DE3309466A1 - PYRIDINE AND PYRAZINE DERIVATIVES - Google Patents
PYRIDINE AND PYRAZINE DERIVATIVESInfo
- Publication number
- DE3309466A1 DE3309466A1 DE19833309466 DE3309466A DE3309466A1 DE 3309466 A1 DE3309466 A1 DE 3309466A1 DE 19833309466 DE19833309466 DE 19833309466 DE 3309466 A DE3309466 A DE 3309466A DE 3309466 A1 DE3309466 A1 DE 3309466A1
- Authority
- DE
- Germany
- Prior art keywords
- oxide
- pyrazinyl
- compounds
- acetophenone
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical class C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000004480 active ingredient Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- -1 O-substituted hydroxylamine Chemical class 0.000 claims description 16
- 238000009472 formulation Methods 0.000 claims description 9
- 241000233866 Fungi Species 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000417 fungicide Substances 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 230000000855 fungicidal effect Effects 0.000 claims description 5
- 238000003898 horticulture Methods 0.000 claims description 5
- 125000001475 halogen functional group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000003216 pyrazines Chemical class 0.000 claims description 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000002270 dispersing agent Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 241000221785 Erysiphales Species 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000004495 emulsifiable concentrate Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- CKPCAYZTYMHQEX-JXAWBTAJSA-N (z)-1-(2,4-dichlorophenyl)-n-methoxy-2-pyridin-3-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=N/OC)\CC1=CC=CN=C1 CKPCAYZTYMHQEX-JXAWBTAJSA-N 0.000 description 2
- CGZQCZNRBCLEOH-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-2-pyridin-3-ylethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)CC1=CC=CN=C1 CGZQCZNRBCLEOH-UHFFFAOYSA-N 0.000 description 2
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960004029 silicic acid Drugs 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LNTHQBNSXNQPPZ-UXBLZVDNSA-N (ne)-n-[[4-(methoxymethyl)cyclohexa-1,4-dien-1-yl]methylidene]hydroxylamine Chemical compound COCC1=CCC(\C=N\O)=CC1 LNTHQBNSXNQPPZ-UXBLZVDNSA-N 0.000 description 1
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- KUZOAJKWVPACQX-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-2-pyrazin-2-ylethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)CC1=CN=CC=N1 KUZOAJKWVPACQX-UHFFFAOYSA-N 0.000 description 1
- MJUZRRQGMFPACE-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-n-ethoxy-2-pyrazin-2-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=NOCC)CC1=CN=CC=N1 MJUZRRQGMFPACE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
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- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
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- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
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- 239000013543 active substance Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JIJAYWGYIDJVJI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate Chemical class C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 JIJAYWGYIDJVJI-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- ZBBGAUHWTZKKQQ-UHFFFAOYSA-N ethyl 2,4-dichlorobenzoate Chemical compound CCOC(=O)C1=CC=C(Cl)C=C1Cl ZBBGAUHWTZKKQQ-UHFFFAOYSA-N 0.000 description 1
- RPWXYCRIAGBAGY-UHFFFAOYSA-N ethyl 2-pyridin-3-ylacetate Chemical compound CCOC(=O)CC1=CC=CN=C1 RPWXYCRIAGBAGY-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XNXVOSBNFZWHBV-UHFFFAOYSA-N hydron;o-methylhydroxylamine;chloride Chemical compound Cl.CON XNXVOSBNFZWHBV-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- SPUACDWLOLSOQO-UHFFFAOYSA-M methoxyazanium;chloride Chemical compound [Cl-].CO[NH3+] SPUACDWLOLSOQO-UHFFFAOYSA-M 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NUXCOKIYARRTDC-UHFFFAOYSA-N o-ethylhydroxylamine;hydron;chloride Chemical compound Cl.CCON NUXCOKIYARRTDC-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000151 polyglycol Chemical class 0.000 description 1
- 239000010695 polyglycol Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-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
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
β β *β β *
DipHng. Reiner F. Meyer-Roxlau ::··..: : ·...··. . ο ο η ο / c £> DipHng. Reiner F. Meyer-Roxlau :: ·· ..:: · ... ··. . ο ο η ο / c £>
öGOO München i»O .:.*„.· *..*·..* ·..**..* O O U D q. D OÖGOO Munich i »O.:. *„. · * .. * · .. * · .. ** .. * O O U D q. D O
Lucfle-Grahn-Str. 22, iel. (OaS?) 472947 *~ -5 -Lucfle-Grahn-Str. 22, iel. (OaS?) 472947 * ~ -5 -
F.Hoffmann-La Roche & Co. Aktiengesellschaft,Basel/SchweizF. Hoffmann-La Roche & Co. Aktiengesellschaft, Basel / Switzerland
1 6. MSiz 19831 6th MSiz 1983
RAN 6103/23RAN 6103/23
10 _ Pyridin- und Pyrazin-Derivate 10 _ Pyridine and Pyrazine Derivatives
15 Die Erfindung betrifft Verbindungen der allgemeinen FormelThe invention relates to compounds of the general formula
N
20 OR4 N
20 OR 4
worin R 2-Halo-, 4-Halo- oder 2,4-Dihaiο-phenyl,wherein R 2-halo-, 4-halo- or 2,4-dihaiο-phenyl,
2
R 3-Pyridyl-l-oxid, 2-Pyrazinyl-l-oxid,2
R 3-pyridyl-1-oxide, 2-pyrazinyl-1-oxide,
2-Pyrazinyl-4-oxid oder 2-Pyrazinyl-l,4-25 dioxid,2-pyrazinyl-4-oxide or 2-pyrazinyl-1,425 dioxide,
R Wasserstoff oder geradkettiges C, .-Alkyl und R C^__g-Alkyl, G3_g-Cycloalkyl, C3_g-Alkenyl R is hydrogen or straight-chain C 1 -alkyl and R C ^ __ g-alkyl, G 3 _g-cycloalkyl, C 3 _ g -alkenyl
oder C3 --Alkinyl bedeuten,or C 3 - alkynyl,
und Säureadditionssalze dieser Verbindungen. 30and acid addition salts of these compounds. 30th
Die Verbindungen der Formel I und deren Säureadditionssalze besitzen fungizide Eigenschaften und eignen sich als fungizide Wirkstoffe, insbesondere zur Verwendung in der Landwirtschaft und im Gartenbau. 35The compounds of the formula I and their acid addition salts have fungicidal properties and are suitable as fungicidal active ingredients, in particular for use in agriculture and horticulture. 35
Pa/13.1.83Pa / 1/13/83
* Μ»* Μ »
Die Erfindung betrifft ferner ein Verfahren zur Herstellung der Verbindungen der Formel I und ihrer Säureadditionssalze, Verbindungen der Formel I und Säureadditionssalze davon als fungizide Wirkstoffe, fungizide Mittel, die Verbindungen der Formel I oder Säureadditionssalze davon als Wirkstoffe enthalten, sowie die Verwendung solcher Verbindungen, Säureadditionssalze und Mittel zur Bekämpfung von Pilzen in der Landwirtschaft und im Gartenbau.The invention also relates to a process for the preparation of the compounds of the formula I and their acid addition salts, Compounds of the formula I and acid addition salts thereof as fungicidal active ingredients, fungicidal agents, the Compounds of the formula I or acid addition salts thereof as active ingredients, and the use of such compounds, Acid addition salts and agents for combating fungi in agriculture and horticulture.
Der Ausdruck "Halo" in der Definition der Formel I umfasst Fluor, Chlor, Brom und Jod, wobei Chlor bevorzugt ist.The term “halo” in the definition of formula I includes fluorine, chlorine, bromine and iodine, with chlorine being preferred is.
Die Halogenatome im Rest R in der Bedeutung 2,4-Dihalo-phenyl können gleich oder verschieden sein.The halogen atoms in the radical R, which means 2,4-dihalophenyl, can be identical or different.
Die Ausdrücke "C1-6-AIkYl", "C3_6-Alkenyl" und "C3-6-Alkinyl" umfassen sowohl geradkettige als auch verzweigte Kohlenwasserstoffreste. Unter Alkyl sind .je nach Anzahl der Kohlenstoffatome z.B. folgende Gruppen zu verstehen: Methyl, Aethyl, n-Propyl, Isopropyl, n-Butyl, tert.Butyl, Isoamyl und n-Hexyl.The terms "C 1-6 -alkyl" include "C 3 _ 6 alkenyl" and "C 3-6 alkynyl" includes both straight and branched chain hydrocarbon radicals. Alkyl is to be understood as meaning, depending on the number of carbon atoms, for example the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isoamyl and n-hexyl.
