FI64360B - SOM FUNGICIDER ANVAENDBARA ALKYL- OCH ARYLSUBSTITUERADE ALFA-AZOLYLMETYLSULFIDER - Google Patents
SOM FUNGICIDER ANVAENDBARA ALKYL- OCH ARYLSUBSTITUERADE ALFA-AZOLYLMETYLSULFIDER Download PDFInfo
- Publication number
- FI64360B FI64360B FI782403A FI782403A FI64360B FI 64360 B FI64360 B FI 64360B FI 782403 A FI782403 A FI 782403A FI 782403 A FI782403 A FI 782403A FI 64360 B FI64360 B FI 64360B
- Authority
- FI
- Finland
- Prior art keywords
- butyl
- tert
- alkyl
- sulfide
- compound
- Prior art date
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- 150000001875 compounds Chemical class 0.000 claims description 42
- -1 tetrazol-2-yl Chemical group 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 21
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 229910052751 metal Chemical class 0.000 claims description 12
- 239000002184 metal Chemical class 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000417 fungicide Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000003626 1,2,4-triazol-1-yl group Chemical group [*]N1N=C([H])N=C1[H] 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 125000001401 1,2,4-triazol-4-yl group Chemical group N=1N=C([H])N([*])C=1[H] 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002962 imidazol-1-yl group Chemical group [*]N1C([H])=NC([H])=C1[H] 0.000 claims description 2
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 claims description 2
- 125000004523 tetrazol-1-yl group Chemical group N1(N=NN=C1)* 0.000 claims description 2
- 125000005059 halophenyl group Chemical group 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 150000004763 sulfides Chemical class 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 66
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 11
- 239000013543 active substance Substances 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 9
- 241000209140 Triticum Species 0.000 description 7
- 235000021307 Triticum Nutrition 0.000 description 7
- 150000001540 azides Chemical class 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 5
- 241000233866 Fungi Species 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 230000000855 fungicidal effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000003462 sulfoxides Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 240000005979 Hordeum vulgare Species 0.000 description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241001480061 Blumeria graminis Species 0.000 description 3
- 241000221785 Erysiphales Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000001665 trituration Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OBOQUELROOUGCI-UHFFFAOYSA-N 2-(1h-pyrrol-2-ylsulfanyl)-1h-pyrrole Chemical class C=1C=CNC=1SC1=CC=CN1 OBOQUELROOUGCI-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- 240000007154 Coffea arabica Species 0.000 description 2
- 240000009088 Fragaria x ananassa Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 235000016213 coffee Nutrition 0.000 description 2
- 235000013353 coffee beverage Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000021012 strawberries Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- BQZRYUOIXPREMR-RLWSFTDUSA-N (4R,4aR,7aR,12bS)-9-methoxy-3-methyl-1,2,4,4a,5,6,7a,13-octahydro-4,12-methanobenzofuro[3,2-e]isoquinolin-7-one N,N-dimethyl-1-phenothiazin-10-ylpropan-2-amine N-(4-hydroxyphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(O)C=C1.C1=CC=C2N(CC(C)N(C)C)C3=CC=CC=C3SC2=C1.C([C@H]1[C@H](N(CC[C@@]112)C)C3)CC(=O)[C@@H]1OC1=C2C3=CC=C1OC BQZRYUOIXPREMR-RLWSFTDUSA-N 0.000 description 1
- SZGOTCJZPFZYRJ-UHFFFAOYSA-N 1-(1H-benzimidazol-2-yl)-3-methoxyurea Chemical compound CONC(=O)NC=1NC2=C(N1)C=CC=C2 SZGOTCJZPFZYRJ-UHFFFAOYSA-N 0.000 description 1
- IXRBSXMUJNFJQV-UHFFFAOYSA-N 1-(chloromethylsulfanyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1SCCl IXRBSXMUJNFJQV-UHFFFAOYSA-N 0.000 description 1
- VGJLTQKULDFCMM-UHFFFAOYSA-N 1-[1-[1,2-bis(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)ethyl]sulfanyl-1,2-bis(2,4-dichlorophenyl)ethyl]-1,2,4-triazole Chemical compound ClC1=CC(Cl)=CC=C1CC(N1N=CN=C1)(C=1C(=CC(Cl)=CC=1)Cl)SC(N1N=CN=C1)(C=1C(=CC(Cl)=CC=1)Cl)CC1=CC=C(Cl)C=C1Cl VGJLTQKULDFCMM-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- YIKWKLYQRFRGPM-UHFFFAOYSA-N 1-dodecylguanidine acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN=C(N)N YIKWKLYQRFRGPM-UHFFFAOYSA-N 0.000 description 1
- SVPKNMBRVBMTLB-UHFFFAOYSA-N 2,3-dichloronaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(Cl)=C(Cl)C(=O)C2=C1 SVPKNMBRVBMTLB-UHFFFAOYSA-N 0.000 description 1
- LIBKURLVAUYWKV-UHFFFAOYSA-N 2,4-dichloro-1-(chloromethylsulfanylmethyl)benzene Chemical compound ClCSCC1=CC=C(Cl)C=C1Cl LIBKURLVAUYWKV-UHFFFAOYSA-N 0.000 description 1
- XEPBBUCQCXXTGR-UHFFFAOYSA-N 2,5-dimethyl-n-phenylfuran-3-carboxamide Chemical compound O1C(C)=CC(C(=O)NC=2C=CC=CC=2)=C1C XEPBBUCQCXXTGR-UHFFFAOYSA-N 0.000 description 1
- NZZRRHNSHYCKJA-UHFFFAOYSA-N 2-(1h-pyrrol-2-ylsulfinyl)-1h-pyrrole Chemical class C=1C=CNC=1S(=O)C1=CC=CN1 NZZRRHNSHYCKJA-UHFFFAOYSA-N 0.000 description 1
- QRNATDQRFAUDKF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate Chemical compound NC(=S)SCCSC(N)=S QRNATDQRFAUDKF-UHFFFAOYSA-N 0.000 description 1
- YAUCKEPYKXHCFF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate;manganese Chemical compound [Mn].NC(=S)SCCSC(N)=S YAUCKEPYKXHCFF-UHFFFAOYSA-N 0.000 description 1
- QSZOMCLHJKGKED-UHFFFAOYSA-N 2-carbamothioylsulfanylpropyl carbamodithioate Chemical compound NC(=S)SC(C)CSC(N)=S QSZOMCLHJKGKED-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/647—Triazoles; Hydrogenated triazoles
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- A—HUMAN NECESSITIES
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
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Description
Γβ, KUULUTUSJULKAISU < λ Ύ (L Π B i11) UTLÄGCN! NGSSKRIFT 64 00UΓβ, ANNOUNCEMENT <λ Ύ (L Π B i11) UTLÄGCN! NGSSKRIFT 64 00U
mjrfS· C (45) Täten iti cyr-rs&liy 10 Π 3903 ^ ^ (51) Kv.ik.^int.ci.3 C 07 D 24-9/08, 257/04, 231/12, ' ; 233/60 SUOMI — FINLAND (21) P*tenttlh»k«mu* — P*t*flttn»öknlng 7 8 2*4 0 3 (22) Htkemltpllvl — Aniöknlngidtj 0 *4.0 8.7 8 (Fl) (23) Alkupllvl — Glltlgheudig 0*4.08.70 (41) Tullut Julkiseksi — Bllvlt offefrtllg g6. 02. 79mjrfS · C (45) Thus, it was Cyr-rs & liy 10 Π 3903 ^ ^ (51) Kv.ik. ^ int.ci.3 C 07 D 24-9 / 08, 257/04, 231/12, '; 233/60 FINLAND - FINLAND (21) P * tenttlh »k« mu * - P * t * flttn »öknlng 7 8 2 * 4 0 3 (22) Htkemltpllvl - Aniöknlngidtj 0 * 4.0 8.7 8 (Fl) (23) Alkupllvl - Glltlgheudig 0 * 4.08.70 (41) Become Public - Bllvlt offefrtllg g6. 02. 79
Patentti· ja rekisterihallitus Niht»yiksip.non j. kuuLJulkaisun pvm. - 2Q 07 83National Board of Patents and Registration Niht »yiksip.non j. Date of publication - 2Q 07 83
Patent- och registerstyrelaen Ansöksn utl»gd och uti.ikrtfwn pubtic*r»d ~' (32)(33)(31) Pyydetty etuoikeus—Begird prlorltet O^-Oo. 77Patent- och registerstyrelaen Ansöksn utl »gd och uti.ikrtfwn pubtic * r» d ~ '(32) (33) (31) Privilege requested — Begird prlorltet O ^ -Oo. 77
Saksan Li ittotasavalta-Förbundsrepubliken Tyskland(DE) P 273531*4.6 (71) BASF Aktiengesellschaft, Ludwigshafen, Saksan Liittotasavalta-Förbunds-republiken Tyskland(DE) (72) Hubert Sauter., Ludwigshafen, Ernst-Heinrich Pommer, Limburgerhof,Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 273531 * 4.6 (71) BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany Förbunds-republiken Tyskland (DE) (72) Hubert Sauter., Ludwigshafen, Ernst-Heinrich Pommer, Lim
Bernd Zeeh, Ludwigshafen, Costin Rentzea, Heidelberg, Saksan Liittotasavalta-Förbundsrepubliken Tyskland(DE) (7*+) Oy Kolster Ab (5*4) Fungisideina käytettävät alkyyli- ja aryylisubstituoidut. o<-atsolyyli-metyylisulfidit - Som fungieider användbara alkyl- och arylsubstitu-erade (X-azolylmetylsulfiderBernd Zeeh, Ludwigshafen, Costin Rentzea, Heidelberg, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (7 * +) Oy Kolster Ab (5 * 4) Alkyl- and aryl-substituted fungicides. o <-azolylmethylsulfides - Som fungieider användbara alkyl- och arylsubstitu-Erade (X-azolylmethylsulfider
Keksintö koskee uusia fungisideina käytettäviä alkyyli- ja aryylisubstituoituja «X-atsolyylimetyylisulfideja ja niiden johdannaisia, (X-atsolyylisulfoksideja ja <X-atsolyylisulfoneja sekä niiden suoloja ja raetallikomplekseja.The invention relates to novel alkyl- and aryl-substituted «X-azolylmethylsulfides and their derivatives, (X-azolylsulfoxides and <X-azolylsulfones and their salts and metal complexes) for use as fungicides.
On tunnettua, että imidatsolijohdannaisilla, esim. 1-/2,4-dikloorifenyyli- -allyylietyylieetteri7-imidatsolilla (DE-hakemus-julkaisu 20 63 857) on hyvä fungisidinen vaikutus. Vaikutus ei ole aina alhaisten käyttökulujen ja alhaisten käyttökonsentraatioiden suhteen tyydyttävä. Sitäpaitsi myrkyllisyys sieniä kohtaan kytkeytyy usein voimakkaaseen myrkyllisyyteen, jota aineella on kasveja kohtaan, niin että ruostesienien torjuntaan tarvittavat konsentraa-tiot vaurioittavat myös viljelyskasveja. Tällä perusteella ne eivät sovellu aina eivätkä kaikille kasvilajeille sienien torjuntaan käytettäviksi kasviensuojeluaineiksi.It is known that imidazole derivatives, e.g. 1- [2,4-dichlorophenyl-allylethyl ether] -imidazole (DE application 20 63 857) have a good fungicidal effect. The effect is not always satisfactory in terms of low operating costs and low operating concentrations. In addition, fungal toxicity is often linked to the high toxicity of the substance to plants, so that the concentrations required to control rust fungi also damage crops. On this basis, they are not always and not suitable for plant protection products for fungicides for all plant species.
Keksinnön kohteena ovat c*-atsolyylimetyylisulfidit joiden kaava on 64360 s2 (O) i n \ 1 3The invention relates to c * -azolylmethyl sulphides of the formula 64360 s2 (O) i n \ 1 3
R - C - S - RR - C - S - R
Az jossa R1 on vety, C -C -alkyyli , (c.-C .-alkcksiikarbonyyli. tai mahdol- 14 2 1 4 3 lisesti substituoitu aryyli, R on vety tai C^_4-alkyyli, R on C^-C^-alkyyli , C^-C^-alkenyyli, C^-C^-alkynyyli , mahdollisesti substituoitu fenyyli tai mahdollisesti substituoitu aryyli (C-^-C^-alkyyli) , Az on imidatsol-l-yyli , pyratsol-l-yyli, 1,2,4-triatsol-l-yyli, 1,2,4-triatsol-4-yyli, tetratsol-l-yyli tai tetratsol-2-yyli, ja n on 0, 1 tai 2, ja niiden suolat ja kuparin, sinkin, mangaanin, raudan, koboltin ja nikkelin kanssa muodostamat metallikompleksit.Az wherein R 1 is hydrogen, C 1 -C 4 alkyl, (C 1 -C 4 alkoxycarbonyl. Or optionally substituted aryl, R is hydrogen or C 1-4 alkyl, R is C 1 -C 4 alkyl). -alkyl, C 1 -C 4 -alkenyl, C 1 -C 4 -alkynyl, optionally substituted phenyl or optionally substituted aryl (C 1 -C 4 -alkyl), Az is imidazol-1-yl, pyrazol-1-yl , 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, tetrazol-1-yl or tetrazol-2-yl, and n is 0, 1 or 2, and their salts and metal complexes with copper, zinc, manganese, iron, cobalt and nickel.
Kaavan I mukaiset yhdisteet vaikuttavat tuhosieniin, erityisesti sellaisiin, jotka kuuluvat Ascomycetes- ja Basidiomycetes-luokkaan.The compounds of the formula I act against fungi, in particular those belonging to the class Ascomycetes and Basidiomycetes.
R merkitsee esimerkiksi vetyä, metyyliä, etyyliä, n-propyy-liä, isopropyyliä, n-butyyliä, n-pentyyliä, n-heksyyliä, n-heptyy-liä, metoksikarbonyyliä, fenyyliä , 4-nitrofenyyliä, 4-bromifenyyliä, 4-syaanifenyyliä, 2-metyylifenyyliä, 4-t-butyylifenyyliä, 3-trifluori-metyylifenyyliä, 4-trifluorimetyylifenyyliä, 4-fluorifenyyliä, 2-kloorifenyyliä, 4-kloorifenyyliä, 2,4-dikloorifenyyliä, 2,6-dikloori- fenyyliä, 3,4-dikloorifenyyliä, -naftyyliä.R is, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, methoxycarbonyl, phenyl, 4-nitrophenyl, 4-bromophenyl, 4-cyanophenyl , 2-methylphenyl, 4-t-butylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl, 3,4 -dichlorophenyl, -naphthyl.
2 R merkitsee esimerkiksi vetyä, metyyliä,n-propyyliä.2 R denotes, for example, hydrogen, methyl, n-propyl.
3 R merkitsee esimerkiksi metyyliä, etyyliä, n-propyyliä, isopropyyliä, n-butyyliä, t-butyyliä, n-pentyyliä, n-heksyyliä, allyyliä, propargyyliä, fenyyliä, 4-metoksifenyyliä, 4-tolyyliä, 4-kloorifenyyliä, 3,4-dikloorifenyyliä, 2,4-dikloorifenyyliä, 2,3,6-trikloorifenyyliä, bentsyyliä, 3-trifluorimetyylibentsyyliä, 4-kloo-ribentsyyliä, 4-bromibentsyyliä, 3,4-diklooribentsyyliä, 2,4-dikloo-ribentsyyliä, 2,3,6-triklooribentsyyliä, 2-fenyylietyyliä.3 R denotes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, allyl, propargyl, phenyl, 4-methoxyphenyl, 4-tolyl, 4-chlorophenyl, 3, 4-dichlorophenyl, 2,4-dichlorophenyl, 2,3,6-trichlorophenyl, benzyl, 3-trifluoromethylbenzyl, 4-chlorobenzyl, 4-bromobenzyl, 3,4-dichlorobenzyl, 2,4-dichlorobenzyl, 2, 3,6-trichlorobenzyl, 2-phenylethyl.
