinyl monomers,
- hydrocarbon resins,
- polystyrene,
- copolymers of styrene or α-methylstyrene or dienes or acrylic derivatives,
- graft copolymers of styrene or α-methylstyrene.
- halogen-containing polymers,
- polymers derived from α,β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates,
- polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof,
- homo- and copolymers of cyclic ethers, polyacetals, polyphenylene oxides and polyphenylene sulfides and mixtures thereof with styrene polymers or polyamides,
- polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other, and precursors thereof,
- polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams,
- polyureas, polyimides, polyamide-imides. poiyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles,
- polyesters,
- polycarbonates and polyester carbonates,
- polysulfones, polyether sulfones and polyether ketones,
- crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins,
- drying and non-drying alkyd resins,
- unsaturated polyester resins,
- crosslinkable acrylic resins,
- alkyd resins, polyester resins and acrylate resins,
- crosslinked epoxy resins,
- natural polymers, such as cellulose, natural rubber, gelatine, and derivatives thereof modified chemically in a polymer-homologous manner, such as cellulose acetates, cellulose propionates cellulose butyrates, or the cellulose ethers, such as methylcellulose; and also rosins and derivatives.
The invention thus also provides a composition comprising
(A) an organic material to be antimicrobially finished and
(B) a compound of the formula (1 ).
The invention also relates to a process for the antimicrobial finishing of an organic material, which comprises adding at least one compound of the formula (1 ) thereto, and to the use of the compound of the formula (1) for the antimicrobial finishing of polymeric materials.
The amount of antimicrobial active substance to be used depends on the organic material to be antimicrobially finished and on the intended use of the material finished in this way. The composition according to the invention generally comprises, per 100 parts by weight of component (A), from 0.01 to 15 parts by weight, in particular from 0.05 to 10 parts by weight, and especially from 0.1 to 5 parts by weight of the antimicrobial active substance (component (B)).
The antimicrobial active substance (component (B)) can also be a mixture of two or more compounds of the formula (1). The compositions according to the invention can, in addition to the compounds according to the invention, also comprise other additives, for example antioxidants or light protection agents.
Incorporation into the organic polymers, for example into the synthetic organic, in particular thermoplastic, polymers can take place by adding the halogenated diphenyl ether compound according to the invention and, if desired, other additives by the methods customary in the art. Incorporation can expediently take place before or during shaping, for example by mixing the pulverulent components or by adding the antimicrobial active substance to the melt or solution of the polymer, or by applying the dissolved or dispersed compounds to the polymer, if desired with subsequent evaporation of the solvent. Another method of incorporating the mixtures according to the invention into polymers involves adding the former before or during polymerization of the corresponding monomers or before crosslinking.
The mixtures according to the invention can also be added to the organic polymers to be finished in the form of a masterbatch which comprises these compounds, for example, in a concentration of from 2.5 to 25% by weight.
The resulting antimicrobially finished polymer compositions can be converted into shaped articles, for example fibres, films, tapes, sheets, multi-wall sheets, containers, tubes and other profiles, by conventional methods, for example by hot pressing, spinning, extrusion or injection moulding.
The diphenyl ether derivatives of the formula (1 ) are also suitable for the antimicrobial finishing of undyed and dyed or printed fibre materials made, for example, of silk, wool, polyamide or polyurethane, and in particular of cellulosic fibre materials of all types. Examples of such fibre materials are the natural cellulose fibres, such as cotton, linen, jute and hemp, and also pulp and regenerated cellulose. Preference is given to textile fibre materials made of cotton. The diphenyl ether derivatives according to the invention are also suitable for the antimicrobial finishing of hydroxyl-group-containing fibres which are present in mixed fabrics, for example, of mixtures of cotton with polyester fibres or polyamide fibres.
For this purpose, one or more compounds of the formula (1) are advantageously applied to the textile fibre material in an amount of from 0.01 to 5% by weight, preferably 0.1-3% by weight, and in particular from 0.25 to 2% by weight, based on the weight of the fibre material, in a process analogous to dyeing.
The diphenyl ether derivatives according to the invention can be applied to the fibre material and fixed to the fibre in different ways, in particular in the form of aqueous dispersions or printing pastes.
The textile fibre materials finished using the compounds of the formula (1 ) according to the invention have an excellent and long-lasting antimicrobial protection.
