CN1016168B - 含吡唑啉化合物的杀虫、杀螨剂 - Google Patents
含吡唑啉化合物的杀虫、杀螨剂Info
- Publication number
- CN1016168B CN1016168B CN87107752A CN87107752A CN1016168B CN 1016168 B CN1016168 B CN 1016168B CN 87107752 A CN87107752 A CN 87107752A CN 87107752 A CN87107752 A CN 87107752A CN 1016168 B CN1016168 B CN 1016168B
- Authority
- CN
- China
- Prior art keywords
- formula
- weight
- composition
- compounds
- preparation
- 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
Links
- 239000002917 insecticide Substances 0.000 title abstract description 7
- 239000000642 acaricide Substances 0.000 title abstract description 4
- -1 pyrazoline compound Chemical class 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 150000003219 pyrazolines Chemical class 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 230000000895 acaricidal effect Effects 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 241000238631 Hexapoda Species 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000000749 insecticidal effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 241000239290 Araneae Species 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012876 carrier material Substances 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 2
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 241001556089 Nilaparvata lugens Species 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 240000006677 Vicia faba Species 0.000 description 4
- 235000010749 Vicia faba Nutrition 0.000 description 4
- 235000002098 Vicia faba var. major Nutrition 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 210000004681 ovum Anatomy 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 3
- 102000002322 Egg Proteins Human genes 0.000 description 3
- 108010000912 Egg Proteins Proteins 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241001674048 Phthiraptera Species 0.000 description 3
- 241000500437 Plutella xylostella Species 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052736 halogen Chemical group 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 241000256118 Aedes aegypti Species 0.000 description 2
- 241000322476 Bovicola bovis Species 0.000 description 2
- 244000304217 Brassica oleracea var. gongylodes Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241001498622 Cixius wagneri Species 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 240000000047 Gossypium barbadense Species 0.000 description 2
- 235000009429 Gossypium barbadense Nutrition 0.000 description 2
- 241001147381 Helicoverpa armigera Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000721451 Pectinophora gossypiella Species 0.000 description 2
- 241000255969 Pieris brassicae Species 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000256250 Spodoptera littoralis Species 0.000 description 2
