JP3397352B2 - Acrylonitrile derivatives and fungicides for agricultural and horticultural use - Google Patents
Acrylonitrile derivatives and fungicides for agricultural and horticultural useInfo
- Publication number
- JP3397352B2 JP3397352B2 JP35138192A JP35138192A JP3397352B2 JP 3397352 B2 JP3397352 B2 JP 3397352B2 JP 35138192 A JP35138192 A JP 35138192A JP 35138192 A JP35138192 A JP 35138192A JP 3397352 B2 JP3397352 B2 JP 3397352B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- disease
- alkyl
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000008360 acrylonitriles Chemical class 0.000 title claims description 9
- 239000000417 fungicide Substances 0.000 title claims description 9
- -1 methylenedioxy group Chemical group 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000004480 active ingredient Substances 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 230000000855 fungicidal effect Effects 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 claims description 2
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052801 chlorine Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004995 haloalkylthio group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims 1
- 125000004438 haloalkoxy group Chemical group 0.000 claims 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 63
- 201000010099 disease Diseases 0.000 description 61
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 60
- 150000001875 compounds Chemical class 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- 238000004519 manufacturing process Methods 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000011541 reaction mixture Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- 240000008067 Cucumis sativus Species 0.000 description 16
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000009472 formulation Methods 0.000 description 15
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 13
- 239000003814 drug Substances 0.000 description 13
- 229940079593 drug Drugs 0.000 description 13
- 229910000104 sodium hydride Inorganic materials 0.000 description 13
- 239000012312 sodium hydride Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 241000209094 Oryza Species 0.000 description 9
- 235000007164 Oryza sativa Nutrition 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 235000009566 rice Nutrition 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004563 wettable powder Substances 0.000 description 9
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 8
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000007605 air drying Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 241000221785 Erysiphales Species 0.000 description 5
- 241000233866 Fungi Species 0.000 description 5
- 241000233679 Peronosporaceae Species 0.000 description 5
- 206010039509 Scab Diseases 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000011081 inoculation Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- OSBIEFWIIINTNJ-UHFFFAOYSA-N 1,2-dichloro-4-isothiocyanatobenzene Chemical compound ClC1=CC=C(N=C=S)C=C1Cl OSBIEFWIIINTNJ-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- APQUJLPLEHEVAU-UHFFFAOYSA-N 2-[2-(trifluoromethyl)benzoyl]prop-2-enenitrile Chemical compound FC(C1=C(C(=O)C(C#N)=C)C=CC=C1)(F)F APQUJLPLEHEVAU-UHFFFAOYSA-N 0.000 description 3
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 3
- 241000223600 Alternaria Species 0.000 description 3
- 241000123650 Botrytis cinerea Species 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000579741 Sphaerotheca <fungi> Species 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 230000002070 germicidal effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000003902 lesion Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 241001157812 Alternaria brassicicola Species 0.000 description 2
- 241000235349 Ascomycota Species 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 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 2
- 241001330975 Magnaporthe oryzae Species 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 241001281805 Pseudoperonospora cubensis Species 0.000 description 2
- 241001361634 Rhizoctonia Species 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 241000228452 Venturia inaequalis Species 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 229910000105 potassium hydride Inorganic materials 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical class C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- ONPPGZKRNYAKNT-UHFFFAOYSA-N 1,3-dichloro-5-isothiocyanato-2-methoxybenzene Chemical compound ClC=1C=C(C=C(C1OC)Cl)N=C=S ONPPGZKRNYAKNT-UHFFFAOYSA-N 0.000 description 1
- JLEMKZDHFGCHLO-UHFFFAOYSA-N 1,3-dichloro-5-isothiocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=S)=C1 JLEMKZDHFGCHLO-UHFFFAOYSA-N 0.000 description 1
- MZZVFXMTZTVUFO-UHFFFAOYSA-N 1-chloro-4-isothiocyanatobenzene Chemical compound ClC1=CC=C(N=C=S)C=C1 MZZVFXMTZTVUFO-UHFFFAOYSA-N 0.000 description 1
- DQEVDFQAYLIBRD-UHFFFAOYSA-N 1-isothiocyanato-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(N=C=S)C=C1 DQEVDFQAYLIBRD-UHFFFAOYSA-N 0.000 description 1
- CJYGGBZSQKPZQL-UHFFFAOYSA-N 2-(3-chlorothiophene-2-carbonyl)-3-(3,4-dichloro-N-methylanilino)-3-methylsulfanylprop-2-enenitrile Chemical compound ClC1=C(SC=C1)C(=O)C(C#N)=C(SC)N(C1=CC(=C(C=C1)Cl)Cl)C CJYGGBZSQKPZQL-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- 125000003541 2-chlorobenzoyl group Chemical group ClC1=C(C(=O)*)C=CC=C1 0.000 description 1
- 125000006304 2-iodophenyl group Chemical group [H]C1=C([H])C(I)=C(*)C([H])=C1[H] 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 description 1
- SBSWHTFHLWSSQS-UHFFFAOYSA-N 3-(2-chlorophenyl)-3-oxopropanenitrile Chemical compound ClC1=CC=CC=C1C(=O)CC#N SBSWHTFHLWSSQS-UHFFFAOYSA-N 0.000 description 1
- PFKFSGXOWIECNG-UHFFFAOYSA-N 3-(2-iodophenyl)-3-oxopropanenitrile Chemical compound IC1=CC=CC=C1C(=O)CC#N PFKFSGXOWIECNG-UHFFFAOYSA-N 0.000 description 1
- DMTQMHCHBQZTOJ-UHFFFAOYSA-N 3-(2-methylphenyl)-3-oxopropanenitrile Chemical compound CC1=CC=CC=C1C(=O)CC#N DMTQMHCHBQZTOJ-UHFFFAOYSA-N 0.000 description 1
- WHJVFNZAENXWGO-UHFFFAOYSA-N 3-(2-nitrophenyl)-3-oxopropanenitrile Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)CC#N WHJVFNZAENXWGO-UHFFFAOYSA-N 0.000 description 1
- KTBGHXLMFANRMG-UHFFFAOYSA-N 3-(3,4-dichloroanilino)-2-(2-iodobenzoyl)-3-methylsulfanylprop-2-enenitrile Chemical compound ClC=1C=C(NC(=C(C#N)C(C2=C(C=CC=C2)I)=O)SC)C=CC1Cl KTBGHXLMFANRMG-UHFFFAOYSA-N 0.000 description 1
- KUKNZNGJKJCXAU-UHFFFAOYSA-N 3-(3,4-dichloroanilino)-3-methylsulfanyl-2-[1-methyl-3-(trifluoromethyl)pyrazole-4-carbonyl]prop-2-enenitrile Chemical compound CN1C=C(C(=N1)C(F)(F)F)C(=O)C(=C(NC2=CC(=C(C=C2)Cl)Cl)SC)C#N KUKNZNGJKJCXAU-UHFFFAOYSA-N 0.000 description 1
- NUFBGNDOAISDQO-UHFFFAOYSA-N 3-(3-chloro-4-methylanilino)-3-methylsulfanyl-2-[2-(trifluoromethyl)benzoyl]prop-2-enenitrile Chemical compound ClC=1C=C(NC(=C(C#N)C(C2=C(C=CC=C2)C(F)(F)F)=O)SC)C=CC1C NUFBGNDOAISDQO-UHFFFAOYSA-N 0.000 description 1
- CDUNTIPJSBVRRV-UHFFFAOYSA-N 3-(3-chlorothiophen-2-yl)-3-oxopropanenitrile Chemical compound ClC=1C=CSC=1C(=O)CC#N CDUNTIPJSBVRRV-UHFFFAOYSA-N 0.000 description 1
- VANXYRRMXMDNEL-UHFFFAOYSA-N 3-(4-chloro-3-methoxyanilino)-3-methylsulfanyl-2-[2-(trifluoromethyl)benzoyl]prop-2-enenitrile Chemical compound ClC1=C(C=C(NC(=C(C#N)C(C2=C(C=CC=C2)C(F)(F)F)=O)SC)C=C1)OC VANXYRRMXMDNEL-UHFFFAOYSA-N 0.000 description 1
- CHSUAOFOPRSMSD-UHFFFAOYSA-N 3-(4-chloroanilino)-2-(2-chlorobenzoyl)-3-methylsulfanylprop-2-enenitrile Chemical compound C=1C=CC=C(Cl)C=1C(=O)C(C#N)=C(SC)NC1=CC=C(Cl)C=C1 CHSUAOFOPRSMSD-UHFFFAOYSA-N 0.000 description 1
- PIVTXPHUGJJEBB-UHFFFAOYSA-N 3-[(5-chloro-6-methoxypyridin-3-yl)amino]-3-methylsulfanyl-2-[2-(trifluoromethyl)benzoyl]prop-2-enenitrile Chemical compound ClC=1C=C(C=NC1OC)NC(=C(C#N)C(C1=C(C=CC=C1)C(F)(F)F)=O)SC PIVTXPHUGJJEBB-UHFFFAOYSA-N 0.000 description 1
- PSGZOBRJOQVCJL-UHFFFAOYSA-N 3-[4-(trifluoromethyl)anilino]prop-2-enenitrile Chemical compound FC(C1=CC=C(NC=CC#N)C=C1)(F)F PSGZOBRJOQVCJL-UHFFFAOYSA-N 0.000 description 1
- JLYQRFMXWRNNRF-UHFFFAOYSA-N 3-anilino-2-(2-chlorobenzoyl)-3-methylsulfanylprop-2-enenitrile Chemical compound C=1C=CC=C(Cl)C=1C(=O)C(C#N)=C(SC)NC1=CC=CC=C1 JLYQRFMXWRNNRF-UHFFFAOYSA-N 0.000 description 1
- RQKFYFNZSHWXAW-UHFFFAOYSA-N 3-chloro-p-toluidine Chemical compound CC1=CC=C(N)C=C1Cl RQKFYFNZSHWXAW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LNKBDFVSILQKSI-UHFFFAOYSA-N 4-Chloro-3-methoxyaniline Chemical compound COC1=CC(N)=CC=C1Cl LNKBDFVSILQKSI-UHFFFAOYSA-N 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 1
- XSUGEKNUDFVPPO-UHFFFAOYSA-N 5-chloro-6-methoxypyridin-3-amine Chemical compound COC1=NC=C(N)C=C1Cl XSUGEKNUDFVPPO-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000221198 Basidiomycota Species 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 241001465180 Botrytis Species 0.000 description 1
- KJELLRIDYRGASA-UHFFFAOYSA-N CC1=C(C(=O)C(C#N)=C)C=CC=C1 Chemical compound CC1=C(C(=O)C(C#N)=C)C=CC=C1 KJELLRIDYRGASA-UHFFFAOYSA-N 0.000 description 1
- ZGXXIZSVALIQKE-UHFFFAOYSA-N CSC=C(C#N)C(=O)C1=CC=CC=C1C(F)(F)F Chemical compound CSC=C(C#N)C(=O)C1=CC=CC=C1C(F)(F)F ZGXXIZSVALIQKE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Natural products CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241000233654 Oomycetes Species 0.000 description 1
- 241000219998 Philenoptera violacea Species 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 241001281802 Pseudoperonospora Species 0.000 description 1
- 241000221300 Puccinia Species 0.000 description 1
- 241001123569 Puccinia recondita Species 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 241000813090 Rhizoctonia solani Species 0.000 description 1
- 241001558929 Sclerotium <basidiomycota> Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000317942 Venturia <ichneumonid wasp> Species 0.000 description 1
- YXOUDYRGGMJGJA-UHFFFAOYSA-N [N+](=O)([O-])C1=C(C(=O)C(C#N)=C)C=CC=C1 Chemical compound [N+](=O)([O-])C1=C(C(=O)C(C#N)=C)C=CC=C1 YXOUDYRGGMJGJA-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000002554 disease preventive effect Effects 0.000 description 1
- PHHWLDOIMGFHOZ-UHFFFAOYSA-L disodium;dinaphthalen-1-ylmethanedisulfonate Chemical compound [Na+].[Na+].C1=CC=C2C(C(C=3C4=CC=CC=C4C=CC=3)(S(=O)(=O)[O-])S([O-])(=O)=O)=CC=CC2=C1 PHHWLDOIMGFHOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- VPGHGGRZCMHQCC-UHFFFAOYSA-N hept-1-en-1-one Chemical class CCCCCC=C=O VPGHGGRZCMHQCC-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical class S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、文献未載の新規化合物
であるアクリロニトリル誘導体及びこれを有効成分とし
て含有する農園芸用殺菌剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylonitrile derivative, which is a novel compound not described in the literature, and an agricultural and horticultural fungicide containing the acrylonitrile derivative as an active ingredient.
