JPS63313773A - Pyrazole compound - Google Patents
Pyrazole compoundInfo
- Publication number
- JPS63313773A JPS63313773A JP14797887A JP14797887A JPS63313773A JP S63313773 A JPS63313773 A JP S63313773A JP 14797887 A JP14797887 A JP 14797887A JP 14797887 A JP14797887 A JP 14797887A JP S63313773 A JPS63313773 A JP S63313773A
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituted
- formula
- alkyl
- general formula
- 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.)
- Pending
Links
- -1 Pyrazole compound Chemical class 0.000 title claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 19
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 5
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 5
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 27
- 230000002363 herbicidal effect Effects 0.000 abstract description 23
- 239000004009 herbicide Substances 0.000 abstract description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000001408 amides Chemical class 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract 1
- 229940100198 alkylating agent Drugs 0.000 abstract 1
- 239000002168 alkylating agent Substances 0.000 abstract 1
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 230000002070 germicidal effect Effects 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 241000196324 Embryophyta Species 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 240000007594 Oryza sativa Species 0.000 description 11
- 235000007164 Oryza sativa Nutrition 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 235000009566 rice Nutrition 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000003217 pyrazoles Chemical class 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 241000234653 Cyperus Species 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 241000233866 Fungi Species 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000035784 germination Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 244000025254 Cannabis sativa Species 0.000 description 3
- 244000301850 Cupressus sempervirens Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 244000184734 Pyrus japonica Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000003226 pyrazolyl group Chemical group 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 240000008574 Capsicum frutescens Species 0.000 description 2
- 241000234646 Cyperaceae Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000254158 Lampyridae Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 241000287116 Paridae Species 0.000 description 2
- 241001600434 Plectroglyphidodon lacrymatus Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 244000000231 Sesamum indicum Species 0.000 description 2
- 235000003434 Sesamum indicum Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000254032 Acrididae Species 0.000 description 1
- 241000254060 Aquatica lateralis Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000221198 Basidiomycota Species 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- 240000004160 Capsicum annuum Species 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 235000007862 Capsicum baccatum Nutrition 0.000 description 1
- 235000002568 Capsicum frutescens Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001604179 Cheilotrema saturnum Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000195955 Equisetum hyemale Species 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 241001522878 Escherichia coli B Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000223221 Fusarium oxysporum Species 0.000 description 1
- 101100134927 Gallus gallus COR8 gene Proteins 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 244000292697 Polygonum aviculare Species 0.000 description 1
- 235000006386 Polygonum aviculare Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000005733 Raphanus sativus var niger Nutrition 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 240000001970 Raphanus sativus var. sativus Species 0.000 description 1
- 241000208422 Rhododendron Species 0.000 description 1
- 241000681978 Rhododendron japonicum Species 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000223229 Trichophyton rubrum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000000260 Typha latifolia Species 0.000 description 1
- 235000005324 Typha latifolia Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 241001148683 Zostera marina Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000269888 azena Species 0.000 description 1
- 244000000005 bacterial plant pathogen Species 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000005452 bending Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001728 capsicum frutescens Substances 0.000 description 1
- 239000001390 capsicum minimum Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002837 defoliant Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 125000006003 dichloroethyl group Chemical group 0.000 description 1
- 125000006001 difluoroethyl group Chemical group 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-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
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 125000006351 ethylthiomethyl group Chemical group [H]C([H])([H])C([H])([H])SC([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004372 methylthioethyl group Chemical group [H]C([H])([H])SC([H])([H])C([H])([H])* 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 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 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004706 n-propylthio group Chemical group C(CC)S* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000008223 sterile water Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BWMISRWJRUSYEX-SZKNIZGXSA-N terbinafine hydrochloride Chemical compound Cl.C1=CC=C2C(CN(C\C=C\C#CC(C)(C)C)C)=CC=CC2=C1 BWMISRWJRUSYEX-SZKNIZGXSA-N 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- 201000004647 tinea pedis Diseases 0.000 description 1
- 125000006000 trichloroethyl group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は，％に除草剤及び殺菌剤として有用な新規なピ
ラゾール化合物を提供するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention provides novel pyrazole compounds that are particularly useful as herbicides and fungicides.
（従来の技術及び発明が解決しようとする問題点）
従来，ピラゾール化合物については数多くのものが合成
されている。例えば、ヴイツセンシャフトリツへ・ラフ
イトシュリフト・ベダゴグ・ホーホシューレ「カールｅ
リープクネヒト」ボッダム（ Ｗｉｓｓ．Ｚ．Ｐａｅｄ
ａｇｏｇ。(Prior art and problems to be solved by the invention) Many pyrazole compounds have been synthesized in the past. For example, ``Karl e
"Liebknecht" Boddam (Wiss.Z.Paed
agog.
Ｈｏｃｈｓｃｈ，”Ｋａｒｌ Ｌｉｅｂｋｎｅｃｈｔ”
Ｐｏｔｓｄａｍ）。Hochsch, “Karl Liebknecht”
Potsdam).
見ユ、４７（１９７７）には、下記式（Ｚ）（ただし、
Ｒは塩素またはメチル基を示す。）で表わされるピラゾ
ール化合物が除草活性を有することが記述されている。Miyu, 47 (1977) contains the following formula (Z) (however,
R represents chlorine or a methyl group. It has been described that pyrazole compounds represented by ) have herbicidal activity.
しかしながらこの化合物の除草活性は弱く、しかも、除
草剤としての重要な要件である選択除草活性が極めて低
い化合物であり、水稲に対して薬害を及ぼすという問題
も有していた。However, the herbicidal activity of this compound is weak, and moreover, the compound has extremely low selective herbicidal activity, which is an important requirement for a herbicide, and also has the problem of causing phytotoxicity to paddy rice.
（問題点を解決するための手段及び効果）本発明者らは
、高い除草活性を有し、かつ選択除草活性に優れたピラ
ゾール化合物の合成について研究を行ってきた。その結
果、特定の構造を有する新規なピラゾール化合物が高い
除草活性を示し、かつ稲に対して安全な優れた選択除草
活性を有する除草剤となり得ること、さらに、これらの
化合物が、強い抗菌活性を有して優れた殺菌剤となり得
ることを確認し、本発明を完成させるに至った。(Means and Effects for Solving the Problems) The present inventors have conducted research on the synthesis of pyrazole compounds that have high herbicidal activity and are excellent in selective herbicidal activity. As a result, new pyrazole compounds with specific structures exhibit high herbicidal activity and can be used as herbicides that are safe and have excellent selective herbicidal activity against rice.Furthermore, these compounds have strong antibacterial activity. The present invention was completed by confirming that it can be used as an excellent bactericidal agent.
すなわち、本発明は、一般式（１）
（ただし、Ｒは水素原子、アルキル基またはン原子、ｆ
ｆｉ換若しくは非置換のフルキル基。That is, the present invention relates to general formula (1) (wherein R is a hydrogen atom, an alkyl group, or an atom, f
fi-substituted or unsubstituted furkyl group.
アルコキシ基、アルキルチオ基、ニトロ基。Alkoxy group, alkylthio group, nitro group.
シフ）基またはアルコキシカルボニル基を示し、また、
Ｒ及びＲ１１は互いに隣接し、−緒になって環を形成し
てもよく、Ｒは置換若しくは非置換のフルキル基、ｌ！
置換若くは非置換のフェニル基または置換若しくは非置
換のピリジル基を示し、Ｒはフルキル基またはＣＯＲ８
，Ｃ０ＯＲ９，Ｃ０ＮＴ（Ｒ”で表わされる基を示し、
Ｒ８、Ｒ９及びＲＩＯは置換若しくは非置換のアルキル
基または置換若しくは非置換のフェニル基を示し、Ａは
炭素原子または窒素原子を示し、ｎは０または正の整数
を示す。）で表わされるピラゾール化合物並びＫ、該ス
ルホン７ミド化合物を有効成分とする除草剤及び殺菌剤
である。Schiff) group or alkoxycarbonyl group, and
R and R11 are adjacent to each other and may be taken together to form a ring, R is a substituted or unsubstituted furkyl group, l!
Represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted pyridyl group, R is a furkyl group or COR8
, C0OR9, C0NT (represents a group represented by R'',
R8, R9 and RIO represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group, A represents a carbon atom or a nitrogen atom, and n represents 0 or a positive integer. ), and a herbicide and fungicide containing the sulfone 7mide compound as active ingredients.