The diphenyl ether derivatives according to the invention are also useful for the disinfection of the skin, mucous membrane and hair, preferably for the disinfection of hands and wounds.
Therefore, these compounds are suitable as an antimicrobial active substance in personal care products as shampoos, bath- and shower additives, hair-care products, liquid and bar soaps, lotions and cremes, deodorants, other aqueous or alcoholic solutions, for example cleaning solutions for the skin, moist cleaning sheets, oils and powders.
A further subject of the present invention is therefore a personal care composition comprising at least one compound of the formula (1) and cosmetically tolerable carriers or auxiliaries.
The personal care composition according to the present invention comprises 0.01 to 15, preferably 0.5 to 10 % b.w. of the diphenyl ether derivative of formula (1) and cosmetically tolerable carriers or auxiliaries.
The personal care composition according to the invention can be formulated as a water-in-oil or oil-in-water emulsion, as an oil-in-alcohol lotion, as a vesicular dispersion of an ionic or non-ionic amphiphilic lipid, as a gel, solid stick or as an aerosol formulation.
As a water-in-oil or oil-in-water emulsion, the cosmetically compatible auxiliary preferably contains 5 to 50% of an oil phase, 5 to 20% of an emulsifier and 30 to 90% of water. The oil phase can in this case contain any oil suitable for cosmetic formulations, e.g. one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol. Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
Furthermore the diphenyl ether derivatives according to the invention are useful as household cleaners for the cleaning and disinfection of hard surfaces.
The examples below serve to illustrate the invention.
Preparation Examples of novel compounds
Example 1 : Reaction equation:
9.0 g (14.5 mmol) of the compound of the formula (101a) are dissolved in 120 ml of methanol. 0.2 ml (1.08 mmol) of an approximately 30% NaOCH3 solution is then added, and the mixture is stirred at room temperature for 2 hours. After 30 minutes, the reaction is virtually complete. A yellow-red solution forms, which is evaporated to give 6.72 g of a beige- reddish substance, which corresponds to the compound of the formula (101), which is purified by column chromatography (column: CHCl3/MeOH 10:1). Yield: 5.87 g
Elemental analysis:
Calculated Found
C 47.86 % 47.4 %
H 3.79 % 3.8 %
CI 23.55 % 23.5 %
Example 2: Reaction equation:
(102a) (102)
14.5 g (50 mmol) of the compound of the formula (102a) are dissolved in 100 ml of a xylene isomer mixture and 3.96 g (50 mmol) of pyridine. The mixture is heated to 130°C, and
11.16 g (50 mmol) of lauroyl chloride, diluted with 20 ml of xylene isomer mixture, are added dropwise over the course of 20 minutes. The mixture is left to cool to room temperature,
150 ml of water are added and the pH is adjusted to slightly acidic using 2 n HCI. The organic phase is separated off using a separating funnel, washed with 1 x 150 ml of water, dried over Na2SO4 and evaporated to dryness.
This gives 23.5 g of crude product of the compound of the formula (102), which is distilled under a high vacuum.
Yield: 20.9 g; b.p.: 215-220°C/0.02 torr.
Example 3: Reaction equation:
72.4 g (25 mmol) of the compound of the formula (102a) are dissolved in 500 ml of methyl Cellosolve at 80°C. 26.5 g (25 mmol) of Na2CO3 are stirred into this solution at 80°C. The solution is then stirred for 30 minutes at from 80 to 85°C. 25.5 g (25 mmol) of epichlorohydrin, which is diluted with 25 ml of methyl Cellosolve, is then added dropwise with stirring over the course of 45 minutes at a temperature of from 80 to 85°C. The warm solution is then decanted and evaporated to dryness. The residue is dissolved in 300 ml of toluene, filtered and extracted by shaking twice with water, dried over Na2SO4 and evaporated to dryness.
Yield:89.8q
Example 4: Reaction equation:
(104)
8.7 g (30 mmol) of the compound of the formula (102a) are introduced into 100 ml of xylene isomer mixture. 8.2 g (30 mmol) of the 1 :1 isomer mixture of the formulae
O O
/ \ / \
(104a) H3C - (CH2)11 - O - CH2 - CH - CH2 and (104b) H3C - (CH2)12 - O - CH2 - CH - CH2 , and 0.5 g of ethyltriphenylphosphonium bromide are added over the course of 8.5 hours at a temperature of from 130 to 140°C.