- 240000004584 Tamarindus indica Species 0.000 description 2
- 235000004298 Tamarindus indica Nutrition 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 150000008105 phosphatidylcholines Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 1
- ASWBNKHCZGQVJV-UHFFFAOYSA-N (3-hexadecanoyloxy-2-hydroxypropyl) 2-(trimethylazaniumyl)ethyl phosphate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)COP([O-])(=O)OCC[N+](C)(C)C ASWBNKHCZGQVJV-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- TZCPCKNHXULUIY-RGULYWFUSA-N 1,2-distearoyl-sn-glycero-3-phosphoserine Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OC[C@H](N)C(O)=O)OC(=O)CCCCCCCCCCCCCCCCC TZCPCKNHXULUIY-RGULYWFUSA-N 0.000 description 1
- XLUSNOUGZQJPRN-UHFFFAOYSA-N 1-(difluoromethoxy)-4-isocyanatobenzene Chemical compound FC(F)OC1=CC=C(N=C=O)C=C1 XLUSNOUGZQJPRN-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RMEJVDDOMGIQFF-UHFFFAOYSA-N 1h-pyrazole;quinoline Chemical compound C=1C=NNC=1.N1=CC=CC2=CC=CC=C21 RMEJVDDOMGIQFF-UHFFFAOYSA-N 0.000 description 1
- MCGBIXXDQFWVDW-UHFFFAOYSA-N 4,5-dihydro-1h-pyrazole Chemical compound C1CC=NN1 MCGBIXXDQFWVDW-UHFFFAOYSA-N 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000254175 Anthonomus grandis Species 0.000 description 1
- 241001425390 Aphis fabae Species 0.000 description 1
- 240000003291 Armoracia rusticana Species 0.000 description 1
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 235000000832 Ayote Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000238659 Blatta Species 0.000 description 1
- 241000238657 Blattella germanica Species 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 235000011303 Brassica alboglabra Nutrition 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000011302 Brassica oleracea Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001674939 Caulanthus Species 0.000 description 1
- 241000255580 Ceratitis <genus> Species 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 240000004244 Cucurbita moschata Species 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001414892 Delia radicum Species 0.000 description 1
- 241000489973 Diabrotica undecimpunctata Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- JZNWSCPGTDBMEW-UHFFFAOYSA-N Glycerophosphorylethanolamin Chemical class NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 description 1
- ZWZWYGMENQVNFU-UHFFFAOYSA-N Glycerophosphorylserin Natural products OC(=O)C(N)COP(O)(=O)OCC(O)CO ZWZWYGMENQVNFU-UHFFFAOYSA-N 0.000 description 1
- 241000255967 Helicoverpa zea Species 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- STECJAGHUSJQJN-USLFZFAMSA-N LSM-4015 Chemical compound C1([C@@H](CO)C(=O)OC2C[C@@H]3N([C@H](C2)[C@@H]2[C@H]3O2)C)=CC=CC=C1 STECJAGHUSJQJN-USLFZFAMSA-N 0.000 description 1