4
R in der Bedeutung C-. _,-Alkyl, C-,_---Alkenyl bzw.
C-jg-Alkinyl ist vorzugsweise C1-4-AIkYl, C,- oder C.-Alkenyl
bzw. C-,- oder C.-Alkinyl. Eine besonders bevorzugte Alkenyl-
bzw. Alkinylgruppe ist die Allyl- bzw. Propargylgruppe.4th
R means C-. _, - alkyl, C -, _--- alkenyl or C 1-4 alkynyl is preferably C 1-4 -alkYl, C, - or C.-alkenyl or C-, - or C.-alkynyl. A particularly preferred alkenyl or alkynyl group is the allyl or propargyl group.
R bedeutet vorzugsweise 4-Chlorphenyl oder 2,4-Dichlorphenyl, insbesondere die letztere Gruppe.R preferably denotes 4-chlorophenyl or 2,4-dichlorophenyl, especially the latter group.
R bedeutet vorzugsweise Wasserstoff, Methyl oder Aethyl, insbesondere Wasserstoff.R preferably denotes hydrogen, methyl or ethyl, in particular hydrogen.
Eine besonders bevorzugte Verbindung der Formel I ist das 2',4'-Dichlor-2-(3"-pyridyl)-acetophenon-O-methyloxim-l"-oxid. A particularly preferred compound of the formula I is 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-methyloxime-1" oxide.
O * * OC *> · ftO * * OC *> ft
Weitere Vertreter von Verbindungen der Formel I sind:Further representatives of compounds of the formula I are:
2',4'-Dichlor-2-(3"-pyridyl)-acetophenon-O-äthyloxim-1"-oxid, 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-ethyloxime-1" oxide,
21,4'-Dichlor-2-(2"-pyrazinyl)-acetophenon-O-methyloxim-1"-oxid, 2 1 , 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-O-methyloxime-1" -oxide,
2',4'-Dichlor-2-(2"-pyrazinyl)-acetophenon-O-methyloxim-4"-oxid, 2 ', 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-O-methyloxime-4" -oxide,
4 ' -Chlor-2-(3"-pyridyl)-acetophenon-O-methyloxim-1"-oxid, 4 '-chloro-2- (3 "-pyridyl) -acetophenone-O-methyloxime-1" oxide,
4'-Chlor-2-(2"-pyrazinyl)-acetophenon-O-methyloximl",4"-dioxid, 4'-chloro-2- (2 "-pyrazinyl) -acetophenone-O-methyloximl", 4 "-dioxide,
4'-Chlor-2-(2"-pyrazinyl)-acetophenon-O-äthyloximl",4"-dioxid, 4'-chloro-2- (2 "-pyrazinyl) -acetophenone-O-ethyloximl", 4 "-dioxide,
4'-Chlor-2-(2"-pyrazinyl)-acetophenon-O-allyloxim-4"-oxid, 4'-chloro-2- (2 "-pyrazinyl) -acetophenone-O-allyloxime-4" -oxide,
2',4'-Dichlor-2-(3"-pyridyl)-acetophenon-O-allyloximl"-oxid, 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-allyloximl" -oxide,
2'-Chlor-2-(2"-pyrazinyl) —acetophenon-O-methyloxim-4"-oxid, 2'-Chloro-2- (2 "-pyrazinyl) -acetophenone-O-methyloxime-4" -oxide,
4'-Fluor-2-(2"-pyrazinyl)-acetophenon-O-methyloximl"-oxid, 4'-Fluoro-2- (2 "-pyrazinyl) -acetophenone-O-methyloximl" -oxide,
4'-Brom-2-(2"-pyrazinyl)-acetophenon-O-methyloximl",4"-dioxid, 4'-Bromo-2- (2 "-pyrazinyl) -acetophenone-O-methyloximl", 4 "-dioxide,
4'-Chlor-2-(2"-pyrazinyl)-propiophenon-O-methyloxim-4"-oxid, 4'-chloro-2- (2 "-pyrazinyl) -propiophenone-O-methyloxime-4" -oxide,
21,4'-Dichlor-2-(2"-pyrazinyl)-butyrophenon-0-methyloxim-1",4"-dioxid, 2 1 , 4'-dichloro-2- (2 "-pyrazinyl) -butyrophenone-0-methyloxime-1", 4 "-dioxide,
2',4'-Dichlor-2-(2"-pyrazinyl)-acetophenon-O-allyloxim-l"-oxid, 2 ', 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-O-allyloxime-1" -oxide,
2',4'-Dichlor-2-(2"-pyrazinyl)-propiophenon-O-methyloxim-1" , 4"-dioxid,2 ', 4'-dichloro-2- (2 "-pyrazinyl) -propiophenone-O-methyloxime-1" , 4 "-dioxide,
2',4'-Dichlor-2-(3"-pyridyl)-acetophenon-O-cyclopropyloxim-1"-oxid, 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-cyclopropyloxime-1" oxide,
21,4'-Dichlor-2-(3"-pyridyl)-acetophenon-O-isopropyloxim-l"-oxid, 2 1 , 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-isopropyloxime-1" oxide,
21,4'-Dichlor-2-(3"-pyridyl)-acetophenon-O-propargyloxim-l"-oxid, 2 1 , 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-propargyloxime-1" -oxide,
4'-Chlor-2-(2"-pyrazinyl)-acetophenon-O-propargyloxim-4"-oxid, 4'-chloro-2- (2 "-pyrazinyl) -acetophenone-O-propargyloxime-4" -oxide,
2',4■-Dichlor-2-(2"-pyrazinyl)-acetophenon-O-propargyloxim-l"-oxid und 2 ' , 4 ■ -Dichloro-2- (2 "-pyrazinyl) -acetophenone-O-propargyloxime-1" -oxide and
4'-Jod-2-(3"-pyridyl)-propiophenon-O-cyclohexyloximl"-oxid. 4'-Iodo-2- (3 "pyridyl) propiophenone-O-cyclohexyloxime" oxide.
Durch das Vorliegen der C=N-Doppelbindung in den Verbindungen der Formel I tritt geometrische Isomerie (E- und Z-Isomere) auf. Zusätzlich können asymmetrische Kohlenstoffatome vorhanden sein, so dass die Verbindungen als optische Antipoden vorliegen können. Die Formel I soll demnach all diese möglichen isomeren Formen umfassen.The presence of the C = N double bond in the compounds of the formula I results in geometric isomerism (E and Z isomers). In addition, asymmetric carbon atoms can be present, so that the compounds as optical Antipodes may be present. The formula I is therefore intended to encompass all of these possible isomeric forms.
Als Säureadditionssalze der Verbindungen der Formel I kommen physiologisch verträgliche Salze mit starken Säuren in Frage. Hierzu gehören vorzugsweise Salze der Verbindungen I mit anorganischen Säuren, wie Salzsäure, Salpetersäure und Phosphorsäure, und mit Sulfonsäuren, wie 1,5-Naphthalin-disulfonsäure.The acid addition salts of the compounds of the formula I are physiologically acceptable salts with strong acids in question. These preferably include salts of the compounds I with inorganic acids, such as hydrochloric acid and nitric acid and phosphoric acid, and with sulfonic acids such as 1,5-naphthalene-disulfonic acid.