上記一般式（１）中、Ｒ１−Ｒ５で示されるハロゲン原
子の具体例としては、塩素、臭素、フッ素、ヨウ素の各
原子が挙げられる。また、前記一般式中、Ｒ及びＲ１−
Ｒ１０で示されるフルキル基は、その炭素数には特１ｃ
ｆｌｌｌＪ限されず直鎖状または分枝状の基が用いられ
るが、原料人手の容易さから、炭素数は１〜６であるこ
とが好適である。該フルキル基の具体例を示すと、メチ
ル基、エチル基、ｎ−プロピル基、 ｉｇｏ−プロピル
基、ｎ−ブチル基、 ｉａ。In the above general formula (1), specific examples of the halogen atoms represented by R1 to R5 include chlorine, bromine, fluorine, and iodine atoms. Furthermore, in the general formula, R and R1-
The furkyl group represented by R10 has particularly 1c carbon atoms.
Although there are no limitations on flllJ, a straight chain or branched group can be used, but from the viewpoint of ease of handling raw materials, it is preferable that the number of carbon atoms is 1 to 6. Specific examples of the furkyl group include methyl group, ethyl group, n-propyl group, igo-propyl group, n-butyl group, and ia.
−ブチル基、ｔ−ブチル基、ｎ−ペンチル基。-butyl group, t-butyl group, n-pentyl group.
ｎ−ヘキシル基等が挙げられる。また、Ｒ１−Ｒ６及び
Ｒ８〜ＲＩＯで示される置換のフルキル基としては、前
記した非置換のアルキル基中の水素の全部あるいは一部
がハロゲン原子。Examples include n-hexyl group. Further, in the substituted furkyl group represented by R1-R6 and R8 to RIO, all or part of the hydrogen atoms in the above-mentioned unsubstituted alkyl group are halogen atoms.
シアノ基またはヒドロキシル基、アルフキシ基、フルキ
ルチオ基またはフェニル基等で置換されたものが好適で
ある。このような置換フルキル基の具体例を示すと、り
ｐｐメチル基、ブロモメチル基、フルオロメチル基、ヨ
ードメチル基、ジクｐロメチル基、ジブロモメチル皇、
ジフルオロメチル基、ショートメチル基、トリクロルメ
チル基、トリブロモメチル基、トリフルオルメチル基、
クロロエチル基、ブロモエチル基、フルオルエチル基。Those substituted with a cyano group, a hydroxyl group, an alphoxy group, a furkylthio group, a phenyl group, etc. are preferred. Specific examples of such substituted fulkyl groups include a pp-methyl group, a bromomethyl group, a fluoromethyl group, an iodomethyl group, a dipromethyl group, a dibromomethyl group,
Difluoromethyl group, short methyl group, trichloromethyl group, tribromomethyl group, trifluoromethyl group,
Chloroethyl group, bromoethyl group, fluoroethyl group.
ジクロルエチル基、ジブロモエチル基、ジフルオロエチ
ル基、トｖクロロエチル基、トリブロモエチル基、トリ
フルオロエチル基、シアノメチル基、シアノエチル基、
ヒドロキシメチル基、ヒドロキシエチル基、メチルチオ
メチル基、メチルチオエチル基、エチルチオメチル基、
メトキシメチル基、メトキシエチル基、メトキシプロピ
ル基、エトキシメチル基、エトキシエチル基、ｎ−プロ
ポキシメチル基、ｔｓｏ−プロポキシメチル基、ベンジ
ル基等が挙げられる。前記ベンジル基等、フェニル基で
置換されたアルキル基の場合、該フェニル基には置換基
があってもよく、後述するＲ 、 Ｒ’ 及びＲ８〜
ＲＩＯの置換フェニル基の置換基がそのまま適用できる
。Dichloroethyl group, dibromoethyl group, difluoroethyl group, trichloroethyl group, tribromoethyl group, trifluoroethyl group, cyanomethyl group, cyanoethyl group,
Hydroxymethyl group, hydroxyethyl group, methylthiomethyl group, methylthioethyl group, ethylthiomethyl group,
Examples include methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, ethoxyethyl group, n-propoxymethyl group, tso-propoxymethyl group, and benzyl group. In the case of an alkyl group substituted with a phenyl group such as the benzyl group, the phenyl group may have a substituent, and R, R' and R8 to be described later.
The substituents of the substituted phenyl group of RIO can be applied as they are.
前記一般式（１）中、Ｒ１−Ｒ５で示されるフルコキシ
基は特に制限されず、直鎖状または分校状の基が用いら
れるが、炭素数１〜６であることが好適である。該フル
コキシ基の具体例を示すと、メトキシ基、エトキシ基、
ｎ−プロポキシ基、 １ｓｏ−プロポキシ基、ｎ−ブト
キシ基、ｔ−ブトキシ基、ｎ−ペントキシ基、ｎ−ヘキ
ソキシ基等が挙げられる。In the general formula (1), the flukoxy group represented by R1 to R5 is not particularly limited, and a linear or branched group may be used, but it is preferable that the group has 1 to 6 carbon atoms. Specific examples of the flukoxy group include methoxy group, ethoxy group,
Examples include n-propoxy group, 1so-propoxy group, n-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, and the like.
前記一般式（１）中、Ｒ１−Ｒ５で示されるフルキルチ
オ基は特に制限されず、直鎖状または分枝状の基が用い
られるが、炭素数１〜６であることが好適である。該ア
ルキルチオ基の具体例を示すと、メチルチオ基、エチル
チオ基、ｎ−プロピルチオ基、 １ｓｏ−プロピルチオ
基、 １ｓｏ−ブチルチオ基等が挙げられる。In the general formula (1), the furkylthio group represented by R1 to R5 is not particularly limited, and a linear or branched group may be used, but it is preferably a group having 1 to 6 carbon atoms. Specific examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, 1so-propylthio group, 1so-butylthio group, and the like.
また、前記一般式（１）中、Ｒ−Ｒで示されるアルコキ
シカルボニル基を具体的に示すと、メトキシカルボニル
基、エトキシカルボニル基等が挙げられる。Further, in the general formula (1), specific examples of the alkoxycarbonyl group represented by R--R include a methoxycarbonyl group, an ethoxycarbonyl group, and the like.
前記一般式（１）中、Ｒ１、Ｒ１１は互いに隣接し相互
に結合して環を形成していてもよく、かがる基を具体的
に示すと、
で示される基が挙げられる。前記一般式（１１中Ｒ、Ｒ
’ 及びＲ８〜ＲＩＯで示される置換フェニル基及び
Ｒで示される置換ピリジル基の置換基の種類は特に制限
されないが、原料人手の容易さにより、ハロゲン原子、
アルキル基。In the general formula (1), R1 and R11 may be adjacent to each other and bonded to each other to form a ring, and specific examples of the bending group include the following groups. The general formula (R, R in 11)
The types of substituents of the substituted phenyl group represented by ' and R8 to RIO and the substituted pyridyl group represented by R are not particularly limited, but depending on the ease of handling raw materials, halogen atoms,
Alkyl group.
フルケニル基、アルキニル基、アルコキシ基。Flukenyl group, alkynyl group, alkoxy group.
アルキルチオ基、＝）ロ基、シアノ基、スルホ基、アル
キルカルボニル基、フルコキシカルボニル基、フルキル
スルホニル基、ヒトμキシル基が好適である。これらの
置換基のうち、アルキル基、フルケニル基、アルキニル
基、フルコキシ基、フルキルチオ基、アルキルカルボニ
ル基、アルコキシカルボニル基。Preferred are an alkylthio group, a =)ro group, a cyano group, a sulfo group, an alkylcarbonyl group, a flukoxycarbonyl group, a furkylsulfonyl group, and a human μxyl group. Among these substituents, alkyl groups, fulkenyl groups, alkynyl groups, flukoxy groups, furkylthio groups, alkylcarbonyl groups, and alkoxycarbonyl groups.
フルフキジスルホニル基を構成する炭素数は１〜６であ
ることが好適である。Ｒ、Ｒ’ 及びＲ８〜ＲＩＯで
示される置換フェニル基、Ｒ６で示される置換ピリジル
基の置換基の数は、原料人手の容易さから１〜３である
ことが好ましい。また置換基の数が複数の場合には、そ
れぞれの置換基は互いに同種または異種であってもよい
。The number of carbon atoms constituting the flufukidisulfonyl group is preferably 1 to 6. The number of substituents in the substituted phenyl group represented by R, R' and R8 to RIO and the substituted pyridyl group represented by R6 is preferably 1 to 3 from the viewpoint of ease of handling raw materials. Furthermore, when there is a plurality of substituents, each substituent may be the same or different.
前記一般式（１）中、ｎは０〜６、好ましくはθ〜３で
あることが好適である。In the general formula (1), n is preferably 0 to 6, preferably θ to 3.
本発明の前記一般式（１）中で示されるピラゾール化合
物は、次の手段によってその構造を確認することができ
る。The structure of the pyrazole compound represented by the general formula (1) of the present invention can be confirmed by the following means.