Suolat ovat esimerkiksi hydroklorideja, bromideja, sulfaatteja, nitraatteja, fosfaatteja, oksalaatteja tai dedekyylibentseeni-sulfonaatteja. Suolojen vaikutus johtuu kationista, joten anionin valinta on mielivaltainen.Salts are, for example, hydrochlorides, bromides, sulphates, nitrates, phosphates, oxalates or dedecylbenzene sulphonates. The effect of the salts is due to the cation, so the choice of anion is arbitrary.
Metallikompleksit ovat seuraavan kaavan mukaisia yhdisteitä: 3 64360 r2 1 ' (0)n 7 /Me (RX - C - S -R )m7 Xk (II)The metal complexes are compounds of the following formula: 3 64360 r2 1 '(0) n 7 / Me (RX - C - S -R) m7 Xk (II)
Az jossa kaavassa 12 3 R :llä, R :11a, R :11a, Az:lla ja n:llä on yllä mainittu merkitys jaAz wherein 12 3 R, R: 11a, R: 11a, Az and n have the meanings given above and
Me merkitsee metallia, esim. kuparia, sinkkiä, tinaa, mangaania, rautaa, kobolttia tai nikkeliä, X merkitsee epäorgaanisen hapon anionia, esim. suolahappoa, rikkihappoa, fosforihappoa, bromivetyhappoa, m ja k ovat lukuja 1-4.We denote a metal, e.g. copper, zinc, tin, manganese, iron, cobalt or nickel, X denotes an anion of an inorganic acid, e.g. hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, m and k are numbers 1-4.
Kaavan I (jossa n = 0) mukaisia atsolyylisulfideja valmistetaan saattamalla kaavan III mukainen c<-kloorisulfidi R2 1 ' 3 R - C - S - R (III)Azolyl sulfides of formula I (where n = 0) are prepared by reacting a c <-chlorosulfide of formula III R2 1 '3 R - C - S - R (III)
Cl jossa kaavassa 12 3 R , R ja R merkitsevät samaa kuin yllä, reagoimaan atsolin H-Az kanssa mahdollisesti emäksen ja mahdollisesti laimentimen läsnäollessa, jolloin Az:lla on yllä mainittu merkitys. Hapettamalla näin saatu kaavan I (n = 0) mukainen ot-atsolyylisulfidi saadaan kaavan I (n = 0) mukainen <X-atsolyylisulfoksidi ja kaavan I (n = 2) mukainen o<-atsolyylisulfoni.Cl wherein R 3, R and R are as defined above, to react with the azole H-Az, optionally in the presence of a base and optionally a diluent, wherein Az has the meaning given above. Oxidation of the α-azolyl sulfide of formula I (n = 0) thus obtained gives the α-azolyl sulfoxide of formula I (n = 0) and the α-azolyl sulfone of formula I (n = 2).
Kaavan I (n = 0) mukaisia atsolyylisulfideja valmistettaessa on tarkoituksenmukaista saattaa kaavan III mukainen (X-kloorisul-fidi reagoimaan noin 0-200°C:ssa, edullisesti 20-160°C:ssa, homogeenisessa tai epähomogeenisessa faasissa, ilman laimenninta tai laimentimen läsnäollessa, noin 0,5-2 ekvivalentin kanssa sopivan atsolin alkalisuolaa, mahdollisesti lisäten 0,5-4 ekvivalenttia emästä.In the preparation of azolyl sulphides of the formula I (n = 0), it is expedient to react the X-chlorosulphide of the formula III at about 0-200 ° C, preferably 20-160 ° C, in a homogeneous or inhomogeneous phase, without diluent or diluent. in the presence of about 0.5-2 equivalents of the alkali salt of a suitable azole, optionally with the addition of 0.5-4 equivalents of base.
Laimentimena voidaan käyttää esim. metanolia, etanolia, isopropanolia, n-butanolia, dietyylieetteriä, tetrahydrofuraania, dioksaania, asetonia, asetonitriiliä, dimetyyliformamidia, dimetyy-lisulfoksidia, kloroformia, metyleenikloridia tai tolueenia.As the diluent, for example, methanol, ethanol, isopropanol, n-butanol, diethyl ether, tetrahydrofuran, dioxane, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, chloroform, methylene chloride or toluene can be used.
Emäksinä voidaan käyttää esim. orgaanisia amiineja, kuten trietyyli-As bases, for example, organic amines such as triethyl
4 6 A 3 6 O4 6 A 3 6 O
amiinia, pyridiiniä tai epäorgaanisia yhdisteitä esim. kaliumkarbonaattia tai natriumhydroksidia.amine, pyridine or inorganic compounds e.g. potassium carbonate or sodium hydroxide.
Lähtöaineina käytetyt cX-kloorisulfidit III ovat osittain tunnettuja kirjallisuuden perusteella ja voidaan valmistaa kirjallisuudessa tunnettujen menetelmien mukaan, esim.The cX-chlorosulphides III used as starting materials are partly known from the literature and can be prepared according to methods known in the literature, e.g.
a) klooraamalla sulfideja N-kloorisukkinimidillä (katso esim. B.L. Tuleen ja T.B. Stephens, J. Org. Chem. 34, 31 (1969)) seuraavan reaktiokaavion mukaisesti: 0 r2 1 ' 3(1- \ R - CH - S - R + I N-Cl ->a) by chlorinating sulphides with N-chlorosuccinimide (see e.g. BL Tuleen and TB Stephens, J. Org. Chem. 34, 31 (1969)) according to the following reaction scheme: 0 r2 1 '3 (1- \ R - CH - S - R + I N-Cl ->
VV
o o f Jt R1 - C - S - R3 ♦ 1/™ (III) 0 tai b) aldehydien ja tiolien välisessä reaktiossa kloorivedyn läsnäollessa (katso esim. H. Fischer ja K. Frank, Liebigs Ann. Chem. 563, 54 (1949)) seuraavaa reaktiokaavion mukaisesti R1-CO + HSR3 + HC1 -^oof Jt R1 - C - S - R3 ♦ 1 / ™ (III) 0 or b) in the reaction between aldehydes and thiols in the presence of hydrogen chloride (see e.g. H. Fischer and K. Frank, Liebigs Ann. Chem. 563, 54 (1949)) ) according to the following reaction scheme R1-CO + HSR3 + HCl - ^
HB
R1-C~SR3 + H90R1-C ~ SR3 + H90
Cl (III)Cl (III)
Kaavaa I (n = 1) vastaavien atsolyylisulfoksidien valmistamiseksi c^-atsolyylisulfidi saatetaan reagoimaan, mahdollisesti laimentimen läsnäollessa, noin yhden ekvivalentin kanssa sopivaa hapetinta, lämpötilassa noin -30 - +100°C. c<-atsolyylisulfonit (kaava I, n = 2) saadaan samalla tavalla hapettamalla c<-atsolyyli-sulfideja (I, n = 0) vähintään kahdella ekvivalentilla sopivaa hapetinta tai hapettamalla 0(-atsolyylisulfoksideja (I, n = 1)To prepare azolyl sulfoxides of formula I (n = 1), cis-azolyl sulfide is reacted, optionally in the presence of a diluent, with about one equivalent of a suitable oxidant at a temperature of about -30 to + 100 ° C. The c <-azolyl sulfones (formula I, n = 2) are obtained in a similar manner by oxidizing the c <-azolyl sulphides (I, n = 0) with at least two equivalents of a suitable oxidant or by oxidizing the 0 <-azolyl sulphoxides (I, n = 1)
IIII
5 64360 vähintään yhdellä ekvivalentilla hapetinta.5,64360 with at least one equivalent of oxidant.
Hapettimena voidaan käyttää esim. kaliumpermanganaattia, vetyperoksidia tai perkarboksyylihappoja kuten peretikkahappoa, perbentsoehappoa tai 3-klooribentsoehappoa. Laimentimena voidaan käyttää esim. vettä, etikkahappoa, metanolia, asetonia, kloroformia tai metyleenikloridia. Sulfoksideja (I, n = 1) valmistetaan edullisesti saattamalla sulfidi (I, n = 0) reagoimaan yhden ekvivalentin kanssa 3-klooriperbentsoehappoa metyleenikloridissa, 0-25°C:n lämpötilassa. Sulfoneja valmistetaan edullisesti saattamalla sulfidi (I, n = 0) reagoimaan kahden ekvivalentin kanssa 3-klooriperbentsoehappoa metyleenikloridissa, 15-41°C:n lämpötilassa.As the oxidant, for example, potassium permanganate, hydrogen peroxide or percarboxylic acids such as peracetic acid, perbenzoic acid or 3-chlorobenzoic acid can be used. As the diluent, for example, water, acetic acid, methanol, acetone, chloroform or methylene chloride can be used. Sulfoxides (I, n = 1) are preferably prepared by reacting sulfide (I, n = 0) with one equivalent of 3-chloroperbenzoic acid in methylene chloride at 0-25 ° C. The sulfones are preferably prepared by reacting the sulfide (I, n = 0) with two equivalents of 3-chloroperbenzoic acid in methylene chloride at a temperature of 15-41 ° C.
Kaavan I (n = 0, 1, 2) mukaiset yhdisteet liukenevat helposti useihin orgaanisiin liuottimiin esim. etyyliasetaattiin, asetoniin, etanoliin, metyleenikloridiin, kloroformiin, dimetyyli-sulfoksidiin, dimetyyliformamidiin ja N-metyylipyrrolidoniin. c*s -atsolyylisulf idit (I = 0) liukenevat hyvin myös tolueeniin.The compounds of formula I (n = 0, 1, 2) are readily soluble in various organic solvents, e.g. ethyl acetate, acetone, ethanol, methylene chloride, chloroform, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone. c * s -azolyl sulfides (I = 0) are also highly soluble in toluene.
Ne voidaan happojen avulla muuttaa suoloikseen esim. hydro-klorideiksi, sulfaateiksi, nitraateiksi, oksalaateiksi, formiaa-teiksi, asetaateiksi tai dodekyylibentsyylisulfonaateiksi.They can be converted into their salts by means of acids, for example into hydrochlorides, sulphates, nitrates, oxalates, formates, acetates or dodecylbenzyl sulphonates.
Kaavan II mukaisia metallikomplekseja valmistetaan saattamalla o<-atsolyylisulfidi tai sen kaavan I mukainen johdannainen reagoimaan liuottimen läsnäollessa kaavan IV mukaisen metalli-suolan kanssa.Metal complexes of formula II are prepared by reacting o <-azolyl sulfide or a derivative thereof of formula I with a metal salt of formula IV in the presence of a solvent.
MeXk . a H20 (IV) jossa kaavassaMeXk. a H 2 O (IV) in which formula
Me, X ja k merkitsevät samaa kuin edellä ja a on 0-4.Me, X and k have the same meaning as above and a is 0-4.
Tässä Me merkitsee etupäässä alkuaineiden jaksollisen järjestelmän I:een, II:een ja (IV - VIII):een sivuryhmään kuuluvia metalleja sekä Ilreen ja IV:een pääryhmään kuuluvia metalleja, etenkin kuparia, sinkkiä, tinaa, mangaania, rautaa, kobolttia ja nikkeliä.Here, We denote primarily metals belonging to side groups I, II and (IV to VIII) of the Periodic Table of the Elements and metals belonging to the main groups of Ilre and IV, especially copper, zinc, tin, manganese, iron, cobalt and nickel.
Kaavan IV mukaiset metallisuolat ovat yleisesti tunnettuja, helposti saatavissa olevia yhdisteitä.The metal salts of formula IV are well known, readily available compounds.
Valmistettaessa kaavan II mukaisia metallikomplekseja kaikki veteen sekoittuvat liuottimet tulevat kysymykseen, esim.In the preparation of metal complexes of the formula II, all water-miscible solvents are suitable, e.g.
64360 metanoli, etanoli, isopropanoli, asetoni, tetrahydrofuraani ja dioksaani. Tällöin työskennellään yleisesti lämpötiloissa, jotka ovat 0:n ja 100°C:n völillä, etupäässä 10-35°C:ssa.64360 methanol, ethanol, isopropanol, acetone, tetrahydrofuran and dioxane. In this case, work is generally carried out at temperatures between 0 and 100 ° C, mainly at 10-35 ° C.
Sulfidit (I, n = 0) ja sulfonit (I, n = 2) sisältävät joskus asymmetrisen hiiliatomin ja muodostavat sen mukaisesti enantio-meerien seoksia, jotka voidaan erottaa optisesti aktiivisiksi yhdisteiksi. Sulfoksidien I (n = 1) tapauksessa esiintyy asymmetrisen hiiliatomin viereisen asymmetrisen rikkiatomin johdosta diastereo-meerien seoksia, jotka voidaan erottaa yksityisiksi komponenteiksi tavalliseen tapaan esim. kiteyttämällä tai kromatografisesti.Sulfides (I, n = 0) and sulfones (I, n = 2) sometimes contain an asymmetric carbon atom and accordingly form mixtures of enantiomers which can be separated into optically active compounds. In the case of sulphoxides I (n = 1), due to the asymmetric sulfur atom adjacent to the asymmetric carbon atom, mixtures of diastereomers exist which can be separated into the individual components in the usual manner, e.g. by crystallization or chromatography.
Enantiomeerien tai diastereomeerien erottaminen ei kuitenkaan ole normaalisti tarpeen, jos yhdisteitä käytetään fungisideina tai kasvien kasvua säätelevinä aineina.However, the separation of enantiomers or diastereomers is not normally necessary if the compounds are used as fungicides or plant growth regulators.
Uusilla oC-atsolyylisulfideilla, o<S-atsolyylisufoksideilla ja ^-atsolyylisulfoneilla ja niiden suoloilla on paljon laajempi fungisidinen vaikutus kuin tunnetulla 1-/2,4-dikloorifenyyli-^-allyylietyylieetteriy-imidatsolilla ja ne sopivat paremmin kasveille kuin mainittu yhdiste. Uusia aktiivisia aineita voidaan käyttää myös suolamuodossaan esim. hydrokloridina, oksalaattina tai nitraattina .The novel oC-azolyl sulfides, o <5-azolyl sulfoxides and? -Azolyl sulfones and their salts have a much broader fungicidal effect than the known 1- [2,4-dichlorophenyl-N-allylethyl ether] imidazole and are more suitable for plants than said compound. The new active substances can also be used in their salt form, e.g. as the hydrochloride, oxalate or nitrate.