- 241000736227 Lucilia sericata Species 0.000 description 1
- 241000171293 Megoura viciae Species 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 244000223072 Narcissus jonquilla Species 0.000 description 1
- 235000013862 Narcissus jonquilla Nutrition 0.000 description 1
- 241000238814 Orthoptera Species 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 241001608567 Phaedon cochleariae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000238680 Rhipicephalus microplus Species 0.000 description 1
- 241000256248 Spodoptera Species 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N Taurine Natural products NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 241000219873 Vicia Species 0.000 description 1
- 208000003152 Yellow Fever Diseases 0.000 description 1
- 235000007244 Zea mays Nutrition 0.000 description 1
- ATBOMIWRCZXYSZ-XZBBILGWSA-N [1-[2,3-dihydroxypropoxy(hydroxy)phosphoryl]oxy-3-hexadecanoyloxypropan-2-yl] (9e,12e)-octadeca-9,12-dienoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(COP(O)(=O)OCC(O)CO)OC(=O)CCCCCCC\C=C\C\C=C\CCCCC ATBOMIWRCZXYSZ-XZBBILGWSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940115440 aluminum sodium silicate Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach 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
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- HCWYXKWQOMTBKY-UHFFFAOYSA-N calcium;dodecyl benzenesulfonate Chemical compound [Ca].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 HCWYXKWQOMTBKY-UHFFFAOYSA-N 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000006838 isophorone group Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000001418 larval effect Effects 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229940031815 mycocide Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000008104 phosphatidylethanolamines Chemical class 0.000 description 1
- 229940067626 phosphatidylinositols Drugs 0.000 description 1
- 150000003905 phosphatidylinositols Chemical class 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 235000015136 pumpkin Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明阐述了通式I的新型吡唑啉、它的制备方法以及作为具有杀虫和杀螨作用的杀害虫剂的应用，式I中的R1和R2相同或不相同，代表氢或氟。
Description
本发明涉及新型吡唑啉，其制法及其作为杀害虫剂的应用。
已知有一系列具有杀虫效果的吡唑啉衍生物（例如：DOS2304584和2529689以及EP 21506和113213）。
在EP 21506中描述了下列通式的吡唑啉：
其中，R1特别是一个游离苯基或一个卤素取代了的苯基，R2特别是一个带有1-6个碳原子的卤代烷氧基，和X和Y是氢或卤素。当R1代表一个苯基时，所指的化合物为二个，其中R1是一个游离苯基和一个对氯苯基，R2代表三氟甲氧基和X代表氯。当R1代表一个卤素取代了的苯基时，所有已公开的化合物具有唯一的X＝氯作为在苯基上第3位的取代基。
本发明任务是提供在较好选择性下具有改善功效的吡唑啉。
现已发现通式（Ⅰ）的吡唑啉比已知吡唑啉衍生物具有优越的效力，
在（Ⅰ）式中，R1和R2相同或不相同，代表氢或氟。
本发明包含以式Ⅰ为特征的化合物所有的异构体形式以及它们的混合物。
将通式Ⅱ的吡唑啉：
与式Ⅲ的一种异氰酸酯作用
以制备本发明式Ⅰ的化合物，
