JP3864298B2 - Cyanomethylene compounds and agricultural and horticultural fungicides - Google Patents
Cyanomethylene compounds and agricultural and horticultural fungicides Download PDFInfo
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- JP3864298B2 JP3864298B2 JP36761599A JP36761599A JP3864298B2 JP 3864298 B2 JP3864298 B2 JP 3864298B2 JP 36761599 A JP36761599 A JP 36761599A JP 36761599 A JP36761599 A JP 36761599A JP 3864298 B2 JP3864298 B2 JP 3864298B2
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- -1 Cyanomethylene compounds Chemical class 0.000 title claims description 112
- 239000000417 fungicide Substances 0.000 title claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000003282 alkyl amino group Chemical group 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 10
- 230000000855 fungicidal effect Effects 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims description 8
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004768 (C1-C4) alkylsulfinyl group Chemical group 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims 1
- 230000003796 beauty Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 25
- 125000000217 alkyl group Chemical group 0.000 description 24
- 239000000203 mixture Substances 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 230000000844 anti-bacterial effect Effects 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 241000221785 Erysiphales Species 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 11
- 201000010099 disease Diseases 0.000 description 11
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 11
- 239000003814 drug Substances 0.000 description 11
- 229940079593 drug Drugs 0.000 description 11
- 238000009472 formulation Methods 0.000 description 11
- 150000002540 isothiocyanates Chemical class 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 241000209140 Triticum Species 0.000 description 5
- 235000021307 Triticum Nutrition 0.000 description 5
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 150000002366 halogen compounds Chemical class 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 240000008067 Cucumis sativus Species 0.000 description 4
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 239000004563 wettable powder Substances 0.000 description 4
- 125000004758 (C1-C4) alkoxyimino group Chemical group 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 3
- 239000000642 acaricide Substances 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000005645 nematicide Substances 0.000 description 3
- 239000005648 plant growth regulator Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- NDTZGAYDRFONFL-UHFFFAOYSA-N 2-[2-fluoro-5-(trifluoromethyl)phenyl]sulfanylacetonitrile Chemical compound FC1=CC=C(C(F)(F)F)C=C1SCC#N NDTZGAYDRFONFL-UHFFFAOYSA-N 0.000 description 2
- DRKWGMXFFCPZLW-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=CC=C1F DRKWGMXFFCPZLW-UHFFFAOYSA-N 0.000 description 2
- KWAZFGPHDLINBM-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)benzenethiol Chemical compound FC1=CC=C(C(F)(F)F)C=C1S KWAZFGPHDLINBM-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KWHOHOVXVXEHPI-UHFFFAOYSA-N C(C)OC(=O)SC=1C=C(C=CC1F)C(F)(F)F Chemical compound C(C)OC(=O)SC=1C=C(C=CC1F)C(F)(F)F KWHOHOVXVXEHPI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 239000002671 adjuvant Substances 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229940117953 phenylisothiocyanate Drugs 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000003626 1,2,4-triazol-1-yl group Chemical group [*]N1N=C([H])N=C1[H] 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
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- HQDLMEUVQFNUSV-UHFFFAOYSA-N 2-(4-chlorophenyl)sulfanyl-2-(3-phenyl-1,3-thiazolidin-2-ylidene)acetonitrile Chemical compound C1=CC(Cl)=CC=C1SC(C#N)=C1N(C=2C=CC=CC=2)CCS1 HQDLMEUVQFNUSV-UHFFFAOYSA-N 0.000 description 1
- WUAPSCHVFHCXGH-UHFFFAOYSA-N 2-[2-fluoro-5-(trifluoromethyl)phenyl]sulfanyl-2-(3-phenyl-1,3-thiazolidin-2-ylidene)acetonitrile Chemical compound FC1=CC=C(C(F)(F)F)C=C1SC(C#N)=C1N(C=2C=CC=CC=2)CCS1 WUAPSCHVFHCXGH-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- ZRADTNJSPQDCDV-UHFFFAOYSA-N 2-butyl-4-methoxyphenol Chemical compound CCCCC1=CC(OC)=CC=C1O ZRADTNJSPQDCDV-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- KKZUMAMOMRDVKA-UHFFFAOYSA-N 2-chloropropane Chemical group [CH2]C(C)Cl KKZUMAMOMRDVKA-UHFFFAOYSA-N 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- HIOADUPRHXVOFG-UHFFFAOYSA-N 2-phenylsulfanyl-2-(3-phenyl-1,3-thiazolidin-2-ylidene)acetonitrile Chemical compound S1CCN(C=2C=CC=CC=2)C1=C(C#N)SC1=CC=CC=C1 HIOADUPRHXVOFG-UHFFFAOYSA-N 0.000 description 1
- QMJWPWCKRKHUNY-UHFFFAOYSA-N 2-phenylsulfanylacetonitrile Chemical compound N#CCSC1=CC=CC=C1 QMJWPWCKRKHUNY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241001330975 Magnaporthe oryzae Species 0.000 description 1
- SDJALYBNMMHYKK-UHFFFAOYSA-N N(CCO)(CCO)CCO.P(=O)(O)(O)O.C1(=CC=CC=C1)OC1=CC=CC=C1 Chemical compound N(CCO)(CCO)CCO.P(=O)(O)(O)O.C1(=CC=CC=C1)OC1=CC=CC=C1 SDJALYBNMMHYKK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- QLDHWVVRQCGZLE-UHFFFAOYSA-N acetyl cyanide Chemical class CC(=O)C#N QLDHWVVRQCGZLE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004666 alkoxyiminoalkyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride 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