After the reaction has ended, the mixture is left to cool to 100°C and 100 ml of water are added, the mixture is thoroughly stirred, and the organic phase is separated off, dried over
Na2SO4 and evaporated to dryness.
Yield: 18.2 g of the 1 :1 mixture of the compound of the formula (104).
Example 5: Reaction equation:
(105)
29.0 g (0.1 mol) of the compound of the formula (102a) and 9.2 g (0.05 mol) of cyanuric chloride are dissolved in 150 ml of toluene. At 0°C, 6.1 g of coliidine are added dropwise, as a result of which, the temperature increases to 10°C. The reaction is then completed by stirring the mixture for 12 hours at room temperature. After the reaction composition has been quenched with 500 ml of water, the organic phase is separated off, washed with 200 ml of water and dried over sodium sulfate. The solvent is stripped off to give the compound of the formula (105) as a viscous oil, which crystallizes at 0°C after some time.
Purity (HPLC, F%): 80%) Yield: 15.0 g
Example 6: Reaction equation:
(106)
24.9 g (0.1 mol) of the compound of the formula (107) and 9.2 g (0.05 mol) of cyanuric chloride are dissolved in 150 ml of toluene. At 0°C, 6.1 g of coliidine are added dropwise, as a result of which the temperature increases to 10°C. The reaction is then completed by
a result of which the temperature increases to 10°C. The reaction is then completed by stirring the mixture for 12 hours at room temperature. After the reaction composition has been quenched with approximately 500 ml of water, the organic phase is separated off, washed with 200 ml of water and dried over sodium sulfate. The solvent is stripped off to give the compound of the formula (106) as a colourless oil which crystallizes slowly at 0°C.
Purity (HPLC, F%): 85% Yield: 14.5 g
Example 7: Reaction equation:
(107) (108)
62.3 g (0.25 mol) of the compound of the formula (107) are dissolved in 500 ml of methyl Cellosolve at 80°C. 26.5 g (0.25 mol) of Na2CO3 are stirred into this solution at 80°C. The solution is then stirred for 30 minutes at from 80 to 85°C. 25.5 g (0.25 mol) of epichlorohydrin, which is diluted with 25 ml of methyl Cellosolve, is then added dropwise with stirring over the course of 45 minutes at a temperature of from 80 to 85°C. The warm solution is then decanted off from the insoluble matter and evaporated to dryness. The residue is taken up in 300 ml of toluene and the solution is filtered, extracted by shaking twice with water, dried over sodium sulfate and evaporated to dryness. Yield: 85.4g
Application Examples:
Example 8: Determination of the antimicrobial activity of the compound of the formula
11321
Test method:
An agar well test is carried out (method CG 126) with the following modifications:
Medium: Casein soybean flour peptone agar (Caso-agar)
Test bacteria: Staphylococcus aureus ATCC 9144 Escherichia coli NCTC 8196
Procedure: 500ml of Caso-agar are inoculated with 3.5 ml of a 1 :100 diluted overnight culture of the bacteria, and plates with a volume of about 18 ml are poured.
After the plates have cooled, wells having a diameter of 1 cm are cut out using a cork borer (a maximum of 4 wells per plate). 100 μi of the compound of the formula (102) are poured into each well, and the plates are incubated at 37°C (E. coli and S. aureus for 24 hours). Dilutions of the compound of the formula (102) are prepared in 96% analytical grade ethanol.
Results:
The zones of inhibition are observed after incubation for 24 hours. The results in Table 1 show that the compound of the formula (102) has excellent antimicrobial activity.
Example 9: Determination of the antimicrobial activity of the compound of the formula (103) An agar well test corresponding to method CG 126 is carried out with the following modifications:
Medium: Casein soybean flour peptone agar (Caso-agar)
Test bacteria: Staphylococcus aureus ATCC 9144 Escherichia coli NCTC 8196
Procedure: 500 ml of Caso-agar are inoculated with 3.5 ml of a 1 :100 diluted overnight culture of the bacteria, and Caso plates (18 ml) are coated with about 5 ml of the bacteria-containing agar.