【０００２】[0002]
【従来の技術】ジャーナル・オブ・プラクティシェ・ヘ
ミー（Journal of Practishe Chemie）３１９巻、
（４）、５４５頁（１９７７年）には、アシルケテン
Ｓ,Ｓ−アセタールとアミン類との反応によって、次に
示すアシルケテン Ｓ,Ｎ−アセタールを製造できるこ
とが記載されている。2. Description of the Related Art Journal of Practishe Chemie, Volume 319,
(4), 545 (1977), acyl ketene.
It is described that the following acylketene S, N-acetal can be produced by the reaction of S, S-acetal and amines.
【０００３】[0003]
【化４】 [Chemical 4]
【０００４】（式中、Ａはフェニル基、４−クロロフェ
ニル基、４−メトキシフェニル基、４−ブロモフェニル
基及び３,４−ジクロロフェニル基等を示し、Ｂはフェ
ニル基、４−メトキシフェニル基、４−ニトロフェニル
基、４−ブロモフェニル基及び３,４−ジクロロフェニ
ル基等を示す。）(In the formula, A represents a phenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group, etc., and B represents a phenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group and the like are shown.)
【０００５】また、旧東独特許第１５９,８７６号公報
明細書は、置換Ｎ−ビニル−Ｓ,Ｓ−ジメチルスホキシ
イミドの製造法に関するものであるが、その製造原料と
して次に示す置換アミルケテン Ｓ,Ｎ−アセタールを
開示している。The former East German Patent No. 159,876 relates to a method for producing a substituted N-vinyl-S, S-dimethyl sulfoxyimide, and the following substituted amylketene S is used as a raw material for the production. , N-acetal is disclosed.
【０００６】[0006]
【化５】 [Chemical 5]
【０００７】（式中、Ｄはベンゾイル基、２−クロロベ
ンゾイル基等を示し、Ｅはフェニル基等を示す。）(In the formula, D represents a benzoyl group, 2-chlorobenzoyl group, etc., and E represents a phenyl group, etc.)
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、これら
文献及び特許に示された化合物については、生理活性を
示唆する旨の何らの記載もない。即ち、本発明は新規か
つ殺菌活性にすぐれたアクリロニトリル誘導体を提供す
るものである。However, the compounds shown in these documents and patents have no description to suggest physiological activity. That is, the present invention provides a novel acrylonitrile derivative having excellent bactericidal activity.
【０００９】[0009]
【課題を解決するための手段】本発明者らはアクリロニ
トリル誘導体を種々合成し、その生理活性について検討
したところ、本発明化合物が幅広い殺菌スペクトラムを
有し、特に稲紋枯病菌、黒星病菌、灰色かび病菌、べと
病菌、コムギ赤さび病菌及びアルタナリア属菌等に対
し、極めてすぐれた殺菌活性を有するとともに有用作物
に対して何らの害も及ぼさないことを見出し、本発明を
完成するに至ったものである。即ち、本発明は一般式
〔Ｉ〕Means for Solving the Problems The present inventors have synthesized various acrylonitrile derivatives and examined their physiological activities. The compounds of the present invention have a broad bactericidal spectrum. It has been found that, against gray mold, downy mildew, wheat leaf rust and alternaria genus, etc., it has extremely excellent bactericidal activity and does not cause any damage to useful crops, and completed the present invention. It is a thing. That is, the present invention has the general formula [I]
【００１０】[0010]
【化６】 [Chemical 6]
【００１１】｛式中、Ｒｘは式{Where Rx is an expression
【００１２】[0012]
【化７】 [Chemical 7]
【００１３】（式中、Ｒ2はアルキル基、アルコキシ
基、ハロゲン原子、ニトロ基またはハロアルキル基を示
し、Ｘはハロゲン原子、アルキル基またはハロアルキル
基を示し、ｌは１または２の整数を示す。）で表される
基を示し、Ｒｙは式(In the formula, R 2 represents an alkyl group, an alkoxy group, a halogen atom, a nitro group or a haloalkyl group, X represents a halogen atom, an alkyl group or a haloalkyl group, and l represents an integer of 1 or 2. ) Is a group represented by
【００１４】[0014]
【化８】 [Chemical 8]
【００１５】〔式中、Ｒ3はハロゲン原子、アルキル
基、ニトロ基、シアノ基、ジアルキルアミノ基、ハロア
ルキル基、式−ＣＯＲ6（式中、Ｒ6はアルキル基、アル
コキシ基、アミノ基、メチルアミノ基、ジメチルアミノ
基、フェニル基または塩素原子置換フェニル基を示す）
で表される基、式−ＳＯ2Ｒ7（式中、Ｒ7はアルキル
基、メチルアミノ基またはジメチルアミノ基を示す。）
で表される基、アルコキシ基、アルケニルオキシ基、ア
ルキニルオキシ基、アルキルチオ基、ハロアルキルチオ
基、メチレンジオキシ基またはアルキルスルホニルオキ
シ基を示し、Ｒ4はハロゲン原子、アルキル基、アルコ
キシ基、ジアルキルアミノ基、アルキルチオ基またはハ
ロアルキル基を示し、Ｒ5はアルキル基またはアルコキ
シ基を示し、ｍは０または１〜５の整数を示し、ｎは０
または１,２の整数を示す。〕で表される基を示し、Ｒ
は水素原子、アルキル基、アシル基またはアルコキシカ
ルボニル基を示し、Ｒ1はアルキル基、アルケニル基ま
たはベンジル基を示す。｝で表されるアクリロニトリル
誘導体及びこれを有効成分として含有する農園芸用殺菌
剤である。[In the formula, R 3 is a halogen atom, an alkyl group, a nitro group, a cyano group, a dialkylamino group, a haloalkyl group, and a formula —COR 6 (wherein, R 6 is an alkyl group, an alkoxy group, an amino group, a methyl group, Amino group, dimethylamino group, phenyl group or chlorine atom-substituted phenyl group)
A group represented by the formula: —SO 2 R 7 (In the formula, R 7 represents an alkyl group, a methylamino group or a dimethylamino group.)
Represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, an alkylthio group, a haloalkylthio group, a methylenedioxy group or an alkylsulfonyloxy group, and R 4 represents a halogen atom, an alkyl group, an alkoxy group or a dialkylamino group. Group, an alkylthio group or a haloalkyl group, R 5 represents an alkyl group or an alkoxy group, m represents 0 or an integer of 1 to 5, and n represents 0.
Alternatively, it represents an integer of 1 or 2. ] Represents a group represented by
Represents a hydrogen atom, an alkyl group, an acyl group or an alkoxycarbonyl group, and R 1 represents an alkyl group, an alkenyl group or a benzyl group. } The acrylonitrile derivative represented by these, and the agricultural and horticultural germicide containing this as an active ingredient.
【００１６】ここでＲｘとしては、２−トリフルオロメ
チルフェニル基、２−ブロムフェニル基、２−ニトロフ
ェニル基、２−ヨードフェニル基、２−メチルフェニル
基、１−メチル−３−トリフルオロメチル−４−ピラゾ
リル基、２,４−ジメチル−５−チアゾリル基、３−ク
ロロ−２−チエニル基、３−クロロ−４−メチル−２−
チエニル基、１,３,５−トリメチル−４−ピラゾリル
基、２−メチル−４−トリフルオロメチル−５−チアゾ
リル基または２−メチル−３−ピリジル基、Ｒｙとして
は、３,４−ジクロロフェニル基、３,５−ジクロロフェ
ニル基、３,５−ジクロロ−４−メチルフェニル基、３,
５−ジクロロ−４−メトキシフェニル基、３,５−ジク
ロロ−４−エトキシフェニル基、４−トリフルオロメチ
ルフェニル基、４−ブロムフェニル基、３−クロロ−４
−メチルフェニル基、３−クロロ−４−メトキシカルボ
ニルフェニル基、２,３,４,５,６−ペンタフルオロフェ
ニル基、４−シアノフェニル基、５−クロロ−６−アル
キルチオ−３−ピリジル基または５−クロロ−６−メト
キシ−３−ピリジル基、Ｒとしては、水素原子、メチル
基またはアセチル基、Ｒ1としては、メチル基である化
合物が特に良好な殺菌効果を示す。Here, Rx is 2-trifluoromethylphenyl group, 2-bromophenyl group, 2-nitrophenyl group, 2-iodophenyl group, 2-methylphenyl group, 1-methyl-3-trifluoromethyl group. -4-Pyrazolyl group, 2,4-dimethyl-5-thiazolyl group, 3-chloro-2-thienyl group, 3-chloro-4-methyl-2-
Thienyl group, 1,3,5-trimethyl-4-pyrazolyl group, 2-methyl-4-trifluoromethyl-5-thiazolyl group or 2-methyl-3-pyridyl group, Ry is 3,4-dichlorophenyl group 3,5-dichlorophenyl group, 3,5-dichloro-4-methylphenyl group, 3,
5-dichloro-4-methoxyphenyl group, 3,5-dichloro-4-ethoxyphenyl group, 4-trifluoromethylphenyl group, 4-bromophenyl group, 3-chloro-4
-Methylphenyl group, 3-chloro-4-methoxycarbonylphenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-cyanophenyl group, 5-chloro-6-alkylthio-3-pyridyl group or A compound having a 5-chloro-6-methoxy-3-pyridyl group, R is a hydrogen atom, a methyl group or an acetyl group, and R 1 is a methyl group exhibits particularly good bactericidal effect.
【００１７】次に、本発明化合物の具体例を表１〜表３
９に示すが、これらに限られるものではない。化合物番
号は以後の記載において参照される。Next, specific examples of the compounds of the present invention are shown in Tables 1 to 3.
9, but is not limited to these. The compound numbers are referred to in the description below.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【表３】 [Table 3]
【００２１】[0021]
【表４】 [Table 4]
【００２２】[0022]
【表５】 [Table 5]
【００２３】[0023]
【表６】 [Table 6]
【００２４】[0024]
【表７】 [Table 7]
【００２５】[0025]
【表８】 [Table 8]
【００２６】[0026]
【表９】 [Table 9]
【００２７】[0027]
【表１０】 [Table 10]
【００２８】[0028]
【表１１】 [Table 11]
【００２９】[0029]
【表１２】 [Table 12]
【００３０】[0030]
【表１３】 [Table 13]
【００３１】[0031]
【表１４】 [Table 14]
【００３２】[0032]
【表１５】 [Table 15]
【００３３】[0033]
【表１６】 [Table 16]
【００３４】[0034]
【表１７】 [Table 17]
【００３５】[0035]
【表１８】 [Table 18]
【００３６】[0036]
【表１９】 [Table 19]
【００３７】[0037]
【表２０】 [Table 20]
【００３８】[0038]
【表２１】 [Table 21]
【００３９】[0039]
【表２２】 [Table 22]
【００４０】[0040]
【表２３】 [Table 23]
【００４１】[0041]
【表２４】 [Table 24]
【００４２】[0042]
【表２５】 [Table 25]
【００４３】[0043]
【表２６】 [Table 26]
【００４４】[0044]
【表２７】 [Table 27]
【００４５】[0045]
【表２８】 [Table 28]
【００４６】[0046]
【表２９】 [Table 29]
【００４７】[0047]
【表３０】 [Table 30]
【００４８】[0048]
【表３１】 [Table 31]
【００４９】[0049]
【表３２】 [Table 32]
【００５０】[0050]
【表３３】 [Table 33]
【００５１】[0051]
【表３４】 [Table 34]
【００５２】[0052]
【表３５】 [Table 35]
【００５３】[0053]
【表３６】 [Table 36]
【００５４】[0054]
【表３７】 [Table 37]
【００５５】[0055]
【表３８】 [Table 38]
【００５６】[0056]
【表３９】 [Table 39]
【００５７】一般式〔Ｉ〕で表される本発明化合物の中
で、Ｒが水素原子の化合物〔II〕については例えば次に
示す製造法１及び２に従って製造することができ、Ｒが
アルキル基、アシル基、アルコキシカルボニル基の化合
物については製造法３に従って製造することが出来る。
製造法１Of the compounds of the present invention represented by the general formula [I], the compound [II] in which R is a hydrogen atom can be produced, for example, according to the following production methods 1 and 2, wherein R is an alkyl group. A compound having an acyl group or an alkoxycarbonyl group can be produced according to the production method 3. Manufacturing method 1
【００５８】[0058]
【化９】 [Chemical 9]
【００５９】（式中、Ｒｘ、Ｒｙ及びＲ1は前記と同じ
意味を表し、Ｚはハロゲン原子、アルコキシスルホニル
オキシ基を示す。）(In the formula, Rx, Ry and R 1 have the same meanings as described above, and Z represents a halogen atom or an alkoxysulfonyloxy group.)