- 230000002365 anti-tubercular Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000005569 butenylene group Chemical group 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000004821 distillation Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000006260 ethylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000006328 iso-butylcarbonyl group Chemical group [H]C([H])([H])C([H])(C(*)=O)C([H])([H])[H] 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 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
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004458 methylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])[H] 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000006095 n-butyl sulfinyl group Chemical group 0.000 description 1
- 125000006126 n-butyl sulfonyl group Chemical group 0.000 description 1
- 125000006093 n-propyl sulfinyl group Chemical group 0.000 description 1
- 125000006124 n-propyl sulfonyl group Chemical group 0.000 description 1
- 125000006252 n-propylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
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- 244000052769 pathogen Species 0.000 description 1
- WWQAGDWTJOKFQB-UHFFFAOYSA-N penta-1,2,3-triene Chemical group CC=C=C=C WWQAGDWTJOKFQB-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000006253 t-butylcarbonyl group Chemical group [H]C([H])([H])C(C(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、シアノメチレン化合物及び該化合物を含有する農園芸用殺菌剤に関する。
【０００２】
【従来の技術】
殺菌剤の長年にわたる使用により、近年、薬剤耐性菌が出現するに至っている。そのため、従来の殺菌剤、例えばベンズイミダゾール剤等による防除が困難になってきており、薬剤感受性菌のみならず薬剤耐性菌に対しても殺菌活性を有する新しいタイプの薬剤の開発が要望されている。
【０００３】
従来、チアゾリジン環の２位にシアノメチレン基が結合した化合物としては、例えば、Ｐｈａｍａｚｉｅ（１９９８），５３（６），３７３−３７６に、一般式
【０００４】
【化２】
で表される化合物が記載され、該化合物が抗結核作用を有することも報告されている。しかしながら、一般式（Ａ）の化合物の殺菌活性については全く記載されていない。
【０００６】
また、国際特許公開第９６−３３９９５号公報には、一般式
【０００７】
【化３】
〔式中、Ｒａは炭素数２〜８のアルキル基を示し、Ｒｂは水素原子等を示し、Ｒｃは複素環基を示し、Ｒｄは水素原子等を示す。〕
で表されるオキソプロピオニトリル誘導体が記載され、該誘導体が殺虫活性を有することも記されている。しかしながら、該誘導体についても殺菌活性については何ら記載されていない。
【０００９】
【発明が解決しようとする課題】
本発明は、薬剤感受性菌のみならず薬剤耐性菌にも優れた殺菌活性を発現し得る新規シアノメチレン化合物を提供することを課題とする。
【００１０】
本発明は、薬剤感受性菌のみならず薬剤耐性菌にも卓効を示す、新しいタイプの農園芸用殺菌剤を提供することを課題とする。
【００１１】
【課題を解決するための手段】
本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、農業上問題となる各種の病原菌に対して優れた殺菌活性を有する新規シアノメチレン化合物を見い出すことに成功し、ここに本発明を完成するに至った。
【００１２】
本発明は、一般式
【００１３】
【化４】
〔式中、ＲはＣ1-20の直鎖もしくは分枝鎖状アルキル基、Ｃ3-8シクロアルキル基、アリール基、アリールＣ1-4アルキル基又はヘテロアリール基を示す。アリール基、アリールＣ1-4アルキル基及びヘテロアリール基上には、ハロゲン原子、Ｃ1-4アルキル基、Ｃ1-4ハロアルキル基、Ｃ1-4アルコキシ基、Ｃ1-4ハロアルコキシ基、Ｃ1-4アルコキシカルボニル基、Ｃ1-4アルキルアミノカルボニル基、Ｃ1-4アルコキシイミノＣ1-4アルキル基、Ｃ1-4アルキルアミノ基、Ｃ1-4アルキルカルボニル基、Ｃ1-4アルキルチオ基、アリールＣ1-4アルキル基、カルバモイル基、フェノキシ基、ベンジルオキシ基、ニトロ基及びシアノ基から選ばれる少なくとも１種の置換基が置換していてもよい。
【００１５】
Ｒ1はＣ1-8の直鎖もしくは分枝鎖状アルキル基、Ｃ3-8シクロアルキル基、アリール基、アリールＣ1-4アルキル基又はヘテロアリール基を示す。アリール基、アリールＣ1-4アルキル基及びヘテロアリール基上には、ハロゲン原子、Ｃ1-4アルキル基、Ｃ1-4ハロアルキル基、Ｃ1-4アルコキシ基、Ｃ1-4ハロアルコキシ基、Ｃ1-4アルコキシカルボニル基、Ｃ1-4アルキルアミノ基、ジＣ1-4アルキルアミノ基、Ｃ2-4アルケニル基、Ｃ1-4アルキルチオ基、Ｃ1-4アルキルスルフィニル基、Ｃ1-4アルキルスルホニル基、フェニル基、フェノキシ基、ニトロ基及びシアノ基から選ばれる少なくとも１種の置換基が置換していてもよい。
【００１６】
ＡはＣ1-6の直鎖もしくは分枝鎖状アルキレン基、Ｃ2-6の直鎖もしくは分枝鎖状アルケニレン基、基−ＣＨ2−Ｂ−ＣＨ2−（Ｂはフェニレン基を示す）、基−ＣＨ2−Ｏ−Ｂ−ＣＨ2−（Ｂは前記に同じ）又は基−Ｚ−ＣＯ−（ＺはＣ1-4アルキレン基を示す）を示す。
【００１７】
Ｙは硫黄原子、スルフィニル基又はスルホニル基を示す。
【００１８】
ａは０又は１を示す。〕
で表されるシアノメチレン化合物（以下「シアノメチレン化合物（１）」という）及び農園芸用殺菌剤に係る。
【００１９】
本発明のシアノメチレン化合物（１）は、広い殺菌スペクトルを有し、薬剤感受性菌のみならず薬剤耐性菌をも防除しうる優れた殺菌活性を有している。
【００２０】
本発明のシアノメチレン化合物（１）にはＥ／Ｚ異性体が存在し、本発明のシアノメチレン化合物（１）にはＥ／Ｚ異性体及びＥ／Ｚ異性体混合物も包含される。
【００２１】
【発明の実施の形態】
上記一般式（１）において、Ｒ、Ｒ1、Ａ及びＺで示される各基は、具体的には以下のものを挙げることができる。
【００２２】
Ｃ1-20の直鎖もしくは分枝鎖状アルキル基としては、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、ｎ−ノニル、ｎ−デシル、ｎ−ウンデシル、ｎ−ドデシル、ｎ−トリデシル、ｎ−テトラデシル、ｎ−ペンタデシル、ｎ−ヘキサデシル、ｎ−ヘプタデシル、ｎ−オクタデシル、ｎ−ノナデシル基等を挙げることができる。
【００２３】
Ｃ3-8シクロアルキル基としては、例えばシクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル基等を挙げることができる。
【００２４】
アリール基としては、例えばフェニル、ナフチル基等を挙げることができる。
【００２５】
アリールＣ1-4アルキル基としては、例えばベンジル、１−フェニルエチル、２−フェニルエチル、１−フェニルプロピル、２−フェニルプロピル、３−フェニルプロピル基等を挙げることができる。
【００２６】
ヘテロアリール基としては、例えばピリジル、ピリミジル、ベンゾトリアゾリル、１，２，４−トリアゾール−１−イル、２−チエニル、ピラジニル、ピリダジニル、２−ベンゾチアゾリル、オキサゾリル、イソキサゾリル、チアゾリル、８−キノリル、オキサジアゾリル基等を挙げることができる。
【００２７】
ハロゲン原子としては、弗素原子、塩素原子、臭素原子、沃素原子等を挙げることができる。
【００２８】
Ｃ1-4アルキル基としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル基等の炭素数１〜４の直鎖状又は分枝鎖状のアルキル基を挙げることができる。
【００２９】
Ｃ1-4ハロアルキル基としては、例えば、フルオロメチル、ブロモメチル、ヨードメチル、ジフルオロメチル、トリフルオロメチル、２−フルオロエチル、２−クロロエチル、１−フルオロエチル、ペンタフルオロエチル、１−フルオロプロピル、２−クロロプロピル、３−フルオロプロピル、３−クロロプロピル、１−フルオロブチル、１−クロロブチル、４−フルオロブチル基等の１〜９個のハロゲン原子で置換された直鎖状又は分枝鎖状のアルキル基を挙げることができる。
【００３０】
Ｃ1-4アルコキシ基としては、例えば、メトキシ、エトキシ、ｎ−プロポキシ、イソプロポキシ、ｎ−ブトキシ、ｓｅｃ−ブトキシ、ｔｅｒｔ−ブトキシ基等の炭素数１〜４の直鎖状又は分枝鎖状のアルコキシ基を挙げることができる。
【００３１】
Ｃ1-4ハロアルコキシ基としては、例えば、フルオロメトキシ、クロロメトキシ、ブロモメトキシ、ヨードメトキシ、ジフルオロメトキシ、トリフルオロメトキシ、２−フルオロエトキシ、２−クロロエトキシ、１−フルオロエトキシ、２，２，２−トリフルオロエトキシ、ペンタフルオロエトキシ、１−フルオロプロポキシ、２−クロロプロポキシ、３−フルオロプロポキシ、３−クロロプロポキシ、１−フルオロブトキシ、１−クロロブトキシ、４−フルオロブトキシ基等の１〜９個のハロゲン原子で置換された直鎖状又は分枝鎖状のアルコキシ基を挙げることができる。
【００３２】
Ｃ1-4アルコキシカルボニル基としては、例えば、メトキシカルボニル、エトキシカルボニル、ｎ−プロポキシカルボニル、イソプロポキシカルボニル、ｎ−ブトキシカルボニル、イソブトキシカルボニル、ｓｅｃ−ブトキシカルボニル、ｔｅｒｔ−ブトキシカルボニル基等の、アルコキシ部分が炭素数１〜４の直鎖状又は分枝鎖状であるアルコキシカルボニル基を挙げることができる。
【００３３】
Ｃ1-4アルキルアミノカルボニル基としては、例えばメチルアミノカルボニル、エチルアミノカルボニル、ｎ−プロピルアミノカルボニル、イソプロピルアミノカルボニル、ｎ−ブチルアミノカルボニル、イソブチルアミノカルボニル、ｓｅｃ−ブチルアミノカルボニル、ｔｅｒｔ−ブチルアミノカルボニル基等の、アルキル部分が炭素数１〜４の直鎖状又は分枝鎖状であるアルキルアミノカルボニル基を挙げることができる。