Suurta mielenkiintoa on keksinnön mukaisilla fungisidisillä aineilla erilaisten viljelykasvien sienisairauksien ollessa kysymyksessä, esimerkiksi:The fungicidal compositions according to the invention are of great interest in the case of various fungal diseases of crops, for example:
Ustilago scitaminea (sokeriruokoruoste)Ustilago scitaminea (sugar cane rust)
Hemileia vastatrix (kahviruoste)Hemileia vastatrix (coffee rust)
Uromyces fabae tai appendiculatus (papuruoste)Uromyces fabae or appendiculatus
Puccinia Arten (viljaruoste)Puccinia Arten (grain rust)
Erysiphe graminis (viljahärmäsieni)Erysiphe graminis (cereal fungus)
Botrytis cinerea viiniköynnöksellä, mansikoilla,Botrytis cinerea on a vine, strawberries,
Uncinula necator,Uncinula necator,
Sphaerotheca fuliginea,Sphaerotheca fuliginea,
Erysiphe cichoracearum,Erysiphe cichoracearum,
Podosphaera leucotricha.Podosphaera leucotricha.
Viljelykasveilla tarkoitetaan tässä yhteydessä erityisesti vehnää, ruista, ohraa, kauraa, riisiä, maissia, omenapuuta, kurkkuja, papuja, kahvia, sokeriruokoa, viiniköynnöstä, mansikoita sekä puutarhan koristekasveja.Crops in this context refer in particular to wheat, rye, barley, oats, rice, maize, apple trees, cucumbers, beans, coffee, sugar cane, vines, strawberries and ornamental plants for the garden.
7 643607 64360
Keksinnön mukaiset aktiiviset aineet ovat systeemisesti vaikuttavia. Näiden aineiden systeemistä vaikutusta käytetään hyväksi erityisesti torjuttaessa sisäisiä kasvitauteja, esim. viljaruostetta, viljahärmäsientä.The active substances according to the invention are systemically active. The systemic effect of these substances is particularly useful in the control of internal plant diseases, e.g. cereal rust, cereal fungus.
Keksinnön mukaisilla aineilla voidaan torjua samanaikaisesti kaksi tai useampia mainituista sienistä, ja kasvit sietävät näitä aineita hyvin. Fytopatogeenisten sienien torjuntaan tarvittavat määrät ovat 0,05-2 kg vaikuttavaa ainetta/ha viljelysalaa.The substances according to the invention can control two or more of said fungi simultaneously, and these substances are well tolerated by plants. The amounts required for the control of phytopathogenic fungi are 0.05-2 kg of active substance / ha of cultivated area.
Keksinnön mukaiset vaikuttavat aineet voidaan valmistaa tavanomaisiksi valmistemuodoiksi, kuten liuoksiksi, emulsioiksi, suspensioiksi, jauheiksi, tahnoiksi ja rakeistetuiksi tuotteiksi. Nämä valmistetaan tunnetulla tavalla, esim. sekoittamalla vaikuttava aine liuottimen ja/tai kantaja-aineen kanssa, mahdollisesti käyttämällä emulgaattoria ja dispergoimisainetta, jolloin siinä tapauksessa että vesi on laimentimena, voidaan käyttää myös muita orgaanisia liuottimia apuliuottimena. Apuaineina tulevat kysymykseen: liuottimet, kuten aromaatit (esim. ksyleeni, bentseeni) , klooratut aromaatit (esim. klooribentseeni), parafiinit (esim. maa-öljyrakeet), alkoholit (esim. metanoli, butanoli), amiinit (esim. etanoliamiini, dimetyyliformamidi), ja vesi, kantaja-aineet, kuten luonnosta peräisin olevat kivijauheet (esim. kaoliini, alumiinioksidi, talkki, liitu) ja synteettiset kivijauheet (esim. hienojakoinen piihappo, silikaatit): emulgaattorit kuten ei-iono-geeniset tai anioniaktiiviset emulgaattorit (esim. polyoksiety-leenirasva-alkoholi-eetterit, alkyylisulfonaatit ja aryylisulfo-naatit) ja dispergoimisaineet, kuten ligniini, sulfiittijätelipeä ja metyyliselluloosa.The active compounds according to the invention can be prepared in the form of conventional preparations, such as solutions, emulsions, suspensions, powders, pastes and granulated products. These are prepared in a known manner, e.g. by mixing the active ingredient with a solvent and / or a carrier, optionally using an emulsifier and a dispersant, in which case, in the case of water as diluent, other organic solvents can also be used as co-solvent. Suitable excipients are: solvents such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzene), paraffins (eg petroleum granules), alcohols (eg methanol, butanol), amines (eg ethanolamine, dimethylformamide) , and water, carriers such as natural stone powders (e.g. kaolin, alumina, talc, chalk) and synthetic rock powders (e.g. fine silica, silicates): emulsifiers such as non-ionic or anionic emulsifiers (e.g. polyoxyethyl -lene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite waste liquor and methylcellulose.
Valmisteet sisältävät yleisesti 0,1-95 painoprosenttia vaikuttavaa ainetta, etupäässä 0,5-90 %. Valmisteita tai niistä saatuja käyttövalmiita tuotteita, kuten liuoksia, emulsioita, suspensioita, jauheita, tahnoja tai rakeita, käytetään tavalliseen tapaan, esim. ruiskuttamalla, sumuttamalla, toimittamalla, sirottelemalla, peittaamalla tai kastelemalla.The preparations generally contain from 0.1 to 95% by weight of active ingredient, in particular from 0.5 to 90%. Preparations or ready-to-use products derived therefrom, such as solutions, emulsions, suspensions, powders, pastes or granules, are used in the usual manner, e.g. by spraying, spraying, delivering, sprinkling, pickling or wetting.
Keksinnön mukaiset aineet voivat näissä käyttömuodoissa olla yhdistettynä muihin vaikuttaviin aineisiin, esim. herbisi-deihin, insektisideihin, kasvunopeutta sääteleviin aineisiin ja fungisideihin, tai ne voivat olla myös sekoitettuna lannoitteisiin. Fungisidit, joiden kanssa keksinnön mukaiset yhdisteet voidaan yhdistää, ovat esimerkiksi ditiokarbamaatteja ja niiden johdannaisia, 64 3 6 0 kuten ferridimetyyliditiokarbamaatti, sinkkidimetyyliditiokarbamaatti, mangaanietyleenibisditiokarbamaatti, mangaani-sinkki-etyleenidiamiini-bis-ditiokarbamaatti, sinkkietyleenibisditiokarbamaatti, tetrametyylitiuramidisulf idi, sinkki-(N,Ν-etyleeni-bis-ditiokarbamaatin) ja N-N'-polyetyleeni-bis-(tiokarbamoyyli)-disulf idin ammoniakki-kompleksi, sinkki-(N,N'-propyleeni-bis-ditiokarbamaatti), tina-(N,N'-propyleeni-bis-ditiokarbamaatin ja N, N'-polypropyleeni-bis-(tiokarbamoyyli)-disulfidin ammoniakki-kompleksi.In these applications, the substances according to the invention can be combined with other active substances, e.g. herbicides, insecticides, growth rate regulators and fungicides, or they can also be mixed with fertilizers. Fungicides with which the compounds of the invention can be combined include, for example, dithiocarbamates and derivatives thereof, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylenediamine, bis-dithiocarbate, ethylene bis-dithiocarbamate) and N-N'-polyethylene bis- (thiocarbamoyl) disulfide ammonia complex, zinc (N, N'-propylene bis-dithiocarbamate), tin (N, N'-propylene ammonia complex of bis-dithiocarbamate and N, N'-polypropylene-bis- (thiocarbamoyl) -disulfide.
Nitrofenolijohdannainen, kuten dinitro-(1-metyyliheptyyli)-fenyylikrotonaatti, 2-sek.-butyyli-4,6-dinitrofenyyli-3,3-dimetyyliakrylaatti, 2-sek.-butyyli-4,6-dinitrofenyyli-isopropyylikarbonaatti;A nitrophenol derivative such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;
Heterosyklisiä yhdisteitä, kuten N-trikloorimetyylitio-tetrahydrofraali-imidi, N-trikloorimetyylitio-ftaali-imidi, 2-heptadekyy1i-2-imidatsoiin-asetaatti, 2,4-dikloori-6-(0-kloorianiliino)-s-triatsiini, O, 0-dietyyli-ftaali-imidofosfonotioaatti, 5-amino-l-(bis-(dimetyyliamino)-fosfinyyli)-3-fenyyli-l,2,4-triätsoli, 5-etoksi-3-trikloorimetyyli-1,2,4-tiadiatsoli, 2.3- disyano-l,4-ditiaanitrakinoni, 2-tio-l,3-ditio-(4,5-b)-kinoksaliini, 1- {butyylikarbamoyyli)-2-bentsimidatsoli-karbamiinihappometyyliesteri, 2- metoksikarbamoyyliamino-bentsimidatsoli, 2-rodaanimetyylitio-bentstiätsoli, 4-(2-kloorifenyylihydratsono)-3-metyyli-5-isoksatsoloni, pyridiini-2-tioli-l-oksidi, 8-hydroksikinoliini tai sen kuparisuola, 2.3- dihydro-5-karboksanilido-6-metyyli-l/4-oksatiini-4,4-dioksidi, 2.3- dihydro-5-karboksanilido-6-metyyli-l,4-oksatiini, 2-(furyyli-(2))-bentsimidatsoli, piperatsiini-1,4-diyyli-bis-l-(2,2,2-trikloorietyyli)-formamidi, 9 64360 2-(tiatsolyyli-(4))-bentsimidatsoli, 2- butyyli-2-d.imetyyliamino-4-hydroksi-6-metyyli-pyrid.iini, bis-(p-kloorifenyyli)-3-pyridiinimetanoli, tioureido)-bentseeni, 1.2- bis-(3-metoksikarbonyyli-2-tioureido)-bentseeni, ja erilaisia fungisidej^ , kuten dodekyyliguanidiiniasetaatti, 3- (2-(3,5-dimetyyli-2-oksisykloheksyyli)-2-hydroksietyyli)-glulaari-imidi, heksaklooribentseeni, N-dikloorifluorimetyylitio-N’N'-dimetyyli-N-fenyyli-rikkihappodiamidi, 2.5- dimetyyli-furaani-3-karboksihappoanilidi, 2.5- dimetyylifuraani-3-karboksihappo-sykloheksyyliamidi, 2-metyyli-bentsoehappo-anilidi, 2-jodi-bentsoehappo-anilidi, 1-(3,4-dikloorianiliino)-l-formyyliamino-2,2,2-trikloorietaani , 2.6- dimetyyli-N-trifekyyli-morfoliini tai sen suolat, 2.6- dimetyyli-N-syklododekyyli-morfOliini tai sen suolat, 2.3- dikloori-l,4-naftokinoni, 1.4- dikloori-2,5-dimetoksibentseeni, p-dimetyyliaminobentseeni-diatsinatriumsulfonaatti, l-kloori-2-nitroli-propaani, polykloorinitrobentseeni, kuten pentakloorinitrobentseeni, metyyli-isosyanaatti, fungisidi-antibiootteja, kuten griseofulviini tai kausgamysiini, tetrafluoridiklooriasetoni, 1-fenyylitiosemikarbatsidi, "Bordeaux"-seos, nikkelipitoiset yhdisteet ja rikki.Heterocyclic compounds such as N-trichloromethylthio-tetrahydrofralimide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (O-chloroanilino) -s-triazine, O, O-Diethyl phthalimidophosphonothioate, 5-amino-1- (bis- (dimethylamino) phosphinyl) -3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4- thiadiazole, 2,3-dicyano-1,4-dithianitraquinone, 2-thio-1,3-dithio- (4,5-b) -quinoxaline, 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester, 2-methoxycarbamoylamino-benzimidazole, 2-Rhodanemethylthio-benzithiazole, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl -1,4-oxatin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxatin, 2- (furyl- (2)) -benzimidazole, piperazine-1,4-diyl -bis-1- (2,2,2-trichloroethyl) -formamide, 9,64360 2- (thiazolyl- (4)) -benzimidazole, 2-butyl-2-dimethyl ylamino-4-hydroxy-6-methyl-pyridine, bis- (p-chlorophenyl) -3-pyridinemethanol, thioureido) benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene, and various fungicides such as dodecylguanidine acetate, 3- (2- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N'N'-dimethyl-N-phenyl-sulfuric acid diamide, 2,5-Dimethyl-furan-3-carboxylic acid anilide, 2,5-Dimethyl-furan-3-carboxylic acid-cyclohexylamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, 1- (3,4-dichloroanilino) -1-formylamino- 2,2,2-trichloroethane, 2,6-dimethyl-N-tripecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, 2,3-dichloro-1,4-naphthoquinone, 1,4-dichloro-2, 5-dimethoxybenzene, p-dimethylaminobenzene diazodium sulfonate, 1-chloro-2-nitrolepropane, polychloronitrobenzene such as pentachloronitrobenzene, methyl isocyanate, fungicide antibiotics such as griseofulvin or seasonal gamycin, tetrafluorodichloroacetone, 1-phenylthiosemicarbazide, "Bordeaux" alloy, nickel-containing compounds and sulfur.
Seuraavissa kokeissa, jotka osoittavat keksinnön mukaisten yhdisteiden fungisidien vaikutuksen, käytettiin vertailuna seuraa-vaa tunnettua, biologisesti aktiivista ainetta (A),In the following experiments demonstrating the fungicidal activity of the compounds of the invention, the following known biologically active substance (A) was used as a reference.
Cl /=^ T\ Cl N N-CH,~CH -v /— V 2 I w (A) 0-CH2~CH=CH2 DE-hakemusjulkaisusta 2 063 857 tunnettu yhdiste ίο 64 3 60Cl / = ^ T \ Cl N N-CH, ~ CH -v / - V 2 I w (A) O-CH2 ~ CH = CH2 Compound known from DE-A-2 063 857 ίο 64 3 60
Kokeessa 1 käytettiin vertailuun myös FI-patenttihakemuk-sesta 752 614 tunnettuja yhdisteitä ^H2 H2 .HC1In Experiment 1, compounds known from FI patent application 752 614 ^ H2 H2 .HCl were also used for comparison.
NOF
0 (B) C1 ^ l!0 (B) C1 ^ 1!
L .1 H CHL .1 H CH
^ I H7 cn2 h2 h2 1 . HC1^ I H7 cn2 h2 h2 1. HC1
NOF
^ // (C)^ // (C)
\___N\___OF
Koe 1Test 1
Ohran härmäsieniBarley mildew
Ruukuissa kasvatettujen ohran (lajike "Firlbecks Union") taimien lehdet ruiskutetaan vesiemusliolla, jossa on 80 % (paino-%) aktiivista ainetta ja 20 % emulgaattoria ja ruiskutusvalmisteen kuivuttua pölytetään ohran härmäsienen (Erysiphe graminis var. hordei) itiöillä. Tämän jälkeen koekasvit kasvatetaan kasvihuoneessa 20-22°C:n lämpötilassa ja suhteellisen kosteuden ollessa 75-80 %. 10 päivän kuluttua saadaan selville härmäsienien kehittymisen määrä. Arvosteluasteikko: 0-5, jossa 0 = ei tartuntaa 5 = tartunta täydellinen N1 11 11 64 360The leaves of potted barley (Firlbecks Union) seedlings are sprayed with a water emulsion containing 80% (w / w) of active substance and 20% emulsifier and, after drying, the pollen is dusted with the spores of barley powdery mildew (Erysiphe graminis var. Hordei). The test plants are then grown in a greenhouse at a temperature of 20-22 ° C and a relative humidity of 75-80%. After 10 days, the rate of development of downy mildew is determined. Rating scale: 0-5, where 0 = no infection 5 = infection complete N1 11 11 64 360
Lehtien tartunta-aste 0,05- ja 0,025 %:sella aktiivisella aineella suoritettujen ruiskutusten jälkeenDegree of leaf adhesion after spraying with 0.05 and 0.025% active substance
Aktiivinen aine_0,05_0,025 4 2 6 0 3 9 0 3 10 0 4 12 0 2 14 0 2 15 0 3 18 0 3 21 0 2-3 25 0 2 26 0 3 27 0 3 30 0 0 31 0 3 40 2 - 41 0 2 48 0 2 N.Active substance_0.05_0.025 4 2 6 0 3 9 0 3 10 0 4 12 0 2 14 0 2 15 0 3 18 0 3 21 0 2-3 25 0 2 26 0 3 27 0 3 30 0 0 31 0 3 40 2 - 41 0 2 48 0 2 N.