【００６０】即ち、本発明化合物〔II〕は一般式〔II
I〕で表されるシアノアセチル誘導体と一般式〔IV〕で
表されるイソチオシアナート類を塩基の存在下に反応さ
せた後、一般式〔Ｖ〕で表される化合物を反応させるこ
とにより製造することができる。That is, the compound [II] of the present invention has the general formula [II
Manufactured by reacting the cyanoacetyl derivative represented by I] with the isothiocyanates represented by the general formula [IV] in the presence of a base, and then reacting the compound represented by the general formula [V]. can do.
【００６１】本反応で使用できる溶媒としては、例えば
ベンゼン、トルエン、キシレン等の炭化水素類、ジクロ
ロメタン、クロロホルム、四塩化炭素等のハロゲン化炭
化水素類、ジイソプロピルエーテル、テトラヒドロフラ
ン、ジオキサン等のエーテル類、アセトニトリル、プロ
ピオニトリル等のニトリル類、さらにはジメチルスルホ
キシド、ジメチルホルムアミド、スルホラン等の非プロ
トン性極性溶媒があげられる。塩基としては、ナトリウ
ム、カリウム等のアルカリ金属、水素化ナトリウム、水
素化カリウム等のアルカリ金属水素化物、水酸化ナトリ
ウム、水酸化カリウム等のアルカリ金属水酸化物、ナト
リウムメトキシド、ナトリウムエトキシド、カリウム−
ｔｅｒｔ−ブトキシド等のアルカリ金属アルコキシド等
があげられる。反応は前半、後半共に通常−１０℃から
溶媒の沸点の範囲、好ましくは０〜３０℃の範囲におい
て行われる。Examples of the solvent which can be used in this reaction include hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, ethers such as diisopropyl ether, tetrahydrofuran and dioxane, Examples thereof include nitriles such as acetonitrile and propionitrile, and aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide and sulfolane. Examples of the base include alkali metals such as sodium and potassium, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium methoxide, sodium ethoxide and potassium. −
Examples include alkali metal alkoxides such as tert-butoxide. The reaction is usually carried out in the first half and the second half in the range of -10 ° C to the boiling point of the solvent, preferably in the range of 0 to 30 ° C.
【００６２】尚、出発原料である一般式〔III〕で示さ
れるシアノアセチル誘導体は、一部はすでに公知である
が、ほとんどは新規物質であり、公知の方法、例えばテ
トラヘドロン（Tetrahedron）３４巻、７２５頁（１９
７８年）記載の方法に準じて、対応するエステル類とア
セトニトリルを水素化ナトリウムの存在下に反応させて
製造するか、シンセシス（Synthesis）３０８頁（１９
８３年）記載の方法に準じて、対応する酸塩化物とシア
ノ酢酸とをｎ−ブチルリチウム及び触媒量の２,２'−ビ
ピリジンの存在下に反応させて製造することができる。
あるいはヨーロッパ特許第３７２,４７０号記載の方法
に準じて対応するアセチル誘導体とギ酸を塩基の存在下
に反応させてβ−オキソプロパナールとし、次いでヒド
ロキシアミンを反応させてアルドキシム誘導体とし、更
に脱水することにより製造することができる。新規な中
間体〔III〕の具体例を表４０〜表４３に示す。The cyanoacetyl derivative represented by the general formula [III], which is a starting material, is a known substance, although a part thereof is already known. Most of them are known substances, for example, tetrahedron (Vol. 34). , 725 (19
1978), or by reacting the corresponding ester with acetonitrile in the presence of sodium hydride, or by synthesis, page 308 (19).
1983), the corresponding acid chloride can be reacted with cyanoacetic acid in the presence of n-butyllithium and a catalytic amount of 2,2′-bipyridine.
Alternatively, according to the method described in European Patent No. 372,470, the corresponding acetyl derivative and formic acid are reacted in the presence of a base to form β-oxopropanal, and then hydroxyamine is reacted to form an aldoxime derivative, which is further dehydrated. It can be manufactured. Specific examples of the novel intermediate [III] are shown in Tables 40 to 43.
【００６３】[0063]
【表４０】 [Table 40]
【００６４】[0064]
【表４１】 [Table 41]
【００６５】[0065]
【表４２】 [Table 42]
【００６６】[0066]
【表４３】 [Table 43]
【００６７】また、一般式〔IV〕で示されるフェニルイ
ソチオシアナート類は相当するアミン類とチオホスゲン
から製造できるが、一部は試薬としての入手も可能であ
る。The phenylisothiocyanates represented by the general formula [IV] can be produced from the corresponding amines and thiophosgene, but some of them are also available as reagents.
【００６８】製造法２Production Method 2
【００６９】[0069]
【化１０】 [Chemical 10]
【００７０】（式中、Ｒｘ、Ｒｙ及びＲ1は前記と同じ
意味を表す。）(In the formula, Rx, Ry and R 1 have the same meanings as described above.)
【００７１】即ち、本発明化合物〔II〕は、一般式〔V
I〕で表されるアシルケテン Ｓ,Ｓ−アセタール類と一
般式〔VII〕で表されるアミン類とを反応させることに
より製造することができる。That is, the compound [II] of the present invention has the general formula [V
It can be produced by reacting an acylketene S, S-acetal represented by I] with an amine represented by the general formula [VII].
【００７２】本反応で使用できる溶媒としては、例えば
ベンゼン、トルエン、キシレン等の炭化水素類、メタノ
ール、エタノール、１−プロパノール、２−プロパノー
ル等のアルコール類、メチルエチルケトン、シクロヘキ
サン等のケトン類、ジクロロメタン、クロロホルム、四
塩化炭素等のハロゲン化炭化水素類、ジイソプロピルエ
ーテル、テトラヒドロフラン、ジオキサン、ジエチレン
グリコールジメチルエーテル等のエーテル類、アセトニ
トリル、プロピオニトリル等のニトリル類、さらにはジ
メチルスルホキシド、ジメチルホルムアミド、スルホラ
ン等の非プロトン性極性溶媒等があげられる。反応は通
常０℃から１５０℃の範囲、好ましくは５０℃から１２
０℃の範囲で行われる。Examples of the solvent which can be used in this reaction include hydrocarbons such as benzene, toluene and xylene, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, ketones such as methyl ethyl ketone and cyclohexane, dichloromethane, Chloroform, halogenated hydrocarbons such as carbon tetrachloride, ethers such as diisopropyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, nitriles such as acetonitrile and propionitrile, and aprotons such as dimethyl sulfoxide, dimethylformamide and sulfolane. Examples thereof include polar solvents. The reaction is usually in the range of 0 ° C to 150 ° C, preferably 50 ° C to 12 ° C.
It is performed in the range of 0 ° C.
【００７３】尚、出発原料である一般式〔VI〕で表され
るアシルケテン Ｓ,Ｓ−アセタール類はそれ自体殺菌
活性を有する新規物質であり、具体例を表４４〜表４５
に示す。The acyl ketene S, S-acetals represented by the general formula [VI], which are the starting materials, are novel substances having bactericidal activity, and specific examples thereof are shown in Tables 44 to 45.
Shown in.
【００７４】[0074]
【表４４】 [Table 44]
【００７５】[0075]
【表４５】 [Table 45]
【００７６】本化合物〔VI〕は、例えば旧東独特許第１
１９,０４１号明細書記載の方法に準ずる次の反応式に
従って、塩基の存在下、一般式〔III〕で表されるアシ
ルアセトニトリル類、二硫化炭素及び一般式〔Ｖ〕で表
される化合物から製造することができる。The compound [VI] is obtained, for example, from the former East German Patent No. 1
From the acylacetonitriles represented by the general formula [III], carbon disulfide and the compound represented by the general formula [V] in the presence of a base, according to the following reaction formula according to the method described in 19,041 specification: It can be manufactured.
【００７７】[0077]
【化１１】 [Chemical 11]
【００７８】（式中、Ｒｘ、Ｚ及びＲ1は前記と同じ意
味を表す。）(In the formula, Rx, Z and R 1 have the same meanings as described above.)
【００７９】本反応に用いる溶媒及び塩基としては、製
造例１と同様のものをあげることができる。反応は通常
−２０℃から溶媒の沸点の範囲、好ましくは−１０℃か
ら３０℃の範囲で行われる。As the solvent and the base used in this reaction, the same ones as in Production Example 1 can be mentioned. The reaction is usually performed in the range of -20 ° C to the boiling point of the solvent, preferably in the range of -10 ° C to 30 ° C.
【００８０】製造法３Manufacturing Method 3
【００８１】[0081]
【化１２】 [Chemical 12]
【００８２】（式中、Ｒｘ、Ｒｙ、Ｒ1、Ｒ及びＺは前
記と同じ意味を表す。）(In the formula, Rx, Ry, R 1 , R and Z have the same meanings as described above.)
【００８３】即ち、本発明化合物〔VIII〕は製造法１及
び２で得られた一般式〔II〕で表される化合物と一般式
〔IX〕で表される化合物を塩基の存在下に反応させるこ
とにより製造することができる。本反応で使用できる溶
媒としては、例えばベンゼン、トルエン、キシレン等の
炭化水素類、ジイソプロピルエーテル、テトラヒドロフ
ラン、ジオキサン等のエーテル類、アセトニトリル、プ
ロピオニトリル等のニトリル類、さらにはジメチルスル
ホキシド、ジメチルホルムアミド、スルホラン等の非プ
ロトン性極性溶媒があげられる。塩基としては、ナトリ
ウム、カリウム等のアルカリ金属、水素化ナトリウム、
水素化カリウム等のアルカリ金属水素化物等があげられ
る。反応は通常−１０℃から溶媒の沸点の範囲、好まし
くは０〜３０℃の範囲において行われる。That is, the compound [VIII] of the present invention is obtained by reacting the compound represented by the general formula [II] obtained by the production methods 1 and 2 with the compound represented by the general formula [IX] in the presence of a base. It can be manufactured. As the solvent that can be used in this reaction, for example, hydrocarbons such as benzene, toluene, xylene, ethers such as diisopropyl ether, tetrahydrofuran, dioxane, acetonitrile, nitriles such as propionitrile, further dimethyl sulfoxide, dimethylformamide, An aprotic polar solvent such as sulfolane can be used. As the base, alkali metals such as sodium and potassium, sodium hydride,
Examples thereof include alkali metal hydrides such as potassium hydride. The reaction is usually performed in the range of -10 ° C to the boiling point of the solvent, preferably 0 to 30 ° C.