（イ）赤外吸収スペクトル（ＩＲ）を測定することによ
り、１７ Ｑ Ｏ−１６５０ｃｍ−”付近にアミド基の
カルボニル結合に基づく吸収、１６００〜１５００（１
）付近に芳香′ｆＲＫ基づく特性吸収等を観察すること
ができる。(a) By measuring the infrared absorption spectrum (IR), it was found that the absorption based on the carbonyl bond of the amide group, 1600 to 1500 (1
) Characteristic absorption based on the aroma 'fRK can be observed.
代表例として、２．４−ジクロロフェノキシ−Ｎ−エト
キシカルボニル−Ｎ −（１’、３’−ジメチル−５１
−ピラゾリル）酢酸アミドの赤外吸収スペクトルを第１
図に示した。As a representative example, 2,4-dichlorophenoxy-N-ethoxycarbonyl-N-(1',3'-dimethyl-51
-pyrazolyl) acetic acid amide
Shown in the figure.
（ロ）質量スペクトル（ＭＳ）を測定し、観察される各
ピーク（一般にはイオンの質量ｍをイオンの荷電数ｅで
除したｍ ／ ｅで表わされる数）に相当する組成式を
求めることにより、測定に供した化合物の分子量ならび
に該分子内における各原子団の結合様式を知ることがで
きる。すなわち、測定に供した試料を一般式
で表わした場合、一般に分子イオンピーク（以下、Ｍ■
と略記する）が観察されるため、測定に供した化合物の
分子量を決定することができる。(b) By measuring a mass spectrum (MS) and determining the composition formula corresponding to each peak observed (generally a number expressed as m / e, which is the mass of the ion divided by the number of charges e of the ion) It is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule. That is, when a sample subjected to measurement is expressed by a general formula, the molecular ion peak (hereinafter referred to as M
) is observed, so the molecular weight of the compound subjected to measurement can be determined.
また、前記一般式で示される化合物につ〜１てを家、
等に対応する特徴的なピークが観察され、該分子の結合
様式を知ることができる。In addition, characteristic peaks corresponding to the compounds represented by the above general formula are observed, and the bonding mode of the molecule can be known.
（ハ）１Ｈ−核磁気共鳴スペクトル（’Ｈ−ＮＭＲ）を
測定することにより、前記一般式で表わされる本発明の
化合物中に存在する水素原子の結合様式を知ることがで
きる。該化合物の ’Ｈ−ＮＭＲ（δｐｐｍ ；テトラ
メチルシラン基準１重りｐロホルム溶媒）の代表例とし
て、２．４−ジクロロフェノキシ−Ｎ −エトキシカル
ボニル−Ｎ−（１，３−ジメチルピラゾリル）酢酸アミ
ドについての１Ｈ−ＮＭＲを第２図に示す。その解析結
果を示すと次のとおりである。(c) By measuring 1H-nuclear magnetic resonance spectrum ('H-NMR), the bonding mode of hydrogen atoms present in the compound of the present invention represented by the above general formula can be determined. As a representative example of 'H-NMR (δppm; tetramethylsilane standard 1 weight p roform solvent) of the compound, 2,4-dichlorophenoxy-N-ethoxycarbonyl-N-(1,3-dimethylpyrazolyl)acetic acid amide The 1H-NMR of the compound is shown in FIG. The analysis results are as follows.
１、３６ ｐｐｍに３個分のプロトンに相当する三重線
が認められ、メチル基Ｃｅ）によるものと帰属できる。A triplet line corresponding to three protons was observed at 1.36 ppm, and can be attributed to the methyl group Ce).
２．２０ ｐｐｍ Ｋ ３個分のプロトンに相当する単
一線が認められ、メチル基（ａ）によるものと帰属でき
る。３゜６７ｐｐｍに３個分のプロトンに相当する単一
線が認められ、メチル基（ｂ）によるものと帰属できる
。４．２６ ｐｐｍに２個分のプロトンに和尚する四重
線が認められ、メチレン基（ｄ）によるものと帰属でき
る。４．９９ｐｐｍ ｋＣ２個分のプロトンに相当する
単一線が認められ、メチレン基（ｆ）によるものと帰属
できる。５．９８ ｐｐｍに１個分のプロトンに相当す
る単一線が認められ、ピラノ一ル環に置換したプロトン
（ｃ）によるものと帰属できる。６．７〜７．４ ｐｐ
ｍに３個分のプロトンに相当する多重線が認められ、ベ
ンゼン環（ｇ）に置換したプロトンによるものと帰属で
きる。A single line corresponding to three protons at 2.20 ppm K was observed and can be attributed to the methyl group (a). A single line corresponding to three protons was observed at 3°67 ppm and can be attributed to the methyl group (b). A quartet corresponding to two protons was observed at 4.26 ppm, and can be attributed to the methylene group (d). A single line corresponding to two protons at 4.99 ppm kC was observed and can be attributed to the methylene group (f). A single line corresponding to one proton was observed at 5.98 ppm, and can be attributed to the proton (c) substituted on the pyranoyl ring. 6.7-7.4pp
A multiplet corresponding to three protons was observed in m, and can be attributed to the proton substituted in the benzene ring (g).
に）元素分析によって、炭素、水素、窒素。) Carbon, hydrogen, and nitrogen by elemental analysis.
硫黄（及びハロゲンを含む場合にはハロゲン）の各重量
％を求め、さらに認知された各元素の重量％の和を１０
０から減じることにより、酸素の重量％を算出すること
ができ、従って、該化合物の組成式を決定することがで
きる。Determine each weight% of sulfur (and halogen if it contains halogen), and then add the sum of the weight% of each recognized element to 10
By subtracting from 0, the weight percent of oxygen can be calculated and therefore the compositional formula of the compound can be determined.
本発明のピラゾール化合物は、前記一般式中のＲ、Ｒ”
〜ＲＩＯの穏類援よってその性状が異なるが、一般に常
温常圧においては、無色。The pyrazole compound of the present invention has R, R'' in the general formula
-Properties vary depending on the moderation of RIO, but it is generally colorless at room temperature and pressure.
淡黄色、淡褐色の固体または液体であり、ある一定温度
以上になると分解する傾向にある。It is a light yellow or light brown solid or liquid, and tends to decompose when it exceeds a certain temperature.
本発明の化合物は、ベンゼン、エーテル。Compounds of the present invention include benzene and ether.
アセトン、フルフール、クロロポル４，７セトニトリル
、 Ｎ、Ｎ−ジメチルホルム７ミド。Acetone, furfur, chloropol 4,7cetonitrile, N,N-dimethylform 7mide.
ジメチルスルホキシド等の一般有機溶媒に可溶であるが
、水にはほとんど溶けない。It is soluble in common organic solvents such as dimethyl sulfoxide, but almost insoluble in water.
本発明の前記一般式（１）・で示されるピラゾール化合
物の製造方法は特に限定されるものではなく、どのよう
な製造方法でもよい。特に好適な製造方法を示すと次の
とおりである。The method for producing the pyrazole compound represented by the general formula (1) of the present invention is not particularly limited, and any production method may be used. A particularly preferred manufacturing method is as follows.
一般式
（ただし、Ｂ 、 Ｒ１−Ｒ６及びｎは前記一般式（１
）と同じ）
で表わされる７ミドと、一般式
％式％
（ただし、Ｒ７はアルキル基を示し、Ｘはハロゲン原子
、 ０８０．Ｒ７，０００，Ｒ’ ｔタハで表わされ
るフルキル化剤を反応〔以下、反応（１）という。〕さ
せるか、一般式
ＲＣＯＹ ・・・・・・・・・・・・・・・・・・・
・・・・・・ （４）（ただし Ｒ８は置換若しくは非
置換のアルキル基°夫たは置換若しくは非置換のフェニ
ル基を示し、Ｙはハロゲン原子、 ０ＣＯＲを示す。）
で表わされる酸ノ・ロゲン化物または酸無水物を反応〔
以下、反応（１１）という。〕させるか、一般式
％式％
（ただし、Ｒ９及びＲ１０は置換若しくは非置換のフル
キル基または置換若しくは非置換のフェニル基を示し、
２はハロゲン原子を示す。）で表わされる炭酸ハロゲン
化物を反応〔以下反応（Ｉｌ＋ ）という。〕させるか
、一般式％式％（７）
（ただし、Ｒ１０は置換若しくは非置換のアルキル基ま
たは置換若しくは非置換のフェニル基を示す。）
で表わされるインシアナートを反応〔以下、反応（１ｖ
）という。〕させることにより、前記一般式（１）で表
わされるピラゾール化合物が得られる。General formula (however, B, R1-R6 and n are the general formula (1)
) is reacted with a fullkylating agent represented by the general formula % (where R7 represents an alkyl group, X is a halogen atom, and 080.R7,000,R' Hereinafter, it will be referred to as reaction (1).] Or, the general formula RCOY
...... (4) (However, R8 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group, and Y represents a halogen atom or 0COR.) React with chloride or acid anhydride [
Hereinafter, this will be referred to as reaction (11). ] or the general formula % formula % (where R9 and R10 represent a substituted or unsubstituted furkyl group or a substituted or unsubstituted phenyl group,
2 represents a halogen atom. ) is called a reaction (hereinafter referred to as reaction (Il+)). [Hereinafter, reaction (1v
). ] By doing so, a pyrazole compound represented by the general formula (1) is obtained.
