JP2861087B2 - N-acyl-5-pyrazolecarboxamides and insecticides and acaricides containing the same as an active ingredient - Google Patents
N-acyl-5-pyrazolecarboxamides and insecticides and acaricides containing the same as an active ingredientInfo
- Publication number
- JP2861087B2 JP2861087B2 JP1205292A JP20529289A JP2861087B2 JP 2861087 B2 JP2861087 B2 JP 2861087B2 JP 1205292 A JP1205292 A JP 1205292A JP 20529289 A JP20529289 A JP 20529289A JP 2861087 B2 JP2861087 B2 JP 2861087B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrogen atom
- atom
- acyl
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002917 insecticide Substances 0.000 title claims description 16
- 230000000895 acaricidal effect Effects 0.000 title claims description 10
- 239000004480 active ingredient Substances 0.000 title claims description 8
- 239000000642 acaricide Substances 0.000 title claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 5
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims 1
- -1 se c- butyl Chemical group 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 27
- 239000000203 mixture Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 241001556089 Nilaparvata lugens Species 0.000 description 5
- 241001454295 Tetranychidae Species 0.000 description 5
- 235000013601 eggs Nutrition 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 241000238876 Acari Species 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 241000239290 Araneae Species 0.000 description 3
- 241000255925 Diptera Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 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
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 3
- 150000002576 ketones Chemical class 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
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 230000035899 viability Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000004797 2,2,2-trichloroethoxy group Chemical group ClC(CO*)(Cl)Cl 0.000 description 2
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 2
- 125000006012 2-chloroethoxy group Chemical group 0.000 description 2
- 125000004791 2-fluoroethoxy group Chemical group FCCO* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- 241001414720 Cicadellidae Species 0.000 description 2
- 241000258937 Hemiptera Species 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 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
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 235000021332 kidney beans Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 125000004706 n-propylthio group Chemical group C(CC)S* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- MIDWNRQXTXNCAL-UHFFFAOYSA-N 4-chloro-5-ethyl-2-methylpyrazole-3-carboxamide Chemical compound CCC1=NN(C)C(C(N)=O)=C1Cl MIDWNRQXTXNCAL-UHFFFAOYSA-N 0.000 description 1
- 241000256118 Aedes aegypti Species 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 241001672694 Citrus reticulata Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000336797 Eoeurysa flavocapitata Species 0.000 description 1
- 241001466042 Fulgoromorpha Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 241000238814 Orthoptera Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 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
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([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
- 239000012046 mixed solvent Substances 0.000 description 1
- RFBIIXCJFYHQCT-UHFFFAOYSA-N n-[[4-(trifluoromethyl)phenyl]methyl]propanamide Chemical compound CCC(=O)NCC1=CC=C(C(F)(F)F)C=C1 RFBIIXCJFYHQCT-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004708 n-butylthio group Chemical group C(CCC)S* 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
- 125000006093 n-propyl sulfinyl group Chemical group 0.000 description 1
- 125000006124 n-propyl sulfonyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100000194 ovacidal Toxicity 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規なＮ−アシル−５−ピラゾールカルボキ
サミド類およびこれを有効成分とする殺虫、殺ダニ剤に
関する。The present invention relates to novel N-acyl-5-pyrazolecarboxamides and insecticides and acaricides containing the same as an active ingredient.
本願発明の化合物と類似の構造を有し、殺虫、殺ダニ
活性を有するものが、特開昭64−25763号公報、特開平
１−156964号公報等に記載されているが、本発明のＮ−
アシル−５−ピラゾールカルボキサミド類については全
く記載されていない。Compounds having a structure similar to that of the compound of the present invention and having insecticidal and acaricidal activity are described in JP-A-64-25763, JP-A-1-156964 and the like. −
No mention is made of acyl-5-pyrazolecarboxamides.
近年、殺虫剤の長年の使用により害虫に抵抗性が生
じ、従来の殺虫剤による防除が困難となっている。例え
ば代表的殺虫剤である有機リン剤、カーバメート剤に対
しては広く抵抗性害虫が発生し防除が困難となってい
る。また、近年注目されてきた合成ピレスロイド系殺虫
剤に対しても抵抗性の発達が報告されている。一方、有
機リン剤あるいはカーバメート剤のあるものは毒性が高
く、またあるものは残留性により生態系を乱すため、極
めて憂慮すべき状況となっている。従って、従来の殺虫
剤に抵抗性を示す害虫に対しても優れた防除効果を示
し、しかも低毒性かつ低残留性の新規な殺虫剤の開発が
期待されている。In recent years, long-term use of insecticides has produced resistance to pests, making it difficult to control with conventional insecticides. For example, organic insecticides and carbamates, which are typical insecticides, have a wide variety of resistant pests and are difficult to control. In addition, the development of resistance to synthetic pyrethroid insecticides, which have recently attracted attention, has been reported. On the other hand, some of the organophosphates and carbamates are highly toxic, and some of them disturb the ecosystem due to persistence, which is extremely alarming. Therefore, development of a novel insecticide which exhibits an excellent control effect even on pests which are resistant to conventional insecticides and which has low toxicity and low residue is expected.
本発明者らは、かかる状況に対処すべく鋭意研究を行
った結果、優れた殺虫剤ダニ活性を有する新規なＮ−ア
シル−５−ピラゾールカルボキサミド類を見出し、本発
明を完成するに至った。The present inventors have conducted intensive studies in order to cope with such a situation, and as a result, have found novel N-acyl-5-pyrazolecarboxamides having excellent insecticide mite activity, and have completed the present invention.
すなわち本発明の要旨は、下記一般式（Ｉ）で表わさ
れるＮ−アシル−５−ピラゾールカルボキサミド類及び
これを有効成分として含有する殺虫、殺ダニ剤に存す
る。That is, the gist of the present invention resides in N-acyl-5-pyrazolecarboxamides represented by the following general formula (I) and insecticides and acaricides containing the same as an active ingredient.
（上記式中、R1は水素原子、C1〜C4のアルキル基または
C3〜C6のシクロアルキル基を示し、Ｘは水素原子、ハロ
ゲン原子、C1〜C3のアルキル基またはC1〜C3のアルコキ
シ基を示す。R1とＸは一緒になって を形成してもよく、R6は水素原子、メチル基またはエチ
ル基を示す。 (In the above formula, R 1 is a hydrogen atom, a C 1 -C 4 alkyl group or
C 3 a cycloalkyl group -C 6, X is a hydrogen atom, a halogen atom, an alkyl group or a C 1 -C 3 alkoxy group C 1 -C 3. R 1 and X come together R 6 represents a hydrogen atom, a methyl group or an ethyl group.