【００８４】[0084]
【実施例】次に実施例をあげて本発明化合物の製造法、
製剤法及び用途を具体的に説明する。
製造例１
３−（３,４−ジクロロアニリノ）−３−メチルチオ−
２−（２−トリフルオロメチルベンゾイル）アクリロニ
トリル（化合物番号６６）の製造法
２−トリフルオロベンゾイルアセトニトリル１.６gをジ
メチルホルムアミド１５mlに溶かし、この溶液に６０％
水素化ナトリウム０.３gを５〜１８℃で加え、室温で３
０分間攪拌した後、更にジメチルホルムアミド５mlに溶
かした３,４−ジクロロフェニルイソチオシアナート１.
５３gを５〜１５℃で加え、室温で２時間撹拌した。次
に、この反応混合物にヨウ化メチル１.９２gを５〜６℃
で加え、室温で２時間攪拌した。反応混合物を水中に注
ぎ込み、固体をトルエンで抽出した。トルエン層を炭酸
水素ナトリウム水溶液、水の順に洗い、無水硫酸マグネ
シウムで乾燥後、減圧下に濃縮した。残渣の固体をエタ
ノールとｎ−ヘキサンの混合溶媒で再結して無色羽毛状
結晶の目的物２.２g（収率６８％）を得た。融点：１２
８−１３１℃EXAMPLES Next, the production method of the compound of the present invention will be described with reference to Examples.
The formulation method and use will be specifically described. Production Example 1 3- (3,4-dichloroanilino) -3-methylthio-
Method for producing 2- (2-trifluoromethylbenzoyl) acrylonitrile (Compound No. 66) 1.6 g of 2-trifluorobenzoylacetonitrile was dissolved in 15 ml of dimethylformamide, and 60% was added to this solution.
Add 0.3 g of sodium hydride at 5 to 18 ° C, and add 3
After stirring for 0 minutes, 3,4-dichlorophenyl isothiocyanate 1. was further dissolved in 5 ml of dimethylformamide.
53 g was added at 5 to 15 ° C., and the mixture was stirred at room temperature for 2 hours. Next, to this reaction mixture was added 1.92 g of methyl iodide at 5 to 6 ° C.
Then, the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and the solid was extracted with toluene. The toluene layer was washed with an aqueous sodium hydrogen carbonate solution and water in this order, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residual solid was recrystallized with a mixed solvent of ethanol and n-hexane to obtain 2.2 g (yield 68%) of the desired product as colorless feathery crystals. Melting point: 12
8-131 ° C
【００８５】製造例２
３−（３−クロロ−４−メチルアニリノ）−３−メチル
チオ−２−（２−トリフルオロメチルベンゾイル）アク
リロニトリル（化合物番号６７）の製造法
３,３−ビス（メチルチオ）−２−（２−トリフルオロ
メチルベンゾイル）アクリロニトリル２.０gと３−クロ
ロ−４−メチルアニリン１.０gをトルエン２０mlに溶か
し、還流下に２時間攪拌した。反応混合物を減圧下に濃
縮し、残渣の固体をイソプロピルエーテルで洗浄後、エ
タノールで再結して淡黄色プリズム状結晶の目的物１.
９g（収率７４％）を得た。融点：１６１−１６４℃Production Example 2 Production method of 3- (3-chloro-4-methylanilino) -3-methylthio-2- (2-trifluoromethylbenzoyl) acrylonitrile (Compound No. 67) 3,3-bis (methylthio)- 2.0 g of 2- (2-trifluoromethylbenzoyl) acrylonitrile and 1.0 g of 3-chloro-4-methylaniline were dissolved in 20 ml of toluene and stirred under reflux for 2 hours. The reaction mixture was concentrated under reduced pressure, the residual solid was washed with isopropyl ether, and then recrystallized with ethanol to obtain the desired product 1.
9 g (74% yield) were obtained. Melting point: 161-164 ° C
【００８６】製造例３
３−（３,４−ジクロロアニリノ）−３−メチルチオ−
２−（２−ニトロベンゾイル）アクリロニトリル（化合
物番号１１５）の製造法
２−ニトロベンゾイルアセトニトリル１.０gをジメチル
ホルムアミド１５mlに溶かし、この溶液に６０％水素化
ナトリウム０.２１gを５〜１０℃で加え、室温で１時間
攪拌した後、更にジメチルホルムアミド５mlに溶かした
３,４−ジクロロフェニルイソチオシアナート１.０６g
を５〜１０℃で加え、室温で２時間攪拌した。次に、こ
の反応混合物にヨウ化メチル０.７５gを５〜１０℃で加
え、室温で２時間攪拌した。反応混合物を水中に注ぎ込
み、固体をエーテルで抽出した。エーテル層を水洗し、
無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残
渣の固体をエタノールで再結して乳白色粉末の目的物
１.０g（収率４７％）を得た。融点：２１９−２２２℃Production Example 3 3- (3,4-dichloroanilino) -3-methylthio-
Method for producing 2- (2-nitrobenzoyl) acrylonitrile (Compound No. 115) 1.0 g of 2-nitrobenzoylacetonitrile was dissolved in 15 ml of dimethylformamide, and 0.21 g of 60% sodium hydride was added to this solution at 5-10 ° C. After stirring at room temperature for 1 hour, 1.06 g of 3,4-dichlorophenyl isothiocyanate further dissolved in 5 ml of dimethylformamide
Was added at 5 to 10 ° C., and the mixture was stirred at room temperature for 2 hours. Next, 0.75 g of methyl iodide was added to this reaction mixture at 5 to 10 ° C., and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and the solid was extracted with ether. Wash the ether layer with water,
After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. The residual solid was recrystallized with ethanol to obtain 1.0 g (yield 47%) of the desired product as a milky white powder. Melting point: 219-222 ° C
【００８７】製造例４
３−（３,５−ジクロロアニリノ）−３−エチルチオ−
２−（２−メチルベンゾイル）アクリロニトリル（化合
物番号９６）の製造法
２−メチルベンゾイルアセトニトリル１.２７gをジメチ
ルホルムアミド１５mlに溶かし、この溶液に６０％水素
化ナトリウム０.３２gを５〜１０℃で加え、室温で１時
間攪拌した後、更にジメチルホルムアミド５mlに溶かし
た３,５−ジクロロフェニルイソチオシアナート１.６３
gを５〜１０℃で加え、室温で２時間攪拌した。次に、
この反応混合物にヨウ化エチル２.２５gを５〜１０℃で
加え、４０〜４５℃で２時間攪拌した。反応混合物を水
中に注ぎ込み、析出した固体をトルエンで抽出した。ト
ルエン層を水洗し、無水硫酸マグネシウムで乾燥後、減
圧下に濃縮した。残渣の固体をエタノールとｎ−ヘキサ
ンの混合溶媒で再結して無色羽毛状結晶の目的物２.５g
（収率８０％）を得た。融点：１３２−１３３℃Production Example 4 3- (3,5-dichloroanilino) -3-ethylthio-
Method for producing 2- (2-methylbenzoyl) acrylonitrile (Compound No. 96) 1.27 g of 2-methylbenzoylacetonitrile was dissolved in 15 ml of dimethylformamide, and 0.32 g of 60% sodium hydride was added to this solution at 5-10 ° C. After stirring for 1 hour at room temperature, 1.63 of 3,5-dichlorophenyl isothiocyanate was dissolved in 5 ml of dimethylformamide.
g was added at 5 to 10 ° C, and the mixture was stirred at room temperature for 2 hours. next,
To this reaction mixture was added 2.25 g of ethyl iodide at 5 to 10 ° C, and the mixture was stirred at 40 to 45 ° C for 2 hours. The reaction mixture was poured into water, and the precipitated solid was extracted with toluene. The toluene layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residual solid was reconstituted with a mixed solvent of ethanol and n-hexane to obtain 2.5 g of the desired product as colorless feathery crystals.
(Yield 80%) was obtained. Melting point: 132-133 ° C
【００８８】製造例５
３−（４−クロロアニリノ）−２−（２−クロロベンゾ
イル）−３−メチルチオアクリロニトリル（化合物番号
１０７）の製造法
２−クロロベンゾイルアセトニトリル５.９３gをジメチ
ルホルムアミド４０mlに溶かし、この溶液に６０％水素
化ナトリウム１.３２gを５〜１０℃で加え、室温で１時
間攪拌した後、更にジメチルホルムアミド２０mlに溶か
した４−クロロフェニルイソチオシアナート５.６gを５
〜１０℃で加え、室温で２時間攪拌した。次に、この反
応混合物にヨウ化メチル７.０４gを５〜１０℃で加え、
３５〜４０℃で１.５時間攪拌した。反応混合物を水中
に注ぎ込み、固体をエーテルで抽出した。エーテル層を
水洗し、無水硫酸マグネシウムで乾燥後、減圧下に濃縮
した。残渣の固体をエタノールとアセトニトリルの混合
溶媒で再結して無色羽毛状結晶の目的物８.３g（収率７
０％）を得た。融点：１６５−１６６.５℃Production Example 5 Method for producing 3- (4-chloroanilino) -2- (2-chlorobenzoyl) -3-methylthioacrylonitrile (Compound No. 107) 2-chlorobenzoylacetonitrile (5.93 g) was dissolved in dimethylformamide (40 ml), To this solution, 1.32 g of 60% sodium hydride was added at 5 to 10 ° C., and the mixture was stirred at room temperature for 1 hour, and then 5.6 g of 4-chlorophenyl isothiocyanate dissolved in 20 ml of dimethylformamide was added.
The mixture was added at -10 ° C and stirred at room temperature for 2 hours. Next, 7.04 g of methyl iodide was added to the reaction mixture at 5 to 10 ° C,
The mixture was stirred at 35-40 ° C for 1.5 hours. The reaction mixture was poured into water and the solid was extracted with ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residual solid was recrystallized with a mixed solvent of ethanol and acetonitrile to give 8.3 g of the desired product as colorless feather-like crystals (yield 7
0%). Melting point: 165-16.5 ° C
【００８９】製造例６
３−（３,４−ジクロロアニリノ）−２−（２−ヨード
ベンゾイル）−３−メチルチオアクリロニトリル（化合
物番号１１３）の製造法
２−ヨードベンゾイルアセトニトリル１.１gをジメチル
ホルムアミド１５mlに溶かし、この溶液に６０％水素化
ナトリウム０.１４gを５〜１０℃で加え、室温で１時間
攪拌した後、更にジメチルホルムアミド５mlに溶かした
３,４−ジクロロフェニルイソチオシアナート０.７８g
を５〜１０℃で加え、室温で２時間攪拌した。次に、こ
の反応混合物をヨウ化メチル０.５５gを５〜１０℃で加
え、室温で２時間攪拌した。反応混合物を水中に注ぎ込
み、固体をエーテルで抽出した。エーテル層を水洗し、
無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残
渣の固体をエタノールで再結して淡黄色プリズム状結晶
の目的物１.３g（収率７１％）を得た。融点：１４５−
１４７℃Production Example 6 Method for producing 3- (3,4-dichloroanilino) -2- (2-iodobenzoyl) -3-methylthioacrylonitrile (Compound No. 113) 2-Iodobenzoylacetonitrile (1.1 g) was added to dimethylformamide. Dissolve in 15 ml, add 0.14 g of 60% sodium hydride to this solution at 5-10 ° C., stir at room temperature for 1 hour, and then add 0.74 g of 3,4-dichlorophenylisothiocyanate dissolved in 5 ml of dimethylformamide.
Was added at 5 to 10 ° C., and the mixture was stirred at room temperature for 2 hours. Next, 0.55 g of methyl iodide was added to this reaction mixture at 5 to 10 ° C., and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and the solid was extracted with ether. Wash the ether layer with water,
After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. The residual solid was recrystallized with ethanol to obtain 1.3 g (yield 71%) of the desired product as pale yellow prismatic crystals. Melting point: 145-
147 ° C
【００９０】製造例７
３−（４−クロロ−３−メトキシアニリノ）−３−メチ
ルチオ−２−（２−トリフルオロメチルベンゾイル）ア
クリロニトリル（化合物番号７１）の製造法
３,３−ビス（メチルチオ）−２−（２−トリフルオロ
メチルベンゾイル）アクリロニトリル０.８gと４−クロ
ロ−３−メトキシアニリン０.４４gをトルエン２０mlに
溶かし、還流下に２時間攪拌した。反応混合物を減圧下
に濃縮し、残渣の固体をイソプロピルエーテルで洗浄
後、エタノールで再結して無色プリズム状結晶の目的物
０.９g（収率８４％）を得た。融点：１５６−１５８℃Production Example 7 Production method of 3- (4-chloro-3-methoxyanilino) -3-methylthio-2- (2-trifluoromethylbenzoyl) acrylonitrile (Compound No. 71) 3,3-bis (methylthio) ) -2- (2-Trifluoromethylbenzoyl) acrylonitrile 0.8 g and 4-chloro-3-methoxyaniline 0.44 g were dissolved in toluene 20 ml, and the mixture was stirred under reflux for 2 hours. The reaction mixture was concentrated under reduced pressure, and the solid residue was washed with isopropyl ether and recrystallized with ethanol to obtain 0.9 g (yield 84%) of the desired product as colorless prism crystals. Melting point: 156-158 ° C
【００９１】製造例８
３−（３,５−ジクロロ−４−メトキシアニリノ）−３
−メチルチオ−２−（１−メチル−３−トリフルオロメ
チル−４−ピラゾリルカルボニル）アクリロニトリル
（化合物番号２０６）の製造法
３−（１−メチル−３−トリフルオロメチル−４−ピラ
ゾリル）−３−オキソプロパンニトリル１.０gをジメチ
ルホルムアミド１５mlに溶かし、この溶液に６０％水素
化ナトリウム０.２gを５〜１０℃で加え、室温で３０分
間攪拌した。さらにジメチルホルムアミド５mlに溶かし
た３,５−ジクロロ−４−メトキシフェニルイソチオシ
アナート１.１gを５〜１５℃で加え、室温で２時間撹拌
した。次に、この反応混合物にヨウ化メチル１.９gを５
〜６℃で加え、室温で２時間攪拌した。反応混合物を水
中に注ぎ込み、固体をトルエンで抽出した。トルエン層
を炭酸水素ナトリウム水溶液、水の順に洗い、無水硫酸
マグネシウムで乾燥後、減圧下に濃縮した。残渣の固体
をエタノールで再結して淡黄色針状結晶の目的物１.３g
（収率６０％）を得た。融点：２０５−２０６℃Production Example 8 3- (3,5-dichloro-4-methoxyanilino) -3
Preparation of 3-methylthio-2- (1-methyl-3-trifluoromethyl-4-pyrazolylcarbonyl) acrylonitrile (Compound No. 206) 3- (1-Methyl-3-trifluoromethyl-4-pyrazolyl) -3- 1.0 g of oxopropanenitrile was dissolved in 15 ml of dimethylformamide, 0.2 g of 60% sodium hydride was added to this solution at 5 to 10 ° C., and the mixture was stirred at room temperature for 30 minutes. Further, 1.1 g of 3,5-dichloro-4-methoxyphenyl isothiocyanate dissolved in 5 ml of dimethylformamide was added at 5 to 15 ° C., and the mixture was stirred at room temperature for 2 hours. Next, 1.9 g of methyl iodide was added to the reaction mixture to give 5 parts.
Added at ~ 6 ° C and stirred at room temperature for 2 hours. The reaction mixture was poured into water and the solid was extracted with toluene. The toluene layer was washed with an aqueous sodium hydrogen carbonate solution and water in this order, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residual solid was reconstituted with ethanol to give 1.3 g of the target substance as pale yellow needle crystals.
(Yield 60%) was obtained. Melting point: 205-206 ° C
【００９２】製造例９
３−（５−クロロ−６−メトキシ−３−ピリジルアミ
ノ）−３−メチルチオ−２−（２−トリフルオロメチル
ベンゾイル）アクリロニトリル（化合物番号３６５）の
製造法
３,３−ビス（メチルチオ）−２−（２−トリフルオロ
メチルベンゾイル）アクリロニトリル２.５gと５−アミ
ノ−３−クロロ−２−メトキシピリジン１.３gをトルエ
ン３０mlに溶かし、還流下に２時間攪拌した。反応混合
物を減圧下に濃縮し、残渣の固体をイソプロピルエーテ
ルで洗浄後、エタノールで再結して無色羽毛状結晶の目
的物２.４g（収率６９％）を得た。融点：１７７−１７
８℃Production Example 9 Method for producing 3- (5-chloro-6-methoxy-3-pyridylamino) -3-methylthio-2- (2-trifluoromethylbenzoyl) acrylonitrile (Compound No. 365) 3,3-bis 2.5 g of (methylthio) -2- (2-trifluoromethylbenzoyl) acrylonitrile and 1.3 g of 5-amino-3-chloro-2-methoxypyridine were dissolved in 30 ml of toluene, and the mixture was stirred under reflux for 2 hours. The reaction mixture was concentrated under reduced pressure, and the solid residue was washed with isopropyl ether and recrystallized with ethanol to obtain 2.4 g (yield 69%) of the desired product as colorless feather crystals. Melting point: 177-17
8 ° C
【００９３】製造例１０
２−（３−クロロ−２−テノイル）−３−メチルチオ−
３−（４−トリフルオロメチルアニリノ）アクリロニト
リル（化合物番号２６９）の製造法
３−（３−クロロ−２−チエニル）−３−オキソプロパ
ンニトリル０.９gをジメチルホルムアミド１５mlに溶か
し、この溶液に６０％水素化ナトリウム０.２gを５〜１
０℃で加え、室温で１時間攪拌した後、更にジメチルホ
ルムアミド５mlに溶かした４−トリフルオロメチルフェ
ニルイソチオシアナート１.０gを５〜１０℃で加え、室
温で２時間攪拌した。次に、この反応混合物にヨウ化メ
チル０.７gを５〜１０℃で加え、室温で２時間攪拌し
た。反応混合物を水中に注ぎ込み、固体をエーテルで抽
出した。エーテル層を水洗し、無水硫酸マグネシウムで
乾燥後、減圧下に濃縮した。残渣の固体をエタノールで
再結して橙黄色粉末の目的物０.９g（収率５８％）を得
た。融点：１３９−１４１℃Production Example 10 2- (3-chloro-2-thenoyl) -3-methylthio-
Method for producing 3- (4-trifluoromethylanilino) acrylonitrile (Compound No. 269) 0.9 g of 3- (3-chloro-2-thienyl) -3-oxopropanenitrile was dissolved in 15 ml of dimethylformamide and added to this solution. 60% sodium hydride 0.2g 5-1
After adding at 0 ° C. and stirring at room temperature for 1 hour, 1.0 g of 4-trifluoromethylphenyl isothiocyanate dissolved in 5 ml of dimethylformamide was further added at 5 to 10 ° C. and stirring at room temperature for 2 hours. Next, 0.7 g of methyl iodide was added to this reaction mixture at 5 to 10 ° C., and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and the solid was extracted with ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residual solid was recrystallized with ethanol to obtain 0.9 g (yield 58%) of the desired product as an orange-yellow powder. Melting point: 139-141 ° C
【００９４】製造例１１
３−（３,４−ジクロロアニリノ）−３−メチルチオ−
２−（１−メチル−３−トリフルオロメチル−４−ピラ
ゾリルカルボニル）アクリロニトリル（化合物番号２０
０）の製造法
３,３−ビス（メチルチオ）−２−（１−メチル−３−
トリフルオロメチル−４−ピラゾリルカルボニル）アク
リロニトリル０.９gと３,４−ジクロロアニリン０.５g
をトルエン２０mlに溶かし、還流下に２時間攪拌した。
反応混合物を減圧下に濃縮し、残渣の固体をイソプロピ
ルエーテルで洗浄後、シリカゲルカラムクロマトグラフ
ィーで精製して黄色プリズム状結晶の目的物０.７g（収
率５７％）を得た。融点：１８２−１８３℃Production Example 11 3- (3,4-dichloroanilino) -3-methylthio-
2- (1-Methyl-3-trifluoromethyl-4-pyrazolylcarbonyl) acrylonitrile (Compound No. 20
0) Production method 3,3-bis (methylthio) -2- (1-methyl-3-)
Trifluoromethyl-4-pyrazolylcarbonyl) acrylonitrile 0.9 g and 3,4-dichloroaniline 0.5 g
Was dissolved in 20 ml of toluene and stirred under reflux for 2 hours.
The reaction mixture was concentrated under reduced pressure, and the solid residue was washed with isopropyl ether and purified by silica gel column chromatography to obtain 0.7 g (yield 57%) of the desired product as yellow prism-like crystals. Melting point: 182-183 ° C
【００９５】製造例１２
２−（３−クロロ−２−テノイル）−３−（３,４−ジ
クロロ−Ｎ−メチルアニリノ）−３−メチルチオアクリ
ロニトリル（化合物番号２７１）の製造法
２−（３−クロロ−２−テノイル）−３−（３,４−ジ
クロロアニリノ）−３−メチルチオアクリロニトリル
３.０gをジメチルホルムアミド４０mlに溶かし、この溶
液へ６０％水素化ナトリウム０.３gを５〜１０℃で加
え、室温で１時間攪拌した後、ヨウ化メチル１.１gを５
〜７℃で加え、室温で１５時間攪拌した。反応混合物を
水中に注ぎ込み、ジエチルエーテルで抽出した。エーテ
ル層を水洗、無水硫酸マグネシウムで乾燥後、減圧下に
濃縮した。残渣をシリカゲルカラムクロマトグラフィー
で精製して黄色ガラス状物質の目的物１.８g（収率５７
％）を得た。融点：６１−６２℃Preparation Example 12 Preparation method of 2- (3-chloro-2-thenoyl) -3- (3,4-dichloro-N-methylanilino) -3-methylthioacrylonitrile (Compound No. 271) 2- (3-chloro) 2-Thenoyl) -3- (3,4-dichloroanilino) -3-methylthioacrylonitrile (3.0 g) was dissolved in dimethylformamide (40 ml), and 60% sodium hydride (0.3 g) was added to the solution at 5-10 ° C. After stirring at room temperature for 1 hour, 5 g of methyl iodide (1.1 g) was added.
Add at ~ 7 ° C and stir at room temperature for 15 hours. The reaction mixture was poured into water and extracted with diethyl ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give 1.8 g of the desired product as a yellow glassy substance (yield 57
%) Was obtained. Melting point: 61-62 ° C
【００９６】製造例１３
３−（Ｎ−アセチル−３,５−ジクロロアニリノ）−３
−メチルチオ−２−（２−トリフルオロメチルベンゾイ
ル）アクリロニトリル（化合物番号２８０）の製造法
３−（３,４−ジクロロアニリノ）−３−メチルチオ−
２−（２−トリフルオロメチルベンゾイル）アクリロニ
トリル３.２gをジメチルホルムアミド４０mlに溶かし、
この溶液へ６０％水素化ナトリウム０.３gを５〜１０℃
で加え、室温で１時間攪拌した後、塩化アセチル０.７g
を５〜７℃で加え、室温で３時間攪拌した。反応混合物
を水中に注ぎ込みジエチルエーテルで抽出した。エーテ
ル層を水洗、無水硫酸マグネシウムで乾燥後、減圧下に
濃縮した。残渣をシリカゲルカラムクロマトグラフィー
で精製して無色鱗片状結晶の目的物（収率７５％）を得
た。融点：１６０−１６２℃Production Example 13 3- (N-acetyl-3,5-dichloroanilino) -3
Method for producing -methylthio-2- (2-trifluoromethylbenzoyl) acrylonitrile (Compound No. 280) 3- (3,4-dichloroanilino) -3-methylthio-
3.2 g of 2- (2-trifluoromethylbenzoyl) acrylonitrile was dissolved in 40 ml of dimethylformamide,
To this solution was added 0.3 g of 60% sodium hydride at 5 to 10 ° C.
