CN1051728A - 硝基胍化合物和杀虫剂 - Google Patents
硝基胍化合物和杀虫剂 Download PDFInfo
- Publication number
- CN1051728A CN1051728A CN90109217A CN90109217A CN1051728A CN 1051728 A CN1051728 A CN 1051728A CN 90109217 A CN90109217 A CN 90109217A CN 90109217 A CN90109217 A CN 90109217A CN 1051728 A CN1051728 A CN 1051728A
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- China
- Prior art keywords
- methyl
- compound
- nitroguanidine
- chloro
- 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.)
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- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical class NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 230000014509 gene expression Effects 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 82
- 238000002360 preparation method Methods 0.000 claims description 21
- -1 6-chloro-3-pyridyl Chemical group 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 6
- ZTLCLYBKONTDBT-UHFFFAOYSA-N 2-[(2-chloro-1,3-thiazol-5-yl)methyl]-1-nitroguanidine Chemical compound [O-][N+](=O)NC(=N)NCC1=CN=C(Cl)S1 ZTLCLYBKONTDBT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- PGOOBECODWQEAB-UHFFFAOYSA-N (E)-clothianidin Chemical compound [O-][N+](=O)\N=C(/NC)NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-UHFFFAOYSA-N 0.000 claims 2
- SOMLAPKNFRZFMC-UHFFFAOYSA-N 1-[(2-chloro-1,3-thiazol-5-yl)methyl]-1-methyl-2-nitroguanidine Chemical compound [O-][N+](=O)N=C(N)N(C)CC1=CN=C(Cl)S1 SOMLAPKNFRZFMC-UHFFFAOYSA-N 0.000 claims 2
- NVPZDFHKMJRGOX-UHFFFAOYSA-N 1-[(6-chloropyridin-3-yl)methyl]-1,2-dimethyl-3-nitroguanidine Chemical compound [O-][N+](=O)N=C(NC)N(C)CC1=CC=C(Cl)N=C1 NVPZDFHKMJRGOX-UHFFFAOYSA-N 0.000 claims 2
- JKAKRCUQKSQKLJ-UHFFFAOYSA-N 1-[(6-chloropyridin-3-yl)methyl]-1-methyl-2-nitroguanidine Chemical compound [O-][N+](=O)N=C(N)N(C)CC1=CC=C(Cl)N=C1 JKAKRCUQKSQKLJ-UHFFFAOYSA-N 0.000 claims 2
- SWHRDLPFZQFSLS-UHFFFAOYSA-N 1-[(6-chloropyridin-3-yl)methyl]-2-methyl-3-nitroguanidine Chemical compound [O-][N+](=O)N=C(NC)NCC1=CC=C(Cl)N=C1 SWHRDLPFZQFSLS-UHFFFAOYSA-N 0.000 claims 2
- GHBBFPGYBPOUCF-UHFFFAOYSA-N 2-[(6-chloropyridin-3-yl)methyl]-1-nitroguanidine Chemical compound [O-][N+](=O)NC(=N)NCC1=CC=C(Cl)N=C1 GHBBFPGYBPOUCF-UHFFFAOYSA-N 0.000 claims 2
- 150000002828 nitro derivatives Chemical class 0.000 claims 2
- 241000238631 Hexapoda Species 0.000 abstract description 9
- 241001465754 Metazoa Species 0.000 abstract description 7
- 241000251468 Actinopterygii Species 0.000 abstract description 6