Das erfxndungsgemasse Verfahren zur Herstellung der Verbindungen der Formel I und von deren Salzen ist dadurch
gekennzeichnet, dass man
25The process according to the invention for the preparation of the compounds of the formula I and of their salts is characterized in that one
25th
a) ein Pyridin- bzw. Pyrazin-Derivat der allgemeinen Formela) a pyridine or pyrazine derivative of the general formula
R3 R 3
1 ' 21 1 '2 1
R C CH R IIR C CH R II
Ii
NIi
N
I 4I 4
OROR
13 4
worin R , R und R die oben angegebenen Bedeutungen13 4
wherein R, R and R have the meanings given above
2'2 '
besitzen und R 3-Pyridyl oder 2-Pyrazinyl bedeutet, N-oxydiert, oderand R is 3-pyridyl or 2-pyrazinyl, N-oxidized, or
b) ein Keton der allgemeinen Formelb) a ketone of the general formula
2 ■C CH R III 2 ■ C CH R III
12 312 3
worin R , R und R die oben angegebenen Bedeutungenwherein R, R and R have the meanings given above
besitzen,own,
mit einem O-substituierten Hydroxylamin der allgemeinen Formelwith an O-substituted hydroxylamine of the general formula
R41ONH0 IVR 41 ONH 0 IV
10 41 10 41
worin R C-. _fi-Alkyl, C-,,--Cycloalkyl oder C,_fi-wherein R C-. _ fi -alkyl, C - ,, - cycloalkyl or C, _ fi -
Alkenyl bedeutet,
umsetzt,Alkenyl means
implements,
und erwünschtenfalls eine erhaltene Verbindung der allgemeinen Formel I in ein Säureadditionssalz überführt.and, if desired, a compound obtained from the general Formula I converted into an acid addition salt.
Die Verfahrensvariante a) kann zweckmässigerweise durchgeführt werden, indem man das Ausgangsmaterial der Formel II mittels Wasserstoffperoxid oder einer Persäure in Gegenwart eines inerten Verdünnungsmittels oxydiert.Process variant a) can expediently be carried out by converting the starting material of formula II using hydrogen peroxide or a peracid oxidized in the presence of an inert diluent.
Im Falle der Verwendung von Wasserstoffperoxid als Oxydationsmittel kommen als Verdünnungsmittel insbesondere "*■ 25 niedere Alkanole, wie Methanol, Aethanol und Isopropanol, in Frage, und die Oxydation wird vorzugsweise in einem Temperaturbereich zwischen 0° und 600C, insbesondere zwischen 20° und 400C, vorgenommen.In the case of using hydrogen peroxide as an oxidising agent suitable diluents particular '* ■ 25 lower alkanols such as methanol, ethanol and isopropanol, in question, and the oxidation is preferably carried out in a temperature range between 0 ° and 60 0 C, in particular between 20 ° and 40 0 C, made.
Als Persäuren kommen vorzugsweise Peressigsäure, Perbenzoesäure und m-Chlorperbenzoesäure in Frage, wobei bevorzugt in einem halogenierten Kohlenwasserstoff, z.B, Methylenchlorid oder Chloroform, als Verdünnungsmittel gearbeitet wird. Die Oxydation mit einer Persäure erfolgt vorzugsweise in einem Temperaturbereich zwischen 00C und der Rückflusstemperatur des Reaktionsgemisches, insbesondere zwischen 00C und der Raumtemperatur. Eine besonders bevorzugte Ausführungsform dieses Verfahrens be-Peracids are preferably peracetic acid, perbenzoic acid and m-chloroperbenzoic acid, the diluent being preferably used in a halogenated hydrocarbon, for example methylene chloride or chloroform. The oxidation with a peracid is preferably carried out in a temperature range between 0 ° C. and the reflux temperature of the reaction mixture, in particular between 0 ° C. and room temperature. A particularly preferred embodiment of this method is
steht darin, dass man die Oxydation mit m-Chlorperbenzoesäure in Chloroform in einem Temperaturbereich zwischen 00C und der Raumtemperatur durchführt.it says that the oxidation is carried out with m-chloroperbenzoic acid in chloroform in a temperature range between 0 ° C. and room temperature.
Gemäss Verfahrensvariante b), die zu Verbindungen derAccording to process variant b), which lead to compounds of
4
Formel I führt, worin R C1 ,.-Alkyl, C0 ,--Cycloalkyl oder4th
Formula I leads, in which RC 1 , .- alkyl, C 0 , - cycloalkyl or
JL- D J-OJL- D J-O
C3 ,-Alkenyl bedeutet, erfolgt die Umsetzung zweckmässiger weise in einem organischen Lösungsmittel, z.B. einem Alkohol, wie Methanol oder Aethanol, einem Dialkylamid, wie Dimethylformamid, oder einem tertiären Amin, wie Pyridin. Man arbeitet vorzugsweise in einem Temperaturbereich zwischen der Raumtemperatur und der Rückflusstemperatur v**/ des Reaktionsgemisches. Da das Ausgangsmaterial der Formel IV vorzugsweise in Form eines Säureadditionssalzes, z.B. des Hydrochlorids oder Hydrosulfats, eingesetzt wird, wird dem Reaktionsgemisch zweckmässigerweise eine Base, wie Natrium- oder Kaliumcarbonat, Triäthylamin oder Pyridin, zugesetzt.C 3 , -alkenyl, the reaction is conveniently carried out in an organic solvent, for example an alcohol such as methanol or ethanol, a dialkylamide such as dimethylformamide, or a tertiary amine such as pyridine. One works preferably in a temperature range between room temperature and the reflux temperature v ** / of the reaction mixture. Since the starting material of the formula IV is preferably used in the form of an acid addition salt, for example the hydrochloride or hydrosulfate, a base such as sodium or potassium carbonate, triethylamine or pyridine is expediently added to the reaction mixture.
Zur Herstellung von Säureadditionssalzen können erwünschtenfalls die Verbindungen der Formel I mit den gewünschten Säuren, wie z.B. Salzsäure, Salpetersäure, Phosphorsäure, oder einer Sulfonsäure, umgesetzt werden.For the preparation of acid addition salts, if desired the compounds of formula I with the desired acids, such as hydrochloric acid, nitric acid, Phosphoric acid, or a sulfonic acid, are implemented.
Die Isolierung und Reinigung der so hergestellten Ver wendungen der Formel I und deren Säureadditionssalze erfolgen nach an sich bekannten Methoden.The uses of the formula I and their acid addition salts prepared in this way are isolated and purified according to methods known per se.
Die Ausgangsmaterialien der Formel II können hergestellt werden, indem man ein Oxim der allgemeinen FormelThe starting materials of formula II can be prepared by adding an oxime of the general formula
R3 R 3
R1 C CH R2' VR 1 C CH R 2 'V
IfIf
II.
J0 OH J0 OH
12' 3
worin R , R und R die oben angegebenen Bedeutungen12 '3
wherein R, R and R have the meanings given above
besitzen,own,
• · β 9 * ·• β 9 *
«•Ο * β β 9 # »«• Ο * β β 9 # »
» β · »β to e »»Β ·» β to e »
mit einer Verbindung der allgemeinen Formelwith a compound of the general formula
R4U VIR 4 U VI
4
worin R die oben angegebene Bedeutung besitzt4th
wherein R has the meaning given above
und U eine Abgangsgruppe, z.B. Chlor, Brom, Jod, Mesyloxy, Tosyloxy oder einen Alkylsulfatrest, bedeutet, umsetzt, oder ein Keton der allgemeinen Formeland U is a leaving group, e.g., chlorine, bromine, iodine, mesyloxy, tosyloxy or one Alkyl sulfate radical, means, reacts, or a ketone of the general formula
1 ι 2'1 ι 2 '
R C CH R VIIR C CH R VII
K 0K 0
12' 3
worin R , R und R die oben angegebenen Bedeutungen besitzen,12 '3
wherein R, R and R have the meanings given above,
mit einem O-substituierten Hydroxylamin der allgemeinen Formelwith an O-substituted hydroxylamine of the general formula
R41ONH2 IVR 41 ONH 2 IV
41
worin R C-, g-Alkyl, C3_g-Cycloalkyl oder C_ e-41
wherein R is C-, g -alkyl, C 3 _ g -cycloalkyl or C_ e-
Alkenyl bedeutet,
umsetzt.Alkenyl means
implements.