\ 50 0 3 54 0 2-3\ 50 0 3 54 0 2-3
NOF
\ 59 0 2 ^64 0 2 65 0 3 7 0 0 80 0 0 85 0 0 90 0 0 92 0 0 94 - 0 0 104 0 0 113 0 0 114 0 0 115 0 0 116 0 0 i2 64360\ 59 0 2 ^ 64 0 2 65 0 3 7 0 0 80 0 0 85 0 0 90 0 0 92 0 0 94 - 0 0 104 0 0 113 0 0 114 0 0 115 0 0 116 0 0 i2 64360
Lehtien tartunta-aste 0,05- ja 0,025-% :sella aktiivisella aineella suoritettujen ruiskutusten jälkeenDegree of leaf adhesion after spraying with 0.05 and 0.025% active substance
Aktiivinen aine_ Q ,05_0,025 125 0 0 126 0 0 127 0 0 128 0 0 B 3 4 C 3 4Active substance_ Q, 05_0,025 125 0 0 126 0 0 127 0 0 128 0 0 B 3 4 C 3 4
Kontrolli 5Check 5
Voidaan todeta, että vertailuyhdisteiden B ja C teho on selvästi huonompi kuin keksinnön mukaisten yhdisteiden teho.It can be stated that the potency of the reference compounds B and C is clearly inferior to that of the compounds according to the invention.
Koe 2Test 2
Vehnän härmäsieniWheat powdery mildew
Kuten kokeessa 1 on kuvattu, ruukuissa kasvatettujen vehnän taimien (lajike "Jubilar") lehdet infektoidaan vehnän härmäsienien (Erysiphe graminis var. tritici) itiöillä ja käsitellään muuten kuten kokeessa 1.As described in Experiment 1, the leaves of potted wheat seedlings (variety "Jubilar") are infected with spores of wheat powdery mildew (Erysiphe graminis var. Tritici) and otherwise treated as in Experiment 1.
Lehtien tartunta-aste 0,05- ja 0,025-%:sella aktiivisella aineella suoritettujen ruiskutusten jälkeenDegree of leaf adhesion after spraying with 0.05 and 0.025% active substance
Aktiivinen aine_0,05_0,025 4 0 2 30 0 0 40 0 2 80 0 0 85 0 0 90 0 0 92 0 0 94 0 0 104 0 0 113 0 0 114 0 0 115 0 0 116 0 0 125 0 0 126 0 0 127 0 1 128 0 2 A 1 3Active substance_0.05_0.025 4 0 2 30 0 0 40 0 2 80 0 0 85 0 0 90 0 0 92 0 0 94 0 0 104 0 0 113 0 0 114 0 0 115 0 0 116 0 0 125 0 0 126 0 0 127 0 1 128 0 2 A 1 3
Kontrolli (käsittelemätön) 5Control (untreated) 5
IIII
6436064360
Koe 3Test 3
Vehnän ruskea ruosteWheat brown rust
Ruukussa kasvaneiden vehnän taimien (lajike "Jubilar") lehdet infektoidaan keinotekoisesti vehnän ruskean ruosteen (Puccinia recondita) itiöillä 24 tuntia ennen ruiskutusta ja taimet viedään vesihöyryllä kyllästettyyn huoneeseen, 20-25°C:seen. Tämän jälkeen kasvit ruiskutetaan vesiemulsiolla, jossa on 80 % (paino-%) aktiivista ainetta ja 20 % emulgaattoria. Ruiskutusvalmisteen kuivuttua asetetaan koekasvit kasvihuoneeseen, jonka lämpötila on 20-22°C ja suhteellinen kosteus 75-80 %. 10 päivän kuluttua tarkastetaan ruostesienen kehittymisen määrä.The leaves of potted wheat seedlings (variety "Jubilar") are artificially infected with spores of wheat brown rust (Puccinia recondita) 24 hours before spraying and the seedlings are taken to a room saturated with water vapor, 20-25 ° C. The plants are then sprayed with an aqueous emulsion containing 80% (w / w) of active substance and 20% of emulsifier. After the spray preparation has dried, the test plants are placed in a greenhouse with a temperature of 20-22 ° C and a relative humidity of 75-80%. After 10 days, the rate of rust development is checked.
Lehtien tartunta-aste 0,05-%:sella Aktiivinen aine aktiivisella aineella suoritetun _ruiskutuksen jälkeen_ 4 2 12 0 27 0 30 0 7 0 80 0 85 0 90 0 92 0 104 0 113 0 116 0 125 0 126 0 127 0 A 3Leaf adhesion rate 0.05% Active substance after spraying with active substance_ 4 2 12 0 27 0 30 0 7 0 80 0 85 0 90 0 92 0 104 0 113 0 116 0 125 0 126 0 127 0 A 3
Kontrolli (käsittelemätön) 5 14 64360Control (untreated) 5 14 64360
Esimerkki 1Example 1
Tert.-butyyli-/2,4-dikloorifenyyli)-1,2,4-triatsol-l-yyli-metyyli7-sulfidi (yhdiste no 65)Tert-butyl- (2,4-dichlorophenyl) -1,2,4-triazol-1-ylmethyl-7-sulfide (Compound No. 65)
Liuokseen, jossa on 22,1 g 1,2,4-triatsolia 500 ml:ssa vedetöntä asetonia lisätään 60,5 g tert. -butyyli-/(2,4-dikloorifenyyli) -kloorimetyylij-sulfidia. Sitten lisätään 44,2 g hienoksijauhettua kaliumkarbonaattia ja seosta kuumennetaan sekoittaen ja palautusjäähdyttäen 7 tuntia. Tämän jälkeen suodatetaan liukenemattomat aineosat, konsentroidaan suodos vakuumissa kuiviin ja laimennetaan jäännös 300 ml :11a vettä. Skstrahoi-daan vesifaasi 3 kertaa 200 ml:11a metyleenikloridia, pestään yhdistetyt ekstraktit 200 ml :11a vettä, kuivataan ja konsentroidaan vakuumissa. Lisätään 100 ml di-isopropyylieetteriä, jolloin saadaan 35,6 g (53 %) värittömiä kiteitä, sp. 9 5-9 7°C.To a solution of 22.1 g of 1,2,4-triazole in 500 ml of anhydrous acetone is added 60.5 g of tert. -butyl - [(2,4-dichlorophenyl) -chloromethyl] sulfide. 44.2 g of finely ground potassium carbonate are then added and the mixture is heated with stirring and reflux for 7 hours. The insoluble constituents are then filtered off, the filtrate is concentrated to dryness in vacuo and the residue is diluted with 300 ml of water. Extract the aqueous phase 3 times with 200 ml of methylene chloride, wash the combined extracts with 200 ml of water, dry and concentrate in vacuo. 100 ml of diisopropyl ether are added to give 35.6 g (53%) of colorless crystals, m.p. 9 5-9 7 ° C.
1H-NMR (10 0 MHz, CDCl^-i/1,3 (s, 9H) , 6,9 5 (s, 1H) , 7,0-7,4 (m, 3H, ABX), 8,0 (s, 1H), 8,8 miljoonasosaa (s, 1H).1 H-NMR (10 MHz, CDCl 3 / 1.3 / s (9H), 6.9 δ (s, 1H), 7.0-7.4 (m, 3H, ABX), 8.0 (s, 1H), 8.8 ppm (s, 1H).
Esimerkki 2Example 2
Bis-<tert. -butyyli-./ (2,4-dikloorifenyyli) -1,2,4-triat-sol-l-yyli-metyyli7-sulfidi>-kupari-(II)-kloridi liuokseen, jossa on 9,5 g tert. -butyyli-/T( 2,4-dikloorifenyyli)- 1,2 ,4-triatsol-l-yyli-metyyli/-sulfidia 100 ml:ssa etanolia, tiputetaan 15 ml kupari-II-kloridi-dihydraatin yksimolaarista etanoliliuosta. Tästä syvänsinisestä liuoksesta eristetään 0°C:ssa tapahtuneen kaksipäiväisen seisotuksen jälkeen 9,8 g sinisiä kiteitä, jotka pestään etanolilla ja eetterillä, sp. 130°C.Bis <tert. -butyl-./ (2,4-dichlorophenyl) -1,2,4-triazol-1-ylmethyl-7-sulfide-copper- (II) chloride to a solution of 9.5 g of tert. -butyl [N- (2,4-dichlorophenyl) -1,2,4-triazol-1-ylmethyl] sulfide in 100 ml of ethanol, 15 ml of a 1 molar solution of copper II chloride dihydrate in ethanol are added dropwise. After standing for two days at 0 [deg.] C., 9.8 g of blue crystals are isolated from this deep blue solution, which is washed with ethanol and ether, m.p. 130 ° C.
Esimerkki 3 1 pentyyli-/!-(1,2,4-triatsol-l-yyli)-pentyyli-(lO-sulfidi (yhdiste no 75) 15 64360Example 3 1 Pentyl-1- (1,2,4-triazol-1-yl) -pentyl- (10-sulfide (Compound No. 75)) 15 64360
Suspensioon, jossa on 13,0 g natriumhydridiä 100 ml:ssa dimetyyliformamidia, tiputetaan sekoittaen liuos, jossa on 43.5 g triatsolia 200 ml:ssa dimetyyliformamidia. Vedynmuo-dostuksen päätyttyä tiputetaan huoneenlämpötilaan jäähdytettyyn seokseen 97,0 g 1-pentyyli/1-klooripentyyli-(1 )_7~sulfi-dia, jolloin seos lämpenee. Tämän jälkeen sekoitetaan vielä 8 tuntia 80°C:ssa. Reaktioseos konsentroidaan sitten vakuu-missa, laimennetaan 500 ml:11a vettä ja ekstrahoidaan 5 kertaa metyleenikloridilla. Yhdistetyt ja konsentroidut ekstrak-tit kromatografioidaan silikageelillä (5 x 70 cm) ensiksi käyttämällä metyleenikloridia liuottimena. Ensimmäisen ruskeahkon fraktion jälkeen metyleenikloridiin lisätään suurenevia määriä asetonia (10 % asetonia saakka). Toisena fraktiona eristetään sitten 15,0 g tuotetta vaaleankeltaisena öljynä. IR (filmi): 2955, 2925, 2860, 1496, 1460, 1271, 1190, 1133, 1008, 677 cm"1.A solution of 43.5 g of triazole in 200 ml of dimethylformamide is added dropwise with stirring to a suspension of 13.0 g of sodium hydride in 100 ml of dimethylformamide. After completion of the hydrogen addition, 97.0 g of 1-pentyl / 1-chloropentyl- (1) -7-sulfide are added dropwise to the mixture cooled to room temperature, whereupon the mixture is heated. It is then stirred for a further 8 hours at 80 ° C. The reaction mixture is then concentrated in vacuo, diluted with 500 ml of water and extracted 5 times with methylene chloride. The combined and concentrated extracts are chromatographed on silica gel (5 x 70 cm) first using methylene chloride as solvent. After the first brownish fraction, increasing amounts of acetone (up to 10% acetone) are added to the methylene chloride. As a second fraction, 15.0 g of product are then isolated as a pale yellow oil. IR (film): 2955, 2925, 2860, 1496, 1460, 1271, 1190, 1133, 1008, 677 cm -1.
1H-NMR (270 MHz, CDC13) : cfo , 9 ("tr", 6H) , 1,3 (m, 8H) , 1.5 (m, 2H), 2,1 (m, 2H), 2,4 (m, 2H), 5,4 (tr. 1H), 8,0 (s, 1H), 8,4 miljoonasosaa (s, 1H).1 H-NMR (270 MHz, CDCl 3): δ 9 ("tr", 6H), 1.3 (m, 8H), 1.5 (m, 2H), 2.1 (m, 2H), 2.4 ( m, 2H), 5.4 (tr. 1H), 8.0 (s, 1H), 8.4 ppm (s, 1H).
Esimerkki 4 l-pentyyli-£T- (1,2,4-triatsol-l-yyli) -pentyyli- (1)_/-sulfoni (yhdiste no 71)Example 4 1-Pentyl-N- (1,2,4-triazol-1-yl) -pentyl- (1) -N-sulfone (Compound No. 71)
Liuokseen, jossa on 10,0 g 85-% 3-kiooriperbentsoe-happoa 140 mltssa metyleenikloridia, tiputetaan jäähauteessa sekoittaen liuosta, jossa on 6,0 g l-pentyyli-7T-(1,2,4-triatsol-l-yyli) -pentyyli- (1 )_7-sulf idia. Alkulämpenemisen päätyttyä sekoitetaan vielä 2 päivää 25°C:ssa. Seosta pestään sitten natriumkarbonaattiliuoksella, natrium-sulfiittiliuoksella ja vedellä ja orgaaninen faasi kuivataan. Konsentroinnin jälkeen jää kirkkaankeltainen öljy, josta di-isopropyylieetterissä hankaamalla saadaan värittömiä kiteitä, sp. 69-71°C.To a solution of 10.0 g of 85% 3-chloroperbenzoic acid in 140 ml of methylene chloride is added dropwise, with stirring, a solution of 6.0 g of 1-pentyl-7T- (1,2,4-triazol-1-yl) -pentyl- (1) -7-sulfide. After completion of the initial warming, stir for a further 2 days at 25 ° C. The mixture is then washed with sodium carbonate solution, sodium sulfite solution and water and the organic phase is dried. After concentration, a bright yellow oil remains, which is triturated with diisopropyl ether to give colorless crystals, m.p. 69-71 ° C.
NMR (CDC13, 100 MHz):of0,9 (m, 6H) , 1,4 (m, 8H) , 1,8 (m, 2H) , ie 64360 2,5 (m, 2H), 2,8 ("dd", 2H), 5,4 (dd, 1H), 8,1 (s, 1H), 8,5 miljoonasosaa (s, 1H) .NMR (CDCl 3, 100 MHz): of0.9 (m, 6H), 1.4 (m, 8H), 1.8 (m, 2H), δ 64360 2.5 (m, 2H), 2.8 ( "dd", 2H), 5.4 (dd, 1H), 8.1 (s, 1H), 8.5 ppm (s, 1H).
