CN116265457B - N-oxa condensed ring amide compound and preparation method and application thereof - Google Patents
N-oxa condensed ring amide compound and preparation method and application thereof Download PDFInfo
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- CN116265457B CN116265457B CN202111555336.0A CN202111555336A CN116265457B CN 116265457 B CN116265457 B CN 116265457B CN 202111555336 A CN202111555336 A CN 202111555336A CN 116265457 B CN116265457 B CN 116265457B
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- -1 amide compound Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 150
- 244000052769 pathogen Species 0.000 claims abstract description 18
- 230000000749 insecticidal effect Effects 0.000 claims abstract description 15
- 230000000895 acaricidal effect Effects 0.000 claims abstract description 4
- 230000000855 fungicidal effect Effects 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 241000607479 Yersinia pestis Species 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- 239000003814 drug Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- WBNUVPGJLHTDTD-UHFFFAOYSA-N 4-ethyl-5-methylimidazolidin-2-one Chemical compound CCC1NC(=O)NC1C WBNUVPGJLHTDTD-UHFFFAOYSA-N 0.000 claims description 5
- 241000238876 Acari Species 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 230000001717 pathogenic effect Effects 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001266 acyl halides Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 4
- 230000001931 phytocidal effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 53
- 230000004071 biological effect Effects 0.000 abstract description 7
- 201000010099 disease Diseases 0.000 description 21
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 21
- XTDZGXBTXBEZDN-UHFFFAOYSA-N 3-(difluoromethyl)-N-(9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl)-1-methylpyrazole-4-carboxamide Chemical compound CC(C)C1C2CCC1C1=C2C=CC=C1NC(=O)C1=CN(C)N=C1C(F)F XTDZGXBTXBEZDN-UHFFFAOYSA-N 0.000 description 20
- 230000000844 anti-bacterial effect Effects 0.000 description 19
- 240000007594 Oryza sativa Species 0.000 description 18
- 235000007164 Oryza sativa Nutrition 0.000 description 18
- 241000209140 Triticum Species 0.000 description 18
- 235000021307 Triticum Nutrition 0.000 description 18
- 235000009566 rice Nutrition 0.000 description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 15
- 240000008042 Zea mays Species 0.000 description 14
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 14
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 14
- 235000005822 corn Nutrition 0.000 description 14
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- 239000005799 Isopyrazam Substances 0.000 description 13
- 241001124076 Aphididae Species 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical class [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
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- 240000008067 Cucumis sativus Species 0.000 description 8
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000012267 brine Substances 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 7
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- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 7
- 229920000053 polysorbate 80 Polymers 0.000 description 7
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
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- 125000000592 heterocycloalkyl group Chemical group 0.000 description 5
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- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 4
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- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 4
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- XNXCINUKGNQCEZ-UHFFFAOYSA-N 3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound CN1C=C(C(N)=O)C(C(F)F)=N1 XNXCINUKGNQCEZ-UHFFFAOYSA-N 0.000 description 3
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- FQKUGOMFVDPBIZ-UHFFFAOYSA-N flusilazole Chemical compound C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 FQKUGOMFVDPBIZ-UHFFFAOYSA-N 0.000 description 3
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- 241000255777 Lepidoptera Species 0.000 description 1
- 241001330975 Magnaporthe oryzae Species 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 241000409991 Mythimna separata Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241001668536 Oculimacula yallundae Species 0.000 description 1
- 241000488581 Panonychus citri Species 0.000 description 1
- 241000736122 Parastagonospora nodorum Species 0.000 description 1
- 241000315044 Passalora arachidicola Species 0.000 description 1
- 241000233614 Phytophthora Species 0.000 description 1
- 241000233616 Phytophthora capsici Species 0.000 description 1
- 241000255969 Pieris brassicae Species 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 241001304534 Puccinia polysora Species 0.000 description 1
- 241000231139 Pyricularia Species 0.000 description 1
- 241000579741 Sphaerotheca <fungi> Species 0.000 description 1
- 241000256247 Spodoptera exigua Species 0.000 description 1
- 241000985245 Spodoptera litura Species 0.000 description 1
- 241001161749 Stenchaetothrips biformis Species 0.000 description 1
- 241001454294 Tetranychus Species 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000007884 disintegrant Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an N-oxa condensed ring amide compound shown in a formula (I), and a preparation method and application thereof.Wherein R, R 1、R2、R3、R4、R5、W1、W2, m and n have the meanings given in the description. The compounds of formula (I) according to the invention have insecticidal/acaricidal or fungicidal biological activity, in particular high activity against harmful pathogens.
Description
Technical Field
The invention belongs to the field of pesticides and bactericides, and in particular relates to N-oxa condensed ring amide compounds with insecticidal and bactericidal biological activity, a preparation method thereof, insecticidal and bactericidal compositions containing the compounds, and application and a method for controlling pests and harmful bacteria by using the compounds.
Background
The control of pests and harmful pathogens is very important in achieving efficient agriculture. The control of pests and harmful pathogens is also important in the fields of forests, pastures, auxiliary, fishing and public health. Although many pest and harmful bacteria prevention and control agents exist in the market, due to the continuous expansion of the market, the external pests and harmful bacteria, the drug resistance of the pests and harmful bacteria, the service life of the drugs, the economy of the drugs and the like, and the increasing importance of people on the environment, scientists are required to continuously research and develop new varieties of pesticides with novel safety, high efficiency, economy, environmental compatibility and unique action modes.
The amide compound has broad-spectrum insecticidal and bactericidal activity, and commercial amide compounds serving as pesticides and bactericides are all N-condensed ring amide compounds, and although reports of the N-condensed ring amide compounds are not visible everywhere, the commercial bactericides are not widely sourced from the N-condensed ring amide compounds, such as the bactericides of isopyrazam (D1) which is introduced by the year 2010. The isopyrazam can effectively prevent and treat powdery mildew, rust disease and other diseases on crops such as wheat, rice, peanut and the like; the isopyrazam is low in toxicity, safe to non-target organisms and safe and friendly to users and environment.
In order to obtain new active molecules with higher biological activity or more convenient synthesis than isopyrazam (D1), based on literature investigation and our earlier work, we designed and synthesized N-oxacondensed ring amide compounds with insecticidal and bactericidal activity shown in formula (I) which are not reported. Compared with the isopyrazam (D1), the compound has simpler structure, simpler and more convenient synthesis process and more economic synthesis cost, has higher insecticidal activity than the isopyrazam (D1) such as 01 and 16, and has the same level of bactericidal activity on corn rust and the like as the isopyrazam (D1).
Disclosure of Invention
The invention provides N-oxa condensed ring amide compounds with insecticidal, bactericidal and other biological activities shown in a formula (I):
Wherein:
I.R represents C 1-C12 alkyl, C 2-C12 alkenyl, C 2-C12 alkynyl, C 3-C8 cycloalkyl or C 3-C8 heterocycloalkyl; r 1 represents hydrogen, halogen, C 1-C12 alkyl, C 2-C12 alkenyl, C 2-C12 alkynyl, C 3-C8 cycloalkyl or C 3-C8 heterocycloalkyl; r 2 represents hydrogen, C 1-C12 alkyl or C 3-C8 cycloalkyl; r 3、R4 are identical or different and represent C 1-C12 alkyl or C 3-C8 cycloalkyl; r 5 are identical or different and represent hydrogen, halogen or C 1-C12 alkyl;
W 1 represents oxygen or sulfur; w 2 represents oxygen, sulfur or CH 2;
M represents an integer of 1,2 or 3; n represents an integer of 1,2 or 3;
The hydrogen atoms in I or II may be partially or fully substituted by identical or different substituents selected from the group consisting of: halogen, C 1-C6 alkyl, C 1-C6 alkoxy or C 1-C6 alkylthio;
In the definition of compound (I) above, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine, iodine;
Alkyl: refers to straight or branched chain alkyl groups;
alkenyl groups; refers to straight or branched alkyl groups and may have double bonds at any position;
alkynyl; refers to straight or branched alkyl groups and may have triple bonds at any position;
Halogenating: means that hydrogen atoms are partially or completely substituted with halogen atoms;
Cycloalkyl: refers to saturated or unsaturated cycloalkyl;
heterocycloalkyl group: refers to saturated or unsaturated heterocycloalkyl groups having at least 1N, O or S heteroatoms in the ring.
Preferred compounds of the invention are: in formula (I):
I.R represents a C 1-C6 alkyl group; r 1 represents hydrogen or halogen; r 2 represents hydrogen or C 1-C6 alkyl; r 3、R4 are identical or different and represent C 1-C6 alkyl; r 5 are identical or different and represent hydrogen, halogen or C 1-C6 alkyl;
W 1 represents oxygen or sulfur; w 2 represents oxygen, sulfur or CH 2;
m represents an integer of 1,2 or 3; n represents an integer of 1,2 or 3.
Further preferred compounds of the invention are: in formula (I):
I.R represents methyl or ethyl; r 1 represents hydrogen or halogen; r 2 represents hydrogen; r 3、R4 are identical or different and represent C 1-C4 alkyl; r 5 are identical or different and represent hydrogen or halogen;
W 1 represents oxygen or sulfur; w 2 represents oxygen, sulfur or CH 2;
m represents an integer of 1; n represents an integer of 1 or 2.
Particularly preferred compounds of formula (I) according to the invention are:
N- (2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;
N- (2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;
n- (2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide;
n- (2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide;
n- (4-fluoro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;
N- (7-fluoro-2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;
n- (4-fluoro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide;
n- (7-fluoro-2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide;
n- (4-chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;
n- (5-chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;
N- (5-bromo-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;
N- (4, 5-dichloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;
n- (2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-ethyl-1H-pyrazole-4-carboxamide;
N- (2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-1-ethyl-1H-pyrazole-4-carboxamide;
n- (2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-5-fluoro-1-ethyl-1H-pyrazole-4-carboxamide;
n- (2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-5-fluoro-1-ethyl-1H-pyrazole-4-carboxamide;
N- (4-fluoro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-ethyl-1H-pyrazole-4-carboxamide;
N- (7-fluoro-2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-1-ethyl-1H-pyrazole-4-carboxamide;
n- (4-fluoro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-5-fluoro-1-ethyl-1H-pyrazole-4-carboxamide;
N- (7-fluoro-2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-5-fluoro-1-ethyl-1H-pyrazole-4-carboxamide;
N- (4-chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-ethyl-1H-pyrazole-4-carboxamide;
n- (5-chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-ethyl-1H-pyrazole-4-carboxamide;
n- (5-bromo-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-ethyl-1H-pyrazole-4-carboxamide;
N- (4, 5-dichloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-ethyl-1H-pyrazole-4-carboxamide.
The compounds of formula (I) of the present invention may exist in one or more isomeric forms. Isomers include enantiomers, diastereomers, geometric isomers and cis-trans isomers. The compounds of formula (I) of the present invention, which may form geometric isomers (different configurations represented by Z and E, respectively) due to the carbon-carbon double bond thereof being linked to different substituents, include Z-type isomers and E-type isomers and mixtures thereof in any ratio; the compounds of formula (I) of the present invention, which comprise R-type isomers and S-type isomers and mixtures thereof in any ratio, form stereoisomers (different configurations are represented by R and S respectively) due to the different substituents attached to one of the carbon or nitrogen atoms; the compounds of formula (I) of the present invention, due to the fact that more than 2 substituents are attached to the cycloalkyl or heterocycloalkyl groups therein to form cis-trans isomers (different configurations are denoted by cis and trans respectively), include cis-type isomers and trans-type isomers and mixtures thereof in any ratio.
The invention also relates to a composition for controlling pests, harmful bacteria, comprising a biologically effective amount of a compound of formula (I) and at least one additional diluent selected from the group consisting of surfactants, solid diluents and liquid diluents.
The invention also relates to a composition for controlling pests, harmful bacteria, comprising a biologically effective amount of a compound of formula (I) and an effective amount of at least one further biologically active compound or formulation.
The invention also relates to a method for controlling pests, harmful pathogens, comprising contacting the pests, harmful pathogens, or the environment thereof with a biologically effective amount of a compound of formula (I). Also disclosed is a method for controlling pests, harmful pathogens, or their environment by contacting the pests, harmful pathogens, or their environment with a biologically effective amount of a compound of formula (I) or a mixture comprising a compound of formula (I) and a biologically effective amount of at least one additional compound or formulation.
The compounds of formula (I) of the present invention have broad spectrum activity: some compounds are useful for controlling harmful pathogens, and also for controlling pests; and some compounds have high activity on some harmful pathogens, and good effect can be obtained at low dosage.
Preferred compositions of the present invention are compositions containing the preferred compounds described above. Preferred methods are those using the preferred compounds described above.
The invention is further illustrated, but not limited, by the following description of some of the compounds of formula (I) listed in Table 1. The melting points given in the present invention are not corrected, and when the compound of formula (I) of the present invention is a viscous solid, some of the viscous solid solidifies to a non-viscous solid after leaving it, and when the compound of formula (I) of the present invention is a viscous liquid, some of the viscous liquid solidifies after leaving it, and molecular ion peaks are observed in LC-MS (APCI, pos or Neg) (Agilent 1100Series LC/MSD) of the compounds of Table 1. 1 H NMR (Varian INOVA-300 spectrometer) of the compounds in Table 1 was used as internal standard TETRAMETHYLSILANE (TMS) with deuterated chloroform (CDCl 3) or deuterated dimethyl sulfoxide (DMSO) as solvent.
Table 1:
The compound of formula (I) of the present invention can be obtained by the following reaction formula 1; (II) in the reaction scheme 1 can be obtained by the following reaction scheme 2; (III) and (IV) in the reaction scheme 1 can be obtained by the following reaction scheme 3; (V) in the reaction formula 2 and (VI) and (VII) in the reaction formula 3 can be prepared by purchasing or referring to the relevant literature; l in the reaction formula is a leaving group such as chlorine, bromine, iodine or sulfonate, etc., R v in the reaction formula 3 is a C 1-C4 alkyl group such as methyl or ethyl, etc., and other substituents are as defined above unless otherwise indicated.
Reaction formula 1-1:
reaction formula 1-2:
Reaction formula 2:
Reaction formula 3:
The compounds of formula (I) can be prepared as such (reaction formula 1): reacting a compound of formula (II) with a compound of formula (III) or a compound of formula (II) with a compound of formula (IV) in the presence of no base or a suitable base such as triethylamine, pyridine, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate in a single solvent or a mixed solvent of any two of dichloromethane, dichloroethane, acetonitrile, toluene, xylene, ethyl acetate, acetone, N-dimethylformamide, tetrahydrofuran or dioxane at a temperature of 25 ℃ to the reflux temperature of the system.
The compound of formula (II) can be prepared as follows (reaction formula 2): in a proper solvent such as dichloromethane, dichloroethane, acetonitrile, acetone, toluene, xylene, tetrahydrofuran or dioxane, at a temperature of 25 ℃ to a reflux temperature of a system, the compound of the formula (V) is reacted with an acyl halide reagent such as sulfoxide halide, phosphorus trihalide or phosgene to obtain a compound of the formula (II), and a catalytic amount of N, N-dimethylformamide is added to assist in preparing the compound of the formula (II).
The compounds of formulae (III) and (IV) can be prepared as such (reaction formula 3): in a proper solvent such as dichloromethane, dichloroethane, acetonitrile, acetone, toluene, methanol, ethanol, isopropanol, butanol, N-dimethylformamide, tetrahydrofuran or dioxane, and the like, in the presence of a proper base such as triethylamine, pyridine, sodium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate and the like at the temperature of 25 ℃ to the reflux temperature of the system, the compound of formula (VI) is reacted with the compound of formula (VII) to obtain the compound of formula (VIII), and a catalytic amount of sodium iodide or potassium iodide and the like are added to assist the preparation of the compound of formula (VIII); in water, methanol, ethanol, isopropanol, butanol, N-dimethylformamide, tetrahydrofuran or dioxane and other single solvents or mixed solvents of any two, reacting a compound of formula (VIII) with ammonia water at a temperature of 25 ℃ to a reflux temperature of a system to obtain a compound of formula (IX), and adding 1, 3-dimethylpropyleneurea to facilitate the preparation of the compound of formula (IX); the compound of formula (IX) can be converted into the compound of formula (III) in the presence of a suitable base such as triethylamine, pyridine, sodium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate in a suitable solvent such as N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran or dioxane at a temperature of 25℃to the reflux temperature of the system; the compound of formula (III) is condensed with the corresponding aldehyde and then reduced or the compound of formula (III) is reacted with RL under suitable conditions to obtain the compound of formula (IV).
Specific synthetic methods are set forth in more detail in the examples below.
The compounds of formula (I) according to the invention have a broad spectrum of biological activity at an active ingredient per hectare of 15-2250 g, and can be used for controlling harmful pathogens and/or for controlling harmful insects. Some compounds have good harmful bacteria preventing and treating effect, and good effect can be obtained at low dosage.
The compounds of the formula (I) according to the invention have biological activity and the compounds have very good biological activity, in particular in the control of agricultural, horticultural, floral and hygienic pests and harmful pathogens. The pests described herein include, but are not limited to:
Harmful pathogenic bacteria: phytophthora species, erysiphe species, gibberella species, ceripomoea species, rhizoctonia species, botrytis species, pyricularia species, fusarium species. Such as rice blast (Pyricularia oryzae); wheat stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust; barley stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita), and other rust; barley and wheat powdery mildew (ERYSIPHE GRAMINIS), cucumber powdery mildew (Sphaerotheca fuligenea), apple powdery mildew (Podosphaera leucotrichar) and grape powdery mildew (Podosphaera leucotrichar); sheath blight and glume blight (Septoria nodorum) of wheat. Vermicular, muzzle, aschersonia, nucleocapsid, pseudocercosporella herpotrichoides and wheat take-all on cereals (Gaeumannomyces graminis). Brown spot (Cercospora arachidicola) and black spot (Cercosporidium personata) of peanuts; alternaria alternata (Botryosphaeria berengriana f.sp piricola), and alternaria alternata (Cytospora sp.); its cercospora disease on beet, soybean and rice. Tomato, cucumber, grape gray mold (Botrytis cinerea). Gemini disease on vegetables such as cucumber. Anthracnose on cucumber, apple scab, cucumber downy mildew, grape downy mildew, epidemic disease on potato and tomato, monocotyledonous Thanatephorus cucumeris on rice and other hosts such as wheat and barley, other rhizoctonia on vegetables; sclerotinia rot of colza (Sclerotonia sclerotiorum); wheat scab (Gibberella zeae); phytophthora capsici (Phytophythora capsici).
Insect pest: lepidoptera pests such as Oriental armyworm, spodoptera litura, plutella xylostella, spodoptera exigua, cabbage caterpillar, orientials such as Blatta seu Blatta, thysanoptera such as Fragilt, rice thrips, and melon thrips, homoptera such as leafhopper, plant hopper, and aphid, hymenoptera such as larva of Apis, diptera such as Aedes, culex, and fly; acarina pest mites such as panonychus citri, tetranychus gossypii, tetranychus urticae, etc.
The compounds of formula (I) of the present invention are effective alone in controlling pests, harmful pathogens, and may be used with other biochemical substances including other insecticides, nematocides, acaricides and fungicides.
The compound of formula (I) of the present invention can be prepared into any desired agricultural preparation as an active ingredient, such as dry compressed granules, flowable mixtures, granules, wettable powders, water dispersible granules, emulsifiable concentrates, powders, powdery concentrates, micro-emulsions, suspensions, emulsifiable concentrates, aqueous emulsions, soluble solutions, aqueous solutions, dispersible solutions, suitable adjuvants including carriers (diluents) and other adjuvants such as spreaders, emulsifiers, wetting agents, dispersants, adhesives and decomposers. These formulations comprise the compound of formula (I) of the present invention admixed with an inert, pharmacologically acceptable solid or liquid diluent.
Examples of compositions of the invention may also be formulated into any desired dosage form such as dry compressed granules, flowable mixtures, granules, wettable powders, water dispersible granules, emulsifiable concentrates, powders, powdered concentrates, microemulsions, suspensions, emulsifiable concentrates, aqueous solutions, dispersible solutions, suitable adjuvants include carriers (diluents) and other adjuvants such as spreaders, emulsifiers, wetting agents, dispersants, adhesives and disintegrants. These formulations comprise the compound of formula (I) of the present invention admixed with an inert, pharmacologically acceptable solid or liquid diluent.
The invention is further illustrated by the following examples, in which the yields are not optimised, and in which other compounds of the invention can be prepared by reference to the following examples and the relevant literature.
Detailed Description
Synthetic examples
Example 1 this example illustrates the preparation of Compound 01 in Table 1
Ethyl 2- ((2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propionate to a solution of 2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-ol (0.10 mol) in acetone (125 mL) was added potassium carbonate (0.20 mol) at room temperature under stirring, after stirring for 5-10min, ethyl 2-bromopropionate (0.12 mol) and sodium iodide (0.01 mol) were added, and the reaction mixture was warmed to reflux and stirred for 5-8h until the reaction was complete. The reaction mixture was cooled, poured into an appropriate amount of ice brine, extracted with ethyl acetate, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 25.80g of the title compound, which was used directly in the next reaction.
A mixture of ethyl 2- ((2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propanamide 2- ((2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propanoate (0.08 mol), aqueous ammonia (25%, 0.50 mol), ethanol (75 mL) and water (25 mL) was stirred overnight at room temperature. The reaction mixture was poured into an appropriate amount of ice brine, extracted with ethyl acetate, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give the title compound 15.00g, which was used directly in the next reaction.
A reaction mixture solution of 2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-amine 2- ((2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propionamide (0.03 mol), potassium hydroxide (0.06 mol) and dimethyl sulfoxide (50 mL) was stirred at 120-150 ℃ for 5-8h until the reaction was completed. The reaction mixture was cooled, poured into an appropriate amount of brine ice, extracted with ethyl acetate, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 3.62g of the title compound, which was used directly in the next reaction, and 1, 3-dimethylpropyleneurea was added to aid the reaction.
3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide sulfoxide chloride (0.25 mol) was added dropwise to a mixture of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (0.10 mol), N-dimethylformamide (0.50 g) and toluene (75 mL) under reflux and stirring for 30-45min, and after the addition was completed, the reflux and stirring reaction was continued for 2-5H until the reaction was completed. After cooling, the mixture was allowed to stand, and the supernatant was concentrated under reduced pressure to give 17.56g of the title compound, which was used directly in the next reaction.
N- (2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide 2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-amine (10 mmol) and 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide (11 mmol) were stirred under reflux in toluene (20 mL) for 2-5H until the reaction was complete. Cooling to room temperature, washing with saturated sodium bicarbonate solution, separating organic phase, washing with water, drying with anhydrous sodium sulfate, concentrating under reduced pressure to obtain crude product, separating and purifying the crude product with ethyl acetate and petroleum ether under reduced pressure column chromatography to obtain yellow solid title compound 1.65g, melting point ：107.0-108.9℃.1H NMR(300MHz,CDCl3)δ:1.487(s,6H,2CH3),3.057(s,2H,CH2),3.968(s,3H,CH3),6.786(t,J＝54.0Hz,1H,CH),6.806-6.946(m,2H,Ph H),7.969(s,1H,Ph H),8.097(s,1H,NH),8.126(s,1H,Pyrazole H).LC-MS(Pos M+)m/z)calc:322,found:322.
Example 2 this example illustrates a process for the preparation of compound 16 in Table 1
Ethyl 2- ((2, 2-dimethylpheno [ d ] [1,3] dioxo-4-yl) oxy) propionate to a solution of 2, 2-dimethylpheno [ d ] [1,3] dioxo-4-phenol (0.10 mol) in acetone (125 mL) was added potassium carbonate (0.20 mol) under stirring at room temperature for 5-10min, and after stirring, ethyl 2-bromopropionate (0.12 mol) and sodium iodide (0.01 mol) were added, and the reaction mixture was warmed to reflux and stirred for 5-8h until completion. The reaction mixture was cooled, poured into an appropriate amount of ice brine, extracted with ethyl acetate, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 24.20g of the title compound, which was used directly in the next reaction.
A mixture of ethyl 2- ((2, 2-dimethylpheno [ d ] [1,3] dioxo-4-yl) oxy) propionamide 2- ((2, 2-dimethylpheno [ d ] [1,3] dioxo-4-yl) oxy) propionate (0.08 mol), aqueous ammonia (25%, 0.50 mol), ethanol (75 mL) and water (25 mL) was stirred overnight at room temperature. The reaction mixture was poured into an appropriate amount of ice brine, extracted with ethyl acetate, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 14.85g of the title compound, which was used directly in the next reaction.
A reaction mixture of 2, 2-dimethyl benzo [ d ] [1,3] dioxo-4-amine 2- ((2, 2-dimethyl benzo [ d ] [1,3] dioxo-4-yl) oxy) propanamide (0.03 mol), potassium hydroxide (0.06 mol) and dimethyl sulfoxide (50 mL) was stirred at 120-150℃for 5-8h until the reaction was complete. The reaction mixture was cooled, poured into an appropriate amount of ice brine, extracted with ethyl acetate, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 3.55g of the title compound, which was used directly in the next reaction, and 1, 3-dimethylpropyleneurea was added to aid the reaction.
N- (2, 2-Dibenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide 2, 2-Dibenzo [ d ] [1,3] dioxo-4-amine (10 mmol) and 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide (11 mmol) were stirred under reflux in toluene (20 mL) for 2-5H to completion. The reaction mixture was cooled to room temperature, washed with saturated sodium bicarbonate solution, and the organic phase was separated, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product, which was purified by ethyl acetate and petroleum ether column chromatography under reduced pressure to give the title compound as a brown solid (1.52 g, melting point) ：145.4-146.7℃.1H NMR(300MHz,CDCl3)δ:1.692(s,6H,2CH3),3.952(s,3H,CH3),6.554-6.791(m,2H,Ph H),6.812(t,J＝54.0Hz,1H,CH),7.666(d,J＝8.1Hz,1H,Ph H),7.955(s,1H,NH),7.987(s,1H,Pyrazole H).LC-MS(Pos M+)m/z)calc:324,found:324.
Example 3 this example illustrates a process for the preparation of compound 131 in Table 1
2- ((5-Chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propanamide to a mixed solution of 2- ((2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propanamide (0.05 mol) and ethyl acetate (100 mL) was added dropwise with stirring while cooling in an ice-water bath, and stirring was continued for 1-2h until the reaction was completed. The reaction mixture was poured into a proper amount of brine ice, extracted with ethyl acetate, the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product, which was purified by ethyl acetate and petroleum ether column chromatography under reduced pressure to give the title 7.95g, which was directly used in the next reaction.
A reaction mixture solution of 5-chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-amine 2- ((4-chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propionamide (0.05 mol), potassium hydroxide (0.10 mol) and dimethyl sulfoxide (80 mL) was stirred at 120-150 ℃ for 5-8h until the reaction was completed. The reaction mixture was cooled, poured into an appropriate amount of brine ice, extracted with ethyl acetate, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 8.15g of the title compound, which was used directly in the next reaction, and 1, 3-dimethylpropyleneurea was added to aid the reaction.
N- (5-chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide 5-chloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-amine (10 mmol) and 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide chloride (11 mmol) were stirred in toluene (20 mL) under reflux for 2-5H until the reaction was complete. The reaction mixture was cooled to room temperature, washed with saturated sodium bicarbonate solution, and the organic phase was separated, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product, which was purified by ethyl acetate and petroleum ether column chromatography under reduced pressure to give the title compound as an off-white solid (1.82 g, melting point: 144.2-144.5 ℃. LC-MS (Pos M +) M/z) calc:356, found:356.
Example 4 this example illustrates a process for the preparation of compound 171 in Table 1
N- (5-bromo-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide reference example 3 can be synthesized to give the title compound as a pale yellow solid 2.15g, melting point ：143.5-145.1℃.1H NMR(300MHz,CDCl3)δ:1.367(s,6H,2CH3),3.047(s,2H,CH2),3.978(s,3H,CH3),6.796(t,J＝54.0Hz,1H,CH),7.020(s,1H,Ph H),7.969(s,1H,Ph H),8.087(s,1H,NH),8.326(s,1H,Pyrazole H).LC-MS(Pos M+)m/z)calc:400,found:400.
Example 5 this example illustrates a method for the preparation of compound 187 in Table 1
N- (4, 5-dichloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide the procedure of example 3 was followed, in the case of 2- ((4, 5-dichloro-2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propanamide synthesis, by increasing the molar ratio of sulfonyl chloride to 2- ((2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) oxy) propanamide to 2 or more, the title compound was prepared 1.66g.1H NMR(300MHz,CDCl3)δ:1.467(s,6H,2CH3),3.127(s,2H,CH2),3.976(s,3H,CH3),6.786(t,J＝54.0Hz,1H,CH),7.989(s,1H,Ph H),8.086(s,1H,NH),8.346(s,1H,Pyrazole H).LC-MS(Pos M+)m/z)calc:390,found:390.
Example of biological measurement
The compounds of the present invention were tested for bactericidal and insecticidal activity, and some of the results are as follows.
Example 6 against Botrytis cinerea Bactericidal activity of (Botrytis cinerea)
The method comprises the following steps: dissolving the compound to be tested in a proper solvent such as N, N-dimethylformamide, diluting to the required concentration by using sterile water containing 0.1% Tween 80 emulsifier, and taking blank without the compound to be tested as a control, wherein each treatment is repeated for 4 times; 3mL of the liquid medicine is taken by a pipette, added into 27mL of potato agar medium (PDA) cooled to 45 ℃ and poured into a culture dish after being sufficiently shaken; after cooling, 6mm diameter mycelium blocks are taken from the edge of a germ colony cultivated for 7 days by an inoculating needle, and the mycelium blocks are moved to the center of a culture dish with the mycelium faces downwards; after the treatment, placing the culture dish in a biochemical incubator with constant temperature of 28 ℃ for culture, measuring the growth diameter of hypha after 4 days, analyzing by adopting EXCEL statistical software, and calculating the growth inhibition rate of hypha. The activity was divided into A, B, C, D four stages in percentage relative to the blank, with 100% > inhibition rate ≡90% being stage A, 90% > inhibition rate ≡70% being stage B, 70% > inhibition rate ≡50% being stage C, 50% > inhibition rate ≡0% being stage D. The results show that the compound has bactericidal activity on the gray mold of cucumber. The following are partial results:
At a concentration of 25mg/L, compound 01 of the present invention and the like have class A activity against Botrytis cinerea and 16, 131, 187 and 171 and the like have class C activity against Botrytis cinerea.
Example 7 bactericidal Activity against Alternaria tabaci and Sclerotinia sclerotiorum
The bactericidal activity of the compound of the invention on alternaria alternata (ALTERNARIA ALTERNATA) and sclerotinia rot of colza (Sclerotonia sclerotiorum) is respectively measured by adopting the method for measuring the bactericidal activity of the cucumber botrytis cinerea.
The results show that the compound has activity on Alternaria tabaci and Sclerotinia sclerotiorum, and the following partial results are shown:
at a concentration of 25mg/L, the compounds 01 and 16 and the like have B-class activity on Alternaria tabaci;
at a concentration of 25mg/L, compound 01 and the like of the present invention have B-stage activity against Sclerotinia sclerotiorum.
Example 8 bactericidal Activity against corn rust (Puccinia Polysora)
Potting method: dissolving the compound to be tested in a proper solvent such as N, N-dimethylformamide, diluting to the required concentration by using sterile water containing 0.1% Tween 80 emulsifier, and taking blank without the compound to be tested as a control; 4 replicates per treatment; shearing diseased corn leaves, washing spores with 0.05% Tween 80 or other suitable surfactant aqueous solution, and filtering with 2-4 layers of gauze to obtain suspension with concentration of 1×10 5 spores/mL; spraying the compound liquid medicine to be tested on the 1-leaf corn until the corn grows to 2-leaf corn, spraying and inoculating spore suspension after 1 day, transferring the inoculated spore suspension to a moisturizing cabinet (the relative humidity is above 95 percent, the temperature is 20-22 ℃), and culturing for 15-24 hours under the condition of weak light (the illumination intensity is 5000-10000 Lux); and when the leaf disease rate of the blank control reaches more than 50%, the disease conditions of each treatment are investigated, and the drug control effect is calculated. The activity is divided into A, B, C, D stages according to the percentage relative to a blank control, 100 percent is larger than or equal to 90 percent and is A stage, 90 percent is larger than or equal to 70 percent and is B stage, 70 percent is larger than or equal to 50 percent and is C stage, and 50 percent is larger than or equal to 0 percent and is D stage. The results show that the compound has a control effect on corn rust, and some compounds have a good control effect at low concentration. The partial results were as follows:
At the concentration of 500mg/L, the compounds 01, 16, 131, 171 and the like have A-level prevention and treatment effects on corn rust;
At the concentration of 100mg/L, the compounds 01, 16 and the like have A-level control effects on corn rust, 131, 171 and the like have B-level control effects;
At 50mg/L concentration, the compounds 01 and 16 and the like have A-level control effects on corn rust, 171 and the like have B-level control effects, 131 and the like have C-level control effects.
In order to further study the control effect of the compound of the invention on corn rust, the compounds 01 and 16 and the like of the invention are selected as targets, and the control effect of the compound on corn rust is compared by using a potting method with isopyrazam (D1) as a commodity control. The results show that the prevention and treatment effects of the compounds of the invention such as 01 and 16 on corn rust are in the same activity level as that of isopyrazam (D1), and the EC 50 value of the compounds on corn rust is 0.25-1.25mg/L.
Example 9 bactericidal Activity against wheat powdery mildew (ERISIPHE GRIMINIS)
Potting method: dissolving the compound to be tested in a proper solvent such as N, N-dimethylformamide, and diluting to the required concentration by using sterile water containing 0.1% of Tween 80 emulsifier; taking pot with straight stem about 15cm, sowing 20 seeds of wheat with full and strong seeds in each pot, and growing two leaves and one core for test; spraying the prepared wheat seedling plant with a certain concentration of agent, and inoculating bacteria after one day. Repeating for 3 times, and setting blank without compound to be tested as blank control; after the control is subjected to moisturizing and temperature-adaptive culture until blank control is sick, the area of the disease spots is checked, and the control effect of the medicament is calculated. The activity is divided into A, B, C, D stages according to the percentage relative to a blank control, 100 percent is larger than or equal to 90 percent and is A stage, 90 percent is larger than or equal to 70 percent and is B stage, 70 percent is larger than or equal to 50 percent and is C stage, and 50 percent is larger than or equal to 0 percent and is D stage. The results show that the compound provided by the invention has a control effect on wheat powdery mildew, and some compounds still have a good effect at low concentration. The partial results were as follows:
At the concentration of 500mg/L, the compounds 01, 16, 187 and the like have A-level prevention and treatment effects on wheat powdery mildew;
at the concentration of 100mg/L, the compounds 01, 16 and the like have A-level control effects on the wheat powdery mildew, and 187 and the like have C-level control effects on the wheat powdery mildew.
In order to further study the control effect of the compound on the wheat powdery mildew, the compound 01 and the like are selected as targets, and the isopyrazam (D1) and the flusilazole (D2) are used as commodity contrast, so that the control effect of the compound on the wheat powdery mildew is compared. The results show that the prevention and treatment effects of the compounds such as 01 and the like on the wheat powdery mildew can be compared favorably with that of isopyrazam (D1) and flusilazole (D2), and the EC 50 value of the compounds on the wheat powdery mildew is 0.35-1.60mg/L.
Example 10 bactericidal Activity against Rhizoctonia solani (Rhizoctonia solani)
Potting method: dissolving the compound to be tested in a proper solvent such as N, N-dimethylformamide, diluting to the required concentration by using sterile water containing 0.1% Tween 80 emulsifier, and taking blank without the compound to be tested as a control, wherein each treatment is repeated for 4 times; transferring the rice sheath blight pathogen to a PDA plate for activation culture, transferring the rice sheath blight pathogen to a PD culture medium, and culturing the rice sheath blight pathogen in a constant-temperature water bath for 4 days. Pulverizing the cultured mycelium pellet with a refiner and blending with clear water to obtain bacterial suspension with a certain concentration. The cucumber was used for the experiment when it was grown to flatten two cotyledons. Spraying the liquid medicine, spraying the bacterial suspension to the surface of the seedling after 24 hours, and carrying out moisturizing culture. Observing the disease condition of seedlings, and when the disease condition of control treatment is obvious, starting to investigate the disease condition of each treatment, and calculating the drug control effect. The activity is divided into A, B, C, D stages according to the percentage relative to a blank control, 100 percent is larger than or equal to 90 percent and is A stage, 90 percent is larger than or equal to 70 percent and is B stage, 70 percent is larger than or equal to 50 percent and is C stage, and 50 percent is larger than or equal to 0 percent and is D stage. The results show that the compound has control effect on rice sheath blight. The partial results were as follows:
at the concentration of 500mg/L, the compounds 01 and 16 and the like have A-level control effects on rice sheath blight disease;
At a concentration of 100mg/L, the compounds 01 and 16 and the like have A-level control effects on rice sheath blight diseases.
To further study the control effect of the compound of the present invention on rice sheath blight disease, the compounds 01 and 16 of the present invention and the like were selected as targets, and their control effects on rice sheath blight disease were compared by potting method with thifluzamide (D3), which is a well-known control agent for rice sheath blight disease. The results show that the compounds of the invention such as 01 and 16 have good control effect on rice sheath blight disease, the control effect on rice sheath blight disease such as compound 16 of the invention is comparable with thifluzamide (D3), the EC 50 value of the compounds of the invention on rice sheath blight disease is 2.50-7.00mg/L, and the control effect on rice sheath blight disease such as compound 01 of the invention is slightly inferior to that of thifluzamide (D3), and the EC 50 value of the compounds of the invention on rice sheath blight disease such as 01 is 10-15mg/L.
EXAMPLE 11 insecticidal Activity against aphids (Aphis fabae)
To evaluate the activity of the compounds of the invention against pests, aphids were selected as targets and the activity of the compounds of the invention against aphids was determined by spraying.
Spraying method: the test compound is dissolved in a suitable solvent such as N, N-dimethylformamide, diluted to the desired concentration with clear water containing 0.1% Tween 80 emulsifier, and a blank without test compound is used as a control, and each treatment is repeated 4 times. Extracting the continuous root of the broad bean seedlings with the 3-day-old broad bean aphids, placing the continuous root of the broad bean seedlings in a beaker filled with clean water, sealing the mouth of the beaker by using a Parafilm sealing film, clamping a plastic gasket, and carrying out spray treatment by using an electric throat sprayer, wherein the spray amount is 2 mL/plant. After the plants are dried, covering Ma Dengzhao, standing for indoor cultivation, checking and recording death conditions after 48 hours, calculating the death rate, and taking an average value of the results. The activity (mortality) is divided into A, B, C, D grades in percentage relative to a blank control, wherein the mortality rate is more than or equal to 100 percent and is more than or equal to 90 percent and is grade A, the mortality rate is more than or equal to 90 percent and is grade B, the mortality rate is more than or equal to 70 percent, the mortality rate is more than or equal to 50 percent and is grade C, and the mortality rate is more than or equal to 50 percent and is more than or equal to 0 and is grade D. The results show that the compounds of the invention are active against aphids. The partial results are listed below:
at a concentration of 500mg/L, compound 01 and the like of the invention have class A insecticidal activity on aphids, and 16, 131, 171 and the like have class C insecticidal activity on aphids;
At a concentration of 200mg/L, compound 01 and the like of the invention have insecticidal activity close to class A on aphids;
at a concentration of 12.5mg/L, compound 01 and the like of the present invention have a class C-approaching insecticidal activity against aphids;
To the inventors' knowledge, there is no report indicating that isopyrazam (D1) has insecticidal activity against aphids.
EXAMPLE 12 evaluation of mite-killing Activity on Cotton Red spider (Tetranychus urticae)
Spraying method: dissolving the compound to be tested in a proper solvent such as acetone or N, N-dimethylformamide, diluting to the required concentration by using clear water containing 0.1% Tween 80 emulsifier, and taking blank without the compound to be tested as a control, wherein each treatment is repeated for 4 times; the broad bean seedlings with mites for test are cut off, placed in a beaker filled with clean water, the mouth of the beaker is sealed by a Parafilm sealing film, and the spray treatment is carried out by an electric throat sprayer, wherein the spraying amount is 2 mL/plant. After the plants are dried, the plants are placed in a recovery room for cultivation, the death condition is checked and recorded after 72 hours, the death rate is calculated, and the result is averaged. The activity (mortality) is divided into A, B, C, D grades in percentage relative to a blank control, wherein the mortality rate is more than or equal to 100 percent and is more than or equal to 90 percent and is grade A, the mortality rate is more than or equal to 90 percent and is grade B, the mortality rate is more than or equal to 70 percent, the mortality rate is more than or equal to 50 percent and is grade C, and the mortality rate is more than or equal to 50 percent and is more than or equal to 0 and is grade D. The results show that the compound has activity on cotton red spiders. Compounds 01 and 171 and the like of the present invention have C-class activity against red spiders, for example, at a concentration of 500 mg/L; to the best of the inventors' knowledge, there is no report indicating that isopyrazam (D1) has acaricidal activity against cotton red spiders.
Claims (10)
- N-oxa condensed ring amide compounds,Characterized in that the compound of formula (I) is:N- (2, 2-dimethyl-2, 3-dihydrobenzo [ b ] furan-7-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;n- (2, 2-dimethylbenzo [ d ] [1,3] dioxo-4-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide.
- 2. The method for preparing the N-oxa condensed ring amide compound according to claim 1, wherein the compound represented by the formula (I) is prepared by the following reaction:Reaction formula 1:Reaction formula 2:Reaction formula 3:Reacting a compound of formula (II) with a compound of formula (III) in the absence of a base or in the presence of a suitable base triethylamine, pyridine, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate in one or two suitable solvents selected from dichloromethane, dichloroethane, acetonitrile, toluene, xylene, ethyl acetate, acetone, N-dimethylformamide, tetrahydrofuran or dioxane at a system reflux temperature to obtain a compound of formula (I);Reacting the compound of formula (V) with acyl halide reagent sulfoxide halide, phosphorus trihalide or phosgene in a suitable solvent of dichloromethane, dichloroethane, acetonitrile, acetone, toluene, xylene, tetrahydrofuran or dioxane at a temperature of 25 ℃ to a reflux temperature of the system to obtain a compound of formula (II), and adding a catalytic amount of N, N-dimethylformamide to assist in the preparation of the compound of formula (II);Reacting a compound of formula (VI) with a compound of formula (VII) in the presence of a suitable solvent of dichloromethane, dichloroethane, acetonitrile, acetone, toluene, methanol, ethanol, isopropanol, butanol, N-dimethylformamide, tetrahydrofuran or dioxane at a temperature of 25 ℃ to reflux temperature of the system, a suitable base of triethylamine, pyridine, sodium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate to give a compound of formula (VIII), and adding a catalytic amount of sodium iodide or potassium iodide to aid in the preparation of the compound of formula (VIII); reacting a compound of formula (VIII) with aqueous ammonia in one or two suitable solvents selected from the group consisting of water, methanol, ethanol, isopropanol, butanol, N-dimethylformamide, tetrahydrofuran or dioxane at a temperature of 25 ℃ to reflux of the system to obtain a compound of formula (IX), adding 1, 3-dimethylpropyleneurea to aid in the preparation of the compound of formula (IX); the compound of formula (IX) can be converted to the compound of formula (III) in the presence of a suitable base, triethylamine, pyridine, sodium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate in a suitable solvent, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran or dioxane, at 25 ℃ to the reflux temperature of the system;Wherein R, R 1、R2、R3、R4、R5、W1、W2, m and n have the meanings given in claim 1, L is a leaving group chlorine, bromine, iodine or sulfonate, R v is C 1-C4 alkyl.
- 3. Use of an N-oxafused ring amide compound according to claim 1 for the preparation of a plant pest or plant pest control medicament.
- 4. Use of an N-oxafused ring amide compound according to claim 1 for the preparation of a phytocidal medicament.
- 5. An insecticidal or fungicidal composition characterized in that: the N-oxacondensed ring amide compound of claim 1 as an active component and an acceptable carrier, wherein the weight percentage of the active component in the composition is 0.5-90%.
- 6. An acaricidal composition characterized in that: the N-oxacondensed ring amide compound of claim 1 as an active component and an acceptable carrier, wherein the weight percentage of the active component in the composition is 0.5-90%.
- 7. The use of N-oxafused ring amides according to claim 1, characterized by their use for controlling plant pests or plant-harmful pathogens.
- 8. The use of N-oxafused ring amides according to claim 1 for controlling plant mites.
- 9. The use of N-oxafused ring amides according to claim 1, characterized in that the method for controlling plant pests or plant harmful pathogens comprises contacting a biologically effective amount of the active ingredient with the pest or harmful pathogen.
- 10. The use of N-oxafused ring amides according to claim 1, characterized in that the method for controlling plant mites comprises contacting the mites with a biologically effective amount of the active ingredient.
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| CN104350050A (en) * | 2012-05-09 | 2015-02-11 | 拜耳农作物科学股份公司 | 5-halogenopyrazole benzofuranyl carboxamides |
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| JP6240666B2 (en) * | 2012-05-09 | 2017-11-29 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | Pyrazole indanyl carboxamides |
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| CN104350050A (en) * | 2012-05-09 | 2015-02-11 | 拜耳农作物科学股份公司 | 5-halogenopyrazole benzofuranyl carboxamides |
| CN111978306A (en) * | 2019-05-24 | 2020-11-24 | 湖南大学 | Furanol pyrazole formamide derivative and preparation method and application thereof |
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