需要时在一种溶剂的作用下来制备。
作为溶剂宜用对反应物为惰性的液体，诸如脂肪烃、脂环烃和芳烃、需要时可以是氯化了的，诸如己烷、环己烷、石油醚、苯、甲苯、二甲苯、二氯甲烷、三氯甲烷、四氯化碳、氯化乙烯、三氯乙烯和氯苯;醚，诸如二乙醚、甲基乙基醚、二异丙醚、二丁醚、二噁烷和四氢呋喃;腈，诸如乙腈、丙腈和苄腈;酯，诸如乙酸乙酯和乙酸戊酯;酰胺，诸如二甲基甲酰胺，N-甲基吡咯烷酮或六甲基磷酰三胺;砜和亚砜，诸如二甲基亚砜和环丁砜。
上述反应能在一宽广温度范围内进行，通常在-20°和100℃之间进行，较好是在室温下进行。
尽管该转变也能在高压或减压下进行，但它是在常压下进行的。
按照上述方法所制备的化合物也可按照惯用方法从反应混合物中分离出来，例如在正常压力或减压下通过将加入的溶剂蒸馏出的方法，通过用水沉淀或通过萃取的方法，通常也可通过柱色谱提纯或结晶的方法达到高纯度。
按照本发明的吡唑啉无色和无气味，在大多数情况下是结晶的化合物，它极难溶于水和甲苯，较易溶于乙酸乙酯和溶于二甲基甲酰胺。
作为原料使用的式Ⅱ的吡唑啉是已知的，或者能按照已知方法制备。
在反应方法中所用的式Ⅲ的异氰酸酯是已知的，或者能按照已知方法制备。
本发明化合物具有杀昆虫的杀螨的作用，因此适于防治多种样的昆虫和螨，其中包括兽类的外寄生虫。例如所谓鳞翅目诸如菜蛾，海灰翅夜蛾（Spodoptera littoralis）、棉铃虫和大菜粉蝶（Pieris brassicae）;双翅目如家蝇、地中海蜡实蝇、甘蓝地种蝇（Erioischia brassicae）、丝光绿蝇和埃及伊蚊（黄热病伊蚊）;同翅目类包括叶蚜虫（Blattlausen）诸如蚕豆修尾蚜（Megoura viciae）和褐飞虱（Nilaparvata lugens）;鞘翅目诸如辣根猿叶甲（Phaedon cochleariae）、棉铃象（Anthonomus grandis）和南瓜十二星叶甲（条叶甲属，例如黄瓜十一星叶甲）;直翅目诸如德国蠊（茶婆虫）;扁虱诸如微小牛蜱和虱诸如牛畜虱（Damalinia bovis）和犊毛虱以及蜘蛛螨
（Spinnmilben）诸如棉红蜘蛛和苹果红蜘蛛。
因此，本发明化合物以卓越的方式适于防治昆虫和蜘蛛螨，特别是防治有害昆虫，并且在这方面提供有价值的技术财富。
本发明化合物可在浓度从0.0005到5.0%，最好从0.001到0.1%下应用，在此浓度下就可得知在100毫升制剂中所含生物活性物质以克所表示的重量。
本发明化合物或可单独、彼此混合，或与其它杀虫活性物质一起应用，必要时，视所需目的而定，可添加其它植物保护剂、杀害虫剂诸如杀昆虫剂、杀螨剂或杀真菌剂。
通过例如活性强化辅助剂诸如有机溶剂、湿润剂和油类可达到提高作用强度和作用速度的效果。在必要时，这些辅助剂的添加可使得作用物质的剂量减少。
作为混入成分还可用磷脂，例如选自磷脂酰胆碱类、氢化的磷脂酰胆碱类，磷脂酰乙醇胺类、N-酰基-磷脂酰乙醇胺类、磷脂酰肌醇、磷脂酰丝氨酸、溶血卵磷脂和磷脂酰甘油这样一些化合物。
按照使用目的，该特征作用物质或其混合物在加入液体和/或固体物质或者稀释剂和在必要时加入胶粘剂、湿润剂、乳化剂和/或分散助剂时，可以制剂形式诸如粉剂、喷洒剂、颗粒、溶液、乳状液或悬浮液使用。
适宜的液体载体物质是例如脂肪烃和芳烃诸如苯、甲苯、二甲苯、环己酮、异佛尔酮、二甲亚砜、二甲基甲酰胺，此外有矿物油馏分和植物油类。
作为固体载体物质，矿物例如斑脱土、硅胶、滑石、高岭土、美国活性白土（Attapulgit）、石灰石和植物产物诸如面粉是适
宜的。
在表面活性剂方面有例如木素磺酸钙、聚乙烯烷基苯基醚、萘磺酸及其盐、苯酚磺酸及其盐、甲醛缩合物、脂肪醇硫酸酯以及取代的苯磺酸及其盐。
在不同制剂中作用物质的份额可在宽广范围内变动，例如，在其中含有约10到90重量%的作用物质、约90到10重量%的液体或固体载体物质以及在必要时含有达20重量%的表面活性剂。
该杀虫剂可用常规方法使用，例如以水作为载体每公顷喷洒约100到3000升，也可以以微粒的形式在所谓低容量和超低容量方法中应用。
为了制备制剂，加入例如下列成分：
A、喷粉
20重量%作用物质
35重量%的白土（Bleicherde）
8重量%木素磺酸钙
2重量%N-甲基-N-油酰基-牛磺酸钠
35重量%硅酸
B、膏
45重量%作用物质
5重量%硅酸钠铝
15重量%带有8摩尔的环氧乙烷的十六烷基聚乙二醇醚
2重量%锭子油
10重量%聚乙二醇
23份水
C、乳状液浓缩物
20重量%作用物质
75重量%异佛尔酮
5重量%的以壬基苯基聚氧 乙烯和十二烷基苯磺酸钙为基的混合物
以下例子阐述本发明化合物的制法：
实施例1
3，4-双（4-氟苯基）-4，5-二氢-1-吡唑碳酸-（4-二氟甲氧基酰替苯胺）
在室温搅拌下，将7.03克（0.038摩尔）的4-二氟甲氧基苯基异氰酸酯加入在80毫升二氯甲烷中的9.85克（0.038摩尔）的3，4-双（4-氟苯基）-4，5-二氢吡唑中，再在室温下搅拌1小时。将反应混合物在硅胶上过滤并挤干，以100毫升二异丙醚处理残渣，抽滤出沉淀的结晶并在真空中（100托）干燥。
产率：14.7克（理论量的87%）
熔点：144℃
下列化合物以类似方法制备，其中的取代基X、Y和Z在式Ⅰ中已定义过。
实施例号 R1R2熔点℃
2 F F 135
3 H F 146
4 H H 140
以下实用例表明本发明化合物的生物活性：
应用例A
处理蚕豆对抵抗黑蚕虫蚜虫〔Schwarze Bohnenlaus（Aphis fabae Scop.）〕的治疗作用。
使蚕豆的秧苗在温室中长到约6厘米高，每盆一株。然后用培育黑蚕豆蚜虫的物质盖上。然后使该植物按每棵100-200个成虫进行移殖，用在水制剂中含0.1%该相应作用物质把盆喷淋湿，并在温室中约24℃下放置，二天后调查被杀死的叶蚜虫的份额。与未处理的空白盆情况对比，按照阿博特方法计算药物作用。
使用按照实施例1和4的本发明化合物，效果达到大于75%。
应用例B
防治稻褐飞虱的预防性叶处理的作用。
在温室中使稻秧（每盆15株）培养到长出第3个叶子，然后用含0.1%作用物质的水制剂把盆喷湿，此喷射层干燥后，在每一盆上盖上一透明圆筒，在每一盆上放入约30只稻褐飞虱，在26℃的温室中放置二天后，确定死亡飞虱的份额，与未处理的空白盆对比，按照阿博特方法计算出作用效果来。
对于按照实施例1-4的本发明化合物来说，其效果为75-100%。
应用例C
对小菜蛾幼虫的杀死作用。