Esimerkki 5Example 5
Tert.-butyyli-/(2-metyylitenyyli)-imidatsol-l-yy1i-metyyli/-sulfidi (yhdiste no. 89)Tert-butyl - [(2-methyltenyl) -imidazol-1-yl] -methyl] sulfide (Compound No. 89)
Liuokseen, jossa on 43,6 g imidatsolia 300 ml:ssa asetonia tiputetaan sekoittaen 82 g tert.-butyyli-/(2-metyylifenyyli)-kloori-metyyliy-sulfidia. 88 g hienoksijauhetun kaliumkarbonaattilisäyksen jälkeen kuumennetaan 5 tuntia palautusjäähdyttäjässä. Senjälkeen liukenemattomat aineosat suodatetaan ja suodos konsentroidaan.A solution of 43.6 g of imidazole in 300 ml of acetone is added dropwise with stirring to 82 g of tert-butyl / (2-methylphenyl) chloromethylsulfide. After the addition of 88 g of finely ground potassium carbonate, the mixture is heated under reflux for 5 hours. The insoluble components are then filtered off and the filtrate is concentrated.
300 ml:11a vettä laimennettua jäännöstä ekstrahoidaan 3 x 200 ml:11a metyleenikloridia. Yhdistetyistä orgaanisista faaseista saadaan vesipesun, kuivauksen ja konsentroinnin jälkeen 69 g ruskeahkoa öljyä, joka liuotetaan 1 1:aan di-isopropyylieetteriä. Lisäämällä sekoittaen ja tiputtaen 90 ml:aa 2,85 molaarista kloorivetyliuosta di-isopropyylieetterissä kiteytyy tästä liuoksesta vaaleankeltaisia hydrokloridin kiteitä, jotka toistokiteytetään asetonista. Näin saadaan 51 g väritöntä tert.-butyyli-/(2-metyylifenyyli)-imidatsol-l-yyli-metyyli/-sulfidihydrokloridia, sp. 168-170°C (yhdiste no. 110).The residue diluted with 300 ml of water is extracted with 3 x 200 ml of methylene chloride. After washing with water, drying and concentration, 69 g of a brownish oil are obtained from the combined organic phases, which are dissolved in 1 l of diisopropyl ether. Addition of 90 ml of a 2.85 molar solution of hydrogen chloride in diisopropyl ether with stirring and dropwise addition gives pale yellow crystals of the hydrochloride from this solution, which are recrystallized from acetone. 51 g of colorless tert-butyl [(2-methylphenyl) imidazol-1-ylmethyl] sulphide hydrochloride are obtained, m.p. 168-170 ° C (comp. No. 110).
Sen jälkeen kun hydrokloridi on kaadettu 25 g natriumvety-karbonaattia sisältävään vesiliuokseen, ekstrahoidaan vapaata emästä 3 x 200 ml:11a eetteriä. Kuivauksen ja konsentroinnin jälkeen saadaan vaaleankeltaista öljyä (27 g), joka vähitellen kiteytyy (sp. 93-95°C).After pouring the hydrochloride into an aqueous solution containing 25 g of sodium bicarbonate, the free base is extracted with 3 x 200 ml of ether. After drying and concentration, a pale yellow oil (27 g) is obtained, which gradually crystallizes (m.p. 93-95 ° C).
1H-NMR (60 MHz, CDCl3): 1,3 (s, 9H) , 2,4 (s, 3H) , 6,25 (s, 1H) , 6,7-7,1 (m, 6H), 7,65 miljoonasosaa (dd, 1H).1 H-NMR (60 MHz, CDCl 3): 1.3 (s, 9H), 2.4 (s, 3H), 6.25 (s, 1H), 6.7-7.1 (m, 6H), 7.65 ppm (dd, 1 H).
Esimerkki 6 4-kloorifenyyli-/!4 ' -kloorif enyyli) -imidatsolyylimetyyli/-sulfidi (yhdiste no. 7)Example 6 4-Chlorophenyl - ((4'-chlorophenyl) imidazolylmethyl] sulfide (Compound No. 7)
Seosta, jossa on 60,7 g 4-kloorifenyyli-(kloorimetyyli-(4’-kloorifenyyli))-sulfidia, 27,2 g imidatsolia ja 55,4 g kalium-karbonaattia 400 ml:ssa asetonia palautusjäähdytetään sekoittaen 5 tunnin ajan. Suodatetaan sitten, suodos konsentroidaan kuivaksi ja laimennetaan 500 ml:11a vettä. Tätä seosta ekstrahoidaan 3 kertaa 200 ml:11a metyleenikloridia. Yhdistetyt ekstraktit kuivataan nat-riumsulfaatin päällä. Vakuumissa kuivaksi konsentroidusta liuoksesta 17 64360 eristetään di-isopropyylieetterissä suoritetun hankauksen jälkeen 26 g (38 %) värittömiä kiteitä, sp. 88°C.A mixture of 60.7 g of 4-chlorophenyl- (chloromethyl- (4'-chlorophenyl)) sulphide, 27.2 g of imidazole and 55.4 g of potassium carbonate in 400 ml of acetone is refluxed with stirring for 5 hours. Filter, then concentrate the filtrate to dryness and dilute with 500 ml of water. This mixture is extracted 3 times with 200 ml of methylene chloride. The combined extracts are dried over sodium sulfate. After trituration with diisopropyl ether, 26 g (38%) of colorless crystals, m.p. At 88 ° C.
1H-NMR (60MHz, CDCl3): 6 6,3 (s. 1H, 6,9-7,4 (m, 10H), 7,5 (levä, s, 1H).1 H-NMR (60MHz, CDCl 3): δ 6.3 (s, 1H, 6.9-7.4 (m, 10H), 7.5 (algae, s, 1H).
Esimerkki 7Example 7
Tert.-butyyli-/ (2,6-dikloorifenyyli)-pyratsolyylimetyyli/-sulfidi (yhdiste no- 53)Tert-butyl / (2,6-dichlorophenyl) -pyrazolylmethyl] sulfide (Compound No. 53)
Liukseen, jossa on 193 g tert.-butyyli-(kloorimetyyli-(2,6-dikloorifenyyli))-sulfidia ja 44 g pyratsolia 1 l:ssa tolueenia, tiputetaan 66 g trietyyliamiinia ja kuumennetaan heikon eksotermisen reaktion loputtua vielä yhden tunnin ajan palautusjäähdyttäen. Liukenemattomat aineet suodtetaan pois, suodos konsentroidaan ja jäännös laimennetaan 500 ml:lla vettä. Sen jälkeen kun on ekstrahoi-tu 3 kertaa 200 ml:11a metyleenikloridia, saadaan yhdistettyjen ekstraktien konsentroinnin jälkeen kiinteä jäännös, josta di-isopro-pyylieetteripesun jälkeen saadaan 117 g (57 %) värittömiä kiteitä, sp. 97-98°C.To a solution of 193 g of tert-butyl (chloromethyl- (2,6-dichlorophenyl)) sulfide and 44 g of pyrazole in 1 l of toluene is added dropwise 66 g of triethylamine and the mixture is refluxed for a further hour after completion of the slight exotherm. The insolubles are filtered off, the filtrate is concentrated and the residue is diluted with 500 ml of water. After extraction 3 times with 200 ml of methylene chloride, concentration of the combined extracts gives a solid residue which, after washing with diisopropyl ether, gives 117 g (57%) of colorless crystals, m.p. 97-98 ° C.
ljj-NMR (60 MHz), CDC13): </ 1,4 miljoonasosaa (s, 9H) , 6,2 ("tr.", 1H, 7,0-7,3 (m, 3H), 7,4 ("d", 1H), 8,2 ("d", 2H).1 H-NMR (60 MHz), CDCl 3): </ 1.4 ppm (s, 9H), 6.2 ("tr.", 1H, 7.0-7.3 (m, 3H), 7.4 ("d", 1H), 8.2 ("d", 2H).
Esimerkki 8 2,4-diklooribentsyyli-(1,2,4-triatsolyylimetyyli)-sulfidi (yhdiste no. 78)Example 8 2,4-Dichlorobenzyl- (1,2,4-triazolylmethyl) sulfide (Compound No. 78)
Seosta, jossa on 60,4 g kloorimetyyli-(2,4-diklooribentsyyli)-sulfidia, 35 g 1,2,4-triatsolia ja 69 g hienonnettua kaliumkarbonaattia 300 ml:ssa vedetöntä aasetonia, palautusjäähdytetään 10 tunnin ajan. Tämän jälkeen suodatetaan liukenemattomat aineosat, konsentroidaan suodos vakuumissa kuiviin ja laimennetaan jäännös 300 ml:11a vettä. Sitten ekstrahoidaan kolme kertaa 200 ml:11a metyleenikloridia, yhdistetyt ekstraktit kuivataan ja konsentroidaan vakuumissa. Jäljellejäävästä ruskeasta öljystä saadaan kiteyttämällä di-isopropyylieetteri/metanolista - 60°C:ssa 39,8 g (58 %) värittömiä kiteitä, sp. 68-70°C.A mixture of 60.4 g of chloromethyl- (2,4-dichlorobenzyl) sulphide, 35 g of 1,2,4-triazole and 69 g of crushed potassium carbonate in 300 ml of anhydrous acetone is refluxed for 10 hours. The insoluble constituents are then filtered off, the filtrate is concentrated to dryness in vacuo and the residue is diluted with 300 ml of water. It is then extracted three times with 200 ml of methylene chloride, the combined extracts are dried and concentrated in vacuo. From the residual brown oil, 39.8 g (58%) of colorless crystals are obtained by crystallization from diisopropyl ether / methanol at -60 [deg.] C., m.p. 68-70 ° C.
1H -NMR (60 MHz, CDCl3 : 3,8 (s. 2H) , 5,0 (s. 2H) , 7,0-7,5 (m, 3H) , 7,9 (s, 1H), 8,2 (s, 1H).1 H-NMR (60 MHz, CDCl 3: 3.8 (s, 2H), 5.0 (s, 2H), 7.0-7.5 (m, 3H), 7.9 (s, 1H), δ , 2 (s, 1 H).
18 6436018 64360
Esimerkki 9 2,4-diklooribentsyyli-(2',4'-dikloorifenyyli-1,2,4-triätso1- 1-yyli-metyyli)-sulfidi (yhdiste no. 61) ja 2,4-diklooribentsyyli /(2 ' , 4 '-dikloorif enyyli- (1,2,4-triatsol-4-yyl.i) -metyyli/-sulf idi (yhdiste no. 64) .Example 9 2,4-Dichlorobenzyl- (2 ', 4'-dichlorophenyl-1,2,4-triazol-1-ylmethyl) sulfide (Compound No. 61) and 2,4-Dichlorobenzyl / (2', 4'-Dichlorophenyl- (1,2,4-triazol-4-yl) methyl] sulfide (Compound No. 64).
Seosta, jossa on 200 g 2,4-diklooribentsyyli-^(2 ',4'-dikloorif enyyli)-kloorimetyyli/-sulfidia, 145 g 1,2,4-triatsolia ja 138 g hienonnettua kaliumkarbonaattia 2 l:ssa vedetöntä asetonia palautusjäähdytetään voimakkaasti sekoittaen 9 tunnin ajan. Tämän jälkeen erotetaan kiinteät aineosat suodattamalla, suodos konsentroidaan vakuumissa kuiviin ja öljymäistä jäännöstä ekstrahoidaan 500 ml vesilisäyksen jälkeen 5 kertaa 2-0 ml:11a metyleenikloridia. Yhdistetyt orgaaniset faasit kuivataan natriumsulfaatin päällä ja konsentroidaan vakuumissa kuiviin. Hankaamalla jäännöstä di-isopropyyli-eetterissä saadaan 157 g värittömiä kiteitä, jotka sisältävät tri-atsolyyliyhdisteiden isomeerejä suhteessa 8:2.A mixture of 200 g of 2,4-dichlorobenzyl-N- (2 ', 4'-dichlorophenyl) -chloromethyl / sulphide, 145 g of 1,2,4-triazole and 138 g of crushed potassium carbonate in 2 l of anhydrous acetone is refluxed with vigorous stirring for 9 hours. The solids are then filtered off, the filtrate is concentrated to dryness in vacuo and the oily residue is extracted 5 times with 2-0 ml of methylene chloride after addition of 500 ml of water. The combined organic phases are dried over sodium sulfate and concentrated to dryness in vacuo. Trituration of the residue in diisopropyl ether gives 157 g of colorless crystals containing 8: 2 isomers of triazolyl compounds.
Tätä seosta ekstrahoidaan useita kertoja kuumalla heksaanilla. Yhdistetyistä heksaaniliuoksista saadaan tislaamalla liuotin pois vakuumissa 122 g (65 %) 2,4-diklooribentsyyli-/(2',4'-dikloorifenyyli) -1,2,4-triatsol-l-yyli-metyyli/-sulfidia värittömien kiteiden muodossa, sp. 120-125°C.This mixture is extracted several times with hot hexane. 122 g (65%) of 2,4-dichlorobenzyl - (2 ', 4'-dichlorophenyl) -1,2,4-triazol-1-ylmethyl / sulfide are obtained in the form of colorless crystals by distilling off the solvent in vacuo from the combined hexane solutions, mp. 120-125 ° C.
^H-NMR (220 MHz), XDXl^):^ 3,9 miljoonasosaa (leveä s, 2H), 6,65 (s, 1H), 7,0-7,5 (m, 6H), 8,0 (s. 1H), 8,6 (s. 1H).1 H-NMR (220 MHz), λ max (λ max): δ 3.9 ppm (broad s, 2H), 6.65 (s, 1H), 7.0-7.5 (m, 6H), 8.0 (s. 1H), 8.6 (s. 1H).
Väritön, liukenematon heksaanifraktion jäännös koostuu 27 g:sta ,(12 %) 2,4-diklooribentsyyli-/'(2', 4 '-dikloorif enyyli) - (1,2 , 4-triatsol-4-yyli)-metyyli/-sulfidia, sp. 132-133°C.The colorless, insoluble residue of the hexane fraction consists of 27 g of (12%) 2,4-dichlorobenzyl - ['(2', 4'-dichlorophenyl) - (1,2,4-triazol-4-yl) methyl] -sulfidia, m.p. 132-133 ° C.
^"H-NMR (220 MHz, CDCl^) : c! = 3,9 miljoonasosaa (s, 2H) , 6,5 (s, 1H), 7,0-7,5 (m, 6H), 8,45 (s. 2H).1 H-NMR (220 MHz, CDCl 3): δ = 3.9 ppm (s, 2H), 6.5 (s, 1H), 7.0-7.5 (m, 6H), δ 45 (p. 2H).