After the plates have cooled, wells having a diameter of 1 cm are cut out using a cork borer (one well per plate; all test substance concentrations are tested twice).
100 μl of the compound of the formula (103) (in 96% ethanol) are poured into each well, and the plates are incubated at 37°C for about 24 hours.
The results are given in Table 2.
All dilutions are tested twice and both results are given in the table.
The results show that the compound of the formula (103) has excellent bacteriostatic activity.
Example 10: Determination of the minimum inhibitory concentration (MIC) of the compound of the formula (101):
An agar incorporation test is carried out to determine the MIC:
Medium: Nutrient agar as test agar for bacteria:
Casein soybean flour peptone agar to cultivate the microorganisms 0.9% sodium chloride (pH 7.2) for obtaining the bacterium suspension Methyl Cellosolve as solvent
Test bacteria Escherichia coli NCTC 8196 Pseudomonas aeruginosa CIP A-22 Serratia marcescens ATCC 14756 Enterococcus faecium ATTC 10'541 Staphylococcus aureus ATCC 9144 Candida albicans ATCC 10'23q
Procedure: The test substances are dissolved in methyl Cellosolve, and a dilution series of the compound of the formula (101) in agar are prepared.
After the cultures have been cultivated on casein soybean flour peptone agar, the cells are floated out using NaCI solution and adjusted to a density of about 106 CFU/ml (live bacterial count).
1 μl of each bacterial suspension is dropped onto the agar plates containing the test substance, and the plates are then incubated at 37°C for 2 days. As controls, the bacterial suspensions are applied to agar plates without test substances. In order to exclude the solvent methyl Cellosolve having an influence on the growth properties, the bacterial suspensions are applied to agar plates containing methyl Cellosolve, but without test substance.
After the plates have been incubated, the growth of the bacteria on the test-substance-containing plates is compared with that on the control plates.
The minimum inhibitory concentration (MIC) is given as the lowest concentration which shows clear inhibition compared with the control.
The MIC values are given in the table below.
The results in Table 3 clearly show that the compound of the formula (101) has antimicrobial activity.
Preparation of formulations
Example 11 : Preparation of a liquid hand soap
Composition (100% active ingredients) % w/w A Compound of formula (102) 1% B Sodium Laureth-2 Sulfate 10.0%
Sodium Cumene sulfonate 3.0% C Hydroxypropylmethylcellulose 1.0% D Perfume / Dyestuff q.s. E Ethanolamine up to pH 5.5 F Deionized water to 100.0%
Preparation procedure:
At room temperature, (C) is added by stirring to 50% of the calculated amount of the formulation. The suspension is heated up to about 60°C and stirred until (C) is dissolved completely.
Compounds of (B) are dissolved in 15% of the calculated amount of formulation by stirring and heating up to about 60°C until a clear solution is formed.
(A) is added to solution B, pH is adjusted with E to about 5.0. Solution (C) is added and after stirring the pH is adjusted to 5.5 with (E). F is added to 100%.
Example 12: Preparation of a liquid hand soap
Composition (100% active ingredients) % w/w
A Compound of formula (101 ) 1 %
B Sodium Laureth-2 Sulfate 10.0%
Sodium Cumene sulfonate 3.0%
C Hydroxypropylmethylcellulose 1.0%
D Perfume / Dyestuff q.s.
E Ethanolamine up to pH 5.5
F Deionized water to 100.0%
Preparation procedure
At room temperature, (C) is added by stirring to 50% of the calculated amount of the formulation. The suspension is heated up to about 60°C and stirred until (C) is dissolved completely.
Compounds of (B) are dissolved in 15% of the calculated amount of formulation by stirring and heating up to about 60°C until a clear solution is formed.
(A) is added to solution (B), pH is adjusted with (E) to about 5.0. Solution (C) is added and after stirring the pH is adjusted to 5.5 with (E).
F is added to 100%.
Example 13: Preparation of a natural bar soap
Composition (100% active inqredients) % w/w
A Compound of formula (102) 0.5%
B Sodium tallowate 90.0%
Sodium cocoate
C Stearic acid 3.0%
D Titanium dioxide 0.3%
E Tetrasodium EDTA 0.03%
F Glycerine 3.0%
G Perfume q.s.