反応（１）〜（ＩＶ ）において、一般式（２）で示さ
れるアミドと一般式（３）〜（７）で示される試薬との
仕込モル比は必要忙応じて適宜決定すればよいが、通常
等モル若しくは（３）〜（７）を少し過剰に用いるのが
一般的である。また、反応（：）には一般に極性溶媒を
用いるのが好ましく、メタノール、エタノール、アセト
ン。In reactions (1) to (IV), the molar ratio of the amide represented by the general formula (2) to the reagent represented by the general formulas (3) to (7) may be determined as appropriate depending on the needs, but It is common to use equimolar amounts or a slight excess of (3) to (7). In addition, it is generally preferable to use a polar solvent for the reaction (:), such as methanol, ethanol, and acetone.
Ｎ、Ｎ−ジメチルホルムアミド、水またはこれら溶媒の
混合液等が好適に使用される。反応（ｉｌ ） 、 （
ｌｉｉ ） ＶＣは一般に有機溶媒を用いるのが好まし
く、ベンゼン、トルエン、塩化メチレン、クロロホルム
、 Ｎ、Ｎ−ジメチルホルムアミド、エーテル等が好適
に使用される。N,N-dimethylformamide, water, a mixture of these solvents, etc. are preferably used. reaction (il), (
lii) It is generally preferable to use an organic solvent for VC, and benzene, toluene, methylene chloride, chloroform, N,N-dimethylformamide, ether, etc. are preferably used.
反応における添加順序は特に限定されないが、一般に溶
媒に前記一般式（２）で示されるアミドを溶解して反応
器に仕込み、前記一般式（３）〜（７）で示される反応
試薬を攪拌下に添加するのがよい。勿論、連続的に反応
系に原料を添加し、生成した反応物を連続的に該反応系
から取り出すこともできる。反応温度は広い範囲から選
択でき、一般には一２０℃〜１５０℃、好ましくは０℃
〜１００℃の範囲で選べば十分である。反応時間は原料
の種類によっても違うが、通常５分〜１０日間、好まし
くは１〜４０時間の範囲から選べば十分である。The order of addition in the reaction is not particularly limited, but generally, the amide represented by the above general formula (2) is dissolved in a solvent and charged into a reactor, and the reaction reagents represented by the above general formulas (3) to (7) are added under stirring. It is best to add it to Of course, it is also possible to continuously add raw materials to the reaction system and to continuously take out the generated reactants from the reaction system. The reaction temperature can be selected from a wide range, generally from -20°C to 150°C, preferably 0°C.
It is sufficient to select the temperature within the range of ~100°C. Although the reaction time varies depending on the type of raw material, it is usually sufficient to select it from the range of 5 minutes to 10 days, preferably 1 to 40 hours.
また、反応中においては、攪拌を行うのが好ましい。Further, it is preferable to stir the reaction mixture during the reaction.
また、反応（１）〜（ｆｉｌ ）においては、ハロゲン
化水累または酸が副生ずるので、通常は反応系内にハロ
ゲン化水素捕捉剤を共存させることが好ましい。該ハロ
ゲン化水素捕捉剤は特に限定されず公知のものを使用す
ることができるが、一般に好適に使用される／Ｓログン
化水累捕捉剤として、トリメチ＋７４ン。Further, in reactions (1) to (fil), since halogenated water or acid is produced as a by-product, it is usually preferable to coexist a hydrogen halide scavenger in the reaction system. The hydrogen halide scavenger is not particularly limited and any known one can be used, but trimethyone+74 is generally suitably used as a /S rogonized water scavenger.
トリエチルアミン等のトリフルキルアミン；ピリジン；
ジアザビシクロオクタン；ナトリウムアルコラード；炭
酸ナトリウム；炭酸カリウム等が挙げられる。Triflukylamines such as triethylamine; pyridine;
Examples include diazabicyclooctane; sodium alcoholade; sodium carbonate; potassium carbonate and the like.
また、反応（１）〜（ＩＶ ’） においては、一般式
（２）で表わされる７ミドの反応性を高めるため、アル
カリ塩に変換して反応させる方法も好適に用いられる。Further, in reactions (1) to (IV'), in order to increase the reactivity of the 7mide represented by the general formula (2), a method of converting it into an alkali salt and reacting it is also suitably used.
一般に好適に用いられるアルカリ化試剤としては、水素
化ナトリウム、水素化リチウム、金属ナトリウム、ナト
リウム７ミド、リチウム７ミド、水酸化ナトリウム、水
酸化カリウム等が挙げられる。Examples of alkalizing reagents that are generally suitably used include sodium hydride, lithium hydride, metallic sodium, sodium 7mide, lithium 7mide, sodium hydroxide, potassium hydroxide, and the like.
反応系から目的生成物、すなわち、前記一般式（１）で
示されるピラゾール化合物を単離生成する方法は、特に
限定されず公知の方法を採用できる。例えば、反応液か
ら過剰の反応試薬及び生成した塩を除去した後、残渣を
ベンゼン、トルエン、クローホルム等の有機溶媒で抽出
する。該有機層については、芒硝。The method for isolating and producing the desired product, ie, the pyrazole compound represented by the general formula (1), from the reaction system is not particularly limited, and any known method can be employed. For example, after removing excess reaction reagents and generated salts from the reaction solution, the residue is extracted with an organic solvent such as benzene, toluene, or chloroform. For the organic layer, mirabilite.
塩化カルシウム等の乾燥剤で乾燥した彼、有機溶媒を留
去し、目的物を得る。精製手段は必要に応じて実施すれ
ばよいが、再結晶、クロマトグラフィー、真空蒸留等が
好適に使用することができる。After drying with a desiccant such as calcium chloride, the organic solvent is distilled off to obtain the desired product. Purification means may be carried out as required, but recrystallization, chromatography, vacuum distillation, etc. can be suitably used.
本発明において、前記一般式（１）で示されるピラゾー
ル化合物は新規な化合物であり、これらの化合物は、２
００．９／１０ａあるいはそれ以下の薬量でノビエ、ホ
タルイ、アゼナ等の水田中の雑草を枯死させ、かつ１０
００１／ ／ １０ ａという高濃度で使用しても水稲
に対して安全である。このように一般式（１）で示され
る化合物は除草活性が高く、選択除草活性に優れるとい
う２つの特性を有しているため除草剤として有用である
。In the present invention, the pyrazole compound represented by the general formula (1) is a new compound, and these compounds have 2
00. Kills weeds in rice fields such as wild grass, firefly, and azalea with a dose of 9/10a or less, and 10
It is safe for paddy rice even when used at a high concentration of 001//10a. As described above, the compound represented by the general formula (1) has two properties: high herbicidal activity and excellent selective herbicidal activity, and is therefore useful as a herbicide.
該ピラゾール化合物は、水田雑草に優れた除草効果を発
揮するが、特にカヤツリグサ科雑草、広葉雑草及び多年
生雑草の発芽前及び発芽後の湛水土壌処理に著しい除草
効果を示す。例えば水田において強害雑草であるホタル
イ、コナギ、７ゼナ等に対して、その発芽時だけでなく
、生育期においても優れた除草効果を示し、しかも水稲
に対しては、１．５葉期の稚苗移植においても高い安全
性を有して〜する。The pyrazole compound exhibits an excellent herbicidal effect on paddy field weeds, and particularly shows a remarkable herbicidal effect in pre-emergence and post-emergence flooded soil treatment of Cyperaceae weeds, broad-leaved weeds, and perennial weeds. For example, it shows excellent herbicidal effects against weeds that are harmful to paddy fields, such as bulrushes, grasshoppers, and 7xena, not only during germination but also during the growing season. It is highly safe even when transplanting young seedlings.
該ピラゾール化合物の水田への施用量としては、一般に
１０アール当り２ｇ〜１０００ｇ、好ましくは１０ｇ〜
５００ｇを有効成分量として使用すればよい。The amount of the pyrazole compound applied to rice fields is generally 2g to 1000g per 10 ares, preferably 10g to 1000g.
500g may be used as the amount of active ingredient.
前記一般式（１）で示される化合物が除草効果を発揮す
る水田雑草を例示すると次のとおりである。Examples of paddy field weeds on which the compound represented by the general formula (1) exhibits herbicidal effects are as follows.
特にホタルイ、タマガヤツリ、ミズガヤツリ等のカヤツ
リグサ科雑草に除草効果が高く広葉雑草、特にキカシグ
サ、７ゼナ、コナギ。Broad-leaved weeds are particularly effective against weeds of the Cyperaceae family, such as firefly, cyperus japonica, and cyperus cyperus, especially broad-leaved weeds, especially cyperus japonica, 7xena, and cyperus japonica.