【００３４】
Ｃ1-4アルコキシイミノＣ1-4アルキル基としては、例えばメトキシイミノメチル、エトキシイミノメチル、１−（ｎ−プロポキシイミノ）エチル、イソプロポキシイミノメチル、２−（ｎ−ブトキシイミノ）エチル、ｓｅｃ−ブトキシイミノメチル、ｔｅｒｔ−ブトキシイミノメチル基等のアルコキシ部分が炭素数１〜４の直鎖状又は分枝鎖状であり、アルキル部分が炭素数１〜４の直鎖状又は分枝鎖状であるアルコキシイミノアルキル基を挙げることができる。
【００３５】
Ｃ1-4アルキルアミノ基としては、例えばメチルアミノ、エチルアミノ、ｎ−プロピルアミノ、イソプロピルアミノ、ｎ−ブチルアミノ、イソブチルアミノ、ｓｅｃ−ブチルアミノ、ｔｅｒｔ−ブチルアミノ基等のアルキル部分が炭素数１〜４の直鎖状又は分枝鎖状であるアルキルアミノ基を挙げることができる。
【００３６】
Ｃ1-4アルキルカルボニル基としては、例えばメチルカルボニル、エチルカルボニル、ｎ−プロピルカルボニル、イソプロピルカルボニル、ｎ−ブチルカルボニル、イソブチルカルボニル、ｓｅｃ−ブチルカルボニル、ｔｅｒｔ−ブチルカルボニル基等の、アルキル部分が炭素数１〜４の直鎖状又は分枝鎖状であるアルキルカルボニル基を挙げることができる。
【００３７】
Ｃ1-8の直鎖もしくは分枝鎖状アルキル基としては、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル基等を挙げることができる。
【００３８】
ジＣ1-4アルキルアミノ基としては、例えばジメチルアミノ、ジエチルアミノ、ジ−ｎ−プロピルアミノ、ジイソプロピルアミノ、ジ−ｎ−ブチルアミノ、ジイソブチルアミノ、ｓｅｃ−ブチルアミノ、ジ−ｔｅｒｔ−ブチルアミノ基等のアルキル部分が炭素数１〜４の直鎖状又は分枝鎖状であるジアルキルアミノ基を挙げることができる。
【００３９】
Ｃ2-4アルケニル基としては、例えばビニル、アリル、２−ブテニル、３−ブテニル、１−メチルアリル基等を挙げることができる。
【００４０】
Ｃ1-4アルキルチオ基としては、例えばメチルチオ、エチルチオ、ｎ−プロピルチオ、イソプロピルチオ、ｎ−ブチルチオ、イソブチルチオ、ｓｅｃ−ブチルチオ、ｔｅｒｔ−ブチルチオ基等の、アルキル部分が炭素数１〜４の直鎖状又は分枝鎖状であるアルキルチオ基を挙げることができる。
【００４１】
Ｃ1-4アルキルスルフィニル基としては、例えばメチルスルフィニル、エチルスルフィニル、ｎ−プロピルスルフィニル、イソプロピルスルフィニル、ｎ−ブチルスルフィニル、イソブチルスルフィニル、ｓｅｃ−ブチルスルフィニル、ｔｅｒｔ−ブチルスルフィニル基等の、アルキル部分が炭素数１〜４の直鎖状又は分枝鎖状であるアルキルスルフィニル基を挙げることができる。
【００４２】
Ｃ1-4アルキルスルホニル基としては、例えばメチルスルホニル、エチルスルホニル、ｎ−プロピルスルホニル、イソプロピルスルホニル、ｎ−ブチルスルホニル、イソブチルスルホニル、ｓｅｃ−ブチルスルホニル、ｔｅｒｔ−ブチルスルホニル基等の、アルキル部分が炭素数１〜４の直鎖状又は分枝鎖状であるアルキルスルホニル基を挙げることができる。
【００４３】
Ｃ1-6の直鎖もしくは分枝鎖状アルキレン基としては、例えばメチレン、エチレン、トリメチレン、２−メチルトリメチレン、２，２−ジメチルトリメチレン、１−メチルトリメチレン、メチルメチレン、エチルメチレン、テトラメチレン、ペンタメチレン、ヘキサメチレン基等を挙げることができる。
【００４４】
Ｃ2-6の直鎖もしくは分枝鎖状アルケニレン基としては、例えばビニリデン、プロピレン、ブテニレン基等を挙げることができる。
【００４５】
Ｃ1-4アルキレン基としては、例えばメチレン、エチレン、トリメチレン、２−メチルトリメチレン、２，２−ジメチルトリメチレン、１−メチルトリメチレン、メチルメチレン、エチルメチレン、テトラメチレン基等を挙げることができる。
【００４６】
本発明のシアノメチレン化合物（１）の中でも、ＲがＣ1-20の直鎖もしくは分枝鎖状アルキル基、Ｃ3-8シクロアルキル基、フェニル基、ベンジル基又はヘテロアリール基（フェニル基、ベンジル基及びヘテロアリール基上には、ハロゲン原子、Ｃ1-4アルキル基、Ｃ1-4ハロアルキル基、Ｃ1-4アルコキシ基、Ｃ1-4ハロアルコキシ基、Ｃ1-4アルコキシカルボニル基、Ｃ1-4アルキルアミノカルボニル基、Ｃ1-4アルコキシイミノＣ1-4アルキル基、Ｃ1-4アルキルアミノ基、Ｃ1-4アルキルカルボニル基、Ｃ1-4アルキルチオ基、カルバモイル基、フェノキシ基、ベンジルオキシ基、ニトロ基及びシアノ基から選ばれる少なくとも１種の置換基が置換していてもよい。）であり、Ｒ1がＣ1-8の直鎖もしくは分枝鎖状アルキル基、Ｃ3-8シクロアルキル基、フェニル基、ベンジル基又はピリジル基（フェニル基、ベンジル基及びピリジル基上には、ハロゲン原子、Ｃ1-4アルキル基、Ｃ1-4ハロアルキル基、Ｃ1-4アルコキシ基、Ｃ1-4ハロアルコキシ基、Ｃ1-4アルコキシカルボニル基、Ｃ1-4アルキルアミノ基、ジＣ1-4アルキルアミノ基、Ｃ2-4アルケニル基、Ｃ1-4アルキルチオ基、Ｃ1-4アルキルスルフィニル基、Ｃ1-4アルキルスルホニル基、フェニル基、フェノキシ基、ニトロ基及びシアノ基から選ばれる少なくとも１種の置換基が置換していてもよい。）であり、ＡがＣ1-6の直鎖もしくは分枝鎖状アルキレン基、Ｃ2-4の直鎖もしくは分枝鎖状アルケニレン基又は基−ＣＨ2−Ｂ−ＣＨ2−（式中Ｂはフェニレン基を示す）であり、Ｙが硫黄原子、スルフィニル基又はスルホニル基であり、ａが０又は１である化合物が好ましい。
【００４７】
また、本発明のシアノメチレン化合物（１）の中でも、Ｒがフェニル基（フェニル基上には、ハロゲン原子、Ｃ1-4アルキル基、Ｃ1-4ハロアルキル基、Ｃ1-4アルコキシ基、Ｃ1-4ハロアルコキシ基、Ｃ1-4アルキルカルボニル基、Ｃ1-4アルキルチオ基及びシアノ基から選ばれる少なくとも１種の置換基が置換していてもよい。）であり、Ｒ1がフェニル基又はピリジル基（フェニル基及びピリジル基上には、ハロゲン原子、Ｃ1-4アルキル基、Ｃ1-4ハロアルキル基、Ｃ1-4アルコキシ基、Ｃ1-4ハロアルコキシ基、Ｃ1-4アルコキシカルボニル基、Ｃ1-4アルキルアミノ基、ジＣ1-4アルキルアミノ基、Ｃ2-4アルケニル基、Ｃ1-4アルキルチオ基、Ｃ1-4アルキルスルフィニル基、Ｃ1-4アルキルスルホニル基、フェニル基、フェノキシ基、ニトロ基及びシアノ基から選ばれる少なくとも１種の置換基が置換していてもよい。）であり、ＡがＣ1-6の直鎖もしくは分枝鎖状アルキレン基であり、Ｙが硫黄原子であり、ａが０又は１であるシアノメチレン化合物が特に好ましい。
【００４８】
本発明のシアノメチレン化合物（１）は、例えば、一般式
Ｒ1−ＮＣＳ （２）
〔式中、Ｒ1は前記に同じ。〕
で表されるイソチオシアネート、一般式
Ｒ−(Ｙ)a−ＣＨ2−ＣＮ （３）
〔式中、Ｒ、Ｙ及びａは前記に同じ。〕
で表されるアセトニトリル及び一般式
Ｘ1−Ａ−Ｘ2 （４）
〔式中、Ａは前記に同じ。Ｘ1及びＸ2は、同一又は異なってハロゲン原子を示す。〕
で表されるハロゲン化合物を反応させることによって製造できる。
【００４９】
本反応において、イソチオシアネート（２）とアセトニトリル（３）との使用割合は特に制限されず、広い範囲から適宜選択できるが、通常イソチオシアネート（２）１モルに対して、アセトニトリル（３）を１〜５モル、好ましくは１モル又はその付近とすればよい。
【００５０】
またイソチオシアネート（２）とハロゲン化合物（４）との使用割合も特に制限されず、広い範囲から適宜選択できるが、通常イソチオシアネート（２）１モルに対して、ハロゲン化合物（４）を１〜５モル、好ましくは１モル又はその付近とすればよい。
【００５１】
本反応は、好ましくは塩基の存在下に実施される。塩基としては、従来公知のものを広く使用でき、例えば、炭酸水素ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、水素化ナトリウム、水素化カリウム等の無機塩基、トリエチルアミン、ピリジン等の有機塩基等を挙げることができる。斯かる塩基は、１種を単独で使用でき又は２種以上を併用できる。塩基の使用量は特に制限されず、広い範囲から適宜選択できるが、通常上記反応により生成するハロゲン化水素を捕捉するに足りる化学量論量又はそれよりも過剰とすればよく、好ましくは化学量論量又はそれよりも１〜５倍程度過剰な量とすればよい。尚、トリエチルアミン、ピリジン等の有機塩基を用いる場合、これらを大過剰に用いて反応溶媒ととして兼用することもできる。
【００５２】
本反応は、通常溶媒中で実施される。溶媒としては本反応に不活性なものであれば特に制限されず、従来公知のものを広く使用でき、例えば、ヘキサン、シクロヘキサン、ヘプタン等の脂肪族乃至脂環式炭化水素類、ベンゼン、クロロベンゼン、トルエン、キシレン等の芳香族炭化水素類、塩化メチレン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素類、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類、ジメチルホルムアミド、ジメチルスルホキシド、又はこれらの２種以上の混合溶媒等を挙げることができる。
【００５３】
本反応は、通常−２０℃から使用される溶媒の沸点温度までの温度下に行われ、通常０．５〜２４時間程度で終了する。
【００５４】
本発明のシアノメチレン化合物（１）を製造する際に使用される原料化合物であるチオイソチアネート（２）、アセトニトリル（３）及びハロゲン化合物（４）は、いずれも商業的に容易に入手できる化合物であるか又は公知の方法に従い容易に製造され得る化合物である。
【００５５】
上記方法で得られる本発明のシアノメチレン化合物（１）は、例えば、濾過、溶媒抽出、蒸留、再結晶、カラムクロマトグラフィー等の通常の単離精製手段によって、反応系から容易に単離、精製できる。
【００５６】
本発明のシアノメチレン化合物（１）は、例えば、殺菌剤の有効成分として使用される。
【００５７】
本発明のシアノメチレン化合物（１）はそのまま殺菌剤として使用できるが、油剤、乳剤、水和剤、フロアブル剤、粒剤、粉剤、エアゾール剤、煙霧剤等の任意の形態に製剤化して使用することもできる。この際、本発明のチアゾリジン化合物（１）の含有量は特に制限されず、製剤形態、対象病害や作物の種類、病害の程度、施用場所、施用時期、施用方法、併用する薬剤（殺虫剤、殺線虫剤、殺ダニ剤、殺菌剤、除草剤、植物成長調節剤、共力剤、土壌改良剤等）や肥料の使用量や種類等の種々の条件に応じて広い範囲から適宜選択できるが、通常殺菌剤全量の０．０１〜９５重量％程度、好ましくは０．１〜５０重量％程度とすればよい。
【００５８】
本発明のシアノメチレン化合物（１）を有効成分として含有する殺菌剤の製剤は、公知の方法に従って製造できる。例えば、シアノメチレン化合物（１）と固体担体、液体担体、ガス状担体等の担体とを混合し、必要に応じて界面活性剤、その他の製剤用補助剤を添加すればよい。
【００５９】
担体としては、この分野で常用されている従来公知のものをいずれも使用できる。
【００６０】
固体担体としては、例えば、粘土類（カオリンクレー、珪藻土、合成含水酸化珪素、ベントナイト、フバサミクレー、酸性白土等）、タルク類、セラミック、その他の無機鉱物（セライト、石英、硫黄、活性炭、炭酸カルシウム、水和シリカ等）、化学肥料（硫安、燐安、硝安、尿素、塩安等）等の微粉末、粒状物等を挙げることができる。
【００６１】
液体担体としては、例えば、水、アルコール類（メタノール、エタノール等）、ケトン類（アセトン、メチルエチルケトン等）、芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン、メチルナフタレン等）、脂肪族炭化水素類（ヘキサン、シクロヘキサン、灯油、軽油等）、エステル類（酢酸エチル、酢酸ブチル等）、ニトリル類（アセトニトリル、イソブチロニトリル等）、エーテル類（ジイソプロピルエーテル、ジオキサン等）、酸アミド類（Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等）、ハロゲン化炭化水素類（ジクロロメタン、トリクロロエタン、四塩化炭素等）、ジメチルスルホキシド、大豆油、綿実油等の植物油等を挙げることができる。