R2は水素原子、C1〜C5のアルキル基、C2〜C3のアルケ
ニル基、C1〜C3のハロアルキル基、C1〜C3のアルコキシ
基、C2〜C4のアルコキシアルキル基、フェニル基または
ベンジル基を示し、R3は水素原子またはメチル基を示
す。R 2 is a hydrogen atom, C 1 -C alkyl group 5, C 2 -C 3 alkenyl group, a haloalkyl group of C 1 ~C 3, C 1 ~C 3 alkoxy groups, C 2 -C 4 alkoxyalkyl A phenyl group or a benzyl group; R 3 represents a hydrogen atom or a methyl group;
R4およびR5はそれぞれ独立して、水素原子、ハロゲン
原子、C1〜C5のアルキル基、C3〜C5のアルケニル基、C3
〜C5のアルキニル基、C3〜C6のシクロアルキル基、C1〜
C4のアルコキシ基、C1〜C4のアルキルチオ基、C1〜C4の
ハロアルコキシ基、トリフルオロメチル基またはトリメ
チルシリル基を示す。R 4 and R 5 are each independently a hydrogen atom, a halogen atom, an alkyl group of C 1 -C 5, alkenyl group of C 3 ~C 5, C 3
Alkynyl group -C 5, a cycloalkyl group of C 3 ~C 6, C 1 ~
An alkoxy group having C 4, alkylthio group of C 1 -C 4, haloalkoxy group C 1 -C 4, a trifluoromethyl group or a trimethylsilyl group shown.
Ａは−CH−または窒素原子を示し、Ａが−CH−を示す
場合、R4及びR5の一方は であってもよい。A represents a -CH- or nitrogen atom, indicating A is -CH-, one of R 4 and R 5 are It may be.
R7およびR8はそれぞれ独立して水素原子、ハロゲン原
子、C1〜C3のアルキル基、C1〜C3のアルコキシ基、C1〜
C3のアルキルチオ基、C1〜C3のハロアルコキシ基、ニト
ロ基、シアノ基、トリフルオロメチル基、C1〜C3のアル
キルスルフィニル基またはC1〜C3のアルキルスルホニル
基を示し、Ｂは−CH−または窒素原子を示す。） 以下、本発明を詳細に説明する。R 7 and R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group of C 1 -C 3, alkoxy group of C 1 ~C 3, C 1 ~
Alkylthio group C 3, a haloalkoxy group C 1 -C 3, a nitro group, a cyano group, a trifluoromethyl group, an alkylsulfinyl group or a C 1 -C 3 alkylsulfonyl group having C 1 -C 3, B Represents -CH- or a nitrogen atom. Hereinafter, the present invention will be described in detail.
一般式（Ｉ）において、R1は水素原子；メチル基、エ
チル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル
基、イソブチル基、sec−ブチル基、ｔ−ブチル基等のC
1〜C4の直鎖または分岐鎖アルキル基；またはシクロプ
ロピル基、シクロブチル基、シクロペンチル基、シクロ
ヘキシル基等のC3〜C6のシクロアルキル基を示し、好ま
しくはC1〜C3のアルキル基である。In the general formula (I), R 1 is a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group or the like;
1 -C 4 straight or branched chain alkyl group; or a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cycloalkyl group of C 3 -C 6, such as a cyclohexyl group, preferably an alkyl group of C 1 -C 3 It is.
Ｘは水素原子；フッ素原子、塩素原子、臭素原子、ヨ
ウ素原子等のハロゲン原子；メチル基、エチル基、ｎ−
プロピル基、イソプロピル基等のC1〜C3の直鎖または分
岐鎖アルキル基；またはメトキシ基、エトキシ基、ｎ−
プロポキシ基、イソプロポキシ基等のC1〜C3の直鎖また
は分岐鎖アルコキシ基を示し、好ましくは、水素原子；
フッ素原子、塩素原子、臭素原子等のハロゲン原子；メ
チル基；エチル基またはメトキシ基である。また、Ｘは
R1と一緒になって を形成してもよい（但し、R6は水素原子、メチル基また
はエチル基である）。X is a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, and n-
Propyl group, a straight-chain or branched-chain alkyl group of C 1 -C 3 such as an isopropyl group; or a methoxy group, an ethoxy group, n-
A C 1 -C 3 linear or branched alkoxy group such as a propoxy group or an isopropoxy group, preferably a hydrogen atom;
A halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a methyl group; an ethyl group or a methoxy group. X is
With R 1 (Where R 6 is a hydrogen atom, a methyl group or an ethyl group).
R2は水素原子；メチル基、エチル基、ｎ−プロピル
基、イソプロピル基、ｎ−ブチル基、イソブチル基、se
c−ブチル基、ｔ−ブチル基、ｎ−アミル基、イソアミ
ル基、ｔ−ペンチル基、ネオペンチル基等のC1〜C5の直
鎖または分岐鎖アルコキシ基；ビニル基、アリル基等の
C2〜C3のアルケニル基；フルオロメチル基、クロロメチ
ル基、ブロモメチル基、１−クロロエチル基、２−クロ
ロエチル基、２−ブロモエチル基、３−クロロプロピル
基、ジフルオロメチル基、トリフルオロメチル基、2,2,
2−トリフルオロエチル等のC1〜C3のハロアルキル基；
メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロ
ポキシ基等のC1〜C3のアルコキシ基；メトキシメチル
基、エトキシメチル基、エトキシエチル基等のC2〜C4の
アルコキシアルキル基；フェニル基またはベンジル基を
示し、好ましくは、水素原子、C1〜C3のアルキル基、C1
〜C3のハロアルキル基、C2〜C3のアルコキシアルキル基
である。R 2 is a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, se
c- butyl, t- butyl group, n- amyl group, isoamyl group, t-pentyl group, a linear or branched alkoxy group having C 1 -C 5, such as a neopentyl group; vinyl group, and allyl group
Alkenyl C 2 -C 3; fluoromethyl group, chloromethyl group, bromomethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-bromoethyl, 3-chloropropyl group, a difluoromethyl group, a trifluoromethyl group, 2,2,
2-haloalkyl group C 1 -C 3 trifluoroethyl and the like;
Methoxy group, ethoxy group, n- propoxy group, an alkoxy group of C 1 -C 3 such as an isopropoxy group, a phenyl group, methoxymethyl group, ethoxymethyl group, an alkoxyalkyl group of C 2 -C 4, such as ethoxyethyl group Or a benzyl group, preferably a hydrogen atom, a C 1 -C 3 alkyl group, C 1
Haloalkyl group -C 3, an alkoxyalkyl group of C 2 -C 3.