アゼトウガラシ等にも除草効果が著しい。これらに次い
でイネ科雑草に対して除草効果を示すが、有効成分の使
用量を増加するとか、公知の除草剤、例えばクロルアセ
トアミド系除草剤、カーバメート系除草剤等を混合して
使用すると、さらによい効果が得られる場合が多い。It also has a remarkable herbicidal effect on red pepper etc. Next to these, it shows a herbicidal effect against grass weeds, but if the amount of active ingredients used is increased or if known herbicides such as chloracetamide herbicides and carbamate herbicides are used in combination, it becomes even more effective. Good results are often obtained.
特に効果的に除草できる雑草は、例えばイヌビエ、タイ
ヌビヱ、タマガヤツリ、ホタルイ、ミズガヤツリ、クロ
グワイ、マツバイ。Weeds that can be particularly effectively weeded are, for example, golden locust, Japanese brown locust, Japanese cypress, Japanese firefly, Japanese cypress, black croaker, and Japanese cypress.
コウキャガラ、オモダカ、ヘラオモダカ、ウリカワ、ヒ
ルムシロウセリ、ヤナギタデ、コナギ、イポクサ、ホシ
クサ、ミゾノ〜コベ、ヒメミソハギ、キカシグサ、チョ
ウジタデ、アゼムシロ、タカサブロウ、タウコギ、アメ
リカセンダングサ、アブツメ、アゼナ、アゼトウガラシ
等の水田雑草である。These are paddy field weeds such as the common chickadee, the common grass, the yellow-bellied chickadee, the yellowtail, the yellowtail, the willow knotweed, the Japanese radish, the Japanese ipokusa, the Japanese starchweed, the Japanese violet, the Japanese violet, the Japanese staghorn, the Japanese stylus, the red-spotted herb, the white-spotted herb, the white-spotted herb, the American lily, the horsetail, the Japanese azalea, and the red capsicum.
さらに前記一般式（１）で示されるピラゾール化合物は
、水田雑草と水稲との間に高度の選択性を有しているた
め、水稲の発芽時から生育期の長期間の生育段階での適
用が可能であり、処理適期幅が著しく長いすぐれた利点
を有している。また湛水直播水稲に対してきわめて安全
に適用できる利点は、該ピラゾール化合物の大きな特徴
である。Furthermore, the pyrazole compound represented by the general formula (1) has a high degree of selectivity between paddy weeds and paddy rice, so it can be applied over a long period of time from germination to the growing season of paddy rice. It has the advantage of being extremely long in processing time. Another major feature of the pyrazole compound is that it can be applied extremely safely to flooded and directly sown rice.
さらにまた、畑地の除草剤として利用するときも選択的
除草効果を発揮するので、小麦。Furthermore, wheat has a selective weeding effect when used as a herbicide in fields.
大麦、トウモロコシ、陸稲等のイネ科作物だけでなく、
大豆、ワタ、ビート等の広葉作物にも適用することがで
きる。In addition to grass crops such as barley, corn, and upland rice,
It can also be applied to broad-leaved crops such as soybeans, cotton, and beets.
また本発明の前記一般式（１）で示されるピラゾール化
合物は植物の生育に影響を及ぼすので、落葉剤、摘果剤
１発芽抑制剤、生育調節剤としても使用することができ
る。Furthermore, since the pyrazole compound represented by the general formula (1) of the present invention affects the growth of plants, it can also be used as a defoliant, a fruit thinning agent, a germination inhibitor, and a growth regulator.
本発明の前記一般式（１）で示されるピラゾール化合物
の使用態様は、特に限定されず公知の除草剤の使用態様
をそのまま利用できる。The manner of use of the pyrazole compound represented by the general formula (1) of the present invention is not particularly limited, and the manner of use of known herbicides can be used as is.
例えば、不活性固体担体、液体担体、乳化分散剤等を用
いて、粒剤、粉剤、乳剤、水利剤。For example, using inert solid carriers, liquid carriers, emulsifying dispersants, etc., granules, powders, emulsions, and water-use preparations.
錠剤、油剤、エアゾール、くん煙剤等任意の剤形にして
使用することができる。勿論、製剤上の補助剤例えば、
展着剤、希釈剤、界面活性剤などを適宜配合することも
できる。It can be used in any dosage form such as tablets, oils, aerosols, and smokes. Of course, formulation auxiliaries such as
Spreading agents, diluents, surfactants, etc. can also be blended as appropriate.
また、本発明の前記一般式（１）で示されるピラゾール
化合物は、ゴマ葉枯病菌や萎ちょう病菌等の植物病原菌
、水虫菌や大腸菌等に対しても強い抗菌活性を有してい
るため、殺菌剤としても有用である。これらの特性は公
知のピラゾール化合物では認められていなかったもので
ある。In addition, the pyrazole compound represented by the general formula (1) of the present invention has strong antibacterial activity against plant pathogenic bacteria such as sesame leaf blight and leaf wilt fungi, athlete's foot fungus, and Escherichia coli. It is also useful as a fungicide. These properties have not been observed in known pyrazole compounds.
本発明の化合物は、例えば担子菌類、そう菌類、子の５
菌類、不完全菌類及び細菌類等に属する多種病原菌に対
して広範囲に適用することができる。特に、本発明のピ
ラゾール化合物は、枯草菌、ゴマ葉枯病菌、萎ちょう病
菌、白鮮菌及び大腸菌等に優れた殺菌力を示すものであ
る。Compounds of the invention may be used, for example, in Basidiomycetes, Oriental fungi,
It can be widely applied to various pathogens belonging to fungi, Deuteromycetes, bacteria, etc. In particular, the pyrazole compound of the present invention exhibits excellent bactericidal activity against Bacillus subtilis, Sesame leaf blight, Powdery mildew, Bacillus aeruginosa, Escherichia coli, and the like.
（実施例）
本発明をさらに具体的に説明するため、以下、実施例を
挙げて説明するが、本発明はこれらの実施例に限定され
るものではない。(Examples) In order to explain the present invention more specifically, Examples will be described below, but the present invention is not limited to these Examples.
実施例 １
２．４−ジク＋ｒｐフェノキシ−Ｎ−（１’、３’−ジ
メチル−５′ −ピラジイル）酢酸アミド１．５ｇの
クロロホルム（ｉｓｍ）溶液に、１゜４−ジアザビシク
ロ（２，２，２）オクタン１．０７ｇを加え、クール蟻
酸エチル１．０４ 、ＩＦのクロロホルム（１０ｍＡり
溶液を滴下した。−晩攪拌後、反応液を氷水中に注加し
、りｐロホルムで抽出した。りｐｐホルム層を無水硫酸
ナトリウムで乾燥後、クロロホルムを留去し、残渣をシ
リカゲルクロマト（クロロホルム／アセトン）により精
製すると、無色固体が０、８１ Ｆ得られた。このもの
のＩＲを測定した結果は第１図に示すとおりである。Example 1 1°4-diazabicyclo(2,2, 2) 1.07 g of octane was added, and a solution of 1.04 g of ethyl formate and IF in chloroform (10 mA) was added dropwise. After stirring overnight, the reaction solution was poured into ice water and extracted with chloroform. After drying the pp form layer over anhydrous sodium sulfate, chloroform was distilled off and the residue was purified by silica gel chromatography (chloroform/acetone) to obtain a colorless solid of 0.81F. As shown in Figure 1.
その元素分析値は、Ｃ４９，５６％、Ｈ４，３０％、
Ｎ １０．５９％であって、組成式Ｃ１６Ｈ１？Ｃ１，
Ｎ、Ｏ，に対する計算値であるＣ ４９．７６％。Its elemental analysis values are C49.56%, H4.30%,
N 10.59%, composition formula C16H1? C1,
Calculated value for N, O, C 49.76%.
Ｈ４，４４％、 Ｎ １０．８８％によく一致した。There was good agreement with H4, 44% and N, 10.88%.
また、ＭＳを測定したところ、ｍ／ｅ ３８５にＭ■
に対応するピーク、 ｍ ／ ｅ ３４０にＭ■−ＣＩ
（，０ＣＨ８に対応するピーク、 ｍ ／ ｅに対応す
る各ピークを示した。In addition, when MS was measured, M■ was found to be m/e 385.
The peak corresponding to M■-CI at m/e 340
(The peak corresponding to 0CH8 and each peak corresponding to m/e are shown.
また、’Ｈ−ＮＭＲ（δ： ｐｐｍ ；テトラメチルシ
ラン基準１重りｐｐホルム溶媒）を測定した結果を第２
図に示した。その解析結果は次のとおりであった。In addition, the results of measuring 'H-NMR (δ: ppm; 1 weight pp form solvent based on tetramethylsilane) were
Shown in the figure. The analysis results were as follows.