- 231100000674 Phytotoxicity Toxicity 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 8
- 241000209094 Oryza Species 0.000 description 8
- 235000007164 Oryza sativa Nutrition 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 235000009566 rice Nutrition 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- 239000002253 acid Substances 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
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- 239000011521 glass Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
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- 241000254173 Coleoptera Species 0.000 description 3
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- KCDQBIMJBRASQE-UHFFFAOYSA-N (2-chloro-1,3-thiazol-5-yl)methanamine Chemical compound NCC1=CN=C(Cl)S1 KCDQBIMJBRASQE-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
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- 241001509962 Coptotermes formosanus Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
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- 241000254022 Locusta migratoria Species 0.000 description 2
- 241000257159 Musca domestica Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 241000346285 Ostrinia furnacalis Species 0.000 description 2
- 241000254154 Sitophilus zeamais Species 0.000 description 2
- 241000985245 Spodoptera litura Species 0.000 description 2
- 241001630065 Unaspis yanonensis Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- 239000008187 granular material Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 230000001418 larval effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DEVSOMFAQLZNKR-RJRFIUFISA-N (z)-3-[3-[3,5-bis(trifluoromethyl)phenyl]-1,2,4-triazol-1-yl]-n'-pyrazin-2-ylprop-2-enehydrazide Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(C2=NN(\C=C/C(=O)NNC=3N=CC=NC=3)C=N2)=C1 DEVSOMFAQLZNKR-RJRFIUFISA-N 0.000 description 1
- VVCMGAUPZIKYTH-VGHSCWAPSA-N 2-acetyloxybenzoic acid;[(2s,3r)-4-(dimethylamino)-3-methyl-1,2-diphenylbutan-2-yl] propanoate;1,3,7-trimethylpurine-2,6-dione Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O.CN1C(=O)N(C)C(=O)C2=C1N=CN2C.C([C@](OC(=O)CC)([C@H](C)CN(C)C)C=1C=CC=CC=1)C1=CC=CC=C1 VVCMGAUPZIKYTH-VGHSCWAPSA-N 0.000 description 1
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 241001672675 Adoxophyes Species 0.000 description 1
- 241000175828 Adoxophyes orana Species 0.000 description 1
- 241000218473 Agrotis Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000519878 Anomala rufocuprea Species 0.000 description 1
- 241001600408 Aphis gossypii Species 0.000 description 1
- 241000238657 Blattella germanica Species 0.000 description 1
- 241000272639 Brachycaudus mimeuri Species 0.000 description 1
- 241000008892 Cnaphalocrocis patnalis Species 0.000 description 1
- 241000255749 Coccinellidae Species 0.000 description 1
- 241001465977 Coccoidea Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000256054 Culex <genus> Species 0.000 description 1
- 241000256059 Culex pipiens Species 0.000 description 1
- 241000785585 Gryllotalpa africana Species 0.000 description 1
- 241001299253 Henosepilachna vigintioctopunctata Species 0.000 description 1
- 241001470017 Laodelphax striatella Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241000272317 Lipaphis erysimi Species 0.000 description 1
- 241000966204 Lissorhoptrus oryzophilus Species 0.000 description 1
- 241000721621 Myzus persicae Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000359016 Nephotettix Species 0.000 description 1
- 241000358422 Nephotettix cincticeps Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000275069 Phyllotreta cruciferae Species 0.000 description 1
- 241000437063 Phyllotreta striolata Species 0.000 description 1
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- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 241000283614 Stephanitis nashi Species 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 241000018135 Trialeurodes Species 0.000 description 1
- 241000018137 Trialeurodes vaporariorum Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 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
- 235000021329 brown rice Nutrition 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 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
- 239000000314 lubricant Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- MCPDALPEUAUISM-UHFFFAOYSA-N methyl n'-methyl-n-nitrocarbamimidothioate Chemical compound CNC(SC)=N[N+]([O-])=O MCPDALPEUAUISM-UHFFFAOYSA-N 0.000 description 1
- FLZZNZJENFNFOJ-UHFFFAOYSA-N methyl n'-nitrocarbamimidothioate Chemical compound CSC(N)=N[N+]([O-])=O FLZZNZJENFNFOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- IGDIAHAWKFKHGG-UHFFFAOYSA-N sodium 1-sulfinatododecane Chemical compound [Na+].CCCCCCCCCCCC[S-](=O)=O IGDIAHAWKFKHGG-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
Abstract
通过使用下面通式(I)表示的硝基胍化合物,得
到比通用杀虫剂更有效的杀虫剂:
式中:R代表氢或甲基;R1和R2相同或不同,代
表氢或甲基;X代表下式表示的基:
或
本发明提供的杀虫剂对防治各种害虫是特别有
效的,对温血动物、鱼类或甲壳纲是低毒性的,使用后
其残留量小,对各种植物不产生植物毒性。
Description
本发明涉及硝基胍化合物,制备硝基胍化合物的方法,和含有作为活性组分的硝基胍化合物的杀虫剂。本发明提供的硝基胍化合物用下面通式(Ⅰ)表示:
式中:R代表氢或甲基;R1和R2相同或不同,代表氢或甲基;X代表下式表示的基:
已经开发各种化学药品,并用作防治害虫的杀虫剂。这样的化学药品有代表性的实例是有机磷化合物,氨基甲酸酯化合物和合成的拟除虫菊酯。然而,由于这些杀虫剂的重复使用,许多害虫对这些化学药品具有抗药性。这样,使其难于防治害虫。另一方面,虽然一些常用的杀虫剂有高的杀虫活性,但是,或者由于它们对温血动物或鱼类和甲壳纲的毒性高,或者由于在使用后它们在环境中长时间大量残留,这些杀虫剂可引起环境污染问题。这样,使生态***混乱。因此,需要开发新的杀虫剂,该杀虫剂能有效的防治对常用的化学药品有抗药性的害虫,并且不仅对温血动物,而且对鱼类和甲壳纲是低毒性的。还需要开发在使用后在植物和土壤中残留量减少的和对各种植物不产生植物毒性的新的杀虫剂。
本发明的目的是提供新的化合物。(1)该化合物能有效地防治对常用的化学药品有抗药性的害虫;(2)该化合物不仅对温血动物,而且对鱼类和甲壳纲是低毒性的;(3)该化合物在使用后在植物和土壤中的残留量减少。最后,该新化合物对各种植物不产生植物毒性。
本发明的中一个目的是提供制备上述化合物的方法。
本发明的再一个目的是提供改进的杀虫剂。(1)该杀虫剂能有效地防治对常用杀虫剂有抗药性的害虫;(2)该杀虫剂不仅对温血动物,而且对鱼类和甲壳纲是低毒性的;(3)该杀虫剂在使用后在植物和土壤中的残留量减少。最后,改进的杀虫剂对各种植物不产生植物毒性。
通过对各种新的硝基胍化合物的开发研究,我们已经发现,下面通式(Ⅰ)表示的硝基胍化合物可以用作显示出快速作用的特别有效的杀虫剂:
式中:R代表氢和甲基;R1和R2相同或不同,代表氢和甲基;X代表由下式表示的基:
本发明是在该研究结果的基础上开发的。
当和具有代表性的实施例一起考虑时,本发明的其他目的、特点和优点可以从下面优选方案的详细说明中清楚地看出。
通式(Ⅰ)表示的本发明的化合物是新的化合物,是在以前公开的文献中没说明过的,是我们首次合成的。这些化合物可以通过下述方法制备。
制备方法(a)
式中:R代表氢或甲基;R1和R2相同或不同,代表氢或甲基;X代表下式表示的基:
正如上述反应式所表示的,在制备方法(a)中,本发明的化合物可以通过通式(Ⅱ)表示的化合物:
式中:R代表氢或甲基;X代表下式表示的基:
与通式(Ⅲ)表示的化合物:
式中:R1和R2相同或不同,代表氢或甲基,在用或不用溶剂的条件下进行反应,容易地制备。
可以用于该反应中的合适溶剂的例子是:醚,例如***和四氢呋喃;醇,例如甲醇和乙醇;乙腈;芳烃;氯代烃;二甲基甲酰胺(DMF);二甲基亚砜(DMSO)。这些溶剂可以单独使用或混合使用。特别优选的溶剂是醇,例如甲醇和乙醇。
反应温度可以随意在室温至150℃范围内变化,优选的温度是室温至80℃。
制备方法(b)
当通式(Ⅰ)中的R、R1和R2处于某一特定的相互关系时,可以采用该方法。
更具体地说,根据本方法,本发明的化合物可以通过通式(Ⅳ)表示的化合物:
式中:Y、Y1和Y2相同或不同,代表氢或甲基,其条件是其中至少一个是氢;X代表下式表示的基:
与通式(Ⅴ)表示的化合物:
其中Z代表卤素,在碱性物质存在下进行反应而容易地制备。通常所使用的化合物(Ⅴ)与化合物(Ⅳ)的摩尔比是1-3.3∶1。因此,制备的是由通式(Ⅰ′)表示的本发明的化合物:
式中:A,A′和A2相同或不同,代表氢或甲基,其条件是其中至少一个是甲基;X代表下式表示的基:
可以用于该反应中的溶剂的例子是:醚,例如***和四氢呋喃;乙腈;芳烃;氯代烃;DMF;DMSO。这些溶剂可以单独使用或混合使用。特别优选的溶剂是DMF和DMSO。可以用作碱性物质的化合物是,例如:无机碱,例如氢化钠、氢氧化钠和碳酸钾;有机碱,例如DBU。可以使用的碱与化合物(Ⅳ)的摩尔比可以是1-3.3∶1。反应温度可以在-20℃至100℃范围内变化,优选的温度是-10℃至60℃。
应再次说明,本发明的化合物是新的化合物。由上述方法制备的本发明的典型化合物(Ⅰ)列于下面的表1中。
表1
化合物 R R1R2熔点
序号
1 CH3H H 在158.0℃分解
2 CH3CH3CH399.0 to 100.0℃
3 H CH3H 152.5 to 153.5℃
4 H H H 198.0 to 199.0℃
5 CH3CH3H 130.0 to 132.0℃
6 CH3H H 116.0 to 117.0℃
7 CH3CH3CH3101.0 to 102.0℃
8 H CH3H 151.0 to 153.0℃
9 H H H 160.0 to 162.0℃
注解:1至5表示的化合物是由通式(Ⅰ)中X是 代表的化合物;6至9表示的化合物是由通式(Ⅰ)中X是 表示的化合物。
有效量的本发明的任何化合物可以直接用作杀虫剂,或者可以用通常的方法配制成乳剂、可湿性粉剂、粉剂、颗粒剂,或可流动剂型,然后,以制剂形式使用。可以使用液体或固体载体制备含有一种或多种本发明化合物的制剂。可以用于该目的的液体载体包括,例如有机溶剂,通常使用的是二甲苯、氯苯、甲基萘、环己酮、异佛尔酮、醇、二甲基甲酰胺和N-甲基吡咯烷酮。固体载体的例子包括高岭土、滑石、膨润土、硅藻土和粘土,合成的化合物,例如氧化铝、沸石,和硅酸盐也可以使用。为了得到具有希望的乳化、分散、悬浮和渗透性质的产物,可以使用各种辅助剂,例如乳化剂、分散剂、铺展剂、湿润剂和渗透剂。