H Deion. water ad 100.0%
Example 14: Preparation of a natural bar soap
Composition (100% active inqredients) % w/w
A Compound of formula (101 ) 0.7%
B Sodium tallowate 93.0%
Sodium cocoate
C Titanium dioxide 0.3%
D Tetrasodium EDTA 0.03%
E Glycerine 3.0%
F Perfume q.s.
G Deion. water ad 100.0%
Example 15: Preparation of a deodorant roll-on
Composition (100% active inqredients) % w/w
A Compound o formula (102) 0.3%
B Steareth-10 4.0%
C PPG-25 Laureth-25 5.0%
D Cetylalcohol 2.0%
E Mineral Oil 9.0%
F Propylene Glycol 4.0%
G Preservatives / Perfume / Dyestuff q.s.
H Deionized water to 100.0%
Preparation procedure for Examples 13-15:
1. (A) is dissolved in F. E and B are added and the mixture is stirred homogeneous.
(D) is added, the suspension is heated up to -70°C and stirred until D is melted.
2. (C) is added to the calculated amount of H, the solution is heated to ~70°C.
3. Solution (2) is added to (1) and stirred at maximum speed. Then slowly cool down under continuos stirring. G is added at ~40°C.
Example 16: Preparation of a Deodorant Roll-on
Composition (100% active ingredients) % w/w
A Compound of formula (101) 0.3%
B Steareth-10 4.0%
C PPG-25 Laureth-25 5.0%
D Cetylalcohol 2.0%
E Mineral Oil 9.0%
F Propylene Glycol 4.0%
G Preservatives / Perfume / Dyestuff q.s.
H Deionized water to 100.0%
Preparation procedure:
1. (A) is dissolved in (F). (E) and (B) are added and the mixture is stirred homogeneous.
(D) is added, the suspension is heated up to ~70°C and stirred until (D) is melted.
2. (C) is added to the calculated amount of H, the solution is heated to ~70°C.
3. Solution (2) is added to (1 ) and stirred at maximum speed. Then slowly cool down under continuos stirring. (G) is added at ~40°C.
Example 17: Preparation of a liguid laundry detergent
Composition (100% active ingredients) % w/w
A Compound of formula (105) 1%
B PEG-7 C14-15 alcohol ether 15%
Sodium Dodecylbenzenesulfonate 10.0%
Propylene Glycol 10.0%
C Deionized water to 100.0%
Preparation procedure:
Dissolve (A) in (B) and 25% of (C).
Add (C) up to 100%
Example 18: Preparation of a liguid laundry detergent
Composition (100% active inqredients) % w/w
A Compound of formula (106) 1 %
B PEG-7 C14-15 alcohol ether 15%
Sodium Dodecylbenzenesulfonate 10.0%
Propylene Glycol 10.0%
C Deionized water to 100.0%
Preparation procedure:
Dissolve (A) in (B) and 25% of (C).
Add (C) up to 100%
Example 19: Preparation of a laundry detergent powder
Composition (100% active ingredients) % w/w
A Compound of formula (105) 0.3%
B Lauryl ammonium sulfate 8.0%
Non-ionic surfactants 2.9%
Soaps 3.5%
Sodium tripolyphosphate 43.8%
Sodium silicate 7.5%
Magnesium silicate 1.9%
Carboxymethylcellulose 1.2%
EDTA 0.2%
Sodium sulfate 21.2%
Water to 100%
Example 20: Preparation of a laundry detergent powder
Composition (100% active ingredients) % w/w
A Compound of formula (106) 0.3%
B Lauryl ammonium sulfate 8.0%
Non-ionic surfactants 2.9%
Soaps 3.5%
Sodium tripolyphosphate 43.8%
Sodium silicate 7.5%
Magnesium silicate 1.9%
Carboxymethylcellulose 1.2%
EDTA 0.2%
Sodium sulfate 21.2%
Water to 100%
Example 21 : Preparation of a dish washing detergent
Composition (100% active ingredients) % w/w
A Compound of formula (102) 0.5%
B Sodium lauryl sulfate 7.0%
C Sodium myrethsulfate 7.0%
D Lauryl glucoside 4.0%
E Coco betaine 1.1%
F Ethanol 5.0%
G Citric acid 1.0%
H Water to 100%
Preparation procedure of Examples 19-21 :
1. (B), (C), (D) and (E) are dissolved in part of H at 40°C.