R3は水素原子またはメチル基を示す。R 3 represents a hydrogen atom or a methyl group.
R4およびR5は、それぞれ独立して、水素原子；フッ素
原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原
子；メチル基、エチル基、ｎ−プロピル基、イソプロピ
ル基、ｎ−ブチル基、イソブチル基、sec−ブチル基、
ｔ−ブチル基、ｎ−アミル基、イソアミル基、ｔ−ペン
チル基、ネオペンチル基等のC1〜C5の直鎖または分岐鎖
アルキル基；アリル基、メタリル基、２−ブテニル基等
のC3〜C5のアルケニル基；プロパルギル基等のC3〜C5の
アルキル基；シクロプロピル基、シクロブチル基、シク
ロペンチル基、シクロヘキシル基等のC3〜C5のシクロア
ルキル基；メトキシ基、エトキシ基、ｎ−ブトキシ基、
イソブトキシ基、sec−ブトキシ基、ｔ−ブトキシ基等
のC1〜C4の直鎖または分岐鎖アルコキシ基；モノフルオ
ロメトキシ基、ジフルオロメトキシ基、トリフルオロメ
トキシ基、２−フルオロエトキシ基、２−クロロエトキ
シ基、2,2,2−トリフルオロエトキシ基、2,2,2−トリク
ロロエトキシ基、３−クロロプロポキシ基、３−ブロモ
プロポキシ基、3,3,3−トリフルオロプロポキシ基、2,
2,3,3−テトラフルオロプロポキシ基、2,2,3,3,3−ペン
タフルオロプロポキシ基、2,2−ジクロロ−3,3,3−トリ
フルオロプロポキシ基、１−トリフルオロメチルエトキ
シ基、1,3−ジフルオロ−２−プロポキシ基、1,1,1,3,
3,3−ヘキサフルオロ−２−プロポキシ基、3,3,3−トリ
クロロプロポキシ基、４−クロロブトキシ基、4,4,4−
トリフルオロブトキシ基、3,3,4,4,4−ペンタフルオロ
ブトキシ基、2,2,3,3,4,4−ヘキサフルオロブトキシ
基、2,2,3,4,4,4−ヘキサフルオロブトキシ基、2,2,3,
3,4,4−ヘプタフルオロブトキシ基、１−トリフルオロ
メチルプロキシ基、1,1,1,2,2−ペンタフルオロ−３−
ブトキシ基等のC1〜C4の直鎖または分岐鎖ハロアルコキ
シ基；トリフルオロメチル基；トリメチルシリル基；ま
たはメチルチオ基、エチルチオ基、ｎ−プロピルチオ
基、イソプロピルチオ基、ｎ−ブチルチオ基、イソブチ
ルチオ基、sec−ブチルチオ基、ｔ−ブチルチオ基等のC
1〜C4の直鎖または分岐鎖アルキルチオ基を示す。Ａは
−CH−または窒素原子を示し、Ａが−CH−を示す場合、
R4、R5の一方は であってもよい。（但し、R7、R8はそれぞれ独立して、
水素原子；フッ素原子、塩素原子、臭素原子、ヨウ素原
子等のハロゲン原子；メチル基、エチル基、ｎ−プロピ
ル基、イソプロピル基等のC1〜C3の直鎖または分岐鎖ア
ルキル基；メトキシ基、エトキシ基、ｎ−プロポキシ
基、イソプロポキシ基等のC1〜C3の直鎖または分岐鎖ア
ルコキシ基；モノフルオロメトキシ基、ジフルオロメト
キシ基、トリフルオロメトキシ基、２−フルオロエトキ
シ基、２−クロロエトキシ基、2,2,2−トリフルオロエ
トキシ基、2,2,2−トリクロロエトキシ基、３−クロロ
プロポキシ基、３−ブロモプロポキシ基、3,3,3−トリ
フルオロプロポキシ基、2,2,3,3−テトラフルオロプロ
ポキシ基、2,2,3,3,3−ペンタフルオロプロポキシ基、
2,2−ジクロロ−3,3,3−トリフルオロプロポキシ基、１
−トリフルオロメチルエトキシ基、1,3−ジフルオロ−
２−プロポキシ基、1,1,1,3,3,3−ヘキサフルオロ−２
−プロポキシ基、3,3,3−トリクロロプロポキシ基等のC
1〜C3の直鎖または分岐鎖ハロアルコキシ基；メチルチ
オ基、エチルチオ基、ｎ−プロピルチオ基、イソプロピ
ルチオ基等のC1〜C3の直鎖または分岐鎖アルキルチオ
基；メチルスルフィニル基、エチルスルフィニル基、ｎ
−プロピルスルフィニル基、イソプロピルスルフィニル
基等のC1〜C3の直鎖または分岐鎖アルキルスルフィニル
基；メチルスルホニル基、エチルスルホニル基、ｎ−プ
ロピルスルホニル基、イソプロピルスルホニル基等のC1
〜C3の直鎖または分岐鎖アルキルスルホニル基；ニトロ
基；シアノ基またはトリフルオロメチル基を示し、Ｂは
−CH−または窒素原子を示す。） 次に、本発明化合物の製法について述べる。R 4 and R 5 are each independently a hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group; Isobutyl group, sec-butyl group,
t-butyl group, n- amyl group, isoamyl group, t-pentyl group, a linear or branched alkyl group of C 1 -C 5, such as a neopentyl group; an allyl group, methallyl group, 2-C 3, such as butenyl alkenyl group ~C 5; C 3 ~C 5 alkyl group such as propargyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, a cycloalkyl group of C 3 -C 5 such as a cyclohexyl group; methoxy group, an ethoxy group, n-butoxy group,
Isobutoxy, sec- butoxy, t-straight or branched chain alkoxy group of C 1 -C 4 or butoxy group; a mono fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 2-fluoroethoxy group, 2- Chloroethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, 3-chloropropoxy group, 3-bromopropoxy group, 3,3,3-trifluoropropoxy group, 2,
2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 2,2-dichloro-3,3,3-trifluoropropoxy group, 1-trifluoromethylethoxy group , 1,3-difluoro-2-propoxy group, 1,1,1,3,
3,3-hexafluoro-2-propoxy group, 3,3,3-trichloropropoxy group, 4-chlorobutoxy group, 4,4,4-
Trifluorobutoxy group, 3,3,4,4,4-pentafluorobutoxy group, 2,2,3,3,4,4-hexafluorobutoxy group, 2,2,3,4,4,4-hexa Fluorobutoxy group, 2,2,3,
3,4,4-heptafluorobutoxy group, 1-trifluoromethyl proxy group, 1,1,1,2,2-pentafluoro-3-
Straight or branched chain haloalkoxy group of C 1 -C 4 or butoxy group; trifluoromethyl group; a trimethylsilyl group; or a methylthio group, ethylthio group, n- propylthio group, isopropylthio group, n- butylthio group, isobutylthio C, a sec-butylthio group, a t-butylthio group, etc.