Esimerkki 10Example 10
Tert.-butyyli-/- (4-kloorifenyyli)-1,2,4-triatsol-l-yyli-metyy-li7-sulfidi (yhdiste no. 30)Tert-butyl N- (4-chlorophenyl) -1,2,4-triazol-1-ylmethyl-7-sulfide (Compound No. 30)
Liuokseen, jossa on 78 g tert.-butyyli-^i4-kloorifenyyli)-kloorimetyyli/-sulfidia 175 ml:ssa kuivaa dimetyyliformamidia (DMF) tiputetaan sekoittaen 350 ml yksimolaarista 1,2,4-triatsolyyli-natriumia DMF:s s a (valmistettu 0,35 moolista natriumhydridiä ja 0,35 moolista 1,2,4-triatsolia 350 ml:ssa DMF:a. Heikon eksotermisen reaktion loputtua sekoitetaan vielä 4 tuntia 80°C:ssa. Seos kaade- 19 0 4 3 6 0 taan 1 1:aan vettä ja ekstrahoidaan 3 kertaa 200 ml:11a metyleeni-kloridia. Yhdistetyt orgaaniset faasit pestään vedellä, kuivataan natriumsulfaatin päällä ja haihdutetaan vakuumissa. Jäännöksestä muodostuu 150 mlrssa di-isopropyylieetteriä hankaamalla 40,0 g:aan (46 %) värittömiä kiteitä, sp. 95°C.To a solution of 78 g of tert-butyl-((4-chlorophenyl) -chloromethyl] sulfide in 175 ml of dry dimethylformamide (DMF) is added dropwise with stirring 350 ml of one molar 1,2,4-triazolyl sodium in DMF (prepared from 0 , 35 moles of sodium hydride and 0.35 moles of 1,2,4-triazole in 350 ml of DMF After completion of the slight exotherm, the mixture is stirred for a further 4 hours at 80 [deg.] C. The mixture is poured into 1 [deg.] C. water and extracted 3 times with 200 ml of methylene chloride The combined organic phases are washed with water, dried over sodium sulphate and evaporated in vacuo to give a residue in 150 ml of diisopropyl ether by trituration with 40.0 g (46%) of colorless crystals, m.p. 95 ° C.
^H-NMR (60 MHz, CDCl^) :cf = 1,3 miljoonasosaa (s, 9H) , 6,6 (s, 1H) 7,2 (AA1BB', 4H) , 8,0 (s, 1H) , 8,7 (s, 1H) .1 H-NMR (60 MHz, CDCl 3): cf = 1.3 ppm (s, 9H), 6.6 (s, 1H) 7.2 (AA1BB ', 4H), 8.0 (s, 1H) , 8.7 (s. 1H).
Esimerkki 11Example 11
Tert.-butyyli-((4-kloorifenyyli)-1,2,4-triatsolyylimetyyli)-sulfoksidi (yhdiste no. 31) .Tert-butyl - ((4-chlorophenyl) -1,2,4-triazolylmethyl) sulfoxide (Compound No. 31).
Liuokseen, jossa on 9,7 g tert.-butyyli-/(4-kloorifenyyli)- 1.2.4- triatsolyylimetyyli7-sulfidia 20 ml:ssa metyleenikloridia tiputetaan jäähauteessa liuos, jossa on 7,1 g 85-%:sta 3-kloori-perbentsoehappoa 70 ml:ssa metyleenikloridia. Sekoitetaan vielä kaksi tuntia 0°C:ssa kunnes ohutkalvokromatografiällä (Si02, metyleeni-kloridi/asetoni 7:3) sulfidi (R^, =0,57 ) ei enää ole näkyvissä ja vain molemmat sulfoksidin diastereomeerit ovat tunnistettavissa (Rp = 0,38 ja 0,20). Liuosta pestään, kunnes Cl2:n kehittyminen on loppunut, natriumvetykarbonaatin vesiliuoksella. Orgaanisen faasin vesipesun jälkeen tämä kuivataan, konsentroidaan ja kiinteä jäännös pestään pienellä määrällä eetteriä. Saadaan 7,0 g (67 %) värittömiä kiteitä, sp. 125-128°C.To a solution of 9.7 g of tert-butyl / (4-chlorophenyl) -1,2,4-triazolylmethyl-7-sulfide in 20 ml of methylene chloride is added dropwise in a ice bath a solution of 7.1 g of 85% 3-chloro perbenzoic acid in 70 ml of methylene chloride. Stir for a further two hours at 0 ° C until sulphide (Rf = 0.57) is no longer visible by thin layer chromatography (SiO 2, methylene chloride / acetone 7: 3) and only both diastereomers of the sulphoxide are identifiable (Rf = 0.38 and 0.20). The solution is washed until the evolution of Cl2 has ceased with aqueous sodium hydrogen carbonate solution. After washing the organic phase with water, this is dried, concentrated and the solid residue is washed with a small amount of ether. 7.0 g (67%) of colorless crystals are obtained, m.p. 125-128 ° C.
^"H-NMR (220 MHz, CDC13) : 1,10 ja 1,15 (kaksi s, lisäksi 9H) , 6,18 ja 6,24 (kaksi s, lisäksi 1H), 7,3-7,7 (m, 4K), 8,01 ja 8,07 (kaksi s, lisäksi 1H), 8,41 ja 8,51 (kaksi s, lisäksi 1H).1 H-NMR (220 MHz, CDCl 3): 1.10 and 1.15 (two s, additional 9H), 6.18 and 6.24 (two s, additional 1H), 7.3-7.7 ( m, 4K), 8.01 and 8.07 (two s, plus 1H), 8.41 and 8.51 (two s, plus 1H).
Esimerkki 12Example 12
Tert. -butyyli-/( 4-kloorif enyyli) -1,2,4ptriatsolyylimetyyli)_/-sulfoni (Yhdiste no 32).Tert. -butyl - [(4-chlorophenyl) -1,2,4-triazolylmethyl] -N-sulfone (Compound No. 32).
Liuokseen, jossa on 10,7 g tert.-butyyli-./'M-kloorifenyyli) - 1.2.4- triatsolyylimetyyli/-sulfoksidia 50 ml:ssa metyleenikloridia tiputetaan 20°C:ssa liuos, jossa on 7,3 g:aa 85-%:sta 3-klooriper-bentsoehappoa 100 ml:ssa metyleenikloridia. Ohutkerroskromarografiän (DC) tuloksen mukaan hapettuu vähemmän polaarinen sulfoksidi nopeammin, vasta huoneenlämpötilassa suoritetun pitemmän sekoituksen jälkeen voimakkaammin polaarinen sulfoksidi hapettuu myös. 18 tunnin kuluttua on DC:n mukaan (Si02, metyleenikloridi/asetoni 7:3) vaihto-reaktio loppunut. Sulfoni (R^, = 0,46) eristetään pesemällä liuos 20 64360 natriumvetykarbonaattiliuoksella ja vedellä, kuivaamalla ja väke-vöimällä orgaaninen faasi.To a solution of 10.7 g of tert-butyl (N-chlorophenyl) -1,2,4-triazolylmethyl / sulfoxide in 50 ml of methylene chloride at 20 ° C is added dropwise a solution of 7.3 g. 85% 3-chloroperbenzoic acid in 100 ml of methylene chloride. According to the result of thin layer chromatography (DC), the less polar sulfoxide oxidizes more rapidly, only after a longer stirring at room temperature does the more polar sulfoxide oxidize more strongly. After 18 hours, according to DC (SiO 2, methylene chloride / acetone 7: 3), the exchange reaction is complete. The sulfone (Rf = 0.46) is isolated by washing the solution with sodium bicarbonate solution and water, drying and concentrating the organic phase.
Pesemällä jäännös di-isopropyylieetterillä saadaan 8,7 g (77 %) värittömiä kiteitä, sp. 150°C.Washing of the residue with diisopropyl ether gives 8.7 g (77%) of colorless crystals, m.p. 150 ° C.
^H-NMR (220 MHz, XDCl^): cf 1,3 miljoonasosaa (s, 9H), 6,75 (s, 1H), 7,5 (AA'BB1, 4H), 8,03 (s, 1H), 8,84 (s, 1H).1 H-NMR (220 MHz, XDCl 3): δ 1.3 ppm (s, 9H), 6.75 (s, 1H), 7.5 (AA'BB1, 4H), 8.03 (s, 1H ), 8.84 (s, 1 H).
Esimerkki 13 4-kloorifenyyli-/' (4+-kloorifenyyli)-tetratsol-l-yyli)-metyy-li/-sulfidi ja 4-kloorifenyyli-/^'-kloorifenyyli)-(tetratsol-2-yyli)-metyyli/-sulfidi (yhdiste no. 15) .Example 13 4-Chloro-phenyl - ['(4 + -chloro-phenyl) -tetrazol-1-yl) -methyl] -sulfide and 4-chloro-phenyl- (4'-chloro-phenyl) - (tetrazol-2-yl) -methyl / sulfide (Compound No. 15).
Seokseen, jossa on 26,1 g tetratsolia ja 102 g 4-kloorifenyy-li-/~(4 '-kloorifenyyli) -kloorimetyyli/-sulfidia 3,5 l:ssa tolueenia, tiputetaan huoneenlämpötilassa 37,4 g trietyyliamiinia sekoittaen. Seosta kuumennetaan sitten 4 tuntia palautusjäähdyttäen. Liukenemattomat aineosat suodatetaan, suodos pestään vedellä, ja orgaaninen faasi kuivataan natriumsulfaatin päällä. Kun liuotin tislataan va-kuumissa, jää kiinteä jäännös, josta kiteytyy 50 ml:n di-isopropyy-lieetterilisäyksen jälkeen 74,7 g (67 %) kellertäviä kiteitä, sp. 104-106°C.To a mixture of 26.1 g of tetrazole and 102 g of 4-chlorophenyl- [(4'-chlorophenyl) -chloromethyl] sulfide in 3.5 l of toluene is added dropwise at room temperature 37.4 g of triethylamine with stirring. The mixture is then heated to reflux for 4 hours. The insoluble constituents are filtered off, the filtrate is washed with water and the organic phase is dried over sodium sulfate. Distillation of the solvent in vacuo left a solid residue which crystallized after the addition of 50 ml of diisopropyl ether to give 74.7 g (67%) of yellowish crystals, m.p. 104-106 ° C.
^H-NMR (60 MHz, CDCl^): /6,7-7,6 miljoonasosaa (m, 9H), 8,4 ja 8,9 (kaksi s, lisäksi 2H).1 H-NMR (60 MHz, CDCl 3): δ 6.7-7.6 ppm (m, 9H), 8.4 and 8.9 (two s, additional 2H).
Esimerkkejä muista kaavan I mukaisista yhdisteistä on annettu taulukossa no. 1.Examples of other compounds of formula I are given in Table no. 1.
Taulukko 1 21 64360Table 1 21 64360
Yhdiste R1 Hg At^amla " a3 SP. (°CCompound R1 Hg At ^ amla "a3 SP. (° C
1 <ÖV H N^S> 0 ~@) 132-13« \J_N V-/ .—« IR(Filmi): 2 H,C- K N /) 0 -<OVcl 1*495 , 1*470, -5 'i-N v=-/ 1270, 1192, 1131, 1088, 1007, 8}7, 666 en -1.1 <ÖV HN ^ S> 0 ~ @) 132-13 «\ J_N V- / .—« IR (Films): 2 H, C- KN /) 0 - <OVcl 1 * 495, 1 * 470, -5 'iN v = - / 1270, 1192, 1131, 1088, 1007, 8} 7, 666 en -1.
fr\ Ji /—\ IR(Filr.j), 3 H M 0 -CH,-(0) 3060, 3C20, 2 11492 , 1 '*50, ” 1271, 1190, 1131, 1008, 695, 677, ^ /—v 658 cm 1 ** Cl·©- H ^ 0 “\θ) 98 5 cl-©- H >Q 1 -© 131-139° » 6 Cl-(^y H 2 ^o) 215 7 Cl·©- H 0 -^5^-Cl 88 8 Cl-®- H .(C00H)2 0 85-87 9 Cl-^5^- H 0 ~(0)~Cl 62"61) 1° ajo)- H 1 -φ*ΐ 116-118° 11 Cl-©- H 2 “@^C1 1^7-150 12 ci-φ- H K^7j o -<Ö>ci 136-138 +) sulfoksidin diastereaneeriseos ++) kaikkien valmistettujen yhdisteiden rakenne on varmistettu ^H-NMR-spektrin avulla.fr \ Ji / - \ IR (Filr.j), 3 HM O -CH 2 - —V 658 cm 1 ** Cl · © - H ^ 0 “\ θ) 98 5 cl- © - H> Q 1 - © 131-139 °» 6 Cl - (^ y H 2 ^ o) 215 7 Cl · © - H 0 - ^ 5 ^ -Cl 88 8 Cl-®-H. (C00H) 2 0 85-87 9 Cl- ^ 5 ^ - H 0 ~ (0) ~ Cl 62 "61) 1 ° driving) - H 1 -φ * ΐ 116-118 ° 11 Cl- © - H 2 “@ ^ Cl 1 ^ 7-150 12 ci-φ- HK ^ 7j o - <Ö> ci 136-138 +) sulfoxide diastereaner mixture ++) the structure of all prepared compounds is confirmed by 1 H-NMR spectrum.
Taulukko 1 (jatkuu) 22 64360Table 1 (continued) 22 64360
Yhdiste R1 R2_Atsidisuola n_^_Sp. (°c) 13 Ci^g)- a '0 1 C1 1,7,1 11 C1^5> H 0 2 -<§>-0! 20.Compound R1 R2_Azide salt n _ ^ _ Sp. (° c) 13 Ci ^ g) - a '0 1 Cl 1,7,1 11 C1 ^ 5> H 0 2 - <§> -0! 20.
t M ) 15 Cl-©>- h 0 . Q4 o -<@K1 10.-106 16 Cl^ÖV h Λ . 0 1 110-1124°t M) 15 Cl- ©> - h 0. Q4 o - <@ K1 10.-106 16 Cl ^ ÖV h Λ. 0 1 110-1124 °
N—y ^N—' N-NN — y ^ N— 'N-N
17 01-/5V H Λ . 0’ 2 -@K1 123-12517 01- / 5V H Λ. 0 ’2 - @ K1 123-125
N-7 N “NN-7 N “N
I _ 18 C1"(C^“ H ^ 0 "^XCH3 150 t 19 Cl-^o)- H 1 ;^5^‘CH3 l!*7"lt,9++) f 20 cl"<§)“ H 1 *{0)*0Η3 15l'"155++*) » 21 ci^oy h 2 ko^h3 24,5 H _yC1 22 Cl •<Ö>- " <J 0 -<2λ°ι 107 i Cl 23 ci·®- H 0 -@ci 135-137I _ 18 Cl "(C ^" H ^ 0 "^ XCH3 150 t 19 Cl- ^ o) - H 1; ^ 5 ^ 'CH3 l! * 7" lt, 9 ++) f 20 cl "<§) “H 1 * {0) * 0Η3 15l '" 155 ++ *) »21 ci ^ oy h 2 ko ^ h3 24.5 H _yC1 22 Cl • <Ö> -" <J 0 - <2λ ° ι 107 i Cl 23 ci · ®- H 0 - @ ci 135-137
Cl · IRiFilniJ: 2*» C1“(0>- H C J 0 tert.-fautyy- ?Slo* 1362’, '—' '—N li 1212, 1152, 1096, ioen, 10*»3, 81»«, 787, 657cm"1 +) tetratsoli-isaneerien seos ++) sulfoksidien diasterearveerien seos +++) voimakkaanmin polaarinen sul f oksidi, kiteyttämällä puhdistettu dlastereaneerlsedksesta no. 19 liCl · IRiFilniJ: 2 * »C1“ (0> - HCJ 0 tert.-fautyy-? Slo * 1362 ',' - '' —N li 1212, 1152, 1096, ioen, 10 * »3, 81» «, 787, 657cm "1 +) mixture of tetrazole isomers ++) mixture of diastereesters of sulphoxides +++) more strongly polar sulphoxide, crystallized purified from dlastereaneerlsedks no. 19 li
Taulukko 1 (jatkuu) 23 64 360Table 1 (continued) 23 64 360
Yhdiste R1__AtsfrMsimla n_^_SP· ( C) t 25 Cl-@- H 0 ^Ö^OCK, ”6 26 Cl-®- H £ 2 >98 27 Cl -®- H Q 0 -™2<Ö)6> 57-58 ,—. N IR( Piiri); 28 Cl/oV H N 7) 0 etyyli 2965, 2925,Compound R1__AtsfrMsimla n _ ^ _ SP · (C) t 25 Cl - @ - H 0 ^ Ö ^ OCK, ”6 26 Cl-®- H £ 2> 98 27 Cl -®- HQ 0 - ™ 2 <Ö) 6> 57 -58, -. N IR (Circuit); 28 Cl / o H N 7) 0 ethyl 2965, 2925,
Nirl/ l*»90, 1271 , 1131, 1088*.Nirl / l * »90, 1271, 1131, 1088 *.