2. (A) is added and stirred at 40°C.
3. (F) and (G) and the rest of (H) is added at 22°C. 4.pH is adjusted to 5.
Example 22: 10 grams of the compound of formula (102) is added into 45 grams of low density polyethylene (Escorene LL6301 XR, from Exxon) and 45 grams of low density polyethylene (Escorene LL6301 RQ, from Exxon). The mixture is tumble mixed for 10 minutes followed by addition into a 29mm twin-extruder to produce a master batch. The extrusion temperature is set at 180°C.
Example 23: 10 gram of the resulting master batch (contains 10% of compound of formula 102) in Example 22 is added into 90 grams of low density polyethylene pellets (Escorene LL6301 XR, from Exxon) and well mixed. The mixture is then charged into an injection moulding machine to produce low density polyethylene plates (10 x 20 cm, thickness 2mm). The resulting low density polyethylene plates contain 1% of compound of formula (102). The plates are then cut into discs of 2 cm in diameter and tested for antimicrobial efficacy in agar diffusion test by using the same procedures as described in Example 8.
The results are listed in Table 4.
The test results show that the compound of formula (102) shows a good antimicrobial efficacy.
Claims
1. An O-derivative of a halogenated diphenyl ether compound of the formula
, in which
R1 and R2 independently of one another are F, CI or Br;
Y is a radical of the formula ;
0┬░) , -(CH2,)
R3 is C^C^alkyl; C^C^alkoxy; phenyl; phenyl-C^C^Ikyl; ΓÇö (CH2)p - A+R5R6R7 ;
4
the radical of the formula
R4 C1-C22alkyl;
R5, R6, R7 and R8 independently of one another are hydrogen; C1-C4all yl; sulfo- C.-C4alkyl; or R5 and R6 together with A form a cyclic radical unsubstituted or substituted by sulfo groups; or R7 and R8 together with N form a cyclic radical unsubstituted or substituted by sulfo groups;
A is N or P; Z, is fluorine, chlorine, the radical of the formula (1g) or Z?
Z2 is fluorine, chlorine, CrC22alkoxy, CrC^alkylthio or C╬╣-C22-monoalkylamino or C C22dialkylamino; each of which is unsubstituted or substituted by OH, NH2 or sulfo; C6- C12aryloxy, C6-C12arylthio or C6-C12monoarylamino or C6-C╬╣2diarylamino, each of which is unsubstituted or substituted by OH, NH2 or sulfo; m is from 1 to 3; n is 1 or 2; and pv p2, p3> p4 and p5 independently of one another are 1-4.
2. A compound according to claim 1 of the formula
in which
R R2, R3, m and n are as defined in claim 1.
3. A compound according to claim 2 wherein, in formula (2), R3 is C-|-Ci2alkyl; or phenyl.
4. A compound according to claim 2 or 3, wherein R, and R2 are chlorine;
R3 is C C12alkyl; m is 2; and n is 1.
5. A compound according to claim 1 of the formula
in which
Rv R2, R4, m, n, p1 and p22 are as defined in claim 1.
6. A compound according to claim 1 of the formula
in which
R1f R2, n, m and p2 are as defined in claim 1.
7. A compound according to claim 1 of the formula
in which
V is a radical of the formula (1 g).
8. A process for the preparation of the compound of the formula (1 ), in which
Y is a radical of the formula (1 b);
R3 is Oj-C^alkyl; C^C^alkoxy; phenyl; phenyl-C1-C4alkyl; and
R R2, m and n are as defined in claim 1 , by esterification of the phenolic OH group of the compound of the formula with an acyl halide compound.
9. A process for the preparation of the compounds of the formula (1 ), in which Y is a radical of the formula (1 a) or (1 c); and
R R2, m and n are as defined in claim 1 , by etherification of the phenolic OH group of the compound of the formula
with the corresponding halide compound.
10. A process for the antimicrobial finishing of organic material, which comprises adding at least one compound of the formula (1 ) thereto.
11. The use of the compounds according to any one of claims 1 to 7 for the antimicrobial finishing of polymeric materials.
12. A composition comprising
(A) an organic material to be antimicrobially finished and
(B) as antimicrobial active substance, at least one compound according to any one of claims 1 to 5.
13. The use of the compounds according to any one of claims 1 to 7 for finishing of undyed and dyed or printed fibre materials.