将本发明化合物以含0.0064%作用物质的配方使用，对此，可以将本发明化合物的丙酮溶液或乳状浓集物用水稀释到所需浓度后使用。将此制剂以每平方厘米喷4毫克的剂量喷于聚苯乙烯培养皿中的球茎甘蓝叶子（Brassica oleracea）上，待喷层干燥后，
在每个培养皿中放入10只小菜蛾幼虫，并在封闭的培养皿中对该处理过的饲料暴露二天，在另外三天用未经处理过的球茎甘蓝叶子进行了一次性的后喂食，作用效果评价的标准是5天后幼虫死亡率的百分数。
以上试验得出，按照实施例1-4的本发明化合物具有80-100%的效果。
应用例D
对埃及棉花虫（Spodoptera littoralis）幼虫（L2）的致死作用
本发明化合物以含0.0064%作用物质加入，对此，可以将本发明化合物的丙酮溶液或乳状浓集物用水稀释到所需浓度后使用，将此制剂对所有酸豆的小羽状叶对（Vicia fabae）以及10只埃及棉花虫幼虫（L2）喷药，在每一试验环节，在聚苯乙烯培养皿内每一平方厘米喷4毫克药液，将此封闭的培养皿在实验室内，于长昼条件下放置2天，然后在另外三天用未经处理的酸豆叶一次性地进行了一次补充喂食。评价作用效果的标准是五天后幼虫的死亡率。
以上实验得出，按照实施例1-4的本发明化合物具有80-100%死亡率作用效果。
应用例E
对美洲烟夜蛾幼虫的触杀作用效果
本发明化合物以含有0.0064%作用物质的制剂使用，对此，可以将本发明化合物的丙酮溶液或乳状浓集物用水稀释到所需浓度后使用，此制剂以培养皿内表面的每1平方厘米4毫克的剂量喷洒，在该喷洒层干燥后，使每一培养皿5个美洲烟夜蛾对该喷洒层暴露24小时，
然后，将幼虫移置于未经处理的培养皿中并以无毒的规定饲料进行另外四个试验阶段的饲养，此试验是在实验室内的长昼条件下进行的。效果评价的标准是五天后幼虫的死亡率。
以上实验得出，按照实施例1-4的本发明化合物具有80-100%死亡率作用效果。
应用例F
对玉米根虫/卵（Diabrotica undecimpunctata）的土壤除虫效果
本发明化合物以含有0.0064%作用物质的制剂使用，对此，可以将本发明化合物的丙酮溶液或乳状浓集物用水稀释到所需浓度后使用每次以20毫升这样的制剂浇于塑料花盆上（66×66×82毫米），该花盆每一只用200毫升土壤充填，并且以每只装约100个玉米根虫卵以及2粒玉米于距表面约1厘米深土壤内，然后，该花盆在温室中于长昼条件下和24-26℃下放置14天，评价作用效果的标准是在14天内在带有卵的未处理过的花盆和无卵的未处理过花盆中的玉米植物的增长。
以上试验得出，用按照实施例1-4的本发明化合物不干扰植物的发育。
Claims (4)
1、一种杀虫、杀螨剂组合物，其特征在于该组合物的成份中至少含有作为活性成份的通式(Ⅰ)的一种吡唑啉化合物
(式中R1和R2相同或不相同，代表氢或氟)，并含有载体物质和/或助剂物质，其中活性成份的含量为10-90%(重量)，液体和/或固体载体物质的含量为90-10%(重量)，在有需要时最多可加入20%(重量)的表面活性剂。
2、制备权利要求1的杀虫、杀螨剂组合物的方法，该方法包括将至少一种通式（Ⅰ）的化合物与载体物质和/或助剂物质相混合。
3、根据权利要求2组合物的制备方法，其中通式（Ⅰ）化合物的制备是由通式（Ⅱ）的吡唑啉
（式中R1的定义与在通式（Ⅰ）中R1的定义相同），
与式（Ⅲ）的一种异氰酸酯反应来制备
（式中R2的定义与在通式（Ⅰ）中R2的定义相同），
并可选择地使用一种溶剂。
4、根据权利要求1组合物的用途，包括将该组合物应用于防治昆虫和蜘蛛螨（Spinnmilben）。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3638631.6 | 1986-11-11 | ||
| DE19863638631 DE3638631A1 (de) | 1986-11-11 | 1986-11-11 | Pyrazoline, ihre herstellung und ihre verwendung als mittel mit insektizider und akarizider wirkung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87107752A CN87107752A (zh) | 1988-05-25 |
| CN1016168B true CN1016168B (zh) | 1992-04-08 |
Family
ID=6313772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107752A Expired CN1016168B (zh) | 1986-11-11 | 1987-11-11 | 含吡唑啉化合物的杀虫、杀螨剂 |
Country Status (26)
| Country | Link |
|---|---|
| US (1) | US4837220A (zh) |
| EP (1) | EP0267869B1 (zh) |
| JP (1) | JPS63135373A (zh) |
| KR (1) | KR880006201A (zh) |
| CN (1) | CN1016168B (zh) |
| AP (1) | AP82A (zh) |
| AT (1) | ATE78468T1 (zh) |
| AU (1) | AU602367B2 (zh) |
| BR (1) | BR8706059A (zh) |
| CA (1) | CA1266674A (zh) |
| CS (1) | CS264299B2 (zh) |
| DD (1) | DD265783A5 (zh) |
| DE (2) | DE3638631A1 (zh) |
| DK (1) | DK167012B1 (zh) |
| ES (1) | ES2043684T3 (zh) |
| FI (1) | FI874976A7 (zh) |
| GR (1) | GR3005908T3 (zh) |
| HU (1) | HU204791B (zh) |
| IE (1) | IE59525B1 (zh) |
| IL (1) | IL84330A (zh) |
| NZ (1) | NZ222468A (zh) |