, 1010,675cm J, 1010,675cm J
/—\ ,/Ns Λ IR(Filmi); 29 ci-<0>- H n y 0 n-butyyli 29 ^ 5, 2920 *—« i486, 1268, 1127, 108HA1 1007,671cm ' /—v ^nn „ tert.- _e 30 Cl·©* h o 95 f ,—v -N tert.- 31 1 butyyli 125-128 t 32 ci-^oV H ^ 2 ΐ^Γ‘7. 150 \ZJ Ni_N butyyli • IR(Filni): /—v 305¾. lL'3°, 33 cl\oy H \ (! 0 aiiyyii 1003, 1270, *—N 1130, 1087, 1007, ./ - \, / Ns Λ IR (Movies); 29 ci- <0> - H ny 0 n-butyl 29 ^ 5, 2920 * - «i486, 1268, 1127, 108HA1 1007,671cm '/ - v ^ nn„ tert.- _e 30 Cl · © * ho 95 f , -V -N tert.- 31 1 butyl 125-128 t 32 c 1 H 2 H 2 N 2 O 7. 150 \ NJ Ni_N butyl • IR (Film): / —v 305¾. 10'3 °, 33 cl \ oy H \ (! 0 aiiyyii 1003, 1270, * -N 1130, 1087, 1007,.
• -t-ö-v-t- 672 cm -1 tGJTt 1“ 3*i Br-^y- H N^jj) 0 77-78 N tert.-• -t-ö-v-t- 672 cm -1 tGJTt 1 “3 * i Br- ^ y- H N ^ jj) 0 77-78 N tert.-
35 h 0 102-10U35 h 0 102-10U
f 36 »o@- H Λ o 73-75 .—. tert.- 37 02N-(O)- H 0 butyyli 76-78f 36 »o @ - H Λ o 73-75 .—. tert.- 37 02N- (O) -H 0 butyl 76-78
Diastereaneeriseos 24 64360Diastereaner mixture 24 64360
TaulukkoI (jatkuu)Table I (continued)
Yhdiste R1_R^_Atsidi (suola) n_R3_Sp. (°c) CH, _ 38 V|? ° tert.-butyyli 94 39 H H ύ ° Cl 47-^9 ΊΟ {θ)~ H N* "/) 0 ~(0) 91The compound R1_R ^ _Azide (salt) n_R3_Sp. (° c) CH, _ 38 V | ° tert-butyl 94 39 H H ύ ° Cl 47- ^ 9 ΊΟ (θ) ~ H N * "/) 0 ~ (0) 91
vi—NVI-N
s' Ci j!| /-Vs' Ci j! | / -V
*»1 <2/ H 1 \Q/ 70-88 ° "2 <Q>^ H νΛ 2 1«5 ^C1 li *3 (oy H M' > 0 tert.- 8¾ N butyyli ^ * Ό * ‘5«-.57‘> pre i j ^5 \Q/~ -h / ^ 2 tert.- 126 Ί- N butyyli /-\ M ^_>CF, IR(Filnd) :* »1 <2 / H 1 \ Q / 70-88 °" 2 <Q> ^ H νΛ 2 1 «5 ^ C1 li * 3 (oy HM '> 0 tert.- 8¾ N butyl ^ * Ό *' 5 «-.57 '> pre ij ^ 5 \ Q / ~ -h / ^ 2 tert.- 126 Ί- N-butyl / - \ M ^ _> CF, IR (Filnd):
'6 p- » Q « -™2^> U& iSS'6 p- »Q« - ™ 2 ^> U & iSS
1115, 1070 3 790, 625,1115, 1070 3 790, 625,
660 cm A660 cm A
ci £ cl\ ¢7 01\^7 H · (cooh)2 0 -CH2-^C^C1 ^3-135 *8 Cl ^Ö>- H νΛ> O -CK2^C1 101ci £ cl \ ¢ 7 01 \ ^ 7 H · (cooh) 2 0 -CH2- ^ C ^ C1 ^ 3-135 * 8 Cl ^ Ö> - H νΛ> O -CK2 ^ C1 101
Cl's. £ Cl “9 H 2 -CH2h(Q)u:1 195-197 *' DiastereomeeriseosCI's. E1 Cl2 -CH2h (Q) u: 1 195-197 * 'Diastereomeric mixture
Taulukko X (jatkuu) 25 64360Table X (continued) 25 64360
Yhdiste R1__Atsidi (suola) n_^_^P· ^ c ^ 50 01¾). H >»'j> 0 -Cl!,-<§)ci 82-8» 51 01¾). « (]}' * Ö ' '^λΙ^1 ^-110° 52 01^)- H * t(% 2 -CH2^gKl 100-105Compound R1__Azide (salt) n _ ^ _ ^ P · ^ c ^ 50 01¾). H> »'j> 0 -Cl!, - <§) ci 82-8» 51 01¾). «(]} '* Ö' '^ λΙ ^ 1 ^ -110 ° 52 01 ^) - H * t (% 2 -CH2 ^ gKl 100-105
r-SCl Nr-SCl N
53 (OV H n' > o tert.-butyyli 97-9? ^ci '—' « 54 Λ-<α1 h /% o tert.-bu tyyli 110-112 (pr '—^ci 55 \Ql/ H ΐΛ) 0 tert.-butyyli 112-115 (O/* <ö> Ji o 56 ?oV~ H 1 tert.-butyyli 122-127 ' (¾ 57 <0>- H /**> 2 tert.-butyyli 180-18353 (OJ H n '> o tert-butyl 97-9? ^ Ci' - '«54 Λ- <α1 h /% o tert.-butyl 110-112 (pr' - ^ ci 55 \ Ql / H ΐΛ) 0 tert-butyl 112-115 (O / * <ö> Ji o 56? oV ~ H 1 tert-butyl 122-127 '(¾ 57 <0> - H / **> 2 tert-butyl 180-183
i-Ni-n
58 Cl <öf H Ö 0 ~^cl 128 59 01^ H Φ 0 -<2^C1 ,,8-15°58 Cl <öf H Ö 0 ~ ^ cl 128 59 01 ^ H Φ 0 - <2 ^ C1 ,, 8-15 °
Ci ACi A
60 Cl-^ H Mj 0 -CH2-(0)ci 105 +) Diastereomeeriseos60 Cl- ^ H Mj 0 -CH2- (O) ci 105 +) Diastereomeric mixture
Taulukko I (jatkuu) 26 64360Table I (continued) 26 64360
Yhdiste R1__Atsidi (suola) n_r3_Sp. (°c) 61 Cl-^5^- H 0 “CH2'^)'C1 120-125 62 Cl k A 1 -CH2i^>.Cl 125-131° 63 C1-<Q>- H 2 -CH^Cl I63-I65 WC1 N- C1v 64 C1-\0/ H f ^ 0 "CH2'<(Ö}-C1 132-133 65 ci-(o)- H o tert.-butyyli 95-97 .d Λ 66 Cl/oV- H N^‘% 0 -CH, 66-88 \_y \L_N 3 _ci ;} 67 C1-(Q>- H /j? 0 95-97 « χΝ. /—\ IR (Filmi) cm-1 68 CH.-O-C- .H N y 0 ~\0) 2950, 1748, ^ i— N ' 1433, 1260, 1196, 1128, 994, 746, 689, 672 t 69 n-heksyyli H Λ o -<Ö>-C1 2850, 1490, 1471, 1270, 1132, 1089, .1008, 818, , 674 cm~l 70 n-butyyli H n' > O “(oVcl IR(Filmi): 'i—K 2950, 2920, 1496-, 1472, 1270, 1132, 1089, 1008, 8l8,672cm_1 +) DiastereaneeriseosCompound R1__Azide (salt) n_r3_Sp. (° c) 61 Cl- ^ 5 ^ - H 0 (CH2 '^)' C1 120-125 62 Cl k A 1 -CH2i ^> Cl 125-131 ° 63 C1- <Q> - H 2 -CH ^ Cl I63-I65 WC1 N-C1v 64 C1- \ 0 / H f ^ 0 "CH2 '<(Ö} -C1 132-133 65 ci- (o) -H o tert-butyl 95-97 .d Λ 66 Cl / oV- HN ^ '% 0 -CH, 66-88 \ _y \ L_N 3 _ci;} 67 C1- (Q> - H / j? 0 95-97 «χΝ. / - \ IR (Film) cm- 188 CH.-OC- .HN y 0 ~ \ 0) 2950, 1748, ^ i— N '1433, 1260, 1196, 1128, 994, 746, 689, 672 t 69 n-hexyl H Λ o - <Ö > -C1 2850, 1490, 1471, 1270, 1132, 1089, .1008, 818,, 674 cm-70 n-butyl H n '> O "(oVcl IR (Film):' i-K 2950, 2920, 1496-, 1472, 1270, 1132, 1089, 1008, 8l8,672cm_1 +) Diastereaner mixture
Taulukko I (jatkuu) 27 6 4 3 6 0Table I (continued) 27 6 4 3 6 0
Yhdiste R1 R2 Atsidi(suola) n R"5 Sp, t 71 n-butyyli H n'% 2 n-pentyyli 69_71Compound R1 R2 Azide (salt) n R "5 Sp, t 71 n-butyl H n '% 2 n-pentyl 69_71
t_Nt_N
72 H3C- H3C- Ö 0 -^)-C1 v M _ IR(Filni) : ” }- H Ό ° -@^ci »n: ^ 1130, 1050, 1007, 815, 673 cm 1 N IRtRiimi) : 74 etyyli H n' > 0 n-propyyli f?|§' ^70,’ N 1192! 1133, 1C03, §17, 675 cm 1 , IR(Filmi): N . 295^ 2°25 75 n-butyyli h n'' ^ O n-pentyyli ^αβό', 1^96’ Ι-n 1460, 1271, 1190, 1133, 1008, _1 677 cm , IR(Filmi): . Ί . A UIT 2955> 2925> 7 6 n-pentyyli h N > 0 n-heksyyli 2860, 1497, vt-N 1460, 1272, 1192, 1135, 1012, , 678 cm 77 h- k ö 0 -«“s·^)*·· ^-45 • Ä C1>_ 78 H- H 0 -CH2-<^^C1 68-70 i CV-<C1 79 H- H 0 -CH2~(oV 60-63 N ciN ^72 H3C- H3C- (O 0 - ^) - C1 v M _ IR (Filni): "} - H Ό ° - @ ^ ci» n: ^ 1130, 1050, 1007, 815, 673 cm-1 ethyl H n '> 0 n-propyl f? | §' ^ 70, 'N 1192! 1133, 1CO 3, §17, 675 cm -1, IR (Film): N. 295 ^ 2 ° 25 75 n-butyl h n '' ^ O n-pentyl ^ αβό ', 1 ^ 96' Ι-n 1460, 1271, 1190, 1133, 1008, -1677 cm -1, IR (Film):. Ί. A UIT 2955> 2925> 7 6 n-pentyl h N> 0 n-hexyl 2860, 1497, vt-N 1460, 1272, 1192, 1135, 1012,, 678 cm 77 h- k ö 0 - «“ s · ^ ) * ·· ^ -45 • Ä C1> _ 78 H- H 0 -CH2 - <^^ C1 68-70 i CV- <C1 79 H- H 0 -CH2 ~ (oV 60-63 N ciN ^
Taulukko I (jatkuu) 28 64 36 0Table I (continued)
Yhdiste r1 r2 Atsidi(suo- n R3 ςη (°c) _La)_?P* 8° H ° 10C"103 31 “ ö 1 Ά _/C1 ^ tert 82 \y)~ H ιζ**Ίΐ 2 butyyli 164-165 'ci ' 83 n-butyyli H 0 ίϊ^ϊ*·Η iH(Filni) : ^ 'L.H butyyli 2953, 1459, 13-:4, 1272, 1190, 1153, 1134, _t 1010, 677 en 84 i-butyyli H Λ o IR(Flln i) : \_N butyyli 2962, 2662, 1494, 1457, 1364, 1270, 1189, 1157, 1132, 1007, 675 cm 85 i-butyyli h ΐζ1^ 0 -^Q^-Cl 45-46 86 i-butyyli H 1 ~(Ö)-C1 110-112 87 i-butyyli H nQ 2 i4o-i4i 64360Compound r1 r2 Azide (vein R3 ςη (° c) _La) _? P * 8 ° H ° 10C "103 31“ ö 1 Ά _ / C1 ^ tert 82 \ y) ~ H ιζ ** Ίΐ 2 butyl 164 -165 'ci' 83 n-butyl H 0 ίϊ ^ ϊ * · Η iH (Filni): ^ 'LH butyl 2953, 1459, 13-: 4, 1272, 1190, 1153, 1134, _t 1010, 677 en 84 i -butyl H Λ o IR (Fnn i): N-butyl 2962, 2662, 1494, 1457, 1364, 1270, 1189, 1157, 1132, 1007, 675 cm-85 i-butyl h ΐζ1 ^ 0 - ^ Q ^ -Cl 45-46 86 i-butyl H 1 ~ (Ö) -C1 110-112 87 i-butyl H nQ 2 i4o-i4i 64360
Taulukko I (jatkuu) 29Table I (continued) 29
Yhdiste r1 r2 Atsidi(suola) n__Sp. (°o) .CH, j—K 3 Λ tert.- 88 {äy H' \jH 0 fcutyyii 98-ioi 89 <ö£3 - 0 ° Sii 93·55 90 3- heptyyli H τζ^7) 0 /o\ci iR(Piimi): L.N N-f 295a, 2°22.Compound r1 r2 Acid (salt) n__Sp. (° o) .CH, j — K 3 Λ tert.- 88 {äy H '\ jH 0 fcutyyii 98-ioi 89 <ö £ 3 - 0 ° Sii 93 · 55 90 3-heptyl H τζ ^ 7) 0 / o \ ci iR (Milk): LN Nf 295a, 2 ° 22.