14. The use of the compounds according to any one of claims 1 to 7 for the disinfection of the skin, mucous membrane and hair in personal care products.
15. A personal care composition comprising at least one compound of the formula (1) and cosmetically tolerable carriers or auxiliaries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98965241A EP1042265A2 (en) | 1997-12-12 | 1998-12-09 | O-derivatives of halogenated diphenyl ether compounds |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97810977 | 1997-12-12 | ||
| EP97810977 | 1997-12-12 | ||
| EP98965241A EP1042265A2 (en) | 1997-12-12 | 1998-12-09 | O-derivatives of halogenated diphenyl ether compounds |
| PCT/EP1998/007997 WO1999031036A2 (en) | 1997-12-12 | 1998-12-09 | O-derivatives of halogenated diphenyl ether compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1042265A2 true EP1042265A2 (en) | 2000-10-11 |
Family
ID=8230519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98965241A Withdrawn EP1042265A2 (en) | 1997-12-12 | 1998-12-09 | O-derivatives of halogenated diphenyl ether compounds |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1042265A2 (en) |
| AU (1) | AU2052599A (en) |
| WO (1) | WO1999031036A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001089518A1 (en) * | 2000-05-23 | 2001-11-29 | Ian Gillam | Method of determining a dosage of anti-oxidant for an individual |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6683056B2 (en) * | 2000-03-30 | 2004-01-27 | Bristol-Myers Squibb Company | O-aryl glucoside SGLT2 inhibitors and method |
| FR2839448A1 (en) * | 2002-05-07 | 2003-11-14 | Oreal | The cosmetic or pharmaceutical use of esters of triclosan and of other antibacterial compounds in controlled release compositions to treat infective skin conditions such as acne, dermatitis, hair loss, dandruff and folliculitis |
| EP1845087A1 (en) | 2006-04-14 | 2007-10-17 | Mutabilis SA | Hydroxyphenyl derivatives and biological applications thereof |
| JP2009541046A (en) * | 2006-07-05 | 2009-11-26 | チバ ホールディング インコーポレーテッド | Dihalogeno-hydroxydiphenyl ether as antibacterial agent in water treatment |
| US8629210B2 (en) | 2008-10-10 | 2014-01-14 | Ndsu Research Foundation | Zwitterionic/amphiphilic pentablock copolymers and coatings therefrom |
| MX2012002580A (en) | 2009-09-01 | 2012-07-20 | Fab Pharma S A S | Novel antibacterial hydroxyphenyl compound. |
| US20110171279A1 (en) * | 2009-11-02 | 2011-07-14 | Ndsu Research Foundation | Polyethylenimine biocides |
| EP2386589A1 (en) | 2010-04-23 | 2011-11-16 | Centre National de la Recherche Scientifique (C.N.R.S) | Novel antimicrobial composition, use and preparation thereof |
| AU2012272804B2 (en) | 2011-06-22 | 2017-07-06 | Vyome Therapeutics Limited | Conjugate-based antifungal and antibacterial prodrugs |
| CN106349718B (en) * | 2016-10-25 | 2019-04-12 | 齐鲁工业大学 | A kind of preparation method of antibiotic property collagen |
| CN115536543B (en) * | 2022-11-10 | 2023-11-03 | 贵州大学 | Triclosan compound containing isopropanolamine structure and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3629477A (en) * | 1966-08-08 | 1971-12-21 | Geigy Chem Corp | Halogenated diphenyether-containing compositions and control of pests therewith |
| MXPA96003950A (en) * | 1995-09-08 | 2009-03-25 | Union Carbide Chem Plastic | Biostatic coatings and processes. |
-
1998
- 1998-12-09 AU AU20525/99A patent/AU2052599A/en not_active Abandoned
- 1998-12-09 EP EP98965241A patent/EP1042265A2/en not_active Withdrawn
- 1998-12-09 WO PCT/EP1998/007997 patent/WO1999031036A2/en not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9931036A3 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001089518A1 (en) * | 2000-05-23 | 2001-11-29 | Ian Gillam | Method of determining a dosage of anti-oxidant for an individual |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2052599A (en) | 1999-07-05 |
| WO1999031036A3 (en) | 1999-11-04 |
| WO1999031036A2 (en) | 1999-06-24 |
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