【００６２】
ガス状担体（即ち噴射剤）としては、例えば、ブタンガス、ＬＰＧ（液化石油ガス）、ジメチルエーテル、炭酸ガス等を挙げることができる。
【００６３】
界面活性剤としては、例えば、アルキル硫酸エステル類、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、アルキルアリールエーテル類及びそのポリオキシエチレン化物、ポリエチレングリコールエーテル類、多価アルコールエステル類、糖アルコール化合物等を挙げることができる。
【００６４】
製剤補助剤としては、例えば、カゼイン、ゼラチン、多糖類（でんぷん粉、アラビアガム、セルロース化合物、アルギン酸等）、リグニン化合物、ベントナイト、糖類、合成水溶性高分子（ポリビニルアルコール、ポリビニルピロリドン、ポリアクリル酸類等）等の固着剤、ＰＡＰ（酸性リン酸イソプロピル）、ＢＢＨ（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール）、ＢＨＡ（２−ｔｅｒｔ−ブチル−４−メトキシフェノールと３−ｔｅｒｔ−ブチル−４−メトキシフェノールとの混合物）、植物油、鉱物油、脂肪酸とそのエステル等の安定剤等を挙げることができる。
【００６５】
このようにして得られる本発明殺菌剤の製剤は、そのまま使用してもよく又は水等で希釈して用いてもよい。また、他の殺虫剤、殺線虫剤、殺ダニ剤、殺菌剤、除草剤、植物成長調節剤、共力剤、土壌改良剤等と予め混合して製剤化しておいてもよい。或いは、本発明の製剤と上記各剤とを使用の際に同時に用いてもよい。
【００６６】
本発明の殺菌剤を農園芸用殺菌剤として使用する場合、その施用量は特に制限されず、有効成分濃度、製剤形態、対象病害や作物の種類、病害の程度、施用時期、施用方法、併用する薬剤（殺虫剤、殺線虫剤、殺ダニ剤、殺菌剤、除草剤、植物成長調節剤、共力剤、土壌改良剤等）や肥料の使用量や種類等の種々の条件に応じて広い範囲から適宜選択できるが、通常１００ｍ2当り０．００１〜１００ｇ程度とすればよい。また、乳剤、水和剤、フロアブル剤等を水で希釈して用いる場合は、その施用濃度は通常０．１〜１０００ｐｐｍ程度、好ましくは１〜５００ｐｐｍ程度とすればよい。粒剤、粉剤等は希釈することなく製剤のままで施用される。
【００６７】
本発明化合物は、優れた殺菌活性と広い活性スペクトルを有することが特徴であり、例えば、イネいもち病菌、イネ紋枯病菌、リンゴうどんこ病菌、リンゴ斑点落葉病菌、カキうどんこ病菌、ブドウうどんこ病菌、オオムギうどんこ病菌、コムギうどんこ病菌、キュウリうどんこ病菌、トマト疫病菌、イチゴうどんこ病菌、タバコうどんこ病菌等の各種病原菌やこれら病原菌の耐性菌による病害の防除に使用することができる。
【００６８】
【実施例】
以下に、参考例、製造例、製剤例及び試験例を挙げ、本発明を更に詳しく説明する。
【００６９】
参考例１
２−フルオロ−５−トリフルオロメチルアニリンの製造
３−ニトロ−４−フルオロベンゾロリフルオリド２０ｇをメタノール５０ｍｌに溶かし、鉄粉１６ｇを加え、撹拌下濃塩酸を滴下した。反応液を１晩撹拌後重曹を加え中和し、ジエチルエーテルを加え、セライトで不溶物を濾別した。エーテル層を分離し、乾燥後減圧濃縮し、目的物１４ｇ（収率８２％）を得た。
【００７０】
参考例２
２−フルオロ−５−トリフルオロメチルフェニルチオアセトニトリルの製造
２−フルオロ−５−トリフルオロメチルアニリン１４ｇを水３０ｍｌ及び濃塩酸１０ｍｌに縣濁し、−５℃に冷却下、亜硝酸ナトリウム５．９３ｇを３０ｍｌの水に溶かした溶液を滴下し、−５℃で２時間撹拌した。反応液を酢酸エチル水溶液で抽出し、乾燥後濃縮し、３−エトキシカルボニルチオ−４−フルオロベンゾトリフルオリド２２ｇを得た。
【００７１】
次に、上記で得られた３−エトキシカルボニルチオ−４−フルオロベンゾトリフルオリドを更に精製することなくテトラヒドロフラン１００ｍｌに溶かし、水素化リチウムアルミニウム４．４ｇのテトラヒドロフラン１００ｍｌ縣濁液中に滴下した。反応液を３時間撹拌後、希塩酸を加え、ｐＨ１として酢酸エチルで抽出し、４−フルオロ−３−メルカプトベンゾトリフルオリド１３ｇを得た。
【００７２】
次に、上記で得られた４−フルオロ−３−メルカプトベンゾトリフルオリドをアセトニトリル１００ｍｌに溶かし、炭酸カリウム７ｇとクロロアセトニトリル５ｇを加え、室温で一晩撹拌し、反応液を水にあけ酢酸エチルで抽出した。酢酸エチル層を乾燥濃縮後、シリカゲルカラムクロマトに付し、５ｇ（３工程の総収率２７％）の目的物を得た。
【００７３】
参考例３
（２−フルオロ−５−トリフルオロメチルフェニルチオ）−２−（３−フェニルチアゾリジン−２−イリデン）アセトニトリルの製造
２−フルオロ−５−トリフルオロメチルフェニルチオアセトニトリル０．７０ｇ及びフェニルイソチオシアネート０．４０ｇをジメチルホルムアミド５ｍｌに溶かし、撹拌した中に水素化ナトリウムの６０％オイル懸濁物０．２５ｇを加え氷冷下０．５時間撹拌した。次に１，２−ジブロモエタン０．５６ｇ加え、１時間撹拌後、水１００ｍｌを加え、更にジエチルエーテル３０ｍｌを加えて撹拌すると結晶が析出した。析出した結晶を濾取し、０．０６ｇ（収率６％）の目的物を得た。
【００７４】
製造例１
２−（４−クロロフェニルチオ）−２−（３−フェニル−１，３−チアゾリジン−２−イリデン）アセトニトリル（化合物１）の製造
４−クロロフェニルイソチオシアネート１．１４ｇ（６．７ミリモル）及びフェニルチオアセトニトリル１．０ｇ（６．７ミリモル）をジメチルホルムアミド１０ｍｌに溶かし、室温で撹拌しながら、水素化ナトリウム０．５９ｇ（油性６０％、１４．８ミリモル）を少しずつ加え、１時間撹拌した。次いで１，２−ジブロモエタン１．３９ｇ（７．４ミリモル）を加え、更に室温で３時間撹拌した。反応液に水５０ｍｌ及びエーテル１０ｍｌを加え撹拌し、析出した結晶を濾取し、標題の目的物０．８ｇを無色結晶として得た（収率３０％）。
融点１４４−１４６℃
1Ｈ−ＮＭＲ（δｐｐｍ／ＣＤＣｌ3）：３．２１（２Ｈ，ｔ，Ｊ＝７．２Ｈｚ）、４．２６（２Ｈ，ｔ，Ｊ＝７．２Ｈｚ）、７．１−７．５（９Ｈ，ｍ）。
【００７５】
製造例２
２−フェニルチオ−２−（３−フェニル−１，３−チアゾリジン−２−イリデン）アセトニトリル（化合物２）の製造
水素化ナトリウム１１．５ｇ（油性６０％、２８７ミリモル）のジメチルホルムアミド２００ｍｌ懸濁液に、室温撹拌下、５０ｍｌのジメチルホルムアミドに溶かしたフェニルイソチオシアネート１８．９ｇ（１４０ミリモル）及びフェニルチオアセトニトリル２０．９ｇ（１４０ミリモル）を滴下した。１時間撹拌後、１，２−ジブロモエタン２８．９ｇ（１５４ミリモル）を室温で滴下し、更に３時間撹拌した。反応液に水３００ｍｌ及びエーテル１００ｍｌを加え撹拌し、析出した結晶を濾取し、標題の目的物２６．１ｇを無色結晶として得た（収率６０％）。
融点１４３−１４５℃
1Ｈ−ＮＭＲ（δｐｐｍ／ＣＤＣｌ3）：３．２１（２Ｈ，ｔ，Ｊ＝７．２Ｈｚ）、４．２９（２Ｈ，ｔ，Ｊ＝７．２Ｈｚ）、７．１−７．６（１０Ｈ，ｍ）。
【００７６】
上記製造例に示した方法に準じて製造した化合物、及びそれらの物理化学的性質を表１〜３０に示す。表１〜３０において、ＯＭｅはメトキシ基、Ｍｅはメチル基、t−Ｂｕはt−ブチル基、Ｐｈはフェニル基、Ｐｙはピリジル基、Ｂｎはベンジル基、ｃｙｃ−Ｃ6Ｈ11はシクロヘキシル基を意味する。尚、1Ｈ−ＮＭＲスペクトルは、テトラメチルシラン（ＴＭＳ）を基準物質として測定した。
【００７７】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
【表７】
【表８】
【表９】
【表１０】
【表１１】
【表１２】
【表１３】
【表１４】
【表１５】
【表１６】
【表１７】
【表１８】
【表１９】
【表２０】
【表２１】
【表２２】
【表２３】
【表２４】
【表２５】
【表２６】
【表２７】
【表２８】
【表２９】
【表３０】
【表３１】
【表３２】
次に製剤例を示す。尚、単に「部」とあるのは「重量部」を意味する。
【０１１０】
製剤例１（乳剤）
本発明化合物の各々１０部を、ソルベッソ１５０ ４５部及びＮ−メチルピロリドン３５部に溶解し、これにソルポール３００５Ｘ（東邦化学製乳化剤）１０部を加え、撹拌混合して各々の１０％乳剤を得た。
【０１１１】
製剤例２（水和剤）
本発明化合物の各々２０部を、ラウリル硫酸ナトリウム２部、リグニンスルホン酸ナトリウム４部、合成含水酸化珪素微粉末２０部及びクレー５４部を混合した中に加え、ジュースミキサーで撹拌混合して２０％水和剤を得た。
【０１１２】
製剤例３（粒剤）
本発明化合物の各々５部にドデシルベンゼンスルホン酸ナトリウム２部、ベントナイト１０部及びクレー８３部を加え十分撹拌混合した。適量の水を加え、更に撹拌し、造粒機で造粒し、通風乾燥して５％粒剤を得た。
【０１１３】
製剤例４（粉剤）
本発明化合物の各々１部を適当量のアセトンに溶解し、これに合成含水酸化珪素微粉末５部、酸性リン酸イソプロピル（ＰＡＰ）０．３部及びクレー９３．７部を加え、ジュースミキサーで撹拌混合し、アセトンを蒸発除去して１％粉剤を得た。
【０１１４】
製剤例５（フロアブル剤）
本発明化合物の各々２０部とポリオキシエチレントリスチリルフェニルエーテルリン酸エステルトリエタノールアミン３部、ローダシル（RHODORSIL）４２６Ｒ０．２部を含む水２０部を混合し、ダイノミルを用いて湿式粉砕後、プロピレングリコール８部、キサンタンガム０．３２部を含む水６０部と混合し、２０％水中懸濁液を得た。
【０１１５】
次に本発明化合物が、殺菌剤の有効成分として有用であることを試験例により示す。
【０１１６】
試験例１（キュウリうどんこ病に対する殺菌試験）
試験化合物のメタノール溶液にソルポール３５５（東邦化学製）水溶液（１００ｐｐｍ）を加えて薬液（２００ｐｐｍ）を調製し、この薬液をポット（径７．５ｃｍ）植えのキュウリ（播種後１４日）に散布した後、風乾した。これにキュウリうどんこ病胞子懸濁液（１．０×１０5個／ｍｌ）をスプレーガンで噴霧した。風乾後、アクリルハウス内に静置し、１０日後に発病度を調査し、無処理区に対する防除価を算出した。
【０１１７】
上記表に示す化合物番号２、３、１２、１８、２２、２３、３１、３２、３３、４５、５２、５６〜６１、６４〜６７、７４〜８０、９０、９３〜９９、１０１、１０２、１０５、１０７、１０９、１１２〜１１４、１１８〜１２２、１２４〜１２７、１３１〜１３９、１４２〜１４７、１５０、１５７〜１５９、１６１、１６５〜１７２、１７９、１８１〜１８８、１９０〜１９５、２０３、２０４、２１６、２１８及び２３９の化合物について調べたところ、いずれの化合物も５０％以上の防除価を示した。
試験例２（コムギうどんこ病に対する殺菌試験）
プラグ苗用育苗箱（商品名：苗作くん、（株）コバヤシ製、１穴縦３０ｍｍ×横３０ｍｍ×深さ４０ｍｍ、１３６穴）に愛菜１号（ＪＡ）を詰め、コムギ（品種：しらさぎ）を播種し、ガラスハウス内で７日間栽培した。パンガードＫＳ−２０の５００倍液に本発明化合物の４０００ｐｐｍメタノール溶液を所定量加えて２００ｐｐｍの薬液を調製した。ターンテーブル上においた直径２４Cｍの筒内にコムギ苗を置き、スプレーガン（オリンポス（株）、ＰＢ−４０８、ノズルキャップ平吹付き、１．５ｋｇｆ／ｃｍ2）を用いて筒内に薬液を散布した。風乾後、うどんこ病菌（Erysiphegraminisf.sp.tritici）を継代培養しているコムギ（品種：しらさぎ）を試験植物の上部で振動させて、分生胞子をふりかけた。恒温器（１８℃、１２時間蛍光灯照明）内に７日間置き、第１葉の発病程度を０（発病なし）から１０（全面に発病）で評価した。
【０１１８】
防除価は無処理区の発病程度と比較し、以下の計算式で計算した。