| OA (1) | OA08774A (zh) |
| PH (1) | PH25609A (zh) |
| PT (1) | PT86104B (zh) |
| TR (1) | TR23185A (zh) |
| ZA (1) | ZA878479B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5116850A (en) * | 1987-11-30 | 1992-05-26 | E. I. Du Pont De Nemours And Co. | Heterocyclic pyrazoline carboxanilides |
| DE3924112A1 (de) * | 1989-07-20 | 1991-01-31 | Bayer Ag | Fungizide mittel auf basis von 1,3,5-triaryl-2-pyrazolin-derivaten, neue 1,3,5-triaryl-2-pyrazoline und ein verfahren zu ihrer herstellung |
| US5369121A (en) * | 1990-01-31 | 1994-11-29 | E. I. Du Pont De Nemours And Company | Arthropodicidal pyrazolines, pyrazolidines and hydrazines |
| WO1993005024A1 (en) * | 1991-08-28 | 1993-03-18 | E.I. Du Pont De Nemours And Company | Arthropodicidal anilides |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL183400C (nl) * | 1976-01-09 | 1988-10-17 | Duphar Int Res | Werkwijze ter bereiding van een insecticide preparaat dat een pyrazoline-verbinding bevat en werkwijze ter bereiding van een pyrazoline-verbinding met insecticide werking. |
| DE3064749D1 (en) * | 1979-07-03 | 1983-10-13 | Duphar Int Res | New pyrazoline derivatives, method of preparing the new compounds, as well as insecticidal composition on the basis of these new compounds |
| EP0113213B1 (en) * | 1982-12-30 | 1988-04-06 | Schering Agrochemicals Limited | Pyrazoline insecticides |
| US4663341A (en) * | 1984-02-16 | 1987-05-05 | Rohm And Haas Company | Insecticidal n-aryl-3-aryl-4,5-dihydro-1h-pyrazole-1-carboxamides |
| DE3545786A1 (de) * | 1985-12-21 | 1987-06-25 | Schering Ag | Pyrazolinderivate, ihre herstellung und ihre verwendung als mittel mit insektizider wirkung |
-
1986
- 1986-11-11 DE DE19863638631 patent/DE3638631A1/de not_active Withdrawn
-
1987
- 1987-11-02 IL IL84330A patent/IL84330A/xx not_active IP Right Cessation
- 1987-11-06 NZ NZ222468A patent/NZ222468A/xx unknown
- 1987-11-09 DD DD87308850A patent/DD265783A5/de not_active IP Right Cessation
- 1987-11-09 JP JP62281179A patent/JPS63135373A/ja active Pending
- 1987-11-09 AP APAP/P/1987/000073A patent/AP82A/en active
- 1987-11-10 PT PT86104A patent/PT86104B/pt not_active IP Right Cessation
- 1987-11-10 IE IE301387A patent/IE59525B1/en not_active IP Right Cessation
- 1987-11-10 CA CA000551554A patent/CA1266674A/en not_active Expired - Lifetime
- 1987-11-10 BR BR8706059A patent/BR8706059A/pt not_active Application Discontinuation
- 1987-11-10 DE DE8787730141T patent/DE3780574T2/de not_active Expired - Fee Related
- 1987-11-10 EP EP87730141A patent/EP0267869B1/en not_active Expired - Lifetime
- 1987-11-10 US US07/119,191 patent/US4837220A/en not_active Expired - Fee Related
- 1987-11-10 TR TR774/87A patent/TR23185A/xx unknown
- 1987-11-10 CS CS878056A patent/CS264299B2/cs unknown