Die Umsetzung des Oxims der Formel V mit der Verbindung der Formel VI kann durchgeführt werden, indem man das Oxim V mit der Verbindung VI, zweckmässigerweise in Gegenwart einer Base, in einem organischen Lösungsmittel und in einem Temperaturbereich zwischen 00C und der Rückflusstemperatur des Reaktionsgemisches versetzt. Das Lösungsmittel kann protisch oder nicht protisch sein. Im Falle von protischen Lösungsmitteln, wie Alkoholen, insbesondere Methanol oder Aethanol, ist die verwendete Base vorzugsweise ein Alkalimetallhydroxid, z.B. Natrium- oder Kaiiumhydroxid, oder ein Alkalimetallalkoholat. Bei Verwendung von nichtprotischen Lösungsmitteln, wie ali-The reaction of the oxime of the formula V with the compound of the formula VI can be carried out by mixing the oxime V with the compound VI, conveniently in the presence of a base, in an organic solvent and in a temperature range between 0 ° C. and the reflux temperature of the reaction mixture offset. The solvent can be protic or non-protic. In the case of protic solvents, such as alcohols, in particular methanol or ethanol, the base used is preferably an alkali metal hydroxide, for example sodium or potassium hydroxide, or an alkali metal alcoholate. When using non-protic solvents such as ali-
phatischen oder alicyclischen Aethern, insbesondere Tetrahydrofuran oder Dimethoxyäthan, und Dialkylamiden, insbesondere Dimethylformamid, ist die Base vorzugsweise ein Alkalimetallhydrid, z.B. Natriumhydrid. In einer bevorzugtenphatic or alicyclic ethers, especially tetrahydrofuran or dimethoxyethane, and dialkylamides, in particular Dimethylformamide, the base is preferably an alkali metal hydride such as sodium hydride. In a preferred
_ Ausführungsform dieses Verfahrens werden Natriumhydrid 5_ An embodiment of this process is sodium hydride 5
als Base und ein aliphatischer oder alicyclischer Aether, insbesondere Tetrahydrofuran oder Dimethoxyäthan, oder ein Dialkylamid, insbesondere Dimethylformamid, als Lösungsmittel verwendet.as a base and an aliphatic or alicyclic ether, especially tetrahydrofuran or dimethoxyethane, or a Dialkylamide, especially dimethylformamide, is used as a solvent.
Die Umsetzung des Ketons der Formel VII mit demThe implementation of the ketone of the formula VII with the
Hydroxylamin der Formel IV, die zu Verbindungen der FormelHydroxylamine of the formula IV, leading to compounds of the formula
4
II führt, worin R C.g-Alkyl, C3 g-Cycloalkyl oder C3-6-4th
II leads, wherein R Cg-alkyl, C3 g-cycloalkyl, or C 3-6 -
Alkenyl bedeutet, erfolgt zweckmässigerweise analog zu derAlkenyl is conveniently carried out analogously to
oben beschriebenen Verfahrensvariante b). 15process variant b) described above. 15th
Die Ausgangsmaterialien der Formel III können hergestellt werden, indem man das obenerwähnte Keton der allgemeinen Formel VII analog zu der oben beschriebenen Verfahrensvariante a) N-oxydiert.The starting materials of formula III can be prepared by using the above-mentioned ketone of general formula VII analogously to process variant a) described above N-oxidized.
Die als Ausgangsmaterialien verwendbaren VerbindungenThe compounds usable as starting materials
der Formeln IV, V, VI und VII sind entweder bekannt oder können nach an sich bekannten Methoden hergestellt werden. Beispielsweise können die Oxime der Formel V aus den entsprechenden Ketonen der Formel VII durch Umsetzung mit 25of the formulas IV, V, VI and VII are either known or can be prepared by methods known per se. For example, the oximes of the formula V from the corresponding ketones of the formula VII by reaction with 25th
Hydroxylamin, und die Ketone selbst gemäss den in der DOS 2 221 546, der DOS 2 800 010 und der britischen Patentschrift Nr. 2 015 5 24 beschriebenen Verfahren, also z.B. durch Kondensation des entsprechenden methylierten Hetero-„_ Zyklus mit einem halogenierten Benzoesäure-alkylester, hergestellt werden.Hydroxylamine, and the ketones themselves according to the DOS 2,221,546, DOS 2,800,010 and British Patent No. 2,015,524, e.g. by condensation of the corresponding methylated hetero- "_ Cycle with a halogenated benzoic acid alkyl ester, getting produced.
Die erfindungsgemässen Verbindungen, d.h. die Verbindungen der Formel I und deren Säureadditionssalze, besitzen fungizide Wirkung und können dementsprechend zur ^ Bekämpfung von Fungi in der Landwirtschaft und im Gartenbau Verwendung finden. Sie eignen sich insbesondere zur Eindämmung des Wachstums oder zur Vernichtung von phytopathogenen Pilzen auf Pflanzenteilen, z.B. Blättern,The compounds of the invention, i.e. the compounds of the formula I and their acid addition salts have fungicidal activity and can accordingly be used for ^ Fungi control in agriculture and horticulture Find use. They are particularly suitable for curbing growth or for killing phytopathogens Fungi on parts of plants, e.g. leaves,
Stengeln, Wurzeln, Knollen, Früchten oder Blüten, und auf Saatgut sowie im Erdboden und sind besonders wirksam bei der Bekämpfung von Botrytis cinerea (Graufäule); von echten Mehltaupilzen, wie beispielsweise Uncinula necator (Rebenmehltau), Erysiphe cichoracearum (Gurkenmehltau), Podosphaera leucotricha (Apfelmehltau) und Erysiphe graminis (Gerstenmehltau); von Venturia inaequalis (Apfelschorf); von Helminthosporium oryzae (Braunfleckenkrankheit von Reis); und von Schadpilzen der Gattungen Puccinia, Uromyces, Rhizoctonia, Penicillium, Septoria und Cercospora. Stems, roots, tubers, fruits or flowers, and on seeds as well as in the ground and are particularly effective at the fight against Botrytis cinerea (gray rot); of powdery mildew, such as Uncinula necator (Powdery mildew), Erysiphe cichoracearum (cucumber powdery mildew), Podosphaera leucotricha (apple powdery mildew) and Erysiphe graminis (Barley powdery mildew); from Venturia inaequalis (apple scab); of Helminthosporium oryzae (brown spot disease of rice); and of harmful fungi of the genera Puccinia, Uromyces, Rhizoctonia, Penicillium, Septoria and Cercospora.
Einzelne Vertreter der erfindungsgemässen Verbindungen besitzen zudem eine ausgeprägte Wirkung gegen holzzerstörende Pilze, wie z.B. Coniophora puteana und Gloeophyllum trabeum.Individual representatives of the compounds according to the invention also have a pronounced effect against wood-destroying fungi, such as Coniophora puteana and Gloeophyllum trabeum.
Die erfindungsgemässen Verbindungen zeichnen sich durchThe compounds according to the invention are distinguished by
lokale und bzw. oder systemische Wirkung aus. 20local and / or systemic effect. 20th
Die erfindungsgemässen Verbindungen wirken unter Gewächshausbedingungen bereits bei einer Konzentration von 10 mg bis 500 mg Wirksubstanz pro Liter Spritzbrühe. Im Freiland werden vorteilhaft Konzentrationen von 50 g bis 2000 g Wirkstoff der Formel I pro Hektar und Behandlung zur Anwendung gebracht.The compounds according to the invention act under greenhouse conditions already at a concentration of 10 mg to 500 mg of active substance per liter of spray liquid. in the In the field, concentrations of 50 g to 2000 g of active ingredient of the formula I per hectare and treatment are advantageous applied.
Unter Verwendung von Formulierungshilfsstoffen können die erfindungsgemässen Verbindungen, also die fungiziden wirkstoffe, in die üblichen Formulierungen übergeführt werden, wie Stäube, Pulver, Granulate, Lösungen, Emulsionen, Suspensionen, emulgierbare Konzentrate, Pasten und dergleichen. Das erfindungsgemässe fungizide Mittel ist dadurch gekennzeichnet, dass es eine wirksame Menge mindestens einer Verbindung der allgemeinen Formel I, wie oben definiert, oder eines Säureadditionssalzes einer solchen Verbindung sowie Formulierungshilfsstoffe enthält. Die Mittel enthalten zweckmässigerweise zumindest einen derUsing formulation auxiliaries you can the compounds according to the invention, that is to say the fungicidally active ingredients, are converted into the customary formulations such as dusts, powders, granulates, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and the same. The fungicidal agent according to the invention is characterized in that it is an effective amount at least one compound of the general formula I, as defined above, or an acid addition salt of a contains such a compound as well as formulation auxiliaries. The means expediently contain at least one of the
folgenden Formulierungshilfsstoffe:the following formulation auxiliaries:
Feste Trägerstoffe; Lösungs- bzw. Dispersionsmittel; Tenside (Netz- und Emulgiermittel); Dispergatoren (ohne Tensidwirkung); und Stabilisatoren.Solid carriers; Solvents or dispersants; Surfactants (wetting and emulsifying agents); Dispersants (without surfactant effect); and stabilizers.