１、３６ ｐｐｍにプロトン３個分の三重線を示し、（
ｅ）のメチルプ＋＝）ンに相当した。２．２０ｐｐｍに
プロトン３個分の単一線を示し、（ａ）のメチルプロト
ンに相当した。３．６７ ｐｐｍにプロトン３個分の単
一線を示し、（ｂ）のメチルプロトンに相当した。４．
２６ ｐｐｍにプロトン２個分の四重線を示し、（ｄ）
のメチレンプロトンに相当した。４．９９ ｐｐｍにプ
ロトン２個分の単一線を示し、（ｆ）のメチレンプロト
ンに相当した。５．９８ ｐｐｍにプロトン１個分の単
一線を示し、（Ｃ）のピラゾール環のプロトンに相当し
た。６．７〜７．４ ｐｐｍにプロトン３個分の多Ｍ線
を示し、Ｃ１１）のベンゼン環のプロトンに相当した。A triplet line for three protons is shown at 1.36 ppm, (
It corresponded to the methylpone in e). A single line corresponding to three protons was shown at 2.20 ppm, which corresponded to the methyl proton in (a). A single line corresponding to three protons was shown at 3.67 ppm, which corresponded to the methyl proton in (b). 4.
The quartet for two protons is shown at 26 ppm, (d)
methylene proton. A single line corresponding to two protons was shown at 4.99 ppm, which corresponded to the methylene proton in (f). A single line corresponding to one proton was shown at 5.98 ppm, which corresponded to the proton of the pyrazole ring in (C). A multi-M line corresponding to 3 protons was shown at 6.7 to 7.4 ppm, which corresponded to the proton of the benzene ring of C11).
上記の結果から、単離生成物が、２．４ジクロロフエノ
キシーＮ−エトキシカルボニル−Ｎ −（１’、３’−
ジメチル−５′ −ピラゾリル）酢酸アミドであるこ
とが明らかとなった。収率は４４．０％であった。From the above results, the isolated product is 2.4dichlorophenoxyN-ethoxycarbonyl-N-(1',3'-
It was found to be dimethyl-5'-pyrazolyl)acetic acid amide. The yield was 44.0%.
実施例 ２
２．４−ジクロルフェノキシ−Ｎ−（１’、３’−ジメ
チル−５１−ピラゾリル）酢酸アミド２、ＯＩをあらか
じめ調製した水酸化ナトリウムｏ、 ｓ １ ｊｉのエ
タノール水溶液４０ｍ１（エタノール／水＝１：３）に
溶解した後、ジメチル硫酸１．６１．９を滴下した。−
晩攪拌後、析出した固体を濾過し、よく水で洗浄した後
、これを乾燥すると、無色固体が１．５５ Ｉ！得られ
た。このもののＩＲを測定した結果は第３図に示すとお
りである。Example 2 2.4-Dichlorophenoxy-N-(1',3'-dimethyl-51-pyrazolyl)acetic acid amide 2, OI was prepared in advance with 40 ml of an ethanol aqueous solution of sodium hydroxide o, s 1 ji (ethanol/ After dissolving in water (1:3), 1.61.9 g of dimethyl sulfate was added dropwise. −
After stirring overnight, the precipitated solid was filtered, thoroughly washed with water, and dried, resulting in a colorless solid of 1.55 I! Obtained. The results of measuring the IR of this material are shown in FIG.
その元素分析値は、Ｃ５１，４６％、Ｈ４，４９％、
Ｎ １２．９１％であって、組成式Ｃ、、Ｈ工。Its elemental analysis values are C51.46%, H4.49%,
N 12.91%, composition formula C, H engineering.
ＣｔＢＮ８０．に対する計算値であるＣ５１．２４％、
Ｈ４，６１％、 Ｎ １２．８０％によく一致した。ま
た、ＭＳを測定したところ、ｍ ／ ｅ３２７にＭ”
Ｋ対応するピーク、 ｍ ／ ｅ ３１３に（ＭＣ９−
ＣＨ８）に対応するピーク、 ｍ ／ ｅに対応する各
ピークを示した。また、’Ｈ−ＮＭＲ（δ： ｐｐ！ｎ
：テトラメチルシラン基準１重クロロホルム溶媒）を
測定した結果を第４図に示した。その解析結果は次のと
おりであった。CtBN80. C51.24%, which is the calculated value for
It was in good agreement with H4, 61% and N 12.80%. In addition, when we measured the MS, we found that M” in m/e327.
K corresponding peak, m/e at 313 (MC9-
The peak corresponding to CH8) and each peak corresponding to m/e are shown. In addition, 'H-NMR (δ: pp!n
: Tetramethylsilane standard monochloroform solvent) The results are shown in FIG. The analysis results were as follows.
２、２１ ｐｐｍ Ｋプ＋＝）７３個分の単一線を示し
、（ａ）のメチルプロトンに相当した。３．１９ｐｐｍ
にプロトン３個分の単一線を示し、（ｄ）のメチルプロ
トンに相当した。３．６２ ｐｐｍにプロトン３個分の
単一線を示し、（ｂ）のメチルプロトンに相当した。４
．４５ ｐｐｍにプロトン２個分の単一線を示し、（ｅ
）のメチレンプロトンに相当した。５．８９ｐｐｍＫプ
ロトン１個分の単一線を示し、（ｅ）のピラゾール環の
プロトンに相当した。６．５〜７．９ ｐｐｍにプロト
ン３個分の多重線を示し、（ｆ）のベンゼン環のプロト
ンに相当した。2.21 ppm K+=) 73 single lines were shown, which corresponded to the methyl protons in (a). 3.19ppm
shows a single line for three protons, which corresponds to the methyl proton in (d). A single line corresponding to three protons was shown at 3.62 ppm, which corresponded to the methyl proton in (b). 4
．． A single line for two protons is shown at 45 ppm, (e
) was equivalent to the methylene proton. A single line corresponding to one 5.89 ppmK proton was shown, which corresponded to the proton of the pyrazole ring in (e). A multiplet of three protons was shown at 6.5 to 7.9 ppm, which corresponded to the proton of the benzene ring in (f).
上記の結果から、単離生成物が、２．４−ジクロロフェ
ノキシ−Ｎ−メチル−Ｎ−（１’。From the above results, the isolated product is 2,4-dichlorophenoxy-N-methyl-N-(1').
３′−ジメチル−５′ −ピラゾリル）酢ｌ！１２７
ミドであることが明らかとなった。収率は７４．２％で
あった。3'-dimethyl-5'-pyrazolyl) vinegar l! 127
It was revealed that it was Mido. The yield was 74.2%.
実施例 ３
実施例１及び実施例２等と同様な方法により、種々の下
記一般式で示される化合物、Ｏ
（ただし、Ｒ＝ＣＯＲ、Ｒ＝Ｃ０ＯＲ。Example 3 Various compounds represented by the following general formulas, O (where R=COR, R=C0OR), were prepared in the same manner as in Examples 1 and 2.
Ｒ７＝Ｃ０ＮＨＲ” の場合とＡ 、 Ｒ、Ｒ”〜１
１０及びｎは第１〜８表に記した。）
を合成した。合成した化合物の収出１兄素分析値を第１
〜８表に示した。In the case of R7=C0NHR” and A, R, R”~1
10 and n are listed in Tables 1-8. ) was synthesized. The first elemental analysis value of the synthesized compound is
-8 Shown in Table.
また、表中の結合位置■及び■は、それぞ飴 Ｒ′′ に結合している位置を示す。In addition, the bond positions ■ and ■ in the table are for candy, respectively. R'' Indicates the position where it is connected to.
更にまた、第１表における略記はそれぞれ次に示すとお
りである。Furthermore, the abbreviations in Table 1 are as shown below.
Ｅｔ ；エチル基、ｎ−Ｐｒ；ノルマルプルピル基、１
ｓｏ−Ｐｒ’、イソプロピル基、ｔ−Ｂｕ；ターシャリ
−ブチル基。Et; ethyl group, n-Pr; normal propyl group, 1
so-Pr', isopropyl group, t-Bu; tertiary-butyl group.
１１間昭６３−３１３７７３ （１６）１８開昭６３−
３１３７７３（１８）
１１開昭６３−３１３７’／Ｊ Ｌどｂノ製剤例１（粒
剤）
実施例１で合成した化合物２重量部、ジオクチルサクシ
ネート１重量部、リグニンスルホン酸ソーダ３重号部、
ベントナイト３０重量部、及びタルク６４重量部をよく
混合粉砕し、水を加えて混練した後、造粒乾燥し、１４
〜３２メツシユに整粒して２％粒剤を得た。11 1983-313773 (16)18 1888 63-
313773 (18) 11 Kaisho 63-3137'/J L-dob formulation example 1 (granules) 2 parts by weight of the compound synthesized in Example 1, 1 part by weight of dioctyl succinate, 3 parts by weight of sodium ligninsulfonate ,
30 parts by weight of bentonite and 64 parts by weight of talc were thoroughly mixed and pulverized, water was added and kneaded, and the mixture was granulated and dried.