1^72, 1269, 1131, 1088, 1008, 819, , 673 cm'* 91 ci<OV H MfN/) 0 3-metyyli- IR(Filmi): *—n butyvli 2962, 1^89, yy 1271, 1130, 1088, 1012, _1 p 676 cm 92 <Ö)- H 0 <ö> Cl 105-107 ,—, λ tert.- 93 (O)- H ^ 0 butyyli 106“1031 72, 1269, 1131, 1088, 1008, 819,, 673 cm -1 * OJ H MfN 3 O 3 -methyl-IR (Film): * -butyl 2962, 1 899, yy 1271, 1130, 1088, 1012, _1 p 676 cm 92 <Ö) - H 0 <ö> Cl 105-107, -, λ tert.- 93 (O) -H ^ 0 butyl 106 “103
FjC f tert.- 94 /qV h Ö 0 ^1^11 « H Ö 0 ra 85'97FjC f tert.- 94 / qV h Ö 0 ^ 1 ^ 11 «H Ö 0 ra 85'97
.,CN., CN
96 <5)- H Ö 1I0'112 97 <ö^- H >Q 0 9*-?5 /-ccl 98 (öy H o etyyli 59-61 99 <^Ö^- H 2 etyyli 103-10* 3096 <5) - H Ö 1'0'112 97 <ö ^ - H> Q 0 9 * -? 5 / -ccl 98 (öy H o ethyl 59-61 99 <^ ^ ^ - H 2 ethyl 103-10 * 30
Taulukko I (jatkuu) 6 4 3 6 0Table I (continued) 6 4 3 6 0
Yhdiste Rl R2 Atsidi (suola) n R3' Sp. /Oc, 100 (o). H Λ o n_butyyli IM Filmy.Compound R1 R2 Azide (salt) n R3 'Sp. / Oc, 100 (o). H Λ o n_butyl IM Filmy.
\—/ 'L.N 2958, 2928 , l4o4, 1274, 1132, 1008, .L.- 2958, 2928, 1440, 1274, 1132, 1008,.
Cl 748, 678 cm 101 /nV H o n-heksyyli iR(Filmi):Cl 748, 678 cm 101 / nV H o n -hexyl iR (Film):
XlJ 2955, 2923, 1491, 1271, 1129, 1007, < ,C1 ( 744, 675 era 102 <ö> H Q 0 _ch2^p) 96-93 103 (Q)~ H n(j! 2 _CH2^\5/ /Cl 104 (p)~ H ° -CH2-CH2^2^ 58-61 /Cl 105 (py H 2 -CH2-CH2-<g> 129-130 ,C1 106 ci-^Cy- H 0 ^p)~zl 108-110 CV\ 107 H H t(*jj o -\Oy-Cl 84-37XlJ 2955, 2923, 1491, 1271, 1129, 1007, <, C1 (744, 675 er 102 <ö> HQ 0 _ch2 ^ p) 96-93 103 (Q) ~ H n (j! 2 _CH2 ^ \ 5 / / Cl 104 (p) ~ H 0 -CH 2 -CH 2 ^ 2 ^ 58-61 / Cl 105 (py H 2 -CH 2 -CH 2 - <g> 129-130, C1 106 ci- ^ Cy- H 0 ^ p) ~ zl 108-110 CV \ 107 HH t (* jj o - \ Oy-Cl 84-37
Cl 108 h H 1 KOVci 152-155 'L.N '—fCl 108 h H 1 KOVci 152-155 'L.N' —f
Cl 109 H H 2 -^0^>-Cl /^3 110 (ny H . HC1 0 tert.- 163-170 \r/ f butyyli m » Ö· HC1 0 n-butyyli 136-139 * 31Cl 109 H H 2 - ^ 0 ^> - Cl / ^ 3 110 (ny H. HCl 0 tert.- 163-170 tert-butyl m »Ö · HCl 0 n-butyl 136-139 * 31
Taulukko I (jatkuu) 64 360Table I (continued) 64 360
Yhdiste H1 R2 Atsidi (suola) n R3 Sp. (°c) yCl 112 (oy H iQ . HCl 0 -CH2-CH2-/o^) 1^5-155 113 P"(ö^· H 0 "“(o)"01 90-92 Π» F© K ,Q 0 © Cl 119-120 ,C1 115 (2/ h ö 0 69-71 s Cl 116 (2/ H lQ 0 ^(2)^01 i3i·*136 ,C1 117 ^OV H Λ 0 tert.- iR(?iiai): \—t «-« butyyli 3098, 2950, 1^63, 1211, 1153, 1002, 1040, 739, _« .Cl ^ 657 en 118 Cl.©. H »{j» 2 940 .Ci /—\ h tert.- 119 C1H\2/ H ö 2 i 53-156 120 <Ö> ” 0 W'U5 /CH, >2' <ö> « Ö 2 SSil 160-162 32 64360Compound H1 R2 Azide (salt) n R3 Sp. (° c) yCl 112 (oy H iQ. HCl O -CH2-CH2- / o ^) 1 ^ 5-155 113 P "(? ^ · H 0" “(o)" 01 90-92 Π »F © K, Q 0 © Cl 119-120, Cl 115 (2 / h δ 0 69-71 s Cl 116 (2 / H 10 Q 0 ^ (2) ^ 01 i3i · * 136, C1 117 ^ OV H Λ 0 tert. - iR (? iiai): n-butyl 3098, 2950, 1 ^ 63, 1211, 1153, 1002, 1040, 739, _ «.Cl ^ 657 and 118 Cl. ©. H» {j »2 940 .Ci / - \ h tert.- 119 C1H \ 2 / H ö 2 i 53-156 120 <Ö> ”0 W'U5 / CH,> 2 '<ö>« Ö 2 SSil 160-162 32 64360
Taulukko I (jatkuu)Table I (continued)
Yhdiste Rl r2 Atsidi (suola) n R3 Sp '°c) vcl 122 <0> H ζΚ 2 tert·" 113-U6 >—' bu tyyli zcl 123 H fÖ 2 ^Ö)-C1 155-158 C/—\ IH(Filmi) : h 0 -< 0>C1 2956 , 2922, ({ N-/ 1 972 , 1968 , 1168, 1090, 1009, 817, rv » 61)7 cm *Compound R1 r2 Acid (salt) n R3 Sp '° c) vcl 122 <0> H ζΚ 2 tert · "113-U6> -' bu style zcl 123 H fÖ 2 ^ Ö) -C1 155-158 C / - \ 1H (Film): h 0 - <0> C1 2956, 2922, ({N- / 1 972, 1968, 1168, 1090, 1009, 817, rv »61) 7 cm *
.3 /K.3 / K
125 CH3-C-CH2- H // 0 -/O Vei 33-86 CHj U_N '—' CH3 >1 126 CH^C-CHg H 0 4? - 51 CH-j »125 CH3-C-CH2- H // 0 - / O Vei 33-86 CHj U_N '-' CH3> 1 126 CH ^ C-CHg H 0 4? - 51 CH »
NOF
127 (O)- H ^ o -<Oy-c: 89 - 90127 (O) -H 2 O - <Oy-c: 89-90
Cl /-< r~\ IH(Fllmi) : 128 Cl-(O)- H \\ // 0 -CHp-(0)-Cl 3103, 1586, '—f '“N d \—f 1953, 1373, 1217, 1090, 1067, 1048, 1012, 825, 659 cm 1‘Cl / - <r ~ \ 1H (Fllmi): 128 Cl- (O) - H \\ // O -CHp- (0) -Cl 3103, 1586, '—f' “N d \ —f 1953, 1373 , 1217, 1090, 1067, 1048, 1012, 825, 659 cm 1 '
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772735314 DE2735314A1 (en) | 1977-08-05 | 1977-08-05 | ALPHA-AZOLYL SULPHIDES AND THEIR DERIVATIVES |
DE2735314 | 1977-08-05 |
Publications (3)
Publication Number | Publication Date |
---|---|
FI782403A FI782403A (en) | 1979-02-06 |
FI64360B true FI64360B (en) | 1983-07-29 |
FI64360C FI64360C (en) | 1983-11-10 |
Family
ID=6015701
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FI782403A FI64360C (en) | 1977-08-05 | 1978-08-04 | SOM FUNGICIDER ANVAENDBARA ALKYL- OCH ARYLSUBSTITUERADE ALFA-AZOLYLMETYLSULFIDER |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0000752B1 (en) |
JP (1) | JPS5430174A (en) |
AT (1) | AT360279B (en) |
CA (1) | CA1112647A (en) |
CS (1) | CS200238B2 (en) |
DD (1) | DD137525A5 (en) |
DE (2) | DE2735314A1 (en) |
DK (1) | DK145597C (en) |
FI (1) | FI64360C (en) |
HU (1) | HU180205B (en) |
IL (1) | IL55241A (en) |
IT (1) | IT1107959B (en) |
PL (1) | PL107615B1 (en) |
SU (1) | SU795436A3 (en) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2821829A1 (en) * | 1978-05-19 | 1979-11-22 | Basf Ag | MEANS OF REGULATING PLANT GROWTH |
DE3100260A1 (en) * | 1981-01-08 | 1982-08-05 | Basf Ag, 6700 Ludwigshafen | SUBSTITUTED AZOLYL-GLYCOLSULFONATES, THESE FUNGICIDES CONTAINING THEM AND METHOD FOR THE PRODUCTION THEREOF |
DE3279417D1 (en) * | 1981-03-18 | 1989-03-09 | Ici Plc | Triazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them |
ATE30322T1 (en) * | 1982-04-01 | 1987-11-15 | Schering Agrochemicals Ltd | HETEROCYCLIC FOGICIDES AND GROWTH REGULATORS COMPOUNDS AND COMPOSITIONS CONTAINING THEM. |
US4517194A (en) * | 1982-06-25 | 1985-05-14 | Ciba-Geigy Corporation | Azolylmandelic acid derivatives and use thereof for controlling microorganisms |
US4701463A (en) * | 1982-08-13 | 1987-10-20 | The Dow Chemical Company | Pyridyl (pyridyloxy or pyriolylthio) azolomethanes |
US4728657A (en) * | 1982-08-13 | 1988-03-01 | The Dow Chemical Company | Aryl(aryloxy or arylthio)azolomethanes |
US4717734A (en) * | 1982-08-13 | 1988-01-05 | The Dow Chemical Company | Aryl(aryloxy or arylthio)azolomethanes and their use as pesticides |
US4720502A (en) * | 1982-08-13 | 1988-01-19 | The Dow Chemical Company | Aryl(aryloxy or arylthio)azolomethanes and their use as pesticides |
US4636514A (en) * | 1982-08-13 | 1987-01-13 | The Dow Chemical Company | Aryl(aryloxy or arylthio)azolomethanes |
US4717732A (en) * | 1982-08-13 | 1988-01-05 | The Dow Chemical Company | Aryl(aryloxy or arylthio)azolomethanes and their use as pesticides |
US4701207A (en) * | 1982-08-13 | 1987-10-20 | The Dow Chemical Company | Phenyl (phenoxy or phenylthio) azolomethanes |
US4716174A (en) * | 1982-08-13 | 1987-12-29 | The Dow Chemical Company | Aryl(aryloxy or arylthio)azolomethanes and their use as pesticides |
US4717733A (en) * | 1982-08-13 | 1988-01-05 | The Dow Chemical Company | Aryl(aryloxy or arylthio)azolomethanes and their use as pesticides |
US4731372A (en) * | 1982-08-13 | 1988-03-15 | The Dow Chemical Company | Aryl(aryloxy or arylthio) azolomethanes, and their use as pesticides |
DK348883A (en) * | 1982-08-13 | 1984-02-14 | Dow Chemical Co | ARYL (ARYLOXY OR ARYLTHIO) AZOLOMETHANES, THEIR PREPARATION AND USE |
US4505919A (en) * | 1982-10-09 | 1985-03-19 | Pfizer Inc. | Antifungal S-arylmethyl- and S-heterocyclylmethyl ethers of 2-aryl-3-mercapto-1-(1H-1,2,4-triazol-1-yl) propan-2-ols |
GB8326210D0 (en) * | 1983-09-30 | 1983-11-02 | Fbc Ltd | Azole compounds |
PH23251A (en) * | 1985-03-18 | 1989-06-16 | Sds Biotech Corp | Propionate derivative and nonmedical fungicide containing the same |
US4749713A (en) * | 1986-03-07 | 1988-06-07 | Ciba-Geigy Corporation | Alpha-heterocycle substituted tolunitriles |
US4978672A (en) * | 1986-03-07 | 1990-12-18 | Ciba-Geigy Corporation | Alpha-heterocyclc substituted tolunitriles |
US4937250A (en) * | 1988-03-07 | 1990-06-26 | Ciba-Geigy Corporation | Alpha-heterocycle substituted tolunitriles |
FR2677983B1 (en) * | 1991-06-24 | 1995-03-03 | Oreal | ALKYLTHIOPOLY (ETHYLIMIDAZOLIUM) COMPOUNDS, PROCESS FOR THE PREPARATION THEREOF AND THEIR USE AS BIOCIDAL AGENTS. |
GB0108592D0 (en) * | 2001-04-05 | 2001-05-23 | Merck Sharp & Dohme | Therapeutic agents |
CN100562516C (en) * | 2001-12-27 | 2009-11-25 | 第一制药株式会社 | Amyloid-beta produces and the excretory inhibitor |
EP1640366A4 (en) | 2003-06-30 | 2009-05-13 | Daiichi Seiyaku Co | Heterocyclic methyl sulfone derivative |
US7314875B2 (en) * | 2004-04-13 | 2008-01-01 | Cephalon, Inc. | Tricyclic aromatic and bis-phenyl sulfinyl derivatives |
-
1977
- 1977-08-05 DE DE19772735314 patent/DE2735314A1/en active Pending
-
1978
- 1978-07-28 IL IL55241A patent/IL55241A/en unknown
- 1978-07-28 DE DE7878100538T patent/DE2860325D1/en not_active Expired
- 1978-07-28 EP EP78100538A patent/EP0000752B1/en not_active Expired
- 1978-07-31 CA CA308,484A patent/CA1112647A/en not_active Expired
- 1978-08-01 IT IT50557/78A patent/IT1107959B/en active
- 1978-08-02 CS CS785091A patent/CS200238B2/en unknown
- 1978-08-02 DD DD20708978A patent/DD137525A5/en unknown
- 1978-08-03 PL PL1978208828A patent/PL107615B1/en unknown
- 1978-08-03 SU SU782646293A patent/SU795436A3/en active
- 1978-08-04 HU HU78BA3683A patent/HU180205B/en unknown
- 1978-08-04 AT AT568678A patent/AT360279B/en active
- 1978-08-04 JP JP9469478A patent/JPS5430174A/en active Pending
- 1978-08-04 DK DK345678A patent/DK145597C/en active
- 1978-08-04 FI FI782403A patent/FI64360C/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EP0000752A2 (en) | 1979-02-21 |
PL107615B1 (en) | 1980-02-29 |
DE2860325D1 (en) | 1981-03-12 |
IL55241A0 (en) | 1978-09-29 |
FI782403A (en) | 1979-02-06 |
IT1107959B (en) | 1985-12-02 |
FI64360C (en) | 1983-11-10 |
ATA568678A (en) | 1980-05-15 |
IT7850557A0 (en) | 1978-08-01 |
CS200238B2 (en) | 1980-08-29 |
JPS5430174A (en) | 1979-03-06 |
CA1112647A (en) | 1981-11-17 |
IL55241A (en) | 1982-01-31 |
EP0000752B1 (en) | 1981-01-14 |
PL208828A1 (en) | 1979-05-21 |
AT360279B (en) | 1980-12-29 |
DK145597C (en) | 1983-08-15 |
DK145597B (en) | 1982-12-20 |
DD137525A5 (en) | 1979-09-12 |
EP0000752A3 (en) | 1979-04-04 |
SU795436A3 (en) | 1981-01-07 |
HU180205B (en) | 1983-02-28 |
DE2735314A1 (en) | 1979-02-22 |
DK345678A (en) | 1979-02-06 |
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Legal Events
Date | Code | Title | Description |
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MM | Patent lapsed |
Owner name: BASF AG |