Als feste Trägerstoffe kommen im wesentlichen in Frage: natürliche Mineralstoffe, wie Kaolin, Tonerden, Kieselgur, Talkum, Bentonit, Kreide, z.B. Schlämmkreide, Magnesiumcarbonat, Kalkstein, Quarz, Dolomit, Attapulgit, Montmorillonit und Diatomeenerde; synthetische Mineralstoffe, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; organische Stoffe, wie Cellulose, Stärke, Harnstoff und Kunstharze;und Düngemittel, wie Phosphate und Nitrate, wobei solche Trägerstoffe z.B. als Granulate oder Pulver vorliegen können.The following solid carriers are essentially: natural minerals such as kaolin, clay, Kieselguhr, talc, bentonite, chalk, e.g. whipped chalk, magnesium carbonate, limestone, quartz, dolomite, attapulgite, Montmorillonite and diatomaceous earth; synthetic minerals such as highly dispersed silica, aluminum oxide and Silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers such as phosphates and Nitrates, whereby such carriers can be in the form of granulates or powders, for example.
Als Lösungs- bzw. Dispersionsmittel kommen im wesentlichen in Frage: Aromaten, wie Benzol, Toluol, Xylole und Alkylnaphthaiine; chlorierte Aromaten und chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene und Methylenchlorid; aliphatische Kohlenwasserstoffe, wie Cyclohexan und Paraffine, z.B. Erdölfraktionen; Alkohole, wie Butanol und Glykol, sowie deren Aether und Ester; Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon und Cyclohexanon; und stark polare Lösungs- bzx-i. Dispersionsmittel, wie Dimethylformamid, N-Methylpyrrolidon und Dimethylsulfoxid, wobei solche Lösungs- bzw. Dispersionsmittel vorzugsweise Flammpunkte von mindestens 300C und Siedepunkte von mindestens 500C aufweisen, und Wasser.The following are essentially suitable solvents or dispersants: aromatics, such as benzene, toluene, xylenes and alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons, such as cyclohexane and paraffins, for example petroleum fractions; Alcohols, such as butanol and glycol, and their ethers and esters; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and strongly polar solution bzx-i. Dispersants such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, such solvents or dispersants preferably having flash points of at least 30 ° C. and boiling points of at least 50 ° C., and water.
Unter den Lösungs- bzw. Dispersionsmitteln kommen auch in Frage sogenannte verflüssigte gasförmige Streckmittel oder Trägerstoffe, die solche Produkte sind, welche bei Raumtemperatur und unter Normaldruck gasförmig sind. Beispiele solcher Produkte sind insbesondere Aerosol-Treibgase, wie Halogenkohlenwasserstoffe, z.B. Dichlordifluormethan. Im Falle der Benutzung von Wasser als Lösungsmittel können z.B. auch organische Lösungsmittel als HilfslösungsmittelAmong the solvents or dispersants, so-called liquefied gaseous extenders or are also suitable Carriers that are products that are gaseous at room temperature and under normal pressure. Examples such products are in particular aerosol propellants such as halogenated hydrocarbons, e.g. dichlorodifluoromethane. in the If water is used as the solvent, organic solvents can also be used as auxiliary solvents, for example
β β ·Λ O -Q *iβ β · Λ O -Q * i
β O β α ·» α β β » «οβ O β α · »α β β» «ο
verwendet werden.be used.
Die Tenside (Netz- und Emulgiermittel) können nichtionische Verbindungen sein, wie Kondensationsprodukte von Fettsäuren, Fettalkoholen oder fettsubstituierten Phenolen mit Aethylenoxid; Fettsäureester und -äther von Zuckern oder mehrwertigen Alkoholen; die Produkte, die aus Zuckern oder mehrwertigen Alkoholen durch Kondensation mit Aethylenoxid erhalten werden; Blockpolymere von Aethylenoxid und Propylenoxid; oder Alkyldimethylaminoxide.The surfactants (wetting and emulsifying agents) can be nonionic compounds, such as condensation products of Fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide; Fatty acid esters and ethers of sugars or polyhydric alcohols; the products made from sugars or polyhydric alcohols by condensation with ethylene oxide obtained; Block polymers of ethylene oxide and propylene oxide; or alkyl dimethyl amine oxides.
Die Tenside können auch anionische Verbindungen darstellen, wie Seifen; Fettsulfatester, z.B. Dodecylnatriumsulfat, Octadecylnatriumsulfat und Cetylnatriumsulfat; Alkylsulfonate, Arylsulfonate und fettaromatische Sulfonate, wie Alkylbenzolsulfonate, z.B. Calcium-dodecylbenzolsulfonat, und Butylnaphthalinsulfonate; und komplexere Fettsulfonate, z.B. die Amidkondensationsprodukte von OeI-säure und N-Methyltaurin und das Natriumsulfonat von Dioctylsuccinat. The surfactants can also be anionic compounds, such as soaps; Fatty sulfate esters, e.g. dodecyl sodium sulfate, Octadecyl sodium sulfate and cetyl sodium sulfate; Alkyl sulfonates, aryl sulfonates and fatty aromatic sulfonates, such as alkylbenzenesulfonates, e.g. calcium dodecylbenzenesulfonate, and butylnaphthalene sulfonates; and more complex fatty sulfonates, e.g. the amide condensation products of oleic acid and N-methyl taurine and the sodium sulfonate of dioctyl succinate.
Die Tenside können schliesslich kationische Verbindungen sein, wie Alkyldimethylbenzylammoniumchloride, Dialkyldimethylammoniumchlori.de, Alkyltrimethylammonium-. chloride und äthoxylierte quaternäre Ammoniumchloride.Finally, the surfactants can be cationic compounds, such as alkyldimethylbenzylammonium chlorides, Dialkyldimethylammoniumchlori.de, Alkyltrimethylammonium-. chlorides and ethoxylated quaternary ammonium chlorides.
Als Dispergatoren (ohne Tensidwirkung) kommen im wesentlichen in Frage: Lignin, Natrium- und Ammoniumsalze von Ligninsulfonsäure, Natriumsalze von Maleinsäureanhydrid-Diisobutylen-Copolymeren, Natrium- und Ammoniumsalze von sulfonierten Polykondensationsprodukten aus Naphthalin und Formaldehyd, und Sulfitablaugen.The dispersants (without surfactant effect) are im essential question: lignin, sodium and ammonium salts of ligninsulphonic acid, sodium salts of maleic anhydride-diisobutylene copolymers, Sodium and ammonium salts of sulfonated polycondensation products from naphthalene and formaldehyde, and sulfite waste liquors.
Als Dispergatoren, die sich insbesondere als Verdickungs- bzw. Antiabsetzmittel eignen, können z.B. Methylcellulose, Carboxymethylcellulose, Hydroxyäthylcellulose, Polyvinylalkohol, Alginate, Caseinate und Blutalbumin eingesetzt werden.As dispersants, which are particularly suitable as thickeners or anti-settling agents, e.g. methyl cellulose, Carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, alginates, caseinates and blood albumin are used will.
Beispiele von geeigneten Stabilisatoren sind säurebindende Mittel, z.B. Epichlorhydrin, Phenylglycidäther und Soyaepoxide; Antioxidantien z.B. Gallussäureester und Butylhydroxytoluol; UV-Absorber z.B. substituierte Benzophenone, Diphenylacrylnitrilsäureester und Zimtsäureester; und Deaktivatoren z.B. Salze der Aethylendiaminotetraessigsäure und Polyglykole.Examples of suitable stabilizers are acid-binding agents, e.g., epichlorohydrin, phenyl glycidyl ether and Soy epoxide; Antioxidants such as gallic acid esters and butylated hydroxytoluene; UV absorbers e.g. substituted benzophenones, Diphenylacrylonitrile acid esters and cinnamic acid esters; and deactivators, e.g. salts of ethylenediaminetetraacetic acid and polyglycols.