- 1987-11-10 HU HU875003A patent/HU204791B/hu not_active IP Right Cessation
- 1987-11-10 KR KR870012625A patent/KR880006201A/ko not_active Ceased
- 1987-11-10 ES ES87730141T patent/ES2043684T3/es not_active Expired - Lifetime
- 1987-11-10 AT AT87730141T patent/ATE78468T1/de not_active IP Right Cessation
- 1987-11-11 ZA ZA878479A patent/ZA878479B/xx unknown
- 1987-11-11 OA OA59223A patent/OA08774A/xx unknown
- 1987-11-11 PH PH36055A patent/PH25609A/en unknown
- 1987-11-11 FI FI874976A patent/FI874976A7/fi not_active Application Discontinuation
- 1987-11-11 CN CN87107752A patent/CN1016168B/zh not_active Expired
- 1987-11-11 AU AU80990/87A patent/AU602367B2/en not_active Ceased
- 1987-11-11 DK DK591687A patent/DK167012B1/da not_active IP Right Cessation
-
1992
- 1992-10-08 GR GR920402128T patent/GR3005908T3/el unknown
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1031544C (zh) | N-苯基吡唑衍生物的组合物及其用途 | |
| RU2109012C1 (ru) | Новые производные пиррола | |
| CN1125727A (zh) | 取代的吡啶基吡唑类化合物 | |
| JPS6029381B2 (ja) | ２’，４‐ジクロロ‐４’‐ベンゾイルウレイド‐ジフエニルエーテル、その製法、およびその殺虫剤としての使用 | |
| JPS6078971A (ja) | ニトロメチレン−テトラヒドロピリミジン誘導体，その製法及び殺虫，殺ダニ，殺センチユウ剤 | |
| CN1159445A (zh) | 新颖的杀虫剂 | |
| JPS62149606A (ja) | 節足動物殺滅剤組成物 | |
| DE69026906T2 (de) | Arylpyrrol enthaltende insekticidale, acaricidale und nematicidale Mittel sowie Verfahren zu ihrer Herstellung | |
| CN1048035A (zh) | N-苯基吡唑衍生物 | |
| CN1016168B (zh) | 含吡唑啉化合物的杀虫、杀螨剂 | |
| JPS62281807A (ja) | 害虫防除剤 | |
| CS240991B2 (en) | Insekticide and akaricide agent and method of effective substances preparation | |
| DE69937771T2 (de) | 1-Aryl-4-cycloalk(en)ylpyrazole als antiparasitäre Mittel | |
| CA1108141A (en) | Combating arthropods with o-alkyl-o-(2-cyclopropyl-6- methyl-pyrimidin-4-yl)-thionophosphonic acid esters | |
| CN1042630C (zh) | 取代的氮杂环烷烃及其制备方法、用途和含其的杀害虫组合物 | |
| CA1050997A (en) | O-triazolylthionophosphoric(phosphonic) acid esters and ester-amides | |
| DE69304011T2 (de) | N-Substituierte Carbonyloxyalkylpyrrol enthaltende insekticide, acarizide und molluskizide Mittel | |
| US4426379A (en) | Insecticidal 2-oxo-3-dialkoxyphosphoro-5-cyclopropyl-1,3,4-oxadiazoline | |
| JPH08506329A (ja) | 置換テトラヒドロピリダジンカルボキサミド類 | |
| CN1045771A (zh) | 取代的苯乙酸三氟乙酯及其制备方法和在杀虫剂上的应用 | |
| JPS62459A (ja) | テトラメチルシクロプロパンカルボン酸エステル | |
| IL30294A (en) | 3-isopropyl-4-methyl-6-chlorophenyl-n-methylcarbamate,its preparation and use as insecticide | |
| CA1085397A (en) | O-quinoxalylthionophosphonic acid esters, and their use as insecticides and acaricides | |
| JPS59170099A (ja) | ホスホン酸エステル、その製法及び殺虫、殺ダニ、殺センチユウ剤 | |
| CA1217495A (en) | O-(pyrazol-4-yl)-n-(x-cyanoalkylsulphenyl)- carbamates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |