JP6199739B2 - テトラゾール置換されたアントラニルアミド誘導体およびこれら誘導体の新規な結晶多形体の製造方法 - Google Patents
テトラゾール置換されたアントラニルアミド誘導体およびこれら誘導体の新規な結晶多形体の製造方法 Download PDFInfo
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- JP6199739B2 JP6199739B2 JP2013514665A JP2013514665A JP6199739B2 JP 6199739 B2 JP6199739 B2 JP 6199739B2 JP 2013514665 A JP2013514665 A JP 2013514665A JP 2013514665 A JP2013514665 A JP 2013514665A JP 6199739 B2 JP6199739 B2 JP 6199739B2
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- 238000000034 method Methods 0.000 title claims description 25
- -1 Tetrazole-substituted anthranilamide Chemical class 0.000 title description 43
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000000460 chlorine Chemical group 0.000 claims description 14
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical class OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000003536 tetrazoles Chemical class 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical class NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 150000003217 pyrazoles Chemical class 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical class [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001503 inorganic bromide Inorganic materials 0.000 claims description 2
- 150000004694 iodide salts Chemical class 0.000 claims description 2
- 125000006664 (C1-C3) perfluoroalkyl group Chemical group 0.000 claims 1
- 229910001505 inorganic iodide Inorganic materials 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 27
- 238000009472 formulation Methods 0.000 description 25
- 230000009969 flowable effect Effects 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000004480 active ingredient Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 239000002671 adjuvant Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000000634 powder X-ray diffraction Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 10
- 230000029936 alkylation Effects 0.000 description 10
- 238000005804 alkylation reaction Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- 0 CC*1*=C(C2*)C2*(C)*1CC*C Chemical compound CC*1*=C(C2*)C2*(C)*1CC*C 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 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 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 3
- PZIHQZWEGCWSHF-UHFFFAOYSA-N 5-(chloromethyl)-1h-pyrazole Chemical compound ClCC=1C=CNN=1 PZIHQZWEGCWSHF-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000004067 bulking agent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 125000004768 (C1-C4) alkylsulfinyl group Chemical group 0.000 description 2
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 description 2
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 description 2
- 125000004771 (C1-C4) haloalkylsulfinyl group Chemical group 0.000 description 2
- 125000006643 (C2-C6) haloalkenyl group Chemical group 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- VRJIBCBHABNTRG-UHFFFAOYSA-N 2-(3-chloropyridin-2-yl)-5-[[5-(trifluoromethyl)tetrazol-2-yl]methyl]pyrazole-3-carboxylic acid Chemical compound N=1N(C=2C(=CC=CN=2)Cl)C(C(=O)O)=CC=1CN1N=NC(C(F)(F)F)=N1 VRJIBCBHABNTRG-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- FOEPLOQMUWYHBM-UHFFFAOYSA-N 5-(trifluoromethyl)-2h-tetrazole Chemical compound FC(F)(F)C=1N=NNN=1 FOEPLOQMUWYHBM-UHFFFAOYSA-N 0.000 description 2
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 2
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 2
- VQUGSSQYJRUCEP-UHFFFAOYSA-N ClC=1C(=NC=CC=1)N1N=C(C=C1C(=O)O)CN1N=NN=C1C(F)(F)F Chemical compound ClC=1C(=NC=CC=1)N1N=C(C=C1C(=O)O)CN1N=NN=C1C(F)(F)F VQUGSSQYJRUCEP-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000303965 Cyamopsis psoralioides Species 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- GKQLYSROISKDLL-UHFFFAOYSA-N EEDQ Chemical compound C1=CC=C2N(C(=O)OCC)C(OCC)C=CC2=C1 GKQLYSROISKDLL-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical class O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910013594 LiOAc Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 2
- 150000008422 chlorobenzenes Chemical class 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
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- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002675 polymer-supported reagent Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- IVRIRQXJSNCSPQ-UHFFFAOYSA-N propan-2-yl carbonochloridate Chemical compound CC(C)OC(Cl)=O IVRIRQXJSNCSPQ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- KNDVJPKNBVIKML-UHFFFAOYSA-N tetraniliprole Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1NC(=O)C1=CC(CN2N=C(N=N2)C(F)(F)F)=NN1C1=NC=CC=C1Cl KNDVJPKNBVIKML-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- 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
- A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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Description
R1、R3はそれぞれ独立に、水素、1もしくは複数の同一もしくは異なるハロゲンもしくはニトロで置換されていても良いC1−C6−アルキル、C1−C6−アルコキシ、C2−C6−アルケニル、C2−C6−アルキニルまたはC3−C6−シクロアルキル、好ましくは(C1−C5)−アルキル、より好ましくはメチル、エチルまたはtert−ブチル、最も好ましくはメチルであり、
R2は、C1−C6−アルキル、C3−C6−シクロアルキル、C1−C6−ハロアルキル、C1−C6−ハロシクロアルキル、C2−C6−アルケニル、C2−C6−ハロアルケニル、C2−C6−アルキニル、C2−C6−ハロアルキニル、C1−C4−アルコキシ、C1−C4−ハロアルコキシ、C1−C4−アルキルチオ、C1−C4−アルキルスルフィニル、C1−C4−アルキルスルホニル、C1−C4−ハロアルキルチオ、C1−C4−ハロアルキルスルフィニル、C1−C4−ハロアルキルスルホニル、ハロゲン、シアノ、ニトロ、アルキルアミノ、ジアルキルアミノ、シクロアルキルアミノまたはC3−C6−トリアルキルシリル、好ましくはハロゲンまたはC1−C6−アルキル、より好ましくはフッ素または塩素、最も好ましくは塩素であり、
R4は、水素、ハロゲン、シアノ、ニトロ、C1−C4−アルキル、C1−C4−ハロアルキル、C2−C6−アルケニル、C2−C6−ハロアルケニル、C2−C6−アルキニル、C1−C4−アルコキシ、C1−C4−ハロアルコキシ、SF5、C1−C4−アルキルチオ、C1−C4−アルキルスルフィニル、C1−C4−アルキルスルホニル、C1−C4−ハロアルキルチオ、C1−C4−ハロアルキルスルフィニル、C1−C4−ハロアルキルスルホニル、C1−C4−アルキルアミノ、ジ(C1−C4−アルキル)アミノ、C3−C6−シクロアルキルアミノ、(C1−C4−アルコキシ)イミノ、(C1−C4−アルキル)(C1−C4−アルコキシ)イミノ、(C1−C4−ハロアルキル)(C1−C4−シアノ、ニトロ、アルコキシ)イミノまたはC3−C6−トリアルキルシリル、好ましくは水素、塩素またはシアノ、より好ましくは塩素またはシアノ、最も好ましくはシアノであり、
R5は、ハロゲンによってモノからトリ置換されていても良いC1−C5−アルキル、好ましくはC1−C3−パーフルオロアルキル、より好ましくはCF3またはC2F5、最も好ましくはCF3であり、
Zは、CHおよびN、好ましくはNであり、
一般式(I)の化合物は、N−オキサイドおよび塩も含む。]
の製造方法であって、
下記式(II)のN−アリール−およびN−ヘタリール−置換されたピラゾール:
R2、Zはそれぞれ上記で定義の通りであり、
Xはフッ素、塩素、臭素、ヨウ素、CH3SO2O、CF3SO3、またはp−CH3−C6H4SO3である。]を、下記式(III)のテトラゾール:
本発明の文脈において、「ハロゲン」(X)という用語は、異なって定義されていない限り、フッ素、塩素、臭素およびヨウ素からなる群から選択される元素を含み、好ましくはフッ素、塩素および臭素の使用であり、特に好ましくはフッ素および塩素の使用である。置換された基はモノ置換または多置換されていることができ、複数置換の場合の置換基は同一であるか異なっていることができる。
アノード材料:Cu
波長:1.54060
走査モード:透過
走査型:2θ:Ω
2θ範囲:±0.2°。
アノード材料:Cu
波長:1.54060
走査モード:透過
走査型:2θ:Ω
2θ範囲:±0.2°。
式(IV)のピラゾールカルボン酸エステルは、下記の方法に従って製造することができる。
例えば式(III)のCF3−テトラゾールの式(II)のクロロメチルピラゾール(X=Cl)によるアルキル化の場合、触媒の使用によって反応を促進する必要がある。使用される触媒は、KBr、CsBrなどの有機および無機臭化物または好ましくはKI、NaI、CsI、Me4NI、Bu4NIなどのヨウ化物である。
段階1で形成される式(IV)の化合物を、式(V)のピラゾールカルボン酸に変換する。
段階2で生成した式(V)の化合物を、式(I)のアントラニルアミド誘導体に変換する。
5−(3−クロロピリジン−2−イル)−3−{[5−(トリフルオロメチル)−2H−テトラゾール−2−イル]メチル}−1H−ピラゾール−5−カルボン酸メチル(主要異性体)および5−(3−クロロピリジン−2−イル)−3−{[5−(トリフルオロメチル)−1H−テトラゾール−1−イル]メチル}−1H−ピラゾール−5−カルボン酸メチル(副成分)の異性体混合物
アセトン50mL中の3−(クロロメチル)−1−(3−クロロピリジン−2−イル)−1H−ピラゾール−5−カルボン酸メチル2.86g(0.01mol)およびナトリウム5−(トリフルオロメチル)テトラゾール−2−イド1.6gおよびKI 0.15gを56℃で9時間加熱した。塩を濾去し、アセトンを減圧下に除去した。これによって、生成物4.59gを二つの異性体の9:1混合物として得た。
主要異性体
1H NMR(CD3CN)δ:8.52(1H、d);7.95(1H、d)、7.45(1H、dd);7.10(1H、s);6.05(2H、s);3.75(3H、s)ppm。
19F NMR−61.46ppm。
1−(3−クロロピリジン−2−イル)−3−{[5−(トリフルオロメチル)−2H−テトラゾール−2−イル]メチル}−1H−ピラゾール−5−カルボン酸(主要異性体)および1−(3−クロロピリジン−2−イル)−3−{[5−(トリフルオロメチル)−1H−テトラゾール−1−イル]メチル}−1H−ピラゾール−5−カルボン酸(副成分)
実施例1からの混合物4.59gをメタノール40mLに溶かし、NaOH 2gを10%水溶液として加えた。その混合物を室温で3時間撹拌した。
1H NMR(CD3CN)δ:13.5(bs);8.52(1H、d);8.2(1H、d);7.6(1H、dd);7.2(1H、s);6.25(2H、s)ppm。
1−(3−クロロピリジン−2−イル)−N−[4−シアノ−2−メチル−6−(メチルカルバモイル)フェニル]−3−{[5−(トリフルオロメチル)−2H−テトラゾール−2−イル]メチル}−1H−ピラゾール−5−カルボキサミド(主要異性体)および1−(3−クロロピリジン−2−イル)−N−[4−シアノ−2−メチル−6−(メチルカルバモイル)フェニル]−3−{[5−(トリフルオロメチル)−1H−テトラゾール−1−イル]メチル}−1H−ピラゾール−5−カルボキサミド(副成分)の94:6の比率での異性体混合物
90:10混合物としての1−(3−クロロピリジン−2−イル)−3−{[5−(トリフルオロメチル)−2H−テトラゾール−2−イル]メチル}−1H−ピラゾール−5−カルボン酸および1−(3−クロロピリジン−2−イル)−3−[5−(トリフルオロメチル)−1H−テトラゾール−1−イル]−1H−ピラゾール−5−カルボン酸10gを最初にジメチルアセトアミド40mLに入れた。2−アミノ−5−シアノ−N,3−ジメチルベンズアミド4.75g、2,6−ジメチルピリジン7.2gおよびメシルクロライド3.9gを加え、混合物を50℃で4時間撹拌した。混合物を冷却して20℃とし、水100mLを加えた。約1時間後、沈殿を濾去し、水で洗浄し、乾燥させた。これによって、生成物12.1g(収率93%)が異性体比94:6および純度95から96%で得られる。
主要異性体94%
実施例4
1−(3−クロロピリジン−2−イル)−3−{[5−(トリフルオロメチル)−2H−テトラゾール−2−イル]メチル}−1H−ピラゾール−5−カルボン酸(主要異性体)および1−(3−クロロピリジン−2−イル)−3−{[5−(トリフルオロメチル)−1H−テトラゾール−1−イル]メチル}−1H−ピラゾール−5−カルボン酸(副成分)
アセトン680mL中の純度98%の3−(クロロメチル)−1−(3−クロロピリジン−2−イル)−1H−ピラゾール−5−カルボン酸メチル105g(0.36mol)、ナトリウム5−(トリフルオロメチル)テトラゾール−2−イド(30%アセトン中溶液)204g(0.384mol)およびKI 24g(0.144mol)を56℃で10時間加熱した。塩を濾去し、アセトンを減圧下に除去した。生成物(油状物)をトルエン300mLに取り、溶液を水100mLで洗浄した。そのトルエン溶液を10%NaOH溶液170gとともに40℃で6時間撹拌した。有機相を除去し、水相を10%HClで徐々にpH3に調節した。沈殿した生成物を濾過し、水で洗浄し、乾燥させた。これによって純度97.3重量%の生成物118g(収率85%)を得た。位置異性体の比:94:6。
実施例1
フロアブル剤を製造するため、下記のものを室温で組み合わせる。
フロアブル剤を製造するため、下記のものを室温で組み合わせる。
室温で3日間保存後、両方のサンプルは均一かつ流動性である。
本発明のフロアブル剤を製造するため、下記のものを室温で組み合わせる。
室温で3日間保存後、両方のサンプルは均一かつ流動性である。
室温で3日間、40℃または54℃で7日間保存後、両方のサンプルとも流動性であるが、若干の相分離を示す(図14から15を参照)。
Claims (5)
- 下記式(I)の化合物:
[式中、
R1、R3はそれぞれ独立に、C 1 −C 5 −アルキルであり、
R2は、C1−C6−アルキルまたはハロゲンであり、
R4は、水素、ハロゲン、またはシアノであり、
R5は、(C1−C3)パーフルオロアルキルであり、
ZはNであり、
一般式(I)の化合物は塩も含む。]の製造方法であって、
下記式(II)のN−ヘタリール−置換されたピラゾール:
[Rは(C1−C6)−アルキル、アリール(C1−C6)−アルキルまたはアリールであり、
R2、Zはそれぞれ上記で定義の通りであり、
Xはフッ素、塩素、臭素、ヨウ素、CH3SO2O、CF3SO3、またはp−CH3−C6H4SO3である。]を、下記式(III)のテトラゾール:
と、有機あるいは無機臭化物又はヨウ化物から選択される触媒の存在下で、反応させて、下記式(IV)のピラゾールカルボン酸エステル:
[R、R2、R5およびZはそれぞれ上記で定義の通りである。]を得て、
任意に、後者を、先に単離せずに、下記式(V)のピラゾールカルボン酸:
[R2、R5およびZはそれぞれ上記で定義の通りである。]に変換し、
後者を下記一般式(VI)の化合物:
[R1、R3、R4はそれぞれ上記で定義の通りである。]と反応させて、式(I)のアントラニルアミド:
[R1、R2、R3、R4、R5およびZはそれぞれ上記で定義の通りである。]を得ることを特徴とする方法。 - R 4 がシアノである請求項1に記載の式(I)の化合物の製造方法。
- R1、R3がそれぞれ独立に、メチル、エチルまたはtert−ブチルであり、
R2がフッ素または塩素であり、
R4が塩素またはシアノであり、
R5がCF3またはC2F5であり、
ZがNである請求項1に記載の式(I)の化合物の製造方法。 - R5がCF3である請求項1から3のうちのいずれか1項に記載の式(I)の化合物の製造方法。
- R2が塩素であり、R3がメチルであり、R4がシアノである請求項1から4のうちのいずれか1項に記載の式(I)の化合物の製造方法。
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US35492010P | 2010-06-15 | 2010-06-15 | |
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US61/354,920 | 2010-06-15 | ||
PCT/EP2011/059735 WO2011157664A1 (de) | 2010-06-15 | 2011-06-10 | Verfahren zur herstellung von tetrazol-substituierten anthranilsäurediamid-derivaten und neue kristalline modifikation dieser derivate |
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JP2015221282A Division JP6170118B2 (ja) | 2010-06-15 | 2015-11-11 | テトラゾール置換されたアントラニルアミド誘導体およびこれら誘導体の新規な結晶多形体の製造方法 |
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JP2015221282A Active JP6170118B2 (ja) | 2010-06-15 | 2015-11-11 | テトラゾール置換されたアントラニルアミド誘導体およびこれら誘導体の新規な結晶多形体の製造方法 |
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JP2016142220A Active JP6254646B2 (ja) | 2010-06-15 | 2016-07-20 | テトラゾール置換されたアントラニルアミド誘導体およびこれら誘導体の新規な結晶多形体の製造方法 |
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US (2) | US8969572B2 (ja) |
EP (2) | EP2582694B1 (ja) |
JP (3) | JP6199739B2 (ja) |
KR (1) | KR101790305B1 (ja) |
CN (1) | CN103261187B (ja) |
BR (1) | BR112012032244A2 (ja) |
DK (2) | DK2955176T3 (ja) |
ES (2) | ES2547314T3 (ja) |
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PT (1) | PT2582694E (ja) |
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SI (1) | SI2582694T1 (ja) |
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EP2582694B1 (de) * | 2010-06-15 | 2015-07-22 | Bayer Intellectual Property GmbH | Verfahren zur herstellung von tetrazol-substituierten anthranilsäurediamid-derivaten und neue kristalline modifikation dieser derivate |
US9198424B2 (en) * | 2010-06-18 | 2015-12-01 | Bayer Intellectual Property Gmbh | Active ingredient combinations having insecticidal and acaricidal properties |
UA111593C2 (uk) * | 2010-07-07 | 2016-05-25 | Баєр Інтеллекчуел Проперті Гмбх | Аміди антранілової кислоти у комбінації з фунгіцидами |
KR20130093086A (ko) * | 2010-07-09 | 2013-08-21 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 농약으로서의 안트라닐산 디아미드 유도체 |
KR102032979B1 (ko) * | 2012-02-07 | 2019-10-16 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 치환된 안트라닐산 유도체의 제조방법 |
EP2649879A1 (en) | 2012-04-10 | 2013-10-16 | Basf Se | Pesticidal mixtures containing fluxapyroxad |
WO2013156331A1 (en) | 2012-04-16 | 2013-10-24 | Basf Se | Synergistic compositions comprising pyraclostrobin and an insecticidal compound |
SI2953942T1 (en) * | 2013-02-06 | 2018-03-30 | Bayer Cropscience Ag | Halogen-substituted pyrazole derivatives such as pesticides |
BR112018015520B8 (pt) | 2016-02-19 | 2022-09-06 | Basf Se | Misturas de pesticidas, métodos de controle de insetos, de proteção de plantas e de proteção de material de propagação vegetal, semente revestida e composição pesticida |
TWI679197B (zh) * | 2016-05-05 | 2019-12-11 | 瑞士商伊蘭科動物健康公司 | 雜芳基-1,2,4-三唑及雜芳基-三唑化合物 |
AU2018389763B2 (en) | 2017-12-20 | 2023-02-23 | Pi Industries Ltd. | Pyrazolopyridine-diamides, their use as insecticide and processes for preparing the same. |
WO2019123194A1 (en) | 2017-12-20 | 2019-06-27 | Pi Industries Ltd. | Anthranilamides, their use as insecticide and processes for preparing the same. |
US20210363134A1 (en) | 2018-01-30 | 2021-11-25 | Pi Industries Ltd. | Novel anthranilamides, their use as insecticide and processes for preparing the same |
MX2020011671A (es) * | 2018-05-21 | 2020-12-10 | Pi Industries Ltd | Nuevo proceso para la preparacion de diamidas antranilicas. |
MX2021000226A (es) | 2018-07-20 | 2021-03-31 | Pi Industries Ltd | Nuevo proceso para la preparacion de diamidas antranilicas. |
BR112021016353A2 (pt) | 2019-02-18 | 2021-10-19 | Pi Industries Ltd. | Processo para preparar diamidas antranílicas e intermediários das mesmas |
WO2020170178A1 (en) | 2019-02-22 | 2020-08-27 | Pi Industries Ltd. | A process for the synthesis anthranilic diamide compounds and intermediates thereof |
EP3964506A1 (de) | 2020-09-04 | 2022-03-09 | Bayer Aktiengesellschaft | Verfahren zur herstellung eines tetrazol-substituierten anthranilsäurediamid-derivates |
AR123526A1 (es) | 2020-09-17 | 2022-12-14 | Pi Industries Ltd | Un proceso para la síntesis de compuestos antranílicos de ácido / amida e intermediarios de los mismos |
AR123593A1 (es) | 2020-09-26 | 2022-12-21 | Pi Industries Ltd | Un proceso para la síntesis de compuestos antranílicos de ácido / amida e intermedios de los mismos |
EP4376616A1 (en) | 2021-07-27 | 2024-06-05 | Syngenta Crop Protection AG | Method for controlling diamide resistant pests & compounds therefor |
WO2023012081A1 (en) | 2021-08-05 | 2023-02-09 | Syngenta Crop Protection Ag | Method for controlling diamide resistant pests & compounds therefor |
KR20240041946A (ko) | 2021-08-19 | 2024-04-01 | 신젠타 크롭 프로텍션 아게 | 디아미드 저항성 해충을 방제하는 방법 및 그를 위한 화합물 |
WO2023110710A1 (en) | 2021-12-13 | 2023-06-22 | Syngenta Crop Protection Ag | Method for controlling diamide resistant pests & compounds therefor |
EP4197333A1 (en) | 2021-12-15 | 2023-06-21 | Syngenta Crop Protection AG | Method for controlling diamide resistant pests & compounds therefor |
WO2024133426A1 (en) | 2022-12-21 | 2024-06-27 | Syngenta Crop Protection Ag | Method for controlling diamide resistant pests and compounds therefor |
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TW200406152A (en) | 2002-08-30 | 2004-05-01 | Syngenta Participations Ag | 4-(3,3-Dihalo-allyloxy) phenol derivatives having pesticidal properties |
AU2004267094A1 (en) * | 2003-08-20 | 2005-03-03 | Vertex Pharmaceuticals Incorporated | (4 -amino -1,2, 5-oxadiazol-4-yl) -hetxiroaromatic compounds useful as protein kinase inhibitors |
WO2006023783A1 (en) | 2004-08-17 | 2006-03-02 | E.I. Dupont De Nemours And Company | Novel anthranilamides useful for controlling invertebrate pests |
DE102006032168A1 (de) | 2006-06-13 | 2007-12-20 | Bayer Cropscience Ag | Anthranilsäurediamid-Derivate mit heteroaromatischen Substituenten |
CN101466702B (zh) * | 2006-06-13 | 2014-04-02 | 拜尔农作物科学股份公司 | 具有杂芳族和杂环族取代基的邻氨基苯甲酰二胺衍生物 |
NZ593481A (en) * | 2008-12-18 | 2013-11-29 | Bayer Cropscience Ag | Tetrazole substituted anthranilic acid amides as pesticides |
EP2582694B1 (de) * | 2010-06-15 | 2015-07-22 | Bayer Intellectual Property GmbH | Verfahren zur herstellung von tetrazol-substituierten anthranilsäurediamid-derivaten und neue kristalline modifikation dieser derivate |
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SI2582694T1 (sl) | 2015-11-30 |
PL2582694T3 (pl) | 2015-12-31 |
EP2582694A1 (de) | 2013-04-24 |
JP2017008062A (ja) | 2017-01-12 |
BR112012032244A2 (pt) | 2016-09-27 |
US20120101133A1 (en) | 2012-04-26 |
EP2955176B1 (de) | 2017-12-06 |
US20150025116A1 (en) | 2015-01-22 |
KR101790305B1 (ko) | 2017-10-25 |
TW201212820A (en) | 2012-04-01 |
JP2013530175A (ja) | 2013-07-25 |
TWI511668B (zh) | 2015-12-11 |
DK2955176T3 (en) | 2018-03-12 |
HUE027943T2 (en) | 2016-11-28 |
ES2547314T3 (es) | 2015-10-05 |
CN103261187B (zh) | 2016-08-03 |
ES2660305T3 (es) | 2018-03-21 |
WO2011157664A1 (de) | 2011-12-22 |
MX347841B (es) | 2017-05-16 |
RS54277B1 (en) | 2016-02-29 |
CN103261187A (zh) | 2013-08-21 |
JP6254646B2 (ja) | 2017-12-27 |
JP6170118B2 (ja) | 2017-07-26 |
EP2955176A1 (de) | 2015-12-16 |
EP2582694B1 (de) | 2015-07-22 |
DK2582694T3 (en) | 2015-10-26 |
US9056861B2 (en) | 2015-06-16 |
PT2582694E (pt) | 2015-10-15 |
HRP20151088T1 (hr) | 2015-11-20 |
MX2012014775A (es) | 2013-01-29 |
JP2016065076A (ja) | 2016-04-28 |
KR20130112860A (ko) | 2013-10-14 |
US8969572B2 (en) | 2015-03-03 |
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