【０１１９】
防除価＝（１−処理区の発病程度／無処理区の発病程度）×１００
上記表に示す化合物番号４２、５８、６０、６４、６６、６７、９８、１０５、１０７、１１８、１１９、１５９、１７１、１８５、１９５及び２３９の化合物について調べたところ、いずれの化合物も５０％以上の防除価を示した。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cyanomethylene compound and an agricultural and horticultural fungicide containing the compound.
[0002]
[Prior art]
The use of disinfectants over the years has led to the emergence of drug-resistant bacteria in recent years. Therefore, it has become difficult to control with conventional bactericides such as benzimidazole, and there is a demand for the development of new types of drugs that have bactericidal activity not only against drug-sensitive bacteria but also drug-resistant bacteria. .
[0003]
Conventionally, examples of the compound in which a cyanomethylene group is bonded to the 2-position of the thiazolidine ring include, for example, Phamazie (1998), 53 (6), 373-376.
[0004]
[Chemical 2]
It has also been reported that the compound has an antitubercular effect. However, there is no description about the bactericidal activity of the compound of the general formula (A).
[0006]
International Patent Publication No. 96-33995 discloses a general formula.
[0007]
[Chemical 3]
[In formula, Ra shows a C2-C8 alkyl group, Rb shows a hydrogen atom etc., Rc shows a heterocyclic group, Rd shows a hydrogen atom etc.]. ]
The oxopropionitrile derivative represented by the formula is described, and it is also described that the derivative has insecticidal activity. However, there is no description of the bactericidal activity of the derivatives.
[0009]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel cyanomethylene compound capable of expressing an excellent bactericidal activity not only for drug-sensitive bacteria but also for drug-resistant bacteria.
[0010]
An object of the present invention is to provide a new type of agricultural and horticultural fungicide that exhibits not only drug-sensitive bacteria but also drug-resistant bacteria.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventor succeeded in finding a novel cyanomethylene compound having excellent bactericidal activity against various pathogenic bacteria that are problematic in agriculture. It came to complete.
[0012]
The present invention provides a general formula
[0013]
[Formula 4]
[Wherein R is C 1-20 A linear or branched alkyl group of 3-8 Cycloalkyl group, aryl group, aryl C 1-4 An alkyl group or a heteroaryl group is shown. Aryl group, aryl C 1-4 On the alkyl group and heteroaryl group, a halogen atom, C 1-4 Alkyl group, C 1-4 Haloalkyl group, C 1-4 Alkoxy group, C 1-4 Haloalkoxy group, C 1-4 Alkoxycarbonyl group, C 1-4 Alkylaminocarbonyl group, C 1-4 Alkoxyimino C 1-4 Alkyl group, C 1-4 Alkylamino group, C 1-4 Alkylcarbonyl group, C 1-4 Alkylthio group, aryl C 1-4 At least one substituent selected from an alkyl group, a carbamoyl group, a phenoxy group, a benzyloxy group, a nitro group and a cyano group may be substituted.
[0015]
R 1 Is C 1-8 A linear or branched alkyl group of 3-8 Cycloalkyl group, aryl group, aryl C 1-4 An alkyl group or a heteroaryl group is shown. Aryl group, aryl C 1-4 On the alkyl group and heteroaryl group, a halogen atom, C 1-4 Alkyl group, C 1-4 Haloalkyl group, C 1-4 Alkoxy group, C 1-4 Haloalkoxy group, C 1-4 Alkoxycarbonyl group, C 1-4 Alkylamino group, di-C 1-4 Alkylamino group, C 2-4 Alkenyl group, C 1-4 Alkylthio group, C 1-4 Alkylsulfinyl group, C 1-4 At least one substituent selected from an alkylsulfonyl group, a phenyl group, a phenoxy group, a nitro group, and a cyano group may be substituted.
[0016]
A is C 1-6 A linear or branched alkylene group of 2-6 A linear or branched alkenylene group of the group —CH 2 -B-CH 2 -(B represents a phenylene group), group -CH 2 -O-B-CH 2 -(B is as defined above) or a group -Z-CO- (Z is C 1-4 Represents an alkylene group).
[0017]
Y represents a sulfur atom, a sulfinyl group or a sulfonyl group.
[0018]
a represents 0 or 1; ]
In relation to an agricultural and horticultural fungicide (hereinafter referred to as “cyanomethylene compound (1)”).
[0019]
The cyanomethylene compound (1) of the present invention has a broad bactericidal spectrum and has an excellent bactericidal activity capable of controlling not only drug-sensitive bacteria but also drug-resistant bacteria.
[0020]
The cyanomethylene compound (1) of the present invention has an E / Z isomer, and the cyanomethylene compound (1) of the present invention includes an E / Z isomer and an E / Z isomer mixture.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (1), R, R 1 Specific examples of each group represented by, A and Z include the following.
[0022]
C 1-20 As the linear or branched alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl group, etc. Can be mentioned.
[0023]
C 3-8 Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
[0024]
Examples of the aryl group include phenyl and naphthyl groups.
[0025]
Aryl C 1-4 Examples of the alkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, and 3-phenylpropyl groups.
[0026]
Examples of the heteroaryl group include pyridyl, pyrimidyl, benzotriazolyl, 1,2,4-triazol-1-yl, 2-thienyl, pyrazinyl, pyridazinyl, 2-benzothiazolyl, oxazolyl, isoxazolyl, thiazolyl, 8-quinolyl, An oxadiazolyl group etc. can be mentioned.