, And after stirring at room temperature for 1 hour, 0.7 g of acetyl chloride
Was added at 5 to 7 ° C., and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into water and extracted with diethyl ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the desired product (yield 75%) as colorless scaly crystals. Melting point: 160-162 ° C
【００９７】参考例
３,３−ビス（メチルチオ）−２−（１−メチル−３−
トリフルオロメチルピラゾール−４−カルボニル）アク
リロニトリル（中間体番号２７）の製造法
ジメチルホルムアミド５０mlへ４−シアノアセチル−１
−メチル−３−トリフルオロメチルピラゾール３.２gを
溶解し、この溶液へ氷水冷却下、５℃で６０％水素化ナ
トリウム１.２gを加えた後、冷媒を取り除き１時間攪拌
した。次にこの懸濁液へ５℃で二硫化炭素１.１gを加え
た後、冷媒を取り除き１時間攪拌し、さらに、ヨウ化メ
チル４.２gを５℃で加え、冷媒を取り除き２時間攪拌し
た。反応混合物に水を加え、エーテルで抽出した。エー
テル層を水洗後、無水硫酸マグネシウムで乾燥し、濃縮
した。残渣の固体をイソプロピルエーテルで洗浄し、茶
褐色の粉末の目的物３.５g（収率７４％）を得た。融
点：１２８−１２９℃Reference Example 3,3-bis (methylthio) -2- (1-methyl-3-)
Process for the preparation of trifluoromethylpyrazole-4-carbonyl) acrylonitrile (intermediate no. 27) 4-cyanoacetyl-1 to 50 ml of dimethylformamide
3.2 g of -methyl-3-trifluoromethylpyrazole was dissolved, 1.2 g of 60% sodium hydride was added to this solution at 5 ° C under ice-water cooling, and then the refrigerant was removed and the mixture was stirred for 1 hour. Next, 1.1 g of carbon disulfide was added to this suspension at 5 ° C., the refrigerant was removed, and the mixture was stirred for 1 hour. Further, 4.2 g of methyl iodide was added at 5 ° C., the refrigerant was removed, and the mixture was stirred for 2 hours. . Water was added to the reaction mixture, which was extracted with ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated. The solid residue was washed with isopropyl ether to obtain 3.5 g (yield: 74%) of the desired product as a brown powder. Melting point: 128-129 ° C
【００９８】本発明の農園芸用殺菌剤は一般式〔Ｉ〕で
示されるアクリロニトリル誘導体を有効成分として含有
してなる。本発明化合物を農園芸用殺菌剤として使用す
る場合には、その目的に応じて有効成分を適当な剤型で
用いることができる。通常は有効成分を不活性な液体ま
たは固体の担体で希釈し、必要に応じて界面活性剤、そ
の他をこれに加え、粉剤、水和剤、乳剤、粒剤等の製剤
形態で使用できる。The agricultural and horticultural germicide of the present invention comprises an acrylonitrile derivative represented by the general formula [I] as an active ingredient. When the compound of the present invention is used as a fungicide for agricultural and horticultural use, the active ingredient can be used in an appropriate dosage form depending on the purpose. Usually, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, a surfactant and the like are added thereto, and it can be used in the form of powders, wettable powders, emulsions, granules and the like.
【００９９】好適な担体としては、例えばタルク、ベン
トナイト、クレー、カオリン、珪藻土、ホワイトカーボ
ン、バーミキュライト、消石灰、珪砂、硫安、尿素等の
固体担体、イソプロピルアルコール、キシレン、シクロ
ヘキサノン、メチルナフタレン等の液体担体等があげら
れる。界面活性剤及び分散剤としては、例えばジナフチ
ルメタンスルホン酸塩、アルコール硫酸エステル塩、ア
ルキルアリールスルホン酸塩、リグニンスルホン酸塩、
ポリオキシエチレングリコールエーテル、ポリオキシエ
チレンアルキルアリールエーテル、ポリオキシエチレン
ソルビタンモノアルキレート等があげられる。補助剤と
してはカルボキシメチルセルロース等があげられる。こ
れらの製剤を適宜な濃度に希釈して散布するか、または
直接施用する。Suitable carriers include, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate and urea, and liquid carriers such as isopropyl alcohol, xylene, cyclohexanone and methylnaphthalene. Etc. As the surfactant and the dispersant, for example, dinaphthylmethanesulfonate, alcohol sulfate ester salt, alkylarylsulfonate, ligninsulfonate,
Examples thereof include polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether, and polyoxyethylene sorbitan monoalkylate. Examples of the auxiliary agent include carboxymethyl cellulose and the like. These formulations are diluted to an appropriate concentration and then sprayed or applied directly.
【０１００】本発明の農園芸用殺菌剤は茎葉散布、土壌
施用または水面施用等により使用することができる。有
効成分の配合割合は必要に応じ適宜選ばれるが、粉剤及
び粒剤とする場合は０.１〜２０％（重量）、また乳剤
及び水和剤とする場合は５〜８０％（重量）が適当であ
る。The agricultural and horticultural fungicides of the present invention can be used by foliage application, soil application or water surface application. The mixing ratio of the active ingredient is appropriately selected as necessary, but it is 0.1 to 20% (weight) for powders and granules, and 5 to 80% (weight) for emulsions and wettable powders. Appropriate.
【０１０１】本発明の農園芸用殺菌剤の施用量は、使用
される化合物の種類、対象病害、発生傾向、被害の程
度、環境条件、使用する剤型などによって変動する。例
えば粉剤及び粒剤のようにそのまま使用する場合には、
有効成分で１０アール当り０.１g〜５kg、好ましくは１
g〜１kgの範囲から適宜選ぶのがよい。また、乳剤及び
水和剤のように液状で使用する場合には、０.１ppm〜１
０,０００ppm、好ましくは１〜３,０００ppmの範囲から
適宜選ぶのがよい。The application rate of the agricultural or horticultural fungicide of the present invention varies depending on the type of compound used, target disease, development tendency, degree of damage, environmental conditions, dosage form used and the like. For example, when using as it is for powders and granules,
The active ingredient is 0.1 g to 5 kg per 10 ares, preferably 1
It is preferable to select it appropriately from the range of g to 1 kg. When it is used in a liquid form such as an emulsion and a wettable powder, it is 0.1 ppm to 1
It may be appropriately selected from the range of 2,000 ppm, preferably 1 to 3,000 ppm.
【０１０２】本発明による化合物は上記の施用形態によ
り、藻菌類（Oomycetes）、子嚢菌類（Ascomycetes）、
不完全菌類（Deuteromycetes）、及び担子菌類（Basidi
omycetes）に属する菌に起因する植物病を防除できる。
次に具体的な菌名を非限定例としてあげる。シュウドペ
ロノスポラ（Pseudoperonospora）属、例えばべと病菌
（Pseudoperonospora cubensis）、スフェロテカ（Spha
erotheca）属、例えばうどんこ病菌（Sphaerotheca ful
iginea）、ベンチュリア（Venturia）属、例えば黒星病
菌（Venturia inaequalis）、ピリキュラリア（Pyricul
aria）属、例えばいもち病菌（Pyricularia oryzae）、
ボトリチス（Botrytis）属、例えば灰色かび病菌（Botr
ytis cinerea）、アルタナリア（Alternaria）属、例え
ばコマツナ黒すす病菌（Alternaria brassicicola）、
リゾクトニア（Rhizoctonia）属、例えば紋枯病菌（Rhi
zoctonia solani）、パクシニア（Puccinia）属、例え
ばさび病菌（Puccinia recondita）。The compounds according to the present invention, according to the above-mentioned application forms, include algal fungi (Oomycetes), ascomycetes (Ascomycetes),
Deuteromycetes, and Basidiomycetes
plant diseases caused by fungi belonging to omycetes) can be controlled.
Next, specific bacterial names will be given as non-limiting examples. Pseudoperonospora genus, such as downy mildew (Pseudoperonospora cubensis), Spheroteca (Spha
erotheca), eg powdery mildew (Sphaerotheca ful)
iginea), Venturia genus, such as scab (Venturia inaequalis), Pyriculia (Pyricul)
aria), such as blast fungus (Pyricularia oryzae),
The genus Botrytis, such as Botrytis cinerea (Botr
ytis cinerea), Alternaria (Alternaria) genus, for example, Komatsuna black scab (Alternaria brassicicola),
The genus Rhizoctonia, for example, Rhizoctonia
zoctonia solani), genus Puccinia (Puccinia recondita), for example.
【０１０３】さらに、本発明の化合物は必要に応じて殺
虫剤、他の殺菌剤、除草剤、植物生長調節剤、肥料等と
混用してもよい。次に本発明の農園芸用殺菌剤の代表的
な製剤例あげて製剤方法を具体的に説明する。以下の説
明において「％」は重量百分率を示す。Further, the compound of the present invention may be mixed with insecticides, other fungicides, herbicides, plant growth regulators, fertilizers and the like, if necessary. Next, the formulation method will be specifically described with reference to typical formulation examples of the agricultural and horticultural germicide of the present invention. In the following description, “%” indicates weight percentage.
【０１０４】製剤例１ 粉剤
化合物（１１）２％、珪藻土５％及びクレ−９３％を均
一に混合粉砕して粉剤とした。Formulation Example 1 2% of the powder compound (11), 5% of diatomaceous earth and 93% of clay were uniformly mixed and ground to give a powder.
【０１０５】製剤例２ 水和剤
化合物（３３）５０％、珪藻土４５％、ジナフチルメタ
ンジスルホン酸ナトリウム２％及びリグニンスルホン酸
ナトリウム３％を均一に混合粉砕して水和剤とした。Formulation Example 2 Wettable powder Compound (33) 50%, diatomaceous earth 45%, sodium dinaphthylmethanedisulfonate 2% and sodium ligninsulfonate 3% were uniformly mixed and ground to obtain a wettable powder.
【０１０６】製剤例３ 乳剤
化合物（６５）３０％、シクロヘキサノン２０％、ポリ
オキシエチレンアルキルアリールエーテル１１％、アル
キルベンゼンスルホン酸カルシウム４％及びメチルナフ
タリン３５％を均一に溶解して乳剤とした。Formulation Example 3 Emulsion compound (65) 30%, cyclohexanone 20%, polyoxyethylene alkylaryl ether 11%, calcium alkylbenzene sulfonate 4% and methylnaphthalene 35% were uniformly dissolved to obtain an emulsion.
【０１０７】製剤例４ 粒剤
化合物（８０）５％、ラウリルアルコール硫酸エステル
のナトリウム塩２％、リグニンスルホン酸ナトリウム５
％、カルボキシメチルセルロース２％及びクレー８６％
を均一に混合粉砕する。この混合物に水２０％を加えて
練合し、押出式造粒機を用いて１４〜３２メッシュの粒
状に加工したのち、乾燥して粒剤とした。Formulation Example 4 Granule compound (80) 5%, lauryl alcohol sulfate sodium salt 2%, sodium ligninsulfonate 5
%, Carboxymethylcellulose 2% and clay 86%
Are uniformly mixed and pulverized. To this mixture, 20% of water was added and kneaded, processed into granules of 14 to 32 mesh using an extrusion type granulator, and then dried to obtain granules.
【０１０８】[0108]
【発明の効果】本発明の農園芸用殺菌剤はイネいもち
病、イネ紋枯病、キュウリ灰色かび病、キュウリべと
病、キュウリうどんこ病、コマツナ黒すす病、リンゴ黒
星病に対して高い防除効果を有し、しかも公知化合物に
比較しても明らかに優る防除効果である。さらに、オオ
ムギうどんこ病、コムギ赤さび病、リンゴ斑点落葉病、
ナシ黒斑病、キュウリ菌核病に対しても有効である。し
かも作物に薬害を生ずることなく、残効性、耐雨性に優
れるという特徴をも併せ持っている。EFFECTS OF THE INVENTION The fungicide for agricultural and horticultural use of the present invention is highly effective against rice blast, rice blight, cucumber gray mold, cucumber downy mildew, cucumber powdery mildew, komatsuna scab and apple scab. It has a controlling effect, and is clearly superior to the known compounds. Furthermore, barley powdery mildew, wheat leaf rust, apple leaf spot disease,
It is also effective against pear black spot and cucumber sclerotium. Moreover, it also has the characteristics of excellent residual efficacy and rain resistance without causing chemical damage to crops.
【０１０９】次に本発明の農園芸用殺菌剤の奏する効果
を試験例をあげて具体的に説明する。
試験例１ イネいもち病予防効果試験
直径７cmの素焼鉢に水稲種子（品種：愛知旭）約１５粒
ずつ播種し、温室内で２〜３週間育成した。第４葉が完
全に展開したイネ苗に製剤例２に準じて調製した水和剤
を有効成分濃度が５００ppmになるように水で希釈し、
１鉢当り１０ml散布した。風乾後、イネいもち病菌（Py
ricularia oryzae）の分生胞子懸濁液を噴霧接種し、直
ちに２５℃の湿室内に２４時間入れた。その後温室内に
移し、接種５日後に第４葉の病斑数を数え、数１に従い
防除価を算出した。結果を表４６〜表４７に示した。
尚、比較薬剤としては旧東独特許第１５９,８７６号公
報明細書に記載された３−アニリノ−２−（２−クロロ
ベンゾイル）−３−メチルチオアクリロニトリルを同様
に製剤して供試した。The effects of the fungicide for agricultural and horticultural use of the present invention will be specifically described with reference to test examples. Test Example 1 Rice blast prevention effect test Approximately 15 rice seeds (variety: Aichi Asahi) were sown in a biscuit pot with a diameter of 7 cm and grown in a greenhouse for 2-3 weeks. A water-dispersible powder prepared according to Formulation Example 2 was diluted with water so that the active ingredient concentration was 500 ppm, and the rice seedling with the fourth leaf completely developed was diluted with water.
10 ml was sprayed per pot. After air-drying, rice blast fungus (Py
The conidia suspension of Ricularia oryzae) was spray-inoculated and immediately placed in a humid chamber at 25 ° C. for 24 hours. Then, it was transferred to a greenhouse, and 5 days after the inoculation, the number of lesions on the fourth leaf was counted, and the control value was calculated according to the equation 1. The results are shown in Tables 46 to 47.
As a comparative drug, 3-anilino-2- (2-chlorobenzoyl) -3-methylthioacrylonitrile described in the specification of the former East German Patent 159,876 was similarly prepared and tested.
【０１１０】[0110]
【数１】 [Equation 1]
【０１１１】[0111]
【表４６】 [Table 46]
【０１１２】[0112]
【表４７】 [Table 47]
【０１１３】試験例２ イネ紋枯病予防効果試験
直径７cmの素焼鉢に水稲種子（品種：金南風）を１５粒
ずつ播種し、温室内で４〜５週間育成した。第５葉が展
開したイネ苗に製剤例２に準じて調製した水和剤を有効
成分濃度が５００ppmになるように水で希釈し、１鉢当
り１０ml散布した。風乾後、モミガラフスマ培地で培養
した紋枯病菌（Rhizoctonia solani）を株元に接種し、
直ちに２８℃の湿室内に入れた。６日後にイネ葉鞘部分
に形成された病斑の高さを測定し、数２に従い防除価を
算出した。結果を表４８〜表５１に示した。尚、比較薬
剤としては試験例１と同じものを使用した。Test Example 2 Test for Preventing Rice Blotch Disease 15 seeds of paddy rice (cultivar: Kinnanfu) were sown in a biscuit pot having a diameter of 7 cm and grown in a greenhouse for 4 to 5 weeks. A wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 500 ppm, and sprayed on the rice seedlings having the fifth leaf developed therein, in an amount of 10 ml per pot. After air-drying, inoculate the strain with a bacterial wilt disease fungus (Rhizoctonia solani), which had been cultivated in fir-puffin medium,
Immediately, it was placed in a humid chamber at 28 ° C. After 6 days, the height of the lesion formed on the leaf sheath part of rice was measured, and the control value was calculated according to equation 2. The results are shown in Tables 48 to 51. The same drug as in Test Example 1 was used as the comparative drug.
【０１１４】[0114]
【数２】 [Equation 2]
【０１１５】[0115]
【表４８】 [Table 48]
【０１１６】[0116]
【表４９】 [Table 49]
【０１１７】[0117]
【表５０】 [Table 50]
【０１１８】[0118]
【表５１】 [Table 51]
【０１１９】
試験例３ キュウリ灰色かび病予防効果試験
９cm×９cmの塩ビ製鉢各々にキュウリ種子（品種：相模
半白）を１２粒づつ播種し、温室内で７日間育成させ
た。子葉が展開したキュウリ幼苗に製剤例２に準じて調
製した水和剤を有効成分濃度が５００ppmになるよう水
で希釈し、１鉢当たり１０mlを散布した。風乾後、キュ
ウリ灰色かび病菌（Botrytis cinerea）の菌糸磨砕液を
噴霧接種し、直ちに２２℃湿室内に入れた。接種３日後
に下記基準により鉢全体の発病程度を調査し、評価し
た。結果を表５２〜表５３に示した。尚、比較薬剤とし
ては試験例１と同じものを使用した。Test Example 3 Cucumber Gray Mold Prevention Effect Test 12 12 cucumber seeds (variety: Sagamihanjiro) were sown in each 9 cm × 9 cm vinyl chloride pot and grown in a greenhouse for 7 days. A wettable powder prepared according to Formulation Example 2 was diluted with water to a cucumber seedling in which cotyledons had spread, so that the concentration of the active ingredient was 500 ppm, and 10 ml was sprayed per pot. After air-drying, a mycelial grinding solution of cucumber gray mold fungus (Botrytis cinerea) was spray-inoculated and immediately placed in a humid chamber at 22 ° C. Three days after the inoculation, the degree of disease in the entire pot was investigated and evaluated according to the following criteria. The results are shown in Tables 52 to 53. The same drug as in Test Example 1 was used as the comparative drug.
【０１２０】発病指数 ０： 発病を認めず 発病指数 １： ２５％未満の発病面積 発病指数 ２： ２５％以上〜５０％未満の発病面積 発病指数 ３： ５０％以上〜７５％未満の発病面積 発病指数 ４： ７５％以上の発病面積Disease onset index 0: No onset of disease Disease incidence index 1: Disease area less than 25% Disease incidence index 2: Disease area of 25% or more and less than 50% Disease incidence index 3: Disease area of 50% to less than 75% Disease incidence index 4: 75% or more disease area
【０１２１】評価 Ａ： 発病指数 ０ 評価 Ｂ： 発病指数 １ 評価 Ｃ： 発病指数 ２ 評価 Ｄ： 発病指数 ３及び４Evaluation A: Disease incidence index 0 Evaluation B: Disease index 1 Evaluation C: Disease incidence index 2 Evaluation D: Disease incidence index 3 and 4
【０１２２】[0122]
【表５２】 [Table 52]
【０１２３】[0123]
【表５３】 [Table 53]
【０１２４】試験例４ キュウリべと病予防効果試験
９cm×９cmの塩ビ製鉢各々にキュウリ種子（品種：相模
半白）を１２粒づつ播種し、温室内で７日間育成させ
た。子葉が展開したキュウリ幼苗に製剤例２に準じて調
製した水和剤を有効成分濃度が５００ppmになるように
水で希釈し、１鉢当たり１０mlを散布した。風乾後、キ
ュウリべと病菌（Pseudoperonospora cubensis）の分生
胞子懸濁液を噴霧接種し、直ちに２２℃の湿室内に２４
時間入れた。その後温室内に移し、接種７日後に、下記
基準により鉢全体の発病程度を調査し、評価した。結果
を表５４に示した。尚、比較薬剤としては試験例１と同
じものを使用した。Test Example 4 Cucumber downy mildew preventive effect test 12 cucumber seeds (variety: Sagamihanjiro) were sown in each 9 cm × 9 cm vinyl chloride pot and grown in a greenhouse for 7 days. A wettable powder prepared according to Formulation Example 2 was diluted with water to a cucumber seedling in which cotyledons had spread, so that the concentration of the active ingredient was 500 ppm, and 10 ml was sprayed per pot. After air drying, spray inoculate with a conidia suspension of cucumber downy mildew (Pseudoperonospora cubensis) and immediately put it in a humid chamber at 22 ° C for 24 hours.
I put in time. After that, it was transferred to a greenhouse, and 7 days after the inoculation, the disease level of the whole pot was investigated and evaluated according to the following criteria. The results are shown in Table 54. The same drug as in Test Example 1 was used as the comparative drug.
【０１２５】発病指数 ０： 発病を認めず 発病指数 １： ２５％未満の発病面積 発病指数 ２： ２５％以上〜５０％未満の発病面積 発病指数 ３： ５０％以上〜７５％未満の発病面積 発病指数 ４： ７５％以上の発病面積Disease onset index 0: No onset of disease Disease incidence index 1: Disease area less than 25% Disease incidence index 2: Disease area of 25% or more and less than 50% Disease incidence index 3: Disease area of 50% to less than 75% Disease incidence index 4: 75% or more disease area
【０１２６】評価 Ａ： 発病指数 ０ 評価 Ｂ： 発病指数 １ 評価 Ｃ： 発病指数 ２ 評価 Ｄ： 発病指数 ３及び４Evaluation A: Disease index 0 Evaluation B: Disease index 1 Evaluation C: Disease incidence index 2 Evaluation D: Disease incidence index 3 and 4
【０１２７】[0127]
【表５４】 [Table 54]
【０１２８】
試験例５ キュウリうどんこ病予防効果試験
９cm×９cmの塩ビ製鉢各々にキュウリ種子（品種：相模
半白）を１２粒づつ播種し、温室内で７日間育成させ
た。子葉が展開したキュウリ幼苗に製剤例２に準じて調
製した水和剤を有効成分濃度が５００ppmになるように
水で希釈し、１鉢当たり１０mlを散布した。風乾後、温
室内に移し、キュウリうどんこ病菌（Sphaerotheca ful
iginea）胞子を接種した。１０日後に下記基準により鉢
全体の発病程度を調査し、評価した。結果を表５５に示
した。尚、比較薬剤としては試験例１と同じものを使用
した。Test Example 5 Cucumber Powdery Mildew Prevention Effect Test Twelve cucumber seeds (variety: Sagamihanjiro) were sown in each 9 cm × 9 cm vinyl chloride pot and grown in a greenhouse for 7 days. A wettable powder prepared according to Formulation Example 2 was diluted with water to a cucumber seedling in which cotyledons had spread, so that the concentration of the active ingredient was 500 ppm, and 10 ml was sprayed per pot. After air-drying, it is transferred to a greenhouse and cucumber powdery mildew (Sphaerotheca ful)
iginea) spores were inoculated. After 10 days, the disease level of the whole pot was investigated and evaluated according to the following criteria. The results are shown in Table 55. The same drug as in Test Example 1 was used as the comparative drug.
【０１２９】発病指数 ０： 発病を認めず 発病指数 １： ２５％未満の発病面積 発病指数 ２： ２５％以上〜５０％未満の発病面積 発病指数 ３： ５０％以上〜７５％未満の発病面積 発病指数 ４： ７５％以上の発病面積Disease index 0: No disease was observed Disease incidence index 1: Disease area less than 25% Disease incidence index 2: Disease area of 25% or more and less than 50% Disease incidence index 3: Disease area of 50% to less than 75% Disease incidence index 4: 75% or more disease area
【０１３０】評価 Ａ： 発病指数 ０ 評価 Ｂ： 発病指数 １ 評価 Ｃ： 発病指数 ２ 評価 Ｄ： 発病指数 ３及び４Evaluation A: Disease incidence index 0 Evaluation B: Disease index 1 Evaluation C: Disease incidence index 2 Evaluation D: Disease incidence index 3 and 4
【０１３１】[0131]
【表５５】 [Table 55]
【０１３２】試験例６ リンゴ黒星病予防効果試験
９cm×９cmの塩ビ製鉢にリンゴ種子（品種：紅玉）を５
粒づつ播種し、温室内で２０日間育成させた。本葉が４
枚展開した実生苗に、製剤例２に準じて調製した水和剤
を有効成分濃度が５０ppmまたは１０ppmになるように水
で希釈し、１鉢当たり２０ml散布した。風乾後、リンゴ
黒星病菌（Venturia inaequalis）の胞子懸濁液を噴霧
接種し、直ちに２２℃の湿室内に４８時間入れた。その
後温室内に移し、接種１４日後に各本葉の発病程度を下
記基準により調査し、得られた指数値をもとに、数３に
より発病度を求め、さらに数４により防除価を算出し
た。結果を濃度が５０ppmのものは表５６に、また濃度
が１０ppmのものは表５７に示した。尚、比較薬剤とし
ては試験例１と同じものを使用した。Test Example 6 Test for Preventing Apple Black Blight Disease 5 apple seeds (variety: red pearl) were placed in a 9 cm × 9 cm vinyl chloride pot.
The seeds were sown individually and grown in a greenhouse for 20 days. 4 true leaves
A wettable powder prepared in accordance with Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 50 ppm or 10 ppm, and 20 ml was sprayed on each pot. After air-drying, a spore suspension of apple scab (Venturia inaequalis) was spray-inoculated and immediately placed in a humid chamber at 22 ° C for 48 hours. After that, the plant was transferred to a greenhouse, and 14 days after the inoculation, the degree of disease of each true leaf was investigated according to the following criteria. Based on the obtained index value, the disease degree was calculated by the equation 3, and the control value was calculated by the equation 4. . The results are shown in Table 56 for the concentration of 50 ppm and in Table 57 for the concentration of 10 ppm. The same drug as in Test Example 1 was used as the comparative drug.
【０１３３】発病指数 ０： 発病を認めず
発病指数 １： ５％未満の発病面積
発病指数 ２： ５％以上〜３３.３％未満の発病面積
発病指数 ３： ３３.３以上〜６６.６％未満の発病面
積
発病指数 ４： ６６.６％以上の発病面積Disease onset index 0: No disease onset disease incidence index 1: Disease area onset disease index of less than 5% 2: Disease area onset disease index of 5% or more to less than 33.3% 3: 33.3 or more to 66.6% Disease area less than 4 Disease area index: 66.6% or more disease area
【０１３４】[0134]
【数３】 [Equation 3]
【０１３５】[0135]
【数４】 [Equation 4]
【０１３６】[0136]
【表５６】 [Table 56]
【０１３７】[0137]
【表５７】 [Table 57]
【０１３８】試験例７ コマツナ黒すす病予防効果試験
９cm×９cmの塩ビ製鉢各々にコマツナ種子（品種：晩生
小松菜）を１２粒づつ播種し、温室内で５日間育成させ
た。子葉が展開したコマツナ幼苗に製剤例２に準じて調
製した水和剤を有効成分で５０ppmになるよう水で希釈
し、１鉢当たり１０mlを散布した。風乾後、コマツナ黒
すす病菌（Alternaria brassicicola）の分生胞子懸濁
液を噴霧接種し、直ちに３０℃の湿室内に入れた。３日
後に、各子葉の病斑数を数え、数１より防除価を算出し
た。結果を表５８〜表５９に示した。尚、比較薬剤とし
ては試験例１と同じものを使用した。Test Example 7 Komatsuna Black Soot Disease Preventive Effect Test 12 seeds of Komatsuna seeds (variety: late komatsuna) were sown in each 9 cm × 9 cm vinyl chloride pot and grown in a greenhouse for 5 days. A wettable powder prepared according to Formulation Example 2 was diluted with water to an active ingredient content of 50 ppm to seedlings of Komatsuna with cotyledons, and 10 ml of each pot was sprayed. After air drying, a conidia suspension of Alternaria brassicicola was spray-inoculated and immediately placed in a humid chamber at 30 ° C. After 3 days, the number of lesions on each cotyledon was counted, and the control value was calculated from equation 1. The results are shown in Tables 58 to 59. The same drug as in Test Example 1 was used as the comparative drug.
【０１３９】[0139]
【表５８】 [Table 58]
【０１４０】[0140]
【表５９】 [Table 59]
【０１４１】[0141]
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ａ０１Ｎ 43/56 Ａ０１Ｎ 43/56 Ａ 43/80 １０２ 43/80 １０２ Ｃ０７Ｄ 213/50 Ｃ０７Ｄ 213/50 213/74 213/74 231/12 231/12 231/16 231/16 233/64 １０６ 233/64 １０６ 241/16 241/16 277/587 307/46 307/46 327/06 327/06 333/22 333/22 401/12 401/12 403/12 403/12 405/12 405/12 409/12 409/12 411/12 411/12 413/12 413/12 417/12 417/12 277/32 261/08 261/10 263/32 263/34 (72)発明者 伊東 茂寿 静岡県磐田郡福田町塩新田408番地の１ 株式会社ケイ・アイ研究所内 (72)発明者 鈴木 千治 静岡県磐田郡福田町塩新田408番地の１ 株式会社ケイ・アイ研究所内 (72)発明者 境 潤悦 静岡県小笠郡菊川町加茂1809番地 (72)発明者 長谷川 恵介 静岡県静岡市新伝馬２丁目４番５号 (72)発明者 林 茂 静岡県小笠郡浜岡町新野970番地の１ (56)参考文献 特開 昭60−81171（ＪＰ，Ａ) 特開 昭60−81172（ＪＰ，Ａ) 特開 昭60−260562（ＪＰ，Ａ) 特開 昭61−57565（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＣＡ（ＳＴＮ)Continuation of front page (51) Int.Cl. 7 Identification symbol FI A01N 43/56 A01N 43/56 A 43/80 102 43/80 102 C07D 213/50 C07D 213/50 213/74 213/74 231/12 231 / 12 231/16 231/16 233/64 106 233/64 106 241/16 241/16 277/587 307/46 307/46 327/06 327/06 333/22 333/22 401/12 401/12 403 / 12 403/12 405/12 405/12 409/12 409/12 411/12 411/12 413/12 413/12 417/12 417/12 277/32 261/08 261/10 263/32 263/34 (72) Inventor Shigetoshi Ito 1 408 Shioshinda, Fukuda-cho, Iwata-gun, Shizuoka Kei Research Institute Co., Ltd. (72) Inventor Chiharu Suzuki 1 408 Shio-shinta, Fukuda-cho, Iwata-gun, Shizuoka Kei Research Institute (72) Inventor Junetsu Sakai 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Inventor Keisuke Hasegawa 2-4-5 Shindenma Shizuoka, Shizuoka Prefecture Inventor Shigeru Hayashi Shizuoka Prefecture 1 970 Shinno, Hamaoka-cho, Ogasa-gun (56) References JP-A-60-81171 (JP, A) JP-A-60-81172 (JP, A) Open Akira 60-260562 (JP, A) JP Akira 61-57565 (JP, A) (58 ) investigated the field (Int.Cl. 7, DB name) REGISTRY (STN) CA (STN )
Claims (2)
子、ニトロ基またはハロアルキル基を示し、Ｘはハロゲ
ン原子、アルキル基またはハロアルキル基を示し、ｌは
１または２の整数を示す。）で表される基を示し、Ｒｙ
は式 【化３】 〔式中、Ｒ3はハロゲン原子、アルキル基、ニトロ基、
シアノ基、ジアルキルアミノ基、ハロアルキル基、ハロ
アルコキシ基、式−ＣＯＲ6（式中、Ｒ6はアルキル基、
アルコキシ基、アミノ基、メチルアミノ基、ジメチルア
ミノ基、フェニル基または塩素原子置換フェニル基を示
す）で表される基、式−ＳＯ2Ｒ7（式中、Ｒ7はアルキ
ル基、メチルアミノ基またはジメチルアミノ基を示
す。）で表される基、アルコキシ基、アルケニルオキシ
基、アルキニルオキシ基、アルキルチオ基、ハロアルキ
ルチオ基、メチレンジオキシ基またはアルキルスルホニ
ルオキシ基を示し、Ｒ4はハロゲン原子、アルキル基、
アルコキシ基、ジアルキルアミノ基、アルキルチオ基ま
たはハロアルキル基を示し、Ｒ5はアルキル基またはア
ルコキシ基を示し、ｍは０または１〜５の整数を示し、
ｎは０または１,２の整数を示す。〕で表される基を示
し、Ｒは水素原子、アルキル基、アシル基またはアルコ
キシカルボニル基を示し、Ｒ1はアルキル基、アルケニ
ル基、アルキニル基またはベンジル基を示す。｝で表さ
れるアクリロニトリル誘導体。1. A general formula: {In the formula, Rx is the formula: (In the formula, R 2 represents an alkyl group, an alkoxy group, a halogen atom, a nitro group or a haloalkyl group, X represents a halogen atom, an alkyl group or a haloalkyl group, and l represents an integer of 1 or 2.) Is represented by Ry
Is the formula [In the formula, R 3 is a halogen atom, an alkyl group, a nitro group,
Cyano group, dialkylamino group, haloalkyl group, haloalkoxy group, formula -COR 6 (wherein R 6 is an alkyl group,
A group represented by an alkoxy group, an amino group, a methylamino group, a dimethylamino group, a phenyl group or a chlorine atom-substituted phenyl group, and a group of the formula —SO 2 R 7 (wherein, R 7 is an alkyl group, a methylamino group) Or a dimethylamino group), an alkoxy group, an alkenyloxy group, an alkynyloxy group, an alkylthio group, a haloalkylthio group, a methylenedioxy group or an alkylsulfonyloxy group, and R 4 is a halogen atom, An alkyl group,
An alkoxy group, a dialkylamino group, an alkylthio group or a haloalkyl group, R 5 represents an alkyl group or an alkoxy group, m represents 0 or an integer of 1 to 5,
n represents an integer of 0 or 1,2. ], R represents a hydrogen atom, an alkyl group, an acyl group or an alkoxycarbonyl group, and R 1 represents an alkyl group, an alkenyl group, an alkynyl group or a benzyl group. } The acrylonitrile derivative represented by these.
を有効成分として含有する農園芸用殺菌剤。2. A fungicide for agricultural and horticultural use containing the acrylonitrile derivative according to claim 1 as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35138192A JP3397352B2 (en) | 1992-01-24 | 1992-12-08 | Acrylonitrile derivatives and fungicides for agricultural and horticultural use |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-32877 | 1992-01-24 | ||
| JP3287792 | 1992-01-24 | ||
| JP21469592 | 1992-07-21 | ||
| JP4-214695 | 1992-07-21 | ||
| JP35138192A JP3397352B2 (en) | 1992-01-24 | 1992-12-08 | Acrylonitrile derivatives and fungicides for agricultural and horticultural use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0687821A JPH0687821A (en) | 1994-03-29 |
| JP3397352B2 true JP3397352B2 (en) | 2003-04-14 |
Family
ID=27287883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35138192A Expired - Fee Related JP3397352B2 (en) | 1992-01-24 | 1992-12-08 | Acrylonitrile derivatives and fungicides for agricultural and horticultural use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3397352B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0873441A (en) * | 1993-11-01 | 1996-03-19 | Nissan Chem Ind Ltd | New 4,5-substituted pyrimidine derivative and herbicide |
| AU5514896A (en) * | 1995-04-27 | 1996-11-18 | Nissan Chemical Industries Ltd. | Oxopropionitrile derivatives and insect rest control agents |
| EP1318145A1 (en) * | 2000-08-16 | 2003-06-11 | Nippon Soda Co., Ltd. | Processes for the preparation of pyrazole compounds |
-
1992
- 1992-12-08 JP JP35138192A patent/JP3397352B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0687821A (en) | 1994-03-29 |
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