Die erfindungsgemässen fungiziden Mittel können neben den Wirkstoffen der Formel I auch andere Wirkstoffe enthalten, z.B. anderweitige fungizide Mittel, insektizide und akarizide Mittel, Bakterizide, Pflanzenwachstumsregulatoren und Düngemittel. Solche Kombinationsmittel eignen sich zur Verbreiterung des Wirkungsspektrums oder zur spezifischen Beeinflussung des Pflanzenwachstums.The fungicidal agents according to the invention can in addition to the active ingredients of the formula I also contain other active ingredients, e.g. other fungicidal agents, insecticides and acaricides, bactericides, plant growth regulators and fertilizers. Such combination means are suitable for broadening the spectrum of activity or for specifically influencing plant growth.
Im allgemeinen enthalten die erfindungsgemässen fungiziden Mittel, je nach Typ, zwischen 0,0001 und 95 Gewichtsprozent an erfindungsgemässer Verbindung bzw. erfindungsgemässen Verbindungen als Wirkstoff(en). Sie können in einer Form vorliegen, die sich für die Lagerung und den Transport eignet. In solchen Formen, z.B. emulgierbaren Konzentraten, ist die Wirkstoffkonzentration normalerweise im höheren Bereich der obigen Konzentrationsreihe.In general, the fungicides according to the invention contain Agent, depending on the type, between 0.0001 and 95 percent by weight of compound according to the invention or according to the invention Compounds as active ingredient (s). They can be in a form that is convenient for storage and use Suitable for transport. In such forms, e.g. emulsifiable concentrates, the active ingredient concentration is normally in the higher range of the above concentration series.
Diese Formen können dann mit gleichen oder verschiedenen Formulierungshilfsstoffen bis zu Wirkstoffkonzentrationen verdünnt werden, die sich für den praktischen Gebrauch eignen, und solche Konzentrationen liegen normalerweise im niedrigeren Bereich der obigen Konzentrationsreihe.These forms can then be mixed with the same or different formulation auxiliaries up to active ingredient concentrations suitable for practical use, and such concentrations are usually in the lower range of the above concentration series.
Emulgierbare Konzentrate enthalten im allgemeinen 5 bis 95 Gewichtsprozent, vorzugsweise 25 bis 75 Gewichtsprozent, der Verbindung bzw. Verbindungen der Formel I. Als Anwendungsformen kommen u.a. gebrauchsfertige Lösungen, Emulsionen und Suspensionen, die sich beispielsweise als Spritzbrühen eignen, in Frage. In solchen Spritzbrühen können z.B. Konzentrationen zwischen 0,0001 und 20 Gewichtsprozent vorliegen. Im Ultra-Low-Volume-Verfahren können Spritzbrühen formuliert werden, in denen die Wirkstoffkonzentra-Emulsifiable concentrates generally contain 5 to 95 percent by weight, preferably 25 to 75 percent by weight, of the compound or compounds of the formula I. The use forms include ready-to-use solutions and emulsions and suspensions, which are suitable, for example, as spray liquors, in question. In such spray mixtures you can e.g. concentrations between 0.0001 and 20 percent by weight are present. Spray mixtures can be used in the ultra-low-volume process be formulated in which the active ingredient concentration
tion vorzugsweise von 0,5 bis 20 Gewichtsprozent beträgt, während die im Low-Volume-Verfahren und im High-Volume-Verfahren formulierten Spritzbrühen vorzugsweise eine Wirkstoffkonzentration von 0,02 bis 1,0 bzw. 0,002 bis 0,1 Gewichtsprozent aufweisen.tion is preferably from 0.5 to 20 percent by weight, while those in the low-volume process and in the high-volume process formulated spray mixtures preferably have an active ingredient concentration from 0.02 to 1.0 or 0.002 to 0.1 percent by weight.
Die erfindungsgemässen fungiziden Mittel können dadurch hergestellt werden, dass man mindestens eine Verbindung der allgemeinen Formel I bzw. ein Säureadditionssalz einer solchen Verbindung mit Formulierungshilfsstoffen vermischt.The fungicidal agents according to the invention can thereby be prepared that at least one compound of the general formula I or an acid addition salt such a connection with formulation auxiliaries mixed.
Die Herstellung der Mittel kann in bekannter Weise durchgeführt werden, z.B. durch Vermischen des Wirkstoffes mit festen Trägerstoffen, durch Auflösen oder Suspendieren in geeigneten Lösungs- bzw. Dispersionsmitteln, eventuell unter Verwendung von Tensiden als Netz- oder Emulgiermitteln oder von Dispergatoren, durch Verdünnen bereits vorbereiteter emulgierbarer Konzentrate mit Lösungs- bzw. Dispersionsmitteln usw.The preparation of the agents can be carried out in a known manner, for example by mixing the active ingredient with solid carriers, by dissolving or suspending in suitable solvents or dispersants, possibly with the use of surfactants as wetting or emulsifying agents or dispersants, by dilution already prepared emulsifiable concentrates with solvents or dispersants etc.
Im Falle von pulverförmigen Mitteln kann der Wirkstoff mit einem festen Trägerstoff vermischt werden, z.B. durch Zusammenmahlen; oder man kann den festen Trägerstoff mit einer Lösung oder Suspension des Wirkstoffes imprägnieren und dann das Lösungs- oder Dispersionsmittel durch Äbdunsten, Erhitzen oder durch Absaugen unter vermindertem Druck entfernen. Durch Zusatz von Tensiden bzw. Dispergatoren kann man solche pulverförmige Mittel mit Wasser leicht benetzbar machen, so dass sie in wässrige Suspensionen, die sich z.B. als Spritzmittel eignen, übergeführt werden können.In the case of powdered agents, the active ingredient can mixed with a solid carrier, e.g., by grinding together; or you can use the solid carrier impregnate with a solution or suspension of the active ingredient and then the solvent or dispersant through Steaming, heating or by suction under reduced conditions Remove pressure. Such pulverulent agents can be mixed with water by adding surfactants or dispersants Make them easily wettable, so that they are transferred into aqueous suspensions that are suitable, for example, as sprays can be.
Die erfindungsgemässen Verbindungen können auch mit einem Tensid und einem festen Trägerstoff zur Bildung eines netzbaren Pulvers vermischt werden, welches in Wasser dispergierbar ist, oder sie können mit einem festen vorgranulierten Trägerstoff zur Bildung eines granulatförmigenThe compounds according to the invention can also be used with a surfactant and a solid carrier to form a wettable powder, which is dispersible in water, or they can be pre-granulated with a solid Carrier for the formation of a granular
β β 9«* 9 αν» «««»β »β «»β β 9 «* 9 αν» «« «» Β »β« »
Produktes vermischt werden.Product are mixed.
Wenn gewünscht, kann eine erfindungsgemässe Verbindung in einem mit Wasser nicht mischbaren Lösungsmittel, wie beispielsweise einem alicyclischen Keton, gelöst werden, das zweckmässigerweise gelöste Emulgiermittel enthält, so dass die Lösung bei Zugabe zu Wasser selbstemulgierend wirkt. Andernfalls kann der Wirkstoff mit einem Emulgiermittel vermischt und das Gemisch dann mit Wasser auf dieIf desired, a compound according to the invention can be dissolved in a water-immiscible solvent, such as an alicyclic ketone, which advantageously contains dissolved emulsifier, so that the solution is self-emulsifying when added to water works. Otherwise, the active ingredient can be mixed with an emulsifying agent and then the mixture with water on the
"Ό gewünschte Konzentration verdünnt werden. Zudem kann der Wirkstoff in einem Lösungsmittel gelöst und danach mit einem Emulgiermittel gemischt werden. Ein solches Gemisch kann ebenfalls mit Wasser auf die gewünschte Konzentration verdünnt werden. Auf diese Weise erhält man emulgierbare Konzentrate bzw. gebrauchsfertige Emulsionen."Ό the desired concentration can be diluted. In addition, the Active ingredient dissolved in a solvent and then mixed with an emulsifying agent. Such a mixture can also be diluted with water to the desired concentration. In this way, emulsifiable ones are obtained Concentrates or ready-to-use emulsions.