[0027]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
[0028]
C 1-4 Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. be able to.
[0029]
C 1-4 Examples of the haloalkyl group include fluoromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, pentafluoroethyl, 1-fluoropropyl, 2-chloropropyl, 3 List linear or branched alkyl groups substituted with 1 to 9 halogen atoms such as -fluoropropyl, 3-chloropropyl, 1-fluorobutyl, 1-chlorobutyl, 4-fluorobutyl group Can do.
[0030]
C 1-4 Examples of the alkoxy group include linear or branched alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy groups. Can be mentioned.
[0031]
C 1-4 Examples of the haloalkoxy group include fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 1-fluoroethoxy, 2,2,2-trifluoro. 1 to 9 halogen atoms such as ethoxy, pentafluoroethoxy, 1-fluoropropoxy, 2-chloropropoxy, 3-fluoropropoxy, 3-chloropropoxy, 1-fluorobutoxy, 1-chlorobutoxy, 4-fluorobutoxy group And a linear or branched alkoxy group substituted with.
[0032]
C 1-4 Examples of the alkoxycarbonyl group include an alkoxy moiety such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl group, etc. Examples thereof include an alkoxycarbonyl group having 1 to 4 linear or branched chains.
[0033]
C 1-4 Examples of the alkylaminocarbonyl group include methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, n-butylaminocarbonyl, isobutylaminocarbonyl, sec-butylaminocarbonyl, tert-butylaminocarbonyl group and the like. And an alkylaminocarbonyl group in which the alkyl moiety is linear or branched having 1 to 4 carbon atoms.
[0034]
C 1-4 Alkoxyimino C 1-4 Examples of the alkyl group include methoxyiminomethyl, ethoxyiminomethyl, 1- (n-propoxyimino) ethyl, isopropoxyiminomethyl, 2- (n-butoxyimino) ethyl, sec-butoxyiminomethyl, tert-butoxyiminomethyl. Examples include an alkoxyiminoalkyl group in which the alkoxy moiety such as a group is linear or branched having 1 to 4 carbon atoms and the alkyl moiety is linear or branched having 1 to 4 carbon atoms. it can.
[0035]
C 1-4 As the alkylamino group, for example, an alkyl moiety such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, tert-butylamino group has 1 to 4 carbon atoms. A linear or branched alkylamino group can be mentioned.
[0036]
C 1-4 As the alkylcarbonyl group, for example, an alkyl moiety such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl group has 1 to 4 carbon atoms. And an alkylcarbonyl group which is linear or branched.
[0037]
C 1-8 As the linear or branched alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, Examples thereof include an n-octyl group.
[0038]
The C 1-4 As the alkylamino group, for example, an alkyl moiety such as dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, sec-butylamino, di-tert-butylamino group is carbon. Examples thereof include a dialkylamino group having a linear or branched chain of formulas 1 to 4.
[0039]
C 2-4 Examples of the alkenyl group include vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl group and the like.
[0040]
C 1-4 Examples of the alkylthio group include linear or branched alkyl groups having 1 to 4 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio groups, and the like. A chain alkylthio group can be mentioned.
[0041]
C 1-4 As the alkylsulfinyl group, for example, an alkyl moiety such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl group has 1 to 4 carbon atoms. And an alkylsulfinyl group which is linear or branched.
[0042]
C 1-4 As the alkylsulfonyl group, for example, an alkyl moiety such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl group has 1 to 4 carbon atoms. And alkylsulfonyl groups which are linear or branched.
[0043]
C 1-6 Examples of the linear or branched alkylene group include methylene, ethylene, trimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, 1-methyltrimethylene, methylmethylene, ethylmethylene, tetramethylene, and pentane. Examples include methylene and hexamethylene groups.
[0044]
C 2-6 Examples of the linear or branched alkenylene group include vinylidene, propylene, and butenylene groups.
[0045]
C 1-4 Examples of the alkylene group include methylene, ethylene, trimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, 1-methyltrimethylene, methylmethylene, ethylmethylene, and tetramethylene groups.
[0046]
Among the cyanomethylene compounds (1) of the present invention, R is C 1-20 A linear or branched alkyl group of 3-8 A cycloalkyl group, a phenyl group, a benzyl group or a heteroaryl group (on the phenyl group, benzyl group and heteroaryl group, a halogen atom, C 1-4 Alkyl group, C 1-4 Haloalkyl group, C 1-4 Alkoxy group, C 1-4 Haloalkoxy group, C 1-4 Alkoxycarbonyl group, C 1-4 Alkylaminocarbonyl group, C 1-4 Alkoxyimino C 1-4 Alkyl group, C 1-4 Alkylamino group, C 1-4 Alkylcarbonyl group, C 1-4 At least one substituent selected from an alkylthio group, a carbamoyl group, a phenoxy group, a benzyloxy group, a nitro group and a cyano group may be substituted. ) And R 1 Is C 1-8 A linear or branched alkyl group of 3-8 A cycloalkyl group, a phenyl group, a benzyl group or a pyridyl group (on the phenyl group, benzyl group and pyridyl group, a halogen atom, C 1-4 Alkyl group, C 1-4 Haloalkyl group, C 1-4 Alkoxy group, C 1-4 Haloalkoxy group, C 1-4 Alkoxycarbonyl group, C 1-4 Alkylamino group, di-C 1-4 Alkylamino group, C 2-4 Alkenyl group, C 1-4 Alkylthio group, C 1-4 Alkylsulfinyl group, C 1-4 At least one substituent selected from an alkylsulfonyl group, a phenyl group, a phenoxy group, a nitro group, and a cyano group may be substituted. ) And A is C 1-6 A linear or branched alkylene group of 2-4 A linear or branched alkenylene group or a group —CH 2 -B-CH 2 -(Wherein B represents a phenylene group), Y is a sulfur atom, a sulfinyl group or a sulfonyl group, and a is 0 or 1 is preferred.
[0047]
In the cyanomethylene compound (1) of the present invention, R is a phenyl group (on the phenyl group, a halogen atom, C 1-4 Alkyl group, C 1-4 Haloalkyl group, C 1-4 Alkoxy group, C 1-4 Haloalkoxy group, C 1-4 Alkylcarbonyl group, C 1-4 At least one substituent selected from an alkylthio group and a cyano group may be substituted. ) And R 1 Is a phenyl group or a pyridyl group (on the phenyl group and the pyridyl group, a halogen atom, C 1-4 Alkyl group, C 1-4 Haloalkyl group, C 1-4 Alkoxy group, C 1-4 Haloalkoxy group, C 1-4 Alkoxycarbonyl group, C 1-4 Alkylamino group, di-C 1-4 Alkylamino group, C 2-4 Alkenyl group, C 1-4 Alkylthio group, C 1-4 Alkylsulfinyl group, C 1-4 At least one substituent selected from an alkylsulfonyl group, a phenyl group, a phenoxy group, a nitro group, and a cyano group may be substituted. ) And A is C 1-6 A cyanomethylene compound in which Y is a sulfur atom and a is 0 or 1 is particularly preferred.
[0048]
The cyanomethylene compound (1) of the present invention has, for example, a general formula
R 1 -NCS (2)
[In the formula, R 1 Is the same as above. ]
Isothiocyanate represented by the general formula
R- (Y) a-CH 2 -CN (3)
[Wherein, R, Y and a are the same as above. ]
Acetonitrile represented by formula and general formula
X 1 -AX 2 (4)
[In the formula, A is the same as defined above. X 1 And X 2 Are the same or different and each represents a halogen atom. ]
It can manufacture by making the halogen compound represented by these react.
[0049]
In this reaction, the use ratio of isothiocyanate (2) and acetonitrile (3) is not particularly limited and can be appropriately selected from a wide range. Usually, 1 mole of isothiocyanate (2) is 1 ˜5 mol, preferably 1 mol or the vicinity thereof.
[0050]
Further, the use ratio of the isothiocyanate (2) and the halogen compound (4) is not particularly limited and can be appropriately selected from a wide range. It may be 5 mol, preferably 1 mol or its vicinity.
[0051]
This reaction is preferably carried out in the presence of a base. As the base, conventionally known ones can be widely used, for example, an inorganic base such as sodium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydride, potassium hydride, an organic base such as triethylamine, pyridine, etc. Can be mentioned. Such bases can be used alone or in combination of two or more. The amount of the base used is not particularly limited and can be appropriately selected from a wide range. Usually, the stoichiometric amount sufficient to capture the hydrogen halide produced by the above reaction or an excess thereof may be used, preferably the stoichiometric amount. What is necessary is just to make it an excessive amount about 1 to 5 times more than a theoretical amount or it. In addition, when using organic bases, such as a triethylamine and a pyridine, these can be used in large excess and can also be used as a reaction solvent.
[0052]
This reaction is usually carried out in a solvent. The solvent is not particularly limited as long as it is inert to this reaction, and conventionally known solvents can be widely used. For example, aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane, heptane, benzene, chlorobenzene, Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform and carbon tetrachloride, ethers such as diethyl ether, tetrahydrofuran and dioxane, dimethylformamide, dimethyl sulfoxide, or these 2 A mixed solvent of seeds or more can be mentioned.
[0053]
This reaction is usually performed at a temperature from −20 ° C. to the boiling point of the solvent used, and is usually completed in about 0.5 to 24 hours.
[0054]
The thioisothiocyanate (2), acetonitrile (3), and halogen compound (4), which are raw material compounds used in the production of the cyanomethylene compound (1) of the present invention, can be easily obtained commercially. It is a compound or a compound that can be easily produced according to a known method.
[0055]
The cyanomethylene compound (1) of the present invention obtained by the above method is easily isolated and purified from the reaction system by usual isolation and purification means such as filtration, solvent extraction, distillation, recrystallization and column chromatography. it can.
[0056]
The cyanomethylene compound (1) of the present invention is used, for example, as an active ingredient of a fungicide.