The granules were sized to ~32 meshes to obtain 2% granules.
製剤例２（水利剤）
実施例２で合成した化合物１０重量部、ポリオキシエチ
レンノニルフェニルエーテル２重量部、微粉クレー４０
重量部、及びジ−クライト４８重量部をハンマーミルで
粉砕混合して１０％水利剤を得た。Formulation Example 2 (Irrigation agent) 10 parts by weight of the compound synthesized in Example 2, 2 parts by weight of polyoxyethylene nonylphenyl ether, 40 parts by weight of fine clay
Parts by weight and 48 parts by weight of Zeekrite were pulverized and mixed in a hammer mill to obtain a 10% irrigation agent.
製剤例３（乳剤）
実施例１で合成した化合物２０重量部、キシレン７０重
Ｊｔ部、ポリオキシエチレンフルキル７リルエーテル５
重量部、及びアルキルベンゼンスルホン酸ソーダ５重量
部を混合溶解して２０％乳剤を得た。Formulation example 3 (emulsion) 20 parts by weight of the compound synthesized in Example 1, 70 parts by weight of xylene, 5 parts by weight of polyoxyethylene furkyl 7lyl ether
Parts by weight and 5 parts by weight of sodium alkylbenzenesulfonate were mixed and dissolved to obtain a 20% emulsion.
実施例 ４
１／８ Ｂ ５０アールの磁製ポットに水を加えて攪拌
した水田土壌（沖積壌土）を充填し水田雑草を播種した
後３葉期のイネ苗（品種＝７キニシキ）を深さ２儂に移
植し、水を加えて２Ｃの湛水状態にした。次いで実施例
１゜実施例２及び実施例３で得られた各化合物の水利剤
の水希釈液を雑草発芽時に所定量滴下処理した。処理後
平均気温２５℃の温室内で生育させ、３週間後に各供試
化合物の除草効果を調査した結果を第９表に示した。た
だし表中に示した広葉とは、アゼナ、キカシグサ。Example 4 A 1/8 B 50 are porcelain pot was filled with paddy soil (alluvial loam) that had been stirred with water, and after sowing paddy weeds, rice seedlings at the 3-leaf stage (variety = 7 Kinishiki) were placed at a depth The plants were transplanted to 2 ml and water was added to make them submerged at 2 C. Next, a predetermined amount of the water diluted water solutions of the compounds obtained in Example 1, Example 2, and Example 3 was dropped at the time of weed germination. After treatment, the plants were grown in a greenhouse at an average temperature of 25°C, and three weeks later, the herbicidal effects of each test compound were investigated. The results are shown in Table 9. However, the broad leaves shown in the table are Azena and Kikashigusa.
７ゼトウガラシなどを言う。評価は６段階とし、除草効
力の評価は下記のようにＯ〜５の数字で表わした。7. It refers to hot peppers, etc. The evaluation was on a 6-level scale, and the evaluation of herbicidal efficacy was expressed as a number from 0 to 5 as shown below.
０・・・・・・・抑草率 ０〜 ９％１−＠・・
―・・ 〃 １０〜２９％２ＩＩ・・・・・・
〃 ３０〜４９％３−−−＠―・・ 〃
５０〜６９％４・＠＋１１１・・・ 〃 ７０〜
８９％５・・・・・・・ 〃 ９０〜１００％移
植イネの薬害に関しては、草丈１分けつ数、全型（風乾
量）の対無処理区比を算出し、３つの要因のもつとも値
の悪いものをとって、θ〜５で評価した。0...Weed suppression rate 0~9%1-@...
--- 〃 10~29%2II...
〃 30～49%3---＠――・・ 〃
50~69%4・@+111...〃70~
89%5・・・・・・〃 90-100% Regarding the chemical damage of transplanted rice, we calculated the ratio of plant height and number of divisions and all types (air dry amount) to untreated plots, and calculated the value of the three factors. The worst ones were selected and evaluated on a scale of θ~5.
０・・・・・対無処理区比 １００％１−ＩＩＩ
Ｉ・命 〃 ９０〜９９
％２・・、、＠８０〜８９ｏ／ｆ＋
３−＠−・ 〃 ６０〜７９％４、、−−
− ／／ ４０〜５９％５＠・・ψ・
〃 ０〜３９％実施例 ５
１．５％寒天を含む栄養培地を１２１℃で１５分加熱殺
菌した後、５０℃まで冷却し、これにあらかじめ生育さ
せておいた菌体または胞子を無菌水に懸濁したものを入
れて良く混合し、シャーレに注入して平板に固化させた
。0...Ratio to untreated area 100% 1-III
I・Life〃 90～99
%2...@80~89o/f+ 3-@-・ 〃60~79%4,,--
− // 40~59%5@・・ψ・
〃 0-39% Example 5 A nutrient medium containing 1.5% agar was heat sterilized at 121°C for 15 minutes, then cooled to 50°C, and the cells or spores grown in advance were added to sterile water. The suspension was added, mixed well, poured into a petri dish, and solidified into a flat plate.
実施例１で合成した２、４−ジクロロフェノキシ−Ｎ−
エトキシカルボニル−Ｎ−（１’、３’−ジメチル−５
′ −ピラゾリル）酢酸７ミドを１５％含有している
メタノール溶液に、直径８Ｈの同温口紙を浸し、口紙上
で余剰分を除き、固化した寒天培地上に置いた。約３０
℃で２４〜４８時間培養後、阻止円の直径を測定した。2,4-dichlorophenoxy-N- synthesized in Example 1
Ethoxycarbonyl-N-(1',3'-dimethyl-5
A piece of isothermal paper with a diameter of 8H was immersed in a methanol solution containing 15% of 7mide (pyrazolyl'-pyrazolyl)acetate, the excess was removed on the paper, and the mixture was placed on the solidified agar medium. Approximately 30
After 24-48 hours of incubation at °C, the diameter of the inhibition zone was measured.
試験細菌、かびとして、エツシエリツチア・コリＢ （
Ｅａｅｈｅｒｉｃｈｉａ Ｃｏ１ｔ Ｂ ） ＊バチラ
ス・サズチリス（Ｂａｔｉｌｌｕｇ ｓｕｂｔｉｌｉｍ
）。As a test bacterium and mold, Escherichia coli B (
Eaeherichia Colt B) *Batillug subtilim
).
アスペルギルス・ニゲル（Ａｓｐｅｒｇｉｌｌｕａｎｉ
ｇｅｒ ） 、コクリオポラス・ミャペ７ナス（Ｃｏ
ｃｈｌｉｏ’ｂｏｌｕｓ ｍ１ｙａｂａａｎｕａ ）
、 ）す＝＋フィト７ ” ルブラム（Ｔｒｉｃｈｏｐ
ｈｙｔｏｎｒｕｂｒｕｍ） 、フサリウム争オキシスポ
ラム（Ｆｕａａｒｉｕｍ ｏｘｙｓｐｏｒｕｍ ）を用
いて行った。Aspergillus niger (Aspergillus niger)
ger), Cochliopolus myape 7 eggplant (Co
chlio'bolus mlyabaanua)
, )su=+phyto7” Rubrum (Trichop
hytonrubrum) and Fusarium oxysporum.
抗菌試験の結果を第１０表に示した。The results of the antibacterial test are shown in Table 10.
第 １０ 表
実施例 ６
実施例２及び実施例３で合成した化合物を実施例５と同
様な方法で抗菌試験を行い、阻止円の直径を測定した。Table 10 Example 6 The compounds synthesized in Examples 2 and 3 were subjected to an antibacterial test in the same manner as in Example 5, and the diameter of the inhibition circle was measured.
その結果を第１１表に示した。ただし、効果のないもの
については−で表わした。The results are shown in Table 11. However, items with no effect are indicated by -.
第１図及び第２図は実施例１で、第３図及び第４図は実
施例２で得られたピラゾール化合物のＩＲ及び’Ｈ−Ｎ
ＭＲスペクトルをそれぞれ示す。Figures 1 and 2 show Example 1, and Figures 3 and 4 show the IR and 'H-N of the pyrazole compound obtained in Example 2.
MR spectra are shown respectively.
Claims (1)
は非置換のフェニル基を示し、Ｒ＾１、Ｒ＾２、Ｒ＾３
、Ｒ＾４及びＲ＾５は同種または異種の水素原子、ハロ
ゲン原子、置換若しくは非置換のアルキル基、アルコキ
シ基、アルキルチオ基、ニトロ基、シアノ基またはアル
コキシカルボニル基を示し、また、Ｒ＾１及びＲ＾２は
互いに隣接し、一緒になつて環を形成してもよく、Ｒ＾
６は置換若しくは非置換のアルキル基、置換若しくは非
置換のフェニル基または置換若しくは非置換のピリジル
基を示し、Ｒ＾７はアルキル基またはＣＯＲ＾８、ＣＯ
ＯＲ＾９、ＣＯＮＨＲ＾１＾０で表わされる基を示し、
Ｒ＾８、Ｒ＾９及びＲ＾１＾０は置換若しくは非置換の
アルキル基または置換若しくは非置換のフェニル基を示
し、Ａは炭素原子または窒素原子を示し、ｎは０または
正の整数を示す。）で表わされるピラゾール化合物。[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (However, R represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted phenyl group, R^1, R^2, R^3
, R^4 and R^5 represent the same or different hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkoxy groups, alkylthio groups, nitro groups, cyano groups or alkoxycarbonyl groups, and R^1 and R^2 are adjacent to each other and may be taken together to form a ring, R^
6 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted pyridyl group, and R^7 is an alkyl group or COR^8, CO
Indicates a group represented by OR^9, CONHR^1^0,
R^8, R^9 and R^1^0 represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group, A represents a carbon atom or a nitrogen atom, and n represents 0 or a positive integer. show. ) pyrazole compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14797887A JPS63313773A (en) | 1987-06-16 | 1987-06-16 | Pyrazole compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14797887A JPS63313773A (en) | 1987-06-16 | 1987-06-16 | Pyrazole compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63313773A true JPS63313773A (en) | 1988-12-21 |
Family
ID=15442400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14797887A Pending JPS63313773A (en) | 1987-06-16 | 1987-06-16 | Pyrazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63313773A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306694A (en) * | 1991-01-18 | 1994-04-26 | Rhone-Poulenc Inc. | Pesticidal 1-(2-pyridyl)-pyrazole |
| WO1995034560A1 (en) * | 1994-06-10 | 1995-12-21 | Bayer Aktiengesellschaft | N-heterocyclyl-heteroaryloxyacetamides |
| WO1996017840A1 (en) * | 1994-12-06 | 1996-06-13 | Agrevo Uk Limited | Heterocyclyl substituted hydroxyacetamide derivatives as fongicides |
| WO1996021653A1 (en) * | 1995-01-13 | 1996-07-18 | Bayer Aktiengesellschaft | Acylated 5-aminopyrazoles and the use thereof to combat animal parasites |
| US5556873A (en) * | 1993-02-24 | 1996-09-17 | Rhone-Poulenc Inc. | Pesticidal 1-aryl-5-(substituted alkyl (thio) amido)pyrazoles |
| WO2000011951A3 (en) * | 1998-08-26 | 2000-05-25 | Bayer Ag | Use of 5-amino-pyrazol-derivatives for combating micro-organisms |
| WO2002008196A1 (en) * | 2000-07-25 | 2002-01-31 | Sankyo Company, Limited | 5-(m-CYANOBENZYLAMINO)PYRAZOLE DERIVATIVES |
| WO2002023986A1 (en) * | 2000-08-25 | 2002-03-28 | Sankyo Company, Limited | 4-acylaminopyrazole derivatives |
| WO2002024656A1 (en) * | 2000-09-22 | 2002-03-28 | Nihon Nohyaku Co., Ltd. | N-(4-pyrazolyl)amide derivatives, chemicals for agricultural and horticultural use, and usage of the same |
| WO2002094793A1 (en) * | 2001-05-23 | 2002-11-28 | Basf Aktiengesellschaft | Acylated 4-aminopyrazoles |
| WO2004058724A1 (en) * | 2002-12-25 | 2004-07-15 | Sumitomo Chemical Company, Limited | Phenylpyrazole compound and method of controlling plant disease with the same |
| EP2196453A1 (en) * | 2008-12-10 | 2010-06-16 | Cellvir | Novel substituted aryl derivatives, their process of preparation and their therapeutical uses as anti-HIV agents |
| CN108069984A (en) * | 2016-11-18 | 2018-05-25 | 沈阳中化农药化工研发有限公司 | Substituted five-membered heterocycle compound of the ring containing pyrimido and its preparation method and application |
| JP2018531236A (en) * | 2015-09-28 | 2018-10-25 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | Acylated N- (1,2,5-oxadiazol-3-yl)-, N- (1,3,4-oxadiazol-2-yl)-, N- (tetrazol-5-yl)- And N- (triazol-5-yl) -arylcarboxamides and their use as herbicides |
| CN109535070A (en) * | 2018-12-27 | 2019-03-29 | 青岛清原化合物有限公司 | Pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application |
-
1987
- 1987-06-16 JP JP14797887A patent/JPS63313773A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306694A (en) * | 1991-01-18 | 1994-04-26 | Rhone-Poulenc Inc. | Pesticidal 1-(2-pyridyl)-pyrazole |
| US5556873A (en) * | 1993-02-24 | 1996-09-17 | Rhone-Poulenc Inc. | Pesticidal 1-aryl-5-(substituted alkyl (thio) amido)pyrazoles |
| WO1995034560A1 (en) * | 1994-06-10 | 1995-12-21 | Bayer Aktiengesellschaft | N-heterocyclyl-heteroaryloxyacetamides |
| WO1996017840A1 (en) * | 1994-12-06 | 1996-06-13 | Agrevo Uk Limited | Heterocyclyl substituted hydroxyacetamide derivatives as fongicides |
| WO1996021653A1 (en) * | 1995-01-13 | 1996-07-18 | Bayer Aktiengesellschaft | Acylated 5-aminopyrazoles and the use thereof to combat animal parasites |
| US5843978A (en) * | 1995-01-13 | 1998-12-01 | Bayer Aktiengesellschaft | Acylated 5-aminopyrazoles and the use thereof to combat animal parasites |
| US5981566A (en) * | 1995-01-13 | 1999-11-09 | Bayer Aktiengesellschaft | Acylated 5-aminopyrazoles and the use thereof to combat animal parasites |
| US6100288A (en) * | 1995-01-13 | 2000-08-08 | Bayer Aktiengesellschaft | Acylated 5-aminopyrazoles and the use thereof to combat animal parasites |
| WO2000011951A3 (en) * | 1998-08-26 | 2000-05-25 | Bayer Ag | Use of 5-amino-pyrazol-derivatives for combating micro-organisms |
| WO2002008196A1 (en) * | 2000-07-25 | 2002-01-31 | Sankyo Company, Limited | 5-(m-CYANOBENZYLAMINO)PYRAZOLE DERIVATIVES |
| WO2002023986A1 (en) * | 2000-08-25 | 2002-03-28 | Sankyo Company, Limited | 4-acylaminopyrazole derivatives |
| WO2002024656A1 (en) * | 2000-09-22 | 2002-03-28 | Nihon Nohyaku Co., Ltd. | N-(4-pyrazolyl)amide derivatives, chemicals for agricultural and horticultural use, and usage of the same |
| WO2002094793A1 (en) * | 2001-05-23 | 2002-11-28 | Basf Aktiengesellschaft | Acylated 4-aminopyrazoles |
| WO2004058724A1 (en) * | 2002-12-25 | 2004-07-15 | Sumitomo Chemical Company, Limited | Phenylpyrazole compound and method of controlling plant disease with the same |
| EP2196453A1 (en) * | 2008-12-10 | 2010-06-16 | Cellvir | Novel substituted aryl derivatives, their process of preparation and their therapeutical uses as anti-HIV agents |
| WO2010066847A1 (en) * | 2008-12-10 | 2010-06-17 | Cellvir | Novel substituted aryl derivatives, their process of preparation and their therapeutical uses as anti-hiv agents |
| JP2018531236A (en) * | 2015-09-28 | 2018-10-25 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | Acylated N- (1,2,5-oxadiazol-3-yl)-, N- (1,3,4-oxadiazol-2-yl)-, N- (tetrazol-5-yl)- And N- (triazol-5-yl) -arylcarboxamides and their use as herbicides |
| CN108069984A (en) * | 2016-11-18 | 2018-05-25 | 沈阳中化农药化工研发有限公司 | Substituted five-membered heterocycle compound of the ring containing pyrimido and its preparation method and application |
| CN108069984B (en) * | 2016-11-18 | 2021-02-05 | 沈阳中化农药化工研发有限公司 | Substituted five-membered heterocyclic compound containing pyrimido ring and preparation method and application thereof |
| CN109535070A (en) * | 2018-12-27 | 2019-03-29 | 青岛清原化合物有限公司 | Pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application |
| CN109535070B (en) * | 2018-12-27 | 2022-03-29 | 青岛清原化合物有限公司 | Pyridyloxycarboxylate derivative, preparation method thereof, herbicidal composition and application |
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