Die Verwendung der erfindungsgemässen Mittel kann nach den im Pflanzenschutz bzw. in der Landwirtschaft üblichen Applikationsmethoden erfolgen, wie Spritzen, ^ Sprühen, Stäuben, Giessen oder Streuen. Das erfindungsgemässe Verfahren zur Bekämpfung von Fungi ist dadurch gekennzeichnet, dass man das zu schützende Gut, z.B. Pflanzen, Pflanzenteile bzw. Samen, mit einer wirksamen Menge einer erfindungsgemässen Verbindung bzw. eines er-,. f ^5 findungsgemässen Mittels behandelt.The compositions according to the invention can be used by the application methods customary in crop protection or in agriculture, such as spraying, spraying, dusting, watering or scattering. The method according to the invention for combating fungi is characterized in that the material to be protected, for example plants, parts of plants or seeds, is mixed with an effective amount of a compound according to the invention or a substance. f ^ 5 means according to the invention treated.
Die nachstehenden Beispiele illustrieren die Erfindung. The following examples illustrate the invention.
3030th
3535
33034663303466
I. Herstellung der Wirkstoffe der Formel I: I. Preparation of the active ingredients of the formula I:
Eine Lösung von 10 g 2',4'-Dichlor-2-(3-pyridyl)-acetophenon-O-methyloxim in 100 ml Chloroform wird bei 00C mit 7,2 g m-Chlorperbenzoesäure versetzt und anschliessend 24 Stunden im Kühlschrank bei ca. 4°C aufbewahrt. Dann wird mit 200 ml Chloroform verdünnt und mit 250 ml 10%-iger Kaliumcarbonatlösung extrahiert. Die organische Phase wird über wasserfreiem Natriumsulfat getrocknet ^ und eingeengt. Als Rückstand erhält man 2',4'-Dichlor-2-(3"-pyridyl)-acetophenon-O-methyloxim-l"-oxid als E,Z-Isomerengemisch in Form einer gelblichen Paste.A solution of 10 g of 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone-O-methyloxime in 100 ml of chloroform is added at 0 0 C with 7.2 g of m-chloroperbenzoic acid followed by 24 hours in the refrigerator stored at approx. 4 ° C. It is then diluted with 200 ml of chloroform and extracted with 250 ml of 10% strength potassium carbonate solution. The organic phase is dried over anhydrous sodium sulfate and concentrated. The residue obtained is 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-methyloxime-1" oxide as E, Z isomer mixture in the form of a yellowish paste.
1515th
Auf analoge Weise erhält man durch Oxydation von 2·,4'— Dichlor-2-(2-pyrazinyl)-acetophenon-O-äthyloxim unter Verwendung von m-Chlorperbenzoesäure als Oxydationsmittel ein Reaktionsprodukt, das sich durch Chromatographie an Kieselgel mit Aethylacetat auftrennen lässt, und zwar in ein Gemisch von 21,4'-Dichlor-2-(2"-pyrazinyl)-acetophenon-O-äthyloxim-l"-oxid und 2',4'-Dichlor-2-(2"-pyrazinyl)-acetophenon-0-äthyloxim-4"-oxid (zähes OeI) sowie 2',4'-Dichlor-2-(2"-pyrazinyl)-acetophenon-O-äthyloxim-l",4"-dioxid, Smp. *■* 25 164-168°C.In an analogous manner, by oxidation of 2 ·, 4'-dichloro-2- (2-pyrazinyl) -acetophenone-O-ethyloxime using m-chloroperbenzoic acid as oxidant, a reaction product is obtained which can be separated by chromatography on silica gel with ethyl acetate , namely in a mixture of 2 1 , 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-O-ethyloxime-1" -oxide and 2 ', 4'-dichloro-2- (2 "-pyrazinyl ) -acetophenone-0-ethyloxime-4 "oxide (viscous oil) and 2 ', 4'-dichloro-2- (2" -pyrazinyl) -acetophenone-O-ethyloxime-1 ", 4" -dioxide, m.p. * ■ * 25 164-168 ° C.
1,41 g 2',4'-Dichlor-2-(3"-pyridyl)-acetophenon-1"-oxid werden in 5 ml Aethanol gelöst, mit 1 g Natriumcarbonat und 0,83 g 0-Methylhydroxylamin-hydrochlorid versetzt und anschliessend während 3 Stunden unter Rückfluss erhitzt. Dann wird auf Eis gegossen und mit Essigester extrahiert, und die organische Phase wird über wasserfreiem Natriumsulfat getrocknet und anschliessend eingeengt. Der Rückstand besteht aus 2',4'-Dichlor-2-(3"-pyridyl)-acetophenon-O-methyloxim-l "-oxid.1.41 g of 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-1" oxide are dissolved in 5 ml of ethanol, 1 g of sodium carbonate and 0.83 g of 0-methylhydroxylamine hydrochloride are added and then heated under reflux for 3 hours. Then it is poured onto ice and extracted with ethyl acetate, and the organic phase is dried over anhydrous sodium sulfate and then concentrated. Of the The residue consists of 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-methyloxime-1 "-oxide.
II. Herstellung der Ausgangsmaterialien: II. Production of the raw materials:
Eine Lösung von 13,3 g 2■,4'-Dichlor-2-(3-pyridyl)-acetophenon in 40 ml Aethanol wird mit 10 g Natriumcarbonat und 8,3 g O-Methylhydroxylamin-hydrochlorid versetzt und anschliessend unter Rühren auf Rückflusstemperatur erhitzt. Nach 4 Stunden wird das Reaktionsgemisch auf Eis gegossen und mit Essigester extrahiert. Die organische Phase wird gewaschen, über wasserfreiem Natriumsulfat getrocknet und unter vermindertem Druck eingeengt. Man erhält 2',4'— Dichlor-2-(3-pyridyl)-acetophenon-O-methyloxim als E,Z-Isomerengemisch in Form eines gelblichen OeIs.A solution of 13.3 g of 2,4'-dichloro-2- (3-pyridyl) acetophenone in 40 ml of ethanol, 10 g of sodium carbonate and 8.3 g of O-methylhydroxylamine hydrochloride are added and then heated to reflux temperature with stirring. After 4 hours the reaction mixture is poured onto ice and extracted with ethyl acetate. The organic phase is washed, dried over anhydrous sodium sulfate and concentrated under reduced pressure. You get 2 ', 4'— Dichloro-2- (3-pyridyl) -acetophenone-O-methyloxime as E, Z-isomer mixture in the form of a yellowish oil.
1515th
Auf analoge Weise erhält man aus 2',4'-Dichlor-2-(2-pyrazinyl)-acetophenon und O-Aethylhydroxylamin-hydrochlorid das 2',4'-Dichlor-2-(2-pyrazinyl)-acetophenon-O-äthyloxim als OeI.In an analogous manner, 2 ', 4'-dichloro-2- (2-pyrazinyl) acetophenone is obtained and O-ethylhydroxylamine hydrochloride the 2 ', 4'-dichloro-2- (2-pyrazinyl) -acetophenone-O-ethyloxime as OeI.
2020th
Eine Lösung von 5 g 2',4'-Dichlor-2-(3-pyridyl)-acetophenon in 20 ml Chloroform wird bei 00C mit 3,6 g m-Chlor-„ 25 perbenzoesäure versetzt und anschliessend 24 Stunden im Kühlschrank bei ca. 4"C aufbewahrt. Dann wird mit 100 ml Chloroform verdünnt und mit 100 ml 10%-iger Kaliumcarbonatlösung extrahiert. Die organische Phase wird über wasserfreiem Natriumsulfat getrocknet und eingeengt. Man erhält 2·,4'-Dichlor-2-(3"-pyridyl)-acetophenon-l"-oxid, Smp. 137-1400C.A solution of 5 g of 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone in 20 ml of chloroform at 0 0 C with 3.6 g of m-chloro- "offset 25 perbenzoic acid followed by 24 hours in the refrigerator stored at about 4 ° C. It is then diluted with 100 ml of chloroform and extracted with 100 ml of 10% strength potassium carbonate solution. The organic phase is dried over anhydrous sodium sulfate and concentrated. 2, 4'-dichloro-2- ( 3 "-pyridyl) acetophenone-l" oxide, mp. 137-140 0 C.