[0057]
The cyanomethylene compound (1) of the present invention can be used as it is as a disinfectant, but it can be formulated into any form such as oil, emulsion, wettable powder, flowable, granule, powder, aerosol, or aerosol. You can also. At this time, the content of the thiazolidine compound (1) of the present invention is not particularly limited, and the formulation form, the target disease or crop type, the degree of the disease, the application place, the application time, the application method, the drug used together (insecticide, Nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, soil conditioners, etc.) and the amount and type of fertilizer can be selected from a wide range. However, it is usually about 0.01 to 95% by weight, preferably about 0.1 to 50% by weight of the total amount of the bactericide.
[0058]
A fungicidal preparation containing the cyanomethylene compound (1) of the present invention as an active ingredient can be produced according to a known method. For example, the cyanomethylene compound (1) may be mixed with a carrier such as a solid carrier, a liquid carrier, or a gaseous carrier, and a surfactant or other formulation adjuvant may be added as necessary.
[0059]
As the carrier, any conventionally known carrier commonly used in this field can be used.
[0060]
Examples of the solid carrier include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fusami clay, acidic clay), talc, ceramics, other inorganic minerals (celite, quartz, sulfur, activated carbon, calcium carbonate, Hydrated silica, etc.), fine fertilizers such as chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride, etc.), granular materials and the like.
[0061]
Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons. (Hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N , N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil and the like.
[0062]
Examples of the gaseous carrier (ie, propellant) include butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, and the like.
[0063]
Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol compounds, and the like. Can be mentioned.
[0064]
Examples of formulation adjuvants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose compounds, alginic acid, etc.), lignin compounds, bentonite, saccharides, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids) Etc.), PAP (isopropyl acid phosphate), BBH (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol and 3-tert- And butyl-4-methoxyphenol), vegetable oils, mineral oils, stabilizers such as fatty acids and esters thereof, and the like.
[0065]
The preparation of the fungicide of the present invention thus obtained may be used as it is or may be diluted with water or the like. Further, it may be preliminarily mixed with other insecticides, nematicides, acaricides, bactericides, herbicides, plant growth regulators, synergists, soil conditioners, and the like. Alternatively, the preparation of the present invention and each of the above agents may be used at the same time.
[0066]
When the fungicide of the present invention is used as an agricultural or horticultural fungicide, the application amount is not particularly limited, and the active ingredient concentration, formulation form, target disease or crop type, degree of disease, application time, application method, combined use Depending on various conditions such as the amount and type of fertilizers used (insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, soil conditioners, etc.) It can be selected from a wide range, but usually 100m 2 What is necessary is just about 0.001-100g per. Moreover, when diluting an emulsion, a wettable powder, a flowable agent, etc. with water, the application density | concentration should just be about 0.1-1000 ppm normally, Preferably it may be about 1-500 ppm. Granules, powders and the like are applied as they are without dilution.
[0067]
The compound of the present invention is characterized by having an excellent bactericidal activity and a broad spectrum of activity, for example, rice blast fungus, rice blight fungus, apple powdery mildew, apple spotted leaf fungus, oyster powdery mildew, grape udon It can be used to control diseases caused by various pathogens such as fungus, barley powdery mildew, wheat powdery mildew, cucumber powdery mildew, tomato blight, strawberry powdery mildew, tobacco powdery mildew and other pathogenic bacteria. it can.
[0068]
【Example】
Hereinafter, the present invention will be described in more detail with reference examples, production examples, formulation examples and test examples.
[0069]
Reference example 1
Production of 2-fluoro-5-trifluoromethylaniline
20 g of 3-nitro-4-fluorobenzolorifluoride was dissolved in 50 ml of methanol, 16 g of iron powder was added, and concentrated hydrochloric acid was added dropwise with stirring. The reaction mixture was stirred overnight, neutralized with sodium bicarbonate, diethyl ether was added, and insolubles were filtered off through celite. The ether layer was separated, dried and concentrated under reduced pressure to obtain 14 g (yield 82%) of the desired product.
[0070]
Reference example 2
Preparation of 2-fluoro-5-trifluoromethylphenylthioacetonitrile
14 g of 2-fluoro-5-trifluoromethylaniline was suspended in 30 ml of water and 10 ml of concentrated hydrochloric acid, and a solution prepared by dissolving 5.93 g of sodium nitrite in 30 ml of water was added dropwise at −5 ° C. while cooling to −5 ° C. For 2 hours. The reaction solution was extracted with an aqueous ethyl acetate solution, dried and then concentrated to obtain 22 g of 3-ethoxycarbonylthio-4-fluorobenzotrifluoride.
[0071]
Next, 3-ethoxycarbonylthio-4-fluorobenzotrifluoride obtained above was dissolved in 100 ml of tetrahydrofuran without further purification, and dropped into a suspension of lithium aluminum hydride 4.4 g in tetrahydrofuran 100 ml. The reaction mixture was stirred for 3 hours, diluted hydrochloric acid was added to adjust the pH to 1, and the mixture was extracted with ethyl acetate to obtain 13 g of 4-fluoro-3-mercaptobenzotrifluoride.
[0072]
Next, 4-fluoro-3-mercaptobenzotrifluoride obtained above is dissolved in 100 ml of acetonitrile, 7 g of potassium carbonate and 5 g of chloroacetonitrile are added, and the mixture is stirred overnight at room temperature. Extracted. The ethyl acetate layer was dried and concentrated, and then subjected to silica gel column chromatography to obtain 5 g of the desired product (total yield of 3 steps: 27%).
[0073]
Reference example 3
Preparation of (2-fluoro-5-trifluoromethylphenylthio) -2- (3-phenylthiazolidine-2-ylidene) acetonitrile
Dissolve 0.70 g of 2-fluoro-5-trifluoromethylphenylthioacetonitrile and 0.40 g of phenylisothiocyanate in 5 ml of dimethylformamide and add 0.25 g of a 60% oil suspension of sodium hydride to the mixture while stirring. The mixture was stirred for 0.5 hours. Next, 0.56 g of 1,2-dibromoethane was added, and after stirring for 1 hour, 100 ml of water was added, and further 30 ml of diethyl ether was added and stirred to precipitate crystals. The precipitated crystals were collected by filtration to obtain 0.06 g (yield 6%) of the desired product.
[0074]
Production Example 1
Preparation of 2- (4-chlorophenylthio) -2- (3-phenyl-1,3-thiazolidine-2-ylidene) acetonitrile (Compound 1)
4-Chlorophenyl isothiocyanate (1.14 g, 6.7 mmol) and phenylthioacetonitrile (1.0 g, 6.7 mmol) are dissolved in 10 ml of dimethylformamide and stirred at room temperature with 0.59 g of sodium hydride (60% oily). 14.8 mmol) was added little by little and stirred for 1 hour. Then, 1.39 g (7.4 mmol) of 1,2-dibromoethane was added, and the mixture was further stirred at room temperature for 3 hours. 50 ml of water and 10 ml of ether were added to the reaction mixture and stirred, and the precipitated crystals were collected by filtration to give 0.8 g of the title compound as colorless crystals (yield 30%).
Melting point 144-146 ° C
1 H-NMR (δppm / CDCl Three ): 3.21 (2H, t, J = 7.2 Hz), 4.26 (2H, t, J = 7.2 Hz), 7.1-7.5 (9H, m).
[0075]
Production Example 2
Preparation of 2-phenylthio-2- (3-phenyl-1,3-thiazolidine-2-ylidene) acetonitrile (Compound 2)
To a suspension of 11.5 g of sodium hydride (60% oily, 287 mmol) in 200 ml of dimethylformamide, 18.9 g (140 mmol) of phenylisothiocyanate dissolved in 50 ml of dimethylformamide and 20. 9 g (140 mmol) was added dropwise. After stirring for 1 hour, 28.9 g (154 mmol) of 1,2-dibromoethane was added dropwise at room temperature, and the mixture was further stirred for 3 hours. 300 ml of water and 100 ml of ether were added to the reaction mixture and stirred, and the precipitated crystals were collected by filtration to give 26.1 g of the title product as colorless crystals (yield 60%).
Melting point 143-145 ° C
1 H-NMR (δppm / CDCl Three ): 3.21 (2H, t, J = 7.2 Hz), 4.29 (2H, t, J = 7.2 Hz), 7.1-7.6 (10H, m).
[0076]
Tables 1 to 30 show the compounds produced according to the methods shown in the above production examples and their physicochemical properties. In Tables 1-30, OMe is a methoxy group, Me is a methyl group, t-Bu is a t-butyl group, Ph is a phenyl group, Py is a pyridyl group, Bn is a benzyl group, cyc-C 6 H 11 Means a cyclohexyl group. still, 1 The H-NMR spectrum was measured using tetramethylsilane (TMS) as a reference substance.
[0077]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
[Table 11]
[Table 12]
[Table 13]
[Table 14]
[Table 15]
[Table 16]
[Table 17]
[Table 18]
[Table 19]
[Table 20]
[Table 21]
[Table 22]
[Table 23]
[Table 24]
[Table 25]
[Table 26]
[Table 27]
[Table 28]
[Table 29]
[Table 30]
[Table 31]
[Table 32]
Next, formulation examples are shown. Note that simply “parts” means “parts by weight”.
[0110]
Formulation Example 1 (emulsion)
10 parts of each of the compounds of the present invention are dissolved in 45 parts of Solvesso 150 and 35 parts of N-methylpyrrolidone, 10 parts of Solpol 3005X (Emulsifier manufactured by Toho Chemical Co., Ltd.) is added thereto, and mixed by stirring to obtain 10% emulsions. It was.
[0111]
Formulation Example 2 (wettable powder)
20 parts of each of the compounds of the present invention were added to a mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of synthetic silicon hydroxide fine powder and 54 parts of clay, and mixed by stirring with a juice mixer to 20%. A wettable powder was obtained.