A linear or branched alkylthio group having 1 -C 4. A represents -CH- or a nitrogen atom, and when A represents -CH-,
One of R 4 and R 5 is It may be. (However, R 7 and R 8 are each independently
Hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom; a methyl group, an ethyl group, n- propyl group, a straight-chain or branched-chain alkyl group of C 1 -C 3 such as isopropyl group; methoxy group , ethoxy, n- propoxy, linear or branched alkoxy group C 1 -C 3 such as an isopropoxy group; a mono fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 2-fluoroethoxy group, 2- Chloroethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, 3-chloropropoxy group, 3-bromopropoxy group, 3,3,3-trifluoropropoxy group, 2, 2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group,
2,2-dichloro-3,3,3-trifluoropropoxy group, 1
-Trifluoromethylethoxy group, 1,3-difluoro-
2-propoxy group, 1,1,1,3,3,3-hexafluoro-2
C such as propoxy group, 3,3,3-trichloropropoxy group
Straight or branched chain haloalkoxy group of 1 -C 3; methylthio group, ethylthio group, n- propylthio group, a straight-chain or branched-chain alkylthio group of C 1 -C 3 such as isopropylthio; methylsulfinyl group, ethylsulfinyl Group, n
- propyl sulfinyl group, a linear or branched chain alkylsulfinyl group of C 1 -C 3 such as isopropyl sulfinyl group; methylsulfonyl group, ethylsulfonyl group, n- propylsulfonyl group, C 1 such as isopropylsulfonyl group
A C 3 -C 3 linear or branched alkylsulfonyl group; a nitro group; a cyano group or a trifluoromethyl group; and B represents —CH— or a nitrogen atom. Next, a method for producing the compound of the present invention will be described.
前記一般式（Ｉ）で表わされる本発明の化合物は、例
えば下記反応式に従って製造することができる。The compound of the present invention represented by the general formula (I) can be produced, for example, according to the following reaction formula.
〔上記反応式中、R1、R2、R3、R4、R5、ＸおよびＡは前
記一般式（Ｉ）中で定義した通りであり、Ｙは塩素原子
または臭素原子を示す。〕 上記反応は、ベンゼン、トルエンまたはキシレン等の
芳香族炭化水素；アセトン、メチルエチルケトンまたは
メチルイソブチルケトン等のケトン類；クロロホルム、
トリクレンまたは塩化メチレン等のハロゲン化炭化水
素；酢酸メチルまたは酢酸エチル等のエステル類；テト
ラヒドロフラン、アセトニトリル、ジオキサン、N,N−
ジメチルホルムアミド、Ｎ−メチルピロリドンまたはジ
メチルスルホキシド等の極性溶媒中；または無溶媒で、
塩基の存在下または非存在下、０℃から使用する溶媒の
沸点まで、好ましくは40℃から使用する溶媒の沸点まで
の温度範囲で行うことができる。塩基としては、水素化
ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カ
リウム、ピリジンまたはトリエチルアミン等が用いられ
る。 [In the above reaction formula, R 1 , R 2 , R 3 , R 4 , R 5 , X and A are as defined in the general formula (I), and Y represents a chlorine atom or a bromine atom. The above reaction is carried out by an aromatic hydrocarbon such as benzene, toluene or xylene; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; chloroform;
Halogenated hydrocarbons such as trichlene or methylene chloride; esters such as methyl acetate or ethyl acetate; tetrahydrofuran, acetonitrile, dioxane, N, N-
In a polar solvent such as dimethylformamide, N-methylpyrrolidone or dimethylsulfoxide; or without solvent,
The reaction can be carried out in the presence or absence of a base at a temperature ranging from 0 ° C. to the boiling point of the solvent used, preferably from 40 ° C. to the boiling point of the solvent used. As the base, sodium hydride, potassium hydroxide, sodium carbonate, potassium carbonate, pyridine or triethylamine is used.
〔上記反応式中、R1、R2、R3、R4、R5、ＸおよびＡは前
記一般式（Ｉ）中で定義した通りであり、Ｚは塩素原
子、臭素原子または を示す〕 上記反応はベンゼン、トルエンまたはキシレン等の芳
香族炭化水素；アセトン、メチルエチルケトンまたはメ
チルイソブチルケトン等のケトン類；クロロホルム、ト
リクレンまたは塩化メチレン等のハロゲン化炭化水素；
酢酸メチルまたは酢酸エチル等のエステル類；テトラヒ
ドロフラン、アセトニトリル、ジオキサン、N,N−ジメ
チルホルムアミド、Ｎ−メチルピロリドンまたはジメチ
ルスルホキシド等の極性溶媒中；または無溶媒で、塩基
の存在下または非存在下、０℃から使用する溶媒の沸点
まで、好ましくは40℃から使用する溶媒の沸点までの温
度範囲で、行うことができる。 [In the above reaction formula, R 1 , R 2 , R 3 , R 4 , R 5 , X and A are as defined in the general formula (I), and Z is a chlorine atom, a bromine atom or The above reaction is carried out with an aromatic hydrocarbon such as benzene, toluene or xylene; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a halogenated hydrocarbon such as chloroform, tricrene or methylene chloride;
Esters such as methyl acetate or ethyl acetate; in a polar solvent such as tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone or dimethylsulfoxide; or in the absence of a solvent in the presence or absence of a base, The reaction can be carried out in a temperature range from 0 ° C. to the boiling point of the solvent used, preferably from 40 ° C. to the boiling point of the solvent used.
塩基としては、水素化ナトリウム、水酸化ナトリウ
ム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、
ピリジンまたはトリエチルアミン等が用いられる。As the base, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Pyridine or triethylamine is used.
また一般式（Ｖ）においてＺが を示す場合には、上記反応条件において、塩基の非存在
下、酸触媒を使用することにより一般式（Ｉ）の化合物
を得ることも可能である。酸触媒としては、硫酸、リン
酸またはＰ−トルエンスルホン酸等が用いられる。In the general formula (V), Z is In the case where is represented, it is also possible to obtain a compound of the general formula (I) by using an acid catalyst under the above reaction conditions in the absence of a base. Sulfuric acid, phosphoric acid, P-toluenesulfonic acid, or the like is used as the acid catalyst.
なお、上記一般式（II）で表わされる化合物は、例え
ば、Annalen der Chemie,Justus Liebig's,536,97（193
8），上記一般式（Ｖ）で表わされる化合物は、例え
ば、特開昭64−25763号公報記載の方法に準じて各々製
造することができる。The compound represented by the general formula (II) is described, for example, in Annalen der Chemie, Justus Liebig's, 536 , 97 (193)
8) The compounds represented by the general formula (V) can be produced, for example, according to the method described in JP-A-64-25763.
一般式（Ｉ）で示される化合物は下記の鞘翅目、鱗翅
目、半翅目、直翅目、双翅目等の昆虫及び植物または動
物に寄生するダニ目の卵、幼虫に著しい防除活性を有す
るが勿論これらのみに限定されるものではない。The compound represented by the general formula (I) has a remarkable controlling activity on the following insects such as Coleoptera, Lepidoptera, Hemiptera, Orthoptera and Diptera and eggs and larvae of the mite order parasitic on plants or animals. However, it is needless to say that the present invention is not limited to these.
１半翅目 ；セジロウンカ、トビイロウンカ、ヒメトビ
ウンカ等のウンカ類、ツマグロヨコバイ、オオヨコバイ
等のヨコバイ類、モモアカアブサムシ等のアブラムシ類 ２鱗翅目 ；ハスモンヨトウ、ニカメイチュウ、コブノ
メイガ等 ３鞘翅目 ；アズキゾウムシ等 ４双翅目 ；イエバエ、ネッタイシマカ、アカイエカ等 ５ハダニ類；ナミハダニ、ニセナミハダニ、ミカンハダ
ニ等 ６マダニ類；オウシマダニ、カズキダニ等の動物寄生ダ
ニ 一般式（Ｉ）で示される本発明の化合物を殺虫剤ある
いは殺ダニ剤として作用する場合には単独で用いてもよ
いが、通常は従来の農薬と同様に補助剤を用いて乳剤、
粉剤、水和剤、液剤などの形態に製剤し、そのまま、あ
るいは希釈して使用する。補助剤としては、殺虫剤の製
剤に用いられる通常のものが用いられる。例えばタル
ク、カオリン、珪藻土、粘土、デンプンなどの固形担
体、水、シクロヘキサン、ベンゼン、キシレン、トルエ
ン等の炭化水素類、クロロベンゼンのようなハロゲン化
炭化水素類、エーテル類、ジメチルホルムアミド等のア
ミド類、ケトン類、アルコール類、アセトニトリル等の
ニトリル類などの溶媒、その他公知の乳化剤、分散剤な
どの界面活性剤があげられる。1 Hemiptera; Planthoppers such as brown planthoppers, brown planthoppers and brown planthoppers; leafhoppers such as black leafhoppers and leafhoppers; aphids such as peach moth aphids; Diptera; house fly, Aedes aegypti, mosquitoes, etc. 5 spider mites; spider mites, spider mites, mandarin mites, etc. 6 ticks; animal parasitic mites such as ox tick, kazuki mite, etc. When acting as an acaricide, it may be used alone, but usually an emulsion using an auxiliary like a conventional pesticide,
Formulated in the form of powders, wettable powders, liquids and the like, and used as such or diluted. As the adjuvant, the usual ones used in the preparation of insecticides are used. For example, talc, kaolin, diatomaceous earth, clay, solid carriers such as starch, water, hydrocarbons such as cyclohexane, benzene, xylene, toluene, halogenated hydrocarbons such as chlorobenzene, ethers, amides such as dimethylformamide, Solvents such as ketones, alcohols, nitriles such as acetonitrile, and other known surfactants such as emulsifiers and dispersants.
また、所望によっては他の殺虫剤、殺ダニ剤、殺菌
剤、昆虫生育調整物質、植物生育調整物質などと混用ま
たは併用することも可能である。If desired, it can be mixed or used in combination with other insecticides, acaricides, fungicides, insect growth regulating substances, plant growth regulating substances, and the like.
製剤された殺虫殺ダニ剤中の有効成分濃度は、特に限
定されるものではないが、通常、粉剤では0.5〜20重量
％、好ましくは１〜10重量％、水和剤は１〜90重量％、
好ましくは10〜80重量％、乳剤は１〜90重量％、好まし
くは10〜40重量％の有効成分を含有する。The concentration of the active ingredient in the prepared insecticide and acaricide is not particularly limited, but usually 0.5 to 20% by weight, preferably 1 to 10% by weight in powders, and 1 to 90% by weight in wettable powders. ,
Preferably 10-80% by weight, the emulsion contains 1-90% by weight, preferably 10-40% by weight, of the active ingredient.
上記一般式（Ｉ）で示される化合物を殺虫剤として使
用する場合、通常活性成分が５〜1000ppm、好ましくは1
0〜500ppmの濃度範囲で使用する。When the compound represented by the above general formula (I) is used as an insecticide, the active ingredient is usually 5 to 1000 ppm, preferably 1 to 1000 ppm.
Use in the concentration range of 0 to 500 ppm.
次に本発明化合物の製造例、製剤例及び試験例によっ
て本発明を更に具体的に説明するが、本発明はその要旨
を越えない限り、以下の例に限定されるものではない。Next, the present invention will be described more specifically with reference to Production Examples, Formulation Examples and Test Examples of the compound of the present invention. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例１ Ｎ−アセチル−Ｎ−（４−ｎ−ブチルベンゼン）−４−
クロロ−３−エチル−１−メチル−５−ピラゾールカル
ボキサミドの製造 Ｎ−（４−ｎ−ブチルベンゼン）−４−クロロ−３−
エチル−１−メチル−５−ピラゾールカルボキサミド3.
34g、無水酢酸15ml、濃硫酸0.05mlの混合物を110℃で４
時間加熱撹拌した。減圧下、濃縮した後、氷水に注ぎ、
酢酸エチルエステルで抽出した。酢酸エチルエステル層
を炭酸ナトリウム水溶液、水、飽和食塩水にて洗浄し
た。無水硫酸ナトリウムで乾燥後、減圧下濃縮した。残
渣をシリカゲルカラムクロマトグラフィーで精製し、下
記表−１記載の化合物（No.24）1.95gを得た。得られた
化合物のNMR、IRを以下に示す。1 H−NMR（CDCl3）δppm;0.90（ｔ、3H）、1.26（ｔ、3
H）、1.1〜1.7（ｍ、4H）、2.39（ｓ、3H）、2.64
（ｑ、2H）、2.4〜2.7（ｍ、2H）、3.47（ｓ、3H）、4.
95（brs、2H）、6.95（ｄ、2H）、7.10（ｄ、2H） IR（Liquid Film）cm-1;2932、1707、1686、1448、136
7、1337、1292、1207、974 実施例２ Ｎ−プロピオニル−Ｎ−（４−トリフルオロメチルベン
ジル）−３−シクロプロピル−１−メチル−５−ピラゾ
ールカルボキサミドの製造 ３−シクロプロピル−１−メチル−５−ピラゾールカ
ルボン酸クロリド0.63gとＮ−（４−トリフルオロメチ
ルベンジル）プロピオンアミド0.65gのトリクレン15ml
溶液を20時間加熱還流した。冷却後、氷水に注ぎクロロ
ホルムで抽出した。クロロホルム層を炭酸ナトリウム水
溶液、水、飽和食塩水にて洗浄した。無水硫酸ナトリウ
ムで乾燥後、減圧下濃縮した。残渣をシリカゲルカラム
クロマトグラフィーで精製し、下記表−１記載の化合物
（NO.2）0.55gを得た。Example 1 N-acetyl-N- (4-n-butylbenzene) -4-
Preparation of chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide N- (4-n-butylbenzene) -4-chloro-3-
Ethyl-1-methyl-5-pyrazolecarboxamide 3.
A mixture of 34 g, 15 ml of acetic anhydride and 0.05 ml of concentrated sulfuric acid was added at 110 ° C for 4 hours.
The mixture was heated and stirred for an hour. After concentration under reduced pressure, pour into ice water,
Extracted with ethyl acetate. The ethyl acetate layer was washed with an aqueous solution of sodium carbonate, water and saturated saline. After drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.95 g of the compound (No. 24) shown in Table 1 below. The NMR and IR of the obtained compound are shown below. 1 H-NMR (CDCl 3 ) δ ppm; 0.90 (t, 3H), 1.26 (t, 3
H), 1.1-1.7 (m, 4H), 2.39 (s, 3H), 2.64
(Q, 2H), 2.4-2.7 (m, 2H), 3.47 (s, 3H), 4.
95 (brs, 2H), 6.95 (d, 2H), 7.10 (d, 2H) IR (Liquid Film) cm -1 ; 2932, 1707, 1686, 1448, 136
7, 1337, 1292, 1207, 974 Example 2 Preparation of N-propionyl-N- (4-trifluoromethylbenzyl) -3-cyclopropyl-1-methyl-5-pyrazolecarboxamide 3-cyclopropyl-1-methyl Trichlorene 15 ml of 0.63 g of -5-pyrazolecarboxylic acid chloride and 0.65 g of N- (4-trifluoromethylbenzyl) propionamide
The solution was heated at reflux for 20 hours. After cooling, the mixture was poured into ice water and extracted with chloroform. The chloroform layer was washed with an aqueous solution of sodium carbonate, water and saturated saline. After drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 0.55 g of the compound (NO.2) shown in Table 1 below.
得られた化合物のNMR、IRを以下に示す。1 H−NMR（CDCl3）δppm;0.53−1.1（ｍ、4H）、1.12
（ｔ、3H）、1.7〜2.1（ｍ、1H）、2.56（ｑ、2H）、3.
89（ｓ、3H）、5.06（ｓ、2H）、6.13（ｓ、1H）、7.36
（ｄ、2H）、7.63（ｄ、2H）、 IR（Liquid Film）cm-1;1686、1665、1323、1185、116
4、1123、1066 実施例３ 実施例１および２の方法に準じて、下記表−１記載の
化合物を得た。粘稠な液体として得たものについてその
1H−NMRを表−２に示す。The NMR and IR of the obtained compound are shown below. 1 H-NMR (CDCl 3 ) δ ppm; 0.53-1.1 (m, 4H), 1.12.
(T, 3H), 1.7-2.1 (m, 1H), 2.56 (q, 2H), 3.
89 (s, 3H), 5.06 (s, 2H), 6.13 (s, 1H), 7.36
(D, 2H), 7.63 (d, 2H), IR (Liquid Film) cm -1 ; 1686, 1665, 1323, 1185, 116
4, 1123, 1066 Example 3 According to the method of Examples 1 and 2, compounds shown in Table 1 below were obtained. About what was obtained as a viscous liquid,
Table 2 shows 1 H-NMR.
次に本発明化合物を製剤例を示す。なお、以下に
「部」、「％」とあるのは、それぞれ「重量部」、「重
量％」を意味する。 Next, Formulation Examples of the compound of the present invention are shown. Hereinafter, "parts" and "%" mean "parts by weight" and "% by weight", respectively.
製剤例1:水和剤 表−１の本発明の化合物20部、カープレックス＃80
（塩野義製薬社、商標名）20部、N,Nカオリンクレー
（土屋カオリン社、商標名）55部、高級アルコール硫酸
エステル系界面活性剤ソルボール8070（東邦化学社、商
標名）５部を配合し、均一に混合粉砕して、有効成分40
％を含有する水和剤を得た。Formulation Example 1: wettable powder 20 parts of the compound of the present invention shown in Table 1, Carplex # 80
(Shionogi Pharmaceutical Co., Ltd., 20 parts), N, N kaolin clay (Tsuchiya Kaolin Co., Ltd., 55 parts), higher alcohol sulfate ester surfactant Sorbol 8070 (Toho Chemical Company, trade name) 5 parts And uniformly mix and grind to obtain 40
% Wettable powder was obtained.
製剤例2:粉剤 表−１の本発明の化合物２部、クレー（日本タルク社
製）93部、ホワイトカーボン５部を均一に混合粉砕し
て、２％粉剤を製造した。Formulation Example 2: Dust 2% of the compound of the present invention in Table 1, 93 parts of clay (manufactured by Nippon Talc), and 5 parts of white carbon were uniformly mixed and pulverized to produce a 2% dust.
製剤例3:乳剤 表−１の本発明の化合物20部を、キシレン35部および
ジメチルホルムアミド30部からなる混合溶媒に溶解さ
せ、これにポリオキシエチレン系界面活性剤ソルボール
3005X（東邦化学社、商標名）15部を加えて、有効成分2
0％を含有する乳剤を得た。Formulation Example 3: Emulsion 20 parts of the compound of the present invention shown in Table 1 was dissolved in a mixed solvent consisting of 35 parts of xylene and 30 parts of dimethylformamide, and the resulting mixture was dissolved in a polyoxyethylene surfactant solbol.
Add 15 parts of 3005X (trade name, Toho Chemical Co., Ltd.)
An emulsion containing 0% was obtained.
製剤例4:フロアブル剤 表−１の本発明化合物30部、あらかじめ混合しておい
たエチレングリコール８部、ソルボールAC3032（東邦化
学社、商標名）５部、キサンタンガム0.1部を水56.9部
に良く混合分散させた。次にこのスラリー状混合物を、
ダイノミル（シンマルエンタープライゼス社）で湿式粉
砕して、有効成分30％を含有する安定なフロアブル剤を
得た。Formulation Example 4: Flowable agent 30 parts of the compound of the present invention shown in Table 1, 8 parts of ethylene glycol previously mixed, 5 parts of Solbol AC3032 (trade name of Toho Chemical Co., Ltd.), and 0.1 part of xanthan gum are thoroughly mixed with 56.9 parts of water. Dispersed. Next, this slurry-like mixture is
It was wet-pulverized with a Dynomill (Shinmaru Enterprises) to obtain a stable flowable agent containing 30% of the active ingredient.
試験例１ ナミハダニの成虫に対する効果 インゲン葉のリーフディスク（径2cm）に10頭のナミ
ハダニ雌成虫を放虫する。これに製剤例１の処法に従っ
て製剤された本発明化合物を水で所定濃度に希釈した液
5mlを、回転式散布塔（みずほ理化製）を用いて散布し
た。（１濃度、２反復。） 処理24時間後に、幼虫の生死を調査し、殺ダニ率
（％）を求めた。その結果を、表−３に示す。Test Example 1 Effect of adult spider mite on adult leaves 10 adult female spider mites were released on leaf disks (diameter 2 cm) of kidney beans. A solution prepared by diluting the compound of the present invention prepared according to the method of Preparation Example 1 to a predetermined concentration with water.
5 ml was sprayed using a rotary spray tower (manufactured by Mizuho Rika). (1 concentration, 2 repetitions.) Twenty-four hours after the treatment, the larvae were examined for viability and the acaricidal rate (%) was determined. Table 3 shows the results.
試験例２ ナミハダニの卵に対する効果 インゲン葉のリーフディスク（径2cm）に５頭のナミ
ハダニ雌成虫を放虫する。放虫後20時間リーフディスク
に産卵させ、その後雌成虫は除去した。これに、製剤例
１の処法に従って製剤された本発明化合物を水で所定濃
度に希釈した液5mlを回転式散布塔（みずほ理化製）を
用い散布した。（１濃度、２反復） 処理５日後に未ふ化卵数とふ化幼虫数を調査し、殺卵
率（％）を求めた。その結果を、下記表−３に示す。Test Example 2 Effect of spider mite on eggs Five adult spider mites were released on leaf disks (2 cm in diameter) of kidney beans. The eggs were laid on leaf disks for 20 hours after the release, and the female adults were then removed. To this, 5 ml of a solution prepared by diluting the compound of the present invention prepared according to the method of Preparation Example 1 to a predetermined concentration with water was sprayed using a rotary spray tower (manufactured by Mizuho Rika). (1 concentration, 2 repetitions) Five days after the treatment, the number of unhatched eggs and the number of hatched larvae were examined, and the ovicidal rate (%) was determined. The results are shown in Table 3 below.
試験例３ ナミハダニの成虫と卵に対する低濃度での効果 化合物No.6、８、10、11、22の５化合物について、試
験例１および２と同じ試験法で、濃度だけを表−４に示
す低濃度に変え、その効果を調査した。結果を下記表−
４に示す。 Test Example 3 Effect at Low Concentration on Adults and Eggs of Spider Mite, Compound No. 6, 8, 10, 11 and 22 Table 5 shows the concentrations of only 5 compounds in the same test method as in Test Examples 1 and 2. The effect was investigated after changing to a low concentration. The results are shown in the following table.
It is shown in FIG.
試験例４ トビイロウンカの幼虫に対する効果 ガラス円筒（径3cm、長さ17cm）に稲の芽出し苗をセ
ットし、トビイロウンカ４令幼虫を５頭放虫する。これ
に、製剤例３の処法に従って製剤された本発明の化合物
を水で希釈した液0.5mlを、散布塔（みずほ理化製）を
用い散布した。（１濃度、４反復。） 処理24時間後に、幼虫の生死を調査し、殺虫率（％）
を求めた。その結果を、下記表−５に示す。 Test Example 4 Effect of brown planthopper on larvae A sprout of rice seedlings was set on a glass cylinder (diameter 3 cm, length 17 cm), and five four-stage larvae of brown planthopper were released. To this, 0.5 ml of a solution prepared by diluting the compound of the present invention with water prepared according to the method of Preparation Example 3 was sprayed using a spray tower (Mizuho Rika). (1 concentration, 4 repetitions.) After 24 hours from the treatment, the larvae were examined for viability and the mortality (%)
I asked. The results are shown in Table 5 below.
試験例５ コナガの幼虫に対する効果 キャベツ切葉（５×5cm）を、製剤例１の処法に従っ
て製剤された本発明化合物を水で希釈した液に１分間浸
漬した。浸漬後風乾し、プラスチックカップ（径7cm）
に入れ、これにコナガの３令幼虫を５頭放虫した。（１
濃度、２反復。） 放虫２日後に幼虫に生死を調査し、殺虫率（％）を求
めた。その結果を下記表−５に示す。Test Example 5 Effect of Japanese moth larvae on larvae Cut cabbage leaves (5 x 5 cm) were immersed in a solution prepared by diluting the compound of the present invention prepared with the method of Preparation Example 1 with water for 1 minute. Air-dry after immersion, plastic cup (diameter 7cm)
, And 5 of the 3rd instar larvae of the Japanese moth were released. (1
Concentration, 2 replicates. 2 days after release, the larvae were examined for viability and the mortality (%) was determined. The results are shown in Table 5 below.
〔発明の効果〕 上記実施例からも明らかなように本発明化合物は優れ
た殺虫、殺ダニ作用を有する。 [Effects of the Invention] As is clear from the above Examples, the compounds of the present invention have excellent insecticidal and acaricidal activity.
Claims (2)
−５−ピラゾールカルボキサミド類。 （上記式中、R1は水素原子、C1〜C4のアルキル基または
C3〜C6のシクロアルキル基を示し、Ｘは水素原子、ハロ
ゲン原子、C1〜C3のアルキル基またはC1〜C3のアルコキ
シ基を示す。R1とＸは一緒になって を形成してもよく、R6は水素原子、メチル基またはエチ
ル基を示す。 R2は水素原子、C1〜C5のアルキル基、C2〜C3のアルケニ
ル基、C1〜C3のハロアルキル基、C1〜C3のアルコキシ
基、C2〜C4のアルコキシアルキル基、フェニル基または
ベンジル基を示し、R3は水素原子またはメチル基を示
す。 R4およびR5はそれぞれ独立して、水素原子、ハロゲン原
子、C1〜C5のアルキル基、C3〜C5のアルケニル基、C3〜
C5のアルキニル基、C3〜C6のシクロアルキル基、C1〜C4
のアルコキシ基、C1〜C4のアルキルチオ基、C1〜C4のハ
ロアルコキシ基、トリフルオロメチル基またはトリメチ
ルシリル基を示す。Ａは−CH−または窒素原子を示し、
Ａが−CH−を示す場合、R4及びR5の一方は であってもよい。 R7およびR8はそれぞれ独立して、水素原子、ハロゲン原
子、C1〜C3のアルキル基、C1〜C3のアルコキシ基、C1〜
C3のアルキルチオ基、C1〜C3のハロアルコキシ基、ニト
ロ基、シアノ基、トリフルオロメチル基、C1〜C3のアル
キルスルフィニル基またはC1〜C3のアルキルスルホニル
基を示し、Ｂは−CH−または窒素原子を示す。）1. N-acyl-5-pyrazolecarboxamides represented by the following general formula (I). (In the above formula, R 1 is a hydrogen atom, a C 1 -C 4 alkyl group or
C 3 a cycloalkyl group -C 6, X is a hydrogen atom, a halogen atom, an alkyl group or a C 1 -C 3 alkoxy group C 1 -C 3. R 1 and X come together R 6 represents a hydrogen atom, a methyl group or an ethyl group. R 2 is a hydrogen atom, C 1 -C alkyl group 5, C 2 -C 3 alkenyl group, a haloalkyl group of C 1 ~C 3, C 1 ~C 3 alkoxy groups, C 2 -C 4 alkoxyalkyl A phenyl group or a benzyl group; R 3 represents a hydrogen atom or a methyl group; R 4 and R 5 are each independently a hydrogen atom, a halogen atom, an alkyl group of C 1 -C 5, alkenyl group of C 3 ~C 5, C 3 ~
Alkynyl group C 5, cycloalkyl group of C 3 ~C 6, C 1 ~C 4
And a C 1 -C 4 alkylthio group, a C 1 -C 4 haloalkoxy group, a trifluoromethyl group or a trimethylsilyl group. A represents -CH- or a nitrogen atom,
When A represents -CH-, one of R 4 and R 5 is It may be. R 7 and R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group of C 1 -C 3, alkoxy group of C 1 ~C 3, C 1 ~
Alkylthio group C 3, a haloalkoxy group C 1 -C 3, a nitro group, a cyano group, a trifluoromethyl group, an alkylsulfinyl group or a C 1 -C 3 alkylsulfonyl group having C 1 -C 3, B Represents -CH- or a nitrogen atom. )
るＮ−アシル−５−ピラゾールカルボキサミド類を有効
成分とする殺虫、殺ダニ剤。2. An insecticide and acaricide comprising an N-acyl-5-pyrazolecarboxamide represented by the general formula (I) according to claim 1 as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1205292A JP2861087B2 (en) | 1989-08-08 | 1989-08-08 | N-acyl-5-pyrazolecarboxamides and insecticides and acaricides containing the same as an active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1205292A JP2861087B2 (en) | 1989-08-08 | 1989-08-08 | N-acyl-5-pyrazolecarboxamides and insecticides and acaricides containing the same as an active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0368560A JPH0368560A (en) | 1991-03-25 |
| JP2861087B2 true JP2861087B2 (en) | 1999-02-24 |
Family
ID=16504557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1205292A Expired - Lifetime JP2861087B2 (en) | 1989-08-08 | 1989-08-08 | N-acyl-5-pyrazolecarboxamides and insecticides and acaricides containing the same as an active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2861087B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150344436A1 (en) * | 2012-10-16 | 2015-12-03 | Tolero Pharmaceuticals, Inc. | Pkm2 modulators and methods for their use |
| US11712433B2 (en) | 2019-03-22 | 2023-08-01 | Sumitomo Pharma Oncology, Inc. | Compositions comprising PKM2 modulators and methods of treatment using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172261A (en) * | 1999-12-20 | 2001-06-26 | Mitsubishi Chemicals Corp | Pyrazolecarboxamides and insecticide and acaricide comprising the same as active ingredient |
-
1989
- 1989-08-08 JP JP1205292A patent/JP2861087B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150344436A1 (en) * | 2012-10-16 | 2015-12-03 | Tolero Pharmaceuticals, Inc. | Pkm2 modulators and methods for their use |
| US9394257B2 (en) * | 2012-10-16 | 2016-07-19 | Tolero Pharmaceuticals, Inc. | PKM2 modulators and methods for their use |
| US10207996B2 (en) | 2012-10-16 | 2019-02-19 | Tolero Pharmaceuticals, Inc. | PKM2 modulators and methods for their use |
| US10472328B2 (en) | 2012-10-16 | 2019-11-12 | Tolero Pharmaceuticals, Inc. | PKM2 modulators and methods for their use |
| US10766865B2 (en) | 2012-10-16 | 2020-09-08 | Sumitomo Dainippon Pharma Oncology, Inc. | PKM2 modulators and methods for their use |
| US11712433B2 (en) | 2019-03-22 | 2023-08-01 | Sumitomo Pharma Oncology, Inc. | Compositions comprising PKM2 modulators and methods of treatment using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0368560A (en) | 1991-03-25 |
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