Ein Gemisch von 27,6 g 2,4-Dichlorbenzoesäure-äthylester und 20,81 g 3-Pyridylessigsäureäthylester bei 20-25"C wird portionenweise mit 10,59 g Natriummethylat versetzt. Das Reaktionsgemisch wird anschliessend auf 65-A mixture of 27.6 g of ethyl 2,4-dichlorobenzoate and 20.81 g of ethyl 3-pyridyl acetate at 20-25 "C. 10.59 g of sodium methylate are added in portions. The reaction mixture is then increased to 65-
70°C erhitzt, und entstehende leichtflüchtige Produkte werden mit trockenem Stickstoff abgeblasen. Nach 20 Stunden wird mit 40 ml konzentrierter Salzsäure versetzt · und 18 Stunden bei Rückflusstemperatur erhitzt. Das Gemisch wird mit Diäthyläther gewaschen und die wässrige Phase durch Zugabe von konzentriertem Ammoniak basisch gestellt und mit Methylenchlorid extrahiert. Die organische Phase wird eingeengt und das Rohprodukt an Kieselgel mit Methylenchlorid/Methanol (98:2) chromatographiert.70 ° C heated, and resulting volatile products are blown off with dry nitrogen. After 20 hours, 40 ml of concentrated hydrochloric acid are added and heated at reflux temperature for 18 hours. The mixture is washed with diethyl ether and the aqueous phase is made basic by adding concentrated ammonia placed and extracted with methylene chloride. The organic phase is concentrated and the crude product on silica gel Chromatographed with methylene chloride / methanol (98: 2).
Das Produkt, 2',4'-Dichlor-2-(3-pyridyl)-acetophenon, kann aus Diäthyläther/n-Pentan zur Kristallisation gebracht werden und schmilzt bei 55-560C.The product, 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone may be selected from diethyl ether / n-pentane are brought to crystallization and melting at 55-56 0 C.
III. Formulierungsbeispiele III. Formulation examples
1. Spritzpulver (für flüssige oder unter ?5°C schmelzende
Wirkstoffe)
201. Wettable powder (for liquid active ingredients or those that melt below? 5 ° C)
20th
Wirkstoff der Formel I 50Active ingredient of formula I 50
Hydratisierte Kieselsäure 37Hydrated silica 37
Kaolin 5Kaolin 5
Alkylphenoläthoxylat 4Alkyl phenol ethoxylate 4
Natrium-polynaphthalinsulfonat 4 Sodium polynaphthalene sulfonate 4
100100
Der flüssige oder geschmolzene Wirkstoff wird auf die Kieselsäure aufgezogen, die übrigen Komponenten zugemischt und das Ganze in einer geeigneten Mühle feingemahlen. The liquid or molten active ingredient is absorbed onto the silica and the other components are mixed in and the whole thing finely ground in a suitable mill.
2. Spritzpulver (für feste, über 750C schmelzende Wirkstoffe) 2. Wettable powder (for solid active ingredients that melt above 75 0 C)
Wirkstoff der Formel I 50Active ingredient of formula I 50
Hydratisierte Kieselsäure 5Hydrated silica 5
Kaolin 42Kaolin 42
Natrium-laurylsulfat ISodium Lauryl Sulphate I.
Natrium-lignosulfonat 2_Sodium lignosulfonate 2_
100100
Die Komponenten werden miteinander vermischt und das Ganze in einer geeigneten Mühle feingemahlen.The components are mixed together and the whole thing finely ground in a suitable mill.
Emulgierbares Konzentrat (für bei 20-250C flüssige Wirkstoffe)Emulsifiable concentrate (for active ingredients that are liquid at 20-25 0 C)
Gewichtsteile Wirkstoff der Formel I Ricinusöl-äthoxylat Calcium-dodecylbenzolsulfonat Parts by weight of active ingredient of the formula I castor oil ethoxylate calcium dodecylbenzenesulfonate
Gemisch von C,„-Alkylbenzolen ad 1000 Vol.-TeileMixture of C, "- alkylbenzenes to 1000 parts by volume
Die Komponenten werden miteinander vermischt, bis eine klare Lösung entsteht.The components are mixed together until a clear solution is obtained.
Claims (10)
R Wasserstoff oder geradkettiges C-^.-R 3-pyridyl-1-oxide, 2-pyrazinyl-1-oxide, 2-pyrazinyl-4-oxide or 2-pyrazinyl-1,4-dioxide,
R hydrogen or straight chain C - ^ .-
und R C- g-Alkyl, C3 g-Cycloalkyl, C3_g-AlkenylAlkyl
and R C 1-6 alkyl, C 3 g cycloalkyl, C 3 -C alkenyl
R 3-Pyridyl-l-oxid, 2-Pyrazinyl-l-oxid, 2-Pyrazinyl-4-oxid oder 2-Pyrazinyl-1,4-2
R 3-pyridyl-1-oxide, 2-pyrazinyl-1-oxide, 2-pyrazinyl-4-oxide or 2-pyrazinyl-1,4-
und R C. g-Alkyl, C, ,--Cycloalkyl, C3_g-Alkenyl4th
and R C. g-alkyl, C 1-10 cycloalkyl, C 3 -C alkenyl
R 3-Pyridyl-l-oxid, 2-Pyrazinyl-l-oxid,2
R 3-pyridyl-1-oxide, 2-pyrazinyl-1-oxide,
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1881/82A CH650253A5 (en) | 1982-03-26 | 1982-03-26 | PYRIDINE AND PYRAZINE DERIVATIVES AND THEIR USE AS FUNGICIDAL ACTIVE SUBSTANCES. |
Publications (1)
Publication Number | Publication Date |
---|---|
DE3309466A1 true DE3309466A1 (en) | 1983-10-06 |
Family
ID=4220764
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Application Number | Title | Priority Date | Filing Date |
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DE19833309466 Withdrawn DE3309466A1 (en) | 1982-03-26 | 1983-03-16 | PYRIDINE AND PYRAZINE DERIVATIVES |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS58174364A (en) |
CH (1) | CH650253A5 (en) |
DE (1) | DE3309466A1 (en) |
FR (1) | FR2523966B1 (en) |
GB (1) | GB2117768B (en) |
IT (1) | IT1205296B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0445069A1 (en) * | 1990-02-16 | 1991-09-04 | Ciba-Geigy Ag | Heterocyclic compounds |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0007679A1 (en) * | 1978-07-25 | 1980-02-06 | Acf Chemiefarma Nv | Oxime ethers, processes for their manufacture and pharmaceutical compositions thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3205234A (en) * | 1961-06-30 | 1965-09-07 | Upjohn Co | Nu-oxides of pyridyl ketone omicron-hydrocarbonoximes |
US4171214A (en) * | 1977-01-06 | 1979-10-16 | Imperial Chemical Industries Limited | Pyrazine-2-ylmethyl-ketones and their fungicidal use |
GB2015524A (en) * | 1978-03-06 | 1979-09-12 | Ici Ltd | Pyridine derivatives |
CA1225092A (en) * | 1980-10-10 | 1987-08-04 | Franz Dorn | Pyridine and pyrazine derivatives |
IT1172404B (en) * | 1982-03-31 | 1987-06-18 | Hoffmann La Roche | HETEROCYCLIC COMPOUNDS |
-
1982
- 1982-03-26 CH CH1881/82A patent/CH650253A5/en not_active IP Right Cessation
-
1983
- 1983-02-25 IT IT19818/83A patent/IT1205296B/en active
- 1983-03-16 DE DE19833309466 patent/DE3309466A1/en not_active Withdrawn
- 1983-03-22 FR FR8304658A patent/FR2523966B1/en not_active Expired
- 1983-03-25 GB GB08308341A patent/GB2117768B/en not_active Expired
- 1983-03-25 JP JP58050279A patent/JPS58174364A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0007679A1 (en) * | 1978-07-25 | 1980-02-06 | Acf Chemiefarma Nv | Oxime ethers, processes for their manufacture and pharmaceutical compositions thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0445069A1 (en) * | 1990-02-16 | 1991-09-04 | Ciba-Geigy Ag | Heterocyclic compounds |
Also Published As
Publication number | Publication date |
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GB2117768A (en) | 1983-10-19 |
CH650253A5 (en) | 1985-07-15 |
FR2523966A1 (en) | 1983-09-30 |
IT1205296B (en) | 1989-03-15 |
IT8319818A0 (en) | 1983-02-25 |
GB2117768B (en) | 1985-10-09 |
FR2523966B1 (en) | 1986-12-05 |
JPS58174364A (en) | 1983-10-13 |
GB8308341D0 (en) | 1983-05-05 |
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