[0112]
Formulation Example 3 (Granule)
2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite and 83 parts of clay were added to 5 parts of each of the compounds of the present invention and mixed sufficiently with stirring. An appropriate amount of water was added, further stirred, granulated with a granulator, and dried by ventilation to obtain 5% granules.
[0113]
Formulation Example 4 (powder)
1 part of each of the compounds of the present invention is dissolved in an appropriate amount of acetone. To this, 5 parts of synthetic silicon hydroxide fine powder, 0.3 part of isopropyl acid phosphate (PAP) and 93.7 parts of clay are added, and a juice mixer is used. After stirring and mixing, acetone was removed by evaporation to obtain a 1% powder.
[0114]
Formulation Example 5 (Flowable)
20 parts of each of the compounds of the present invention, 3 parts of polyoxyethylene tristyryl phenyl ether phosphate triethanolamine, and 20 parts of water containing 0.2 part of Rhodosyl 426R are mixed, and after wet grinding using dynomill, propylene It was mixed with 60 parts of water containing 8 parts of glycol and 0.32 part of xanthan gum to obtain a 20% suspension in water.
[0115]
Next, it is shown by test examples that the compound of the present invention is useful as an active ingredient of a fungicide.
[0116]
Test Example 1 (Bactericidal test for cucumber powdery mildew)
An aqueous solution (100 ppm) of Solpol 355 (manufactured by Toho Chemical) was added to a methanol solution of the test compound to prepare a chemical solution (200 ppm), and this chemical solution was sprayed on a cucumber planted in a pot (diameter 7.5 cm) (14 days after sowing). After that, it was air-dried. Cucumber powdery mildew spore suspension (1.0 × 10 Five Spray / ml) with a spray gun. After air drying, it was left in the acrylic house, and after 10 days, the disease severity was investigated, and the control value for the untreated area was calculated.
[0117]
Compound Nos. 2, 3, 12, 18, 22, 23, 31, 32, 33, 45, 52, 56-61, 64-67, 74-80, 90, 93-99, 101, 102, shown in the above table 105, 107, 109, 112-114, 118-122, 124-127, 131-139, 142-147, 150, 157-159, 161, 165-172, 179, 181-188, 190-195, 203, When the compounds 204, 216, 218 and 239 were examined, all the compounds showed a control value of 50% or more.
Test Example 2 (Bactericidal test for wheat powdery mildew)
A nursery box for plug seedlings (trade name: Naezu-kun, manufactured by Kobayashi Co., Ltd., 1 hole length 30 mm x width 30 mm x depth 40 mm, 136 holes) is packed with Aina 1 (JA) and wheat (variety: Shirasagi) Was cultivated in a glass house for 7 days. A 200 ppm chemical solution was prepared by adding a predetermined amount of a 4000 ppm methanol solution of the compound of the present invention to a 500 times solution of PANGARD KS-20. Place wheat seedlings in a cylinder with a diameter of 24 cm on a turntable, spray gun (Olympos Co., PB-408, with nozzle cap flat spray, 1.5 kgf / cm 2 ) Was used to spray the chemical solution into the cylinder. After air-drying, wheat (cultivar: Shirasagi), subcultured with powdery mildew (Erysiphegraminisf.sp.tritici), was vibrated at the top of the test plant and sprinkled with conidia. It was placed in a thermostatic chamber (18 ° C., fluorescent lamp illumination for 12 hours) for 7 days, and the first leaf disease severity was evaluated from 0 (no disease) to 10 (all diseased).
[0118]
The control value was calculated by the following formula, compared with the disease severity in the untreated area.
[0119]
Control value = (1—degree of disease in treated area / degree of disease in untreated area) × 100
The compounds Nos. 42, 58, 60, 64, 66, 67, 98, 105, 107, 118, 119, 159, 171, 185, 195 and 239 shown in the above table were examined. The above control values were shown.
Claims (2)
Ｒ1はフェニル基又はピリジル基を示す。フェニル基及びピリジル基上には、ハロゲン原子、Ｃ1-4アルキル基、Ｃ1-4ハロアルキル基、Ｃ1-4アルコキシ基、Ｃ1-4ハロアルコキシ基、Ｃ1-4アルコキシカルボニル基、Ｃ1-4アルキルアミノ基、ジＣ1-4アルキルアミノ基、Ｃ2-4アルケニル基、Ｃ1-4アルキルチオ基、Ｃ1-4アルキルスルフィニル基、Ｃ1-4アルキルスルホニル基、フェニル基、フェノキシ基、ニトロ基及びシアノ基から選ばれる少なくとも１種の置換基が置換していてもよい。
ＡはＣ1-6の直鎖もしくは分枝鎖状アルキレン基を示す。
Ｙは硫黄原子を示す。〕
で表されるシアノメチレン化合物。General formula (1)
R 1 represents a phenyl group or a pyridyl group. On the phenyl group and pyridyl group, a halogen atom, C 1-4 alkyl group, C 1-4 haloalkyl group, C 1-4 alkoxy group, C 1-4 haloalkoxy group, C 1-4 alkoxycarbonyl group, C 1-4 1-4 alkylamino group, di-C 1-4 alkylamino group, C 2-4 alkenyl group, C 1-4 alkylthio group, C 1-4 alkylsulfinyl group, C 1-4 alkylsulfonyl group, phenyl group, phenoxy At least one substituent selected from a group, a nitro group, and a cyano group may be substituted.
A represents a C 1-6 linear or branched alkylene group .
Y is a sulfur atom. ]
A cyanomethylene compound represented by:
Priority Applications (17)
| Application Number | Priority Date | Filing Date | Title |
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| JP36761599A JP3864298B2 (en) | 1999-03-11 | 1999-12-24 | Cyanomethylene compounds and agricultural and horticultural fungicides |
| KR10-2002-7008042A KR100483920B1 (en) | 1999-12-24 | 2000-09-05 | Cyanomethylene compounds, process for producing the same, and agricultural or horticultural bactericide |
| BRPI0017034-8A BR0017034B1 (en) | 1999-12-24 | 2000-09-05 | cyanomethylene compound, process for its preparation and fungicide for agriculture and horticulture. |
| EP00956916A EP1243584B8 (en) | 1999-12-24 | 2000-09-05 | Cyanomethylene compounds, process for producing the same, and agricultural or horticultural bactericide |
| CA002394720A CA2394720C (en) | 1999-12-24 | 2000-09-05 | Cyanomethylene compounds and fungicidal compositions |
| DE60043072T DE60043072D1 (en) | 1999-12-24 | 2000-09-05 | CYANOMETHYLENE COMPOUNDS, PROCESS FOR THEIR PREPARATION AND USE AS BACTERICIDES FOR AGRICULTURE AND GARDENING |
| CNB008177244A CN1235889C (en) | 1999-12-24 | 2000-09-05 | Cyanomethylene compounds, process for producing the same, and agricultural or horticultural bactericide |
| IL15029300A IL150293A0 (en) | 1999-12-24 | 2000-09-05 | Cyanomethylene compounds, process for producing the same, and agricultural or horticultural bactericide |
| ES00956916T ES2332171T3 (en) | 1999-12-24 | 2000-09-05 | CYANOMETILENE COMPOUNDS, PROCEDURE FOR ITS PRODUCTION, AND BACTERICIDE AGRICOLA OR HORTICOLA. |
| AT00956916T ATE444291T1 (en) | 1999-12-24 | 2000-09-05 | CYANOMETHYLENE COMPOUNDS, METHOD FOR THE PRODUCTION AND USE THEREOF AS BACTERICIDES FOR AGRICULTURE AND HORTICULTURE |
| US10/149,437 US6710062B1 (en) | 1999-12-24 | 2000-09-05 | Cyanomethylene compounds, process for producing the same, and agricultural or horticultural bactericide |
| PCT/JP2000/006001 WO2001047902A1 (en) | 1999-12-24 | 2000-09-05 | Cyanomethylene compounds, process for producing the same, and agricultural or horticultural bactericide |
| AU68701/00A AU783913B2 (en) | 1999-12-24 | 2000-09-05 | Cyanomethylene compounds, process for producing the same, and agricultural or horticultural bactericide |
| TW089118496A TW568909B (en) | 1999-12-24 | 2000-09-08 | Cyanomethylene compound, process of producing the compound and agricultural or horticultural bactericide |
| IL150293A IL150293A (en) | 1999-12-24 | 2002-06-18 | Agricultural or horticultural fungicidal compositions containing cyanomethylene compounds, some such novel compounds and process for preparing them |
| ZA200204979A ZA200204979B (en) | 1999-12-24 | 2002-06-20 | Cyanomethylene compounds, process for producing the same, and agriculturel or horticultural bactericide. |
| HK03107547A HK1055300A1 (en) | 1999-12-24 | 2003-10-17 | Cyanomethylene compounds, process for producing the same, and agricultural or horticultural bactericide |
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| JP6465699 | 1999-03-11 | ||
| JP11-64656 | 1999-03-11 | ||
| JP36761599A JP3864298B2 (en) | 1999-03-11 | 1999-12-24 | Cyanomethylene compounds and agricultural and horticultural fungicides |
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| JP3864298B2 true JP3864298B2 (en) | 2006-12-27 |
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| AU2006296781B2 (en) | 2005-09-29 | 2012-06-14 | Syngenta Participations Ag | Fungicidal compositions |
| MX2008012707A (en) * | 2006-04-06 | 2008-10-10 | Syngenta Participations Ag | Fungicidal compositions. |
| CN104430378A (en) | 2009-07-16 | 2015-03-25 | 拜尔农作物科学股份公司 | Synergistic active substance combinations containing phenyl triazoles |
| US9288986B2 (en) | 2009-12-22 | 2016-03-22 | Mitsui Chemicals Agro, Inc. | Plant disease control composition and method for controlling plant disease by applying the same |
| JP6011045B2 (en) | 2012-06-12 | 2016-10-19 | 住友化学株式会社 | Plant disease control composition and plant disease control method |
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