上面列出的由通式(Ⅰ)表示的本发明的化合物对各种害虫具有强的杀虫活性,害虫包括半翅目(Hemiptera)、鳞翅目(Lepidoptera)、鞘翅目(Coleoptera)、双翅目(Diptera)、支翅目(Orehoptera)、等翅目(Isoptera),和对人类和动物还是低毒性的,对各种植物不产生植物毒性,因此,实际上可用作优秀杀虫剂。
可以用本发明的化合物有效地防治的害虫的例子如下:
半翅目,例如稻褐飞虱(Nilaparvata lugens)、灰稻虱(Laodel-phax striatellus)、黑尾叶蝉(Nephotettix cinctieeps)、康氏粉蚧(Pseudococcus comstocki)、矢尖蚧(Unaspis Yanonensis)、桃蚜(Myzus persicae)、棉蚜(Aphis gossypii)、萝卜蚜(Lipaphis erysimi)、梨花网蝽(Stephanitis nashi)、稻黑蝽(Scotinophara Lurida)和温室粉虱(Trialeurodes vaporariorus);鳞翅目,例如菜粉蝶(Pieris rapae)、斜纹夜蛾(Spodoptera litura)、甘蓝夜蛾(Mamesera brassicae)、二化螟(Chilosuppressalis)、小菜蛾(Plutera xylostella)、棉褐带卷蛾(Adoxophyes orana)、Agrotis fucosa、稻纵卷叶螟(Cnaphalocrocis medinalis)和亚洲玉米螟(Ostrinia furnacalis);鞘翅目,例如茄二十八星瓢虫(Henosepilachna vigintiocto punctata)、黄守瓜(Aulacophora Femoralis)、曲条跳甲(Phyllotreta striolata)、美洲稻象甲(Lissorhoptrus oryzophilus)、玉米象(Sitophilus zeamais)和Anomala rufocuprea;双翅目,例如家蝇(Musca domestica)、种蝇(Hylemia platura)、库蚊(Culex pipiens);支翅目,例如非洲蝼蛄(Ghryllotalpa africana)、德国小 (Blatella germanica)和飞蝗(Locusta migratoria);等翅目,例如家白蚁(Coptotermes formosanus)和Reticulitermes speratus。
本发明通过下面非限制性的实施例作进一步地说明。
实施例
本发明化合物的制备方法通过参考几个合成实施例进行详细说明。
合成实施例1
N-[(6-氯-3-吡啶基)甲基]-N-甲基-N1-硝基胍的合成
将13.8g 6-氯-N-甲基-3-吡啶甲胺,10.8gs-甲基-N-硝基异硫脲和60ml乙醇的混合物,在搅拌下在50℃加热2小时,然后,再回流5小时。冷却后用过滤收集分离出来的结晶,用少量乙醇洗涤,干燥,得到14.7g标题化合物。该化合物是表1中的化合物1,熔点:158.0℃(分解)。
合成实施例2
N-[(6-氯-3-吡啶基)甲基]-N,N1,N1-三甲基-N1-硝基胍的合成
在搅拌和冰冷却下,向0.21g氢化钠(60%油状物)和4ml二甲基甲酰胺的混合物中,分批加入1.22gN-[(6-氯-3-吡啶基)甲基]-N-甲基-N1-硝基胍。然后,在室温下搅拌混合物。接着再搅拌1小时,逐滴加入0.74g甲基碘。搅拌一夜后,将反应混合物倒入冰水中,过滤出不溶的物质。滤液用二氯甲烷萃取。二氯甲烷层用水洗涤、干燥、浓缩。残余物用硅胶柱色谱提纯(溶剂∶氯仿/甲醇=50/1),得到0.31g标题化合物。该化合物是表1中的化合物2,熔点:99.0-100.0℃。
合成实施例3
N-[(2-氯-5-噻唑基)甲基]-N-甲基-N1-硝基胍的合成
1.50g 2-氯-N-甲基-5-噻唑基甲胺,1.13gs-甲基-N-硝基异硫脲和6ml乙醇的混合物回流加热6小时。冷却后,反应混合物在减压下浓缩。残余物用硅胶柱色谱提纯(溶剂∶氯仿/甲醇=20/1),得到1.00g结晶的标题化合物。该化合物是表1中的化合物6,熔点:116.0-117.0℃
合成实施例4
N-[(2-氯-5-噻唑基)甲基]-N,N1,N1-三甲基-N″-硝基胍的合成
在搅拌和用冰水冷却下,将0.15g氢化钠(60%油状物)分批加入0.83gN-[(2-氯-5-噻唑基)甲基]-N-甲基-N′-硝基胍和10mlN,N-二甲基甲酰胺的混合物中。加完后,反应混合物再搅拌1.5小时。向反应混合物中逐滴加入0.54g甲基碘。反应混合物的温度回升至室温后,搅拌一夜。反应混合物倒入冰水中,用氯仿萃取。氯仿层用水洗涤,干燥,浓缩,然后,用硅胶柱色谱提纯(溶剂∶氯仿/甲醇=50/1-10/1),得到0.15g结晶的标题化合物。该化合物是表1中的化合物7,熔点:101.0-102.0℃。
合成实施例5
N-[(2-氯-5-噻唑基)甲基]-N′-甲基-N″-硝基胍的合成
0.48g 2-氯-5-噻唑基甲胺,0.31g S-甲基-N-甲基-N′-硝基异硫脲(由the Journal of Medical Chemistry,1977,Vol.20,No.7,P.905中描述的方法制备的),和3ml乙醇的混合物回流加热6小时。冷却后,反应混合物在减压下浓缩,残余物用硅胶柱色谱提纯(溶剂∶氯仿/甲醇=20/1),得到0.37g结晶的标题化合物。该化合物是表1中的化合物8,熔点:151.0-153.0℃。
合成实施例6
N-[(2-氯-5-噻唑基)甲基]-N′-硝基胍的合成
0.35g 2-氯-5-噻唑基甲胺,0.31g S-甲基-N-硝基异硫脲和3ml乙醇的混合物回流加热6小时。冷却后,用过滤收集分离出来的结晶,用少量乙醇洗涤,然后从乙醇中重结晶,得到0.42g结晶的标题化合物。该化合物是表1中的化合物9,熔点:160.0-162.0℃。
一些具体的制剂实施例如下所述。可是,应指出,可以用于根据本发明的杀虫剂配制中的载体、表面活性剂和其他添加剂不受下面配制实施例的限制。在下面配制实施例中,“份”代表“重量份”。
配制实施例1
将32.5份表1中的化合物1,3份木质素磺酸,4份聚氧乙烯烷基苯基醚,2份二氧化硅水合物和58.5份粘土均匀混合,同时粉碎,得到可湿性粉剂。
配制实施例2
将5.4份表1中的化合物2,2份二氧化硅水合物和92.6份滑石均匀混合,同时粉碎,得到粉剂。
配制实施例3
将5.4份表1中的化合物8,3份木质素磺酰盐,1份十二烷基磺酰钠,30份膨润土和60份粘土均匀混合,同时粉碎。然后,混合物与水捏合,颗粒化,干燥,得到颗粒剂。
本发明化合物的杀虫作用通过参考一些试验实施例加以说明。
试验实施例1
将5棵7cm高的稻苗浸入可湿性粉剂的水稀释液中10秒中,每个水稀释液含有预先测定浓度的每个试样化合物,可湿性粉剂是根据配制实施例1中描述的方法制备的。在空气干燥后,5棵稻苗的根用水湿润的卫生棉包起来,然后将其放在直径3cm高20cm的玻璃园筒中。将10只对化学药品具有抗药性的黑尾叶蝉(green rice leafhopper)的第二龄幼虫放入每个玻璃园筒中。园筒放在保持在26℃的房间中。处理后48小时,检验幼虫死亡率。结果列于表2中。
表2
化合物序号 死亡率(%),500ppm
1 100
2 100
3 100
4 100
5 100
6 100
7 100
8 100
9 100
比较化合物 70
注解:表2中的比较化合物是杀螟松(商品名),由下式表示:
试验实施例2
将5棵7cm高的稻苗浸入可润性粉剂的水稀释液中10秒中,每个水稀释液含有预先测定浓度的每个试样化合物,可湿性粉剂是根据配制实施例1中描述的方法制备的。在空气干燥后,5棵稻苗用水湿润的卫生棉包起来,放入直径3cm高20cm的玻璃园筒中。将10只对化学药品具有抗药性的灰褐稻虱(brown rice planthopper)的第二龄幼虫放入每个玻璃园筒中。园筒放在保持26℃的房间中。在处理后48小时,检验幼虫死亡率。结果列于表3中。
表3
化合物序号 死亡率(%),500ppm
1 100
2 100
3 100
4 100
5 100
6 100
7 100
8 100
表3(续)
化合物序号 死亡率(%),500ppm
9 100
比较化合物 65
注解:表3中的比较化合物与表2中的相同。
由上述内容明显地看出,本发明的化合物对防治各种害虫是特别有效的,对温血动物、鱼类和甲壳纲是低毒性的,其使用后的残留量小,对各种植物不产生植物毒性。
Claims (22)
2、根据权利要求1的硝基化合物,该化合物是N-[(6-氯-3-吡啶基)甲基]-N-甲基-N′-硝基胍。
3、根据权利要求1的硝基化合物,该化合物是N-[(6-氯-3-吡啶基)甲基]-N,N1,N1-三甲基-N″-硝基胍。
4、根据权利要求1的硝基胍化合物,该化合物是N-[(6-氯-3-吡啶基)甲基]-N′-甲基-N″-硝基胍。
5、根据权利要求1的硝基胍化合物,该化合物是N-[(6-氯-3-吡啶基)甲基]-N′硝基胍。
6、根据权利要求1的硝基胍化合物,该化合物是N-[(6-氯-3-吡啶基)甲基]-N,N′-二甲基-N″-硝基胍。
7、根据权利要求1的硝基胍化合物,该化合物是N-[(2-氯-5-噻唑基)甲基]-N-甲基-N′-硝基胍。
8、根据权利要求1的硝基胍化合物,该化合物是N-[(2-氯-5-噻唑基)甲基]-N,N′,N′-三甲基-N″-硝基胍。
9、根据权利要求1的硝基胍化合物,该化合物是N-[(2-氯-5-噻唑基)甲基]-N′-甲基-N″-硝基胍。
10、根据权利要求1的硝基胍化合物,该化合物是N-[(2-氯-5-噻唑基)甲基]-N′-硝基胍。
14、根据权利要求13的杀虫剂,其中化合物是N-[(6-氯-3-吡啶基)甲基]-N-甲基-N′-硝基胍。
15、根据权利要求13的杀虫剂,其中化合物是N-[(6-氯-3-吡啶基)甲基]-N,N′,N′-三甲基-N″-硝基胍。
16、根据权利要求13的杀虫剂,其中化合物是N-[(6-氯-3-吡啶基)甲基]-N′-甲基-N″-硝基胍。
17、根据权利要求13的杀虫剂,其中化合物是N-[(6-氯-3-吡啶基)甲基]-N′-硝基胍。
18、根据权利要求13的杀虫剂,其中化合物是N-[(6-氯-3-吡啶基)甲基]-N,N′-二甲基-N″-硝基胍。
19、根据权利要求13的杀虫剂,其中化合物是N-[(2-氯-5-噻唑基)甲基]-N-甲基-N′-硝基胍。
20、根据权利要求13的杀虫剂,其中化合物是N-[(2-氯-5-噻唑基)甲基]-N,N′,N′-三甲基-N″-硝基胍。
21、根据权利要求13的杀虫剂,其中化合物是N-[(2-氯-5-噻唑基)甲基]-N′-甲基-N″-硝基胍。
22、根据权利要求13的杀虫剂,其中化合物是N-[(2-氯-5-噻唑基)甲基]-N′-硝基胍。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27663389 | 1989-10-24 | ||
JP276633/89 | 1989-10-24 | ||
JP1328888A JPH03200768A (ja) | 1989-10-24 | 1989-12-19 | ニトログアニジン化合物及び殺虫剤 |
JP328888/89 | 1989-12-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1051728A true CN1051728A (zh) | 1991-05-29 |
Family
ID=26552033
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN90109217A Pending CN1051728A (zh) | 1989-10-24 | 1990-10-23 | 硝基胍化合物和杀虫剂 |
Country Status (6)
Country | Link |
---|---|
US (1) | US5166164A (zh) |
EP (1) | EP0425978A3 (zh) |
JP (1) | JPH03200768A (zh) |
KR (1) | KR910007880A (zh) |
CN (1) | CN1051728A (zh) |
AU (1) | AU6396490A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102372700A (zh) * | 2010-04-02 | 2012-03-14 | 上海师范大学 | 1,5-二取代六氢三嗪化合物及制备方法和应用 |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3059559B2 (ja) * | 1991-12-17 | 2000-07-04 | 日本バイエルアグロケム株式会社 | 殺虫性グアニジン誘導体 |
JP3068930B2 (ja) * | 1991-12-19 | 2000-07-24 | 日本バイエルアグロケム株式会社 | 殺虫性グアニジン類 |
US5531981A (en) * | 1992-05-01 | 1996-07-02 | Takeda Chemical Industries, Ltd. | Method for treatment of termite |
DE4236204A1 (de) * | 1992-10-27 | 1994-04-28 | Bayer Ag | Substituierte Aza(cyclo)alkane |
DE4414569A1 (de) * | 1994-04-27 | 1995-11-02 | Bayer Ag | Verwendung von substituierten Aminen zur Behandlung von Hirnleistungsstörungen |
DE4426753A1 (de) * | 1994-07-28 | 1996-02-01 | Bayer Ag | Mittel zur Bekämpfung von Pflanzenschädlingen |
DE19548872A1 (de) | 1995-12-27 | 1997-07-03 | Bayer Ag | Synergistische insektizide Mischungen |
US6828275B2 (en) * | 1998-06-23 | 2004-12-07 | Bayer Aktiengesellschaft | Synergistic insecticide mixtures |
DE19622355A1 (de) | 1996-06-04 | 1997-12-11 | Bayer Ag | Formkörper die agrochemische Mittel freisetzen |
TW533055B (en) * | 1997-02-10 | 2003-05-21 | Takeda Chemical Industries Ltd | Aqueous suspension of agrochemical |
PL193056B1 (pl) * | 1997-02-10 | 2007-01-31 | Sumitomo Chem Takeda Agro Co | Zwilżalna lub rozpuszczalna w wodzie granulowana kompozycja agrochemiczna, sposób jej wytwarzania oraz sposób zwalczania szkodników |
DE19807633A1 (de) * | 1998-02-23 | 1999-08-26 | Bayer Ag | Dermal applizierbare wasserhaltige Formulierungen von Parasitiziden |
DE19807630A1 (de) | 1998-02-23 | 1999-08-26 | Bayer Ag | Wasserhaltige Mittel zur Bekämpfung parasitierender Insekten und Milben an Menschen |
DE19823396A1 (de) * | 1998-05-26 | 1999-12-02 | Bayer Ag | Synergistische insektizide Mischungen |
US6149913A (en) * | 1998-11-16 | 2000-11-21 | Rhone-Poulenc Ag Company, Inc. | Compositions and methods for controlling insects |
DE19913174A1 (de) | 1999-03-24 | 2000-09-28 | Bayer Ag | Synergistische insektizide Mischungen |
US6156703A (en) * | 1999-05-21 | 2000-12-05 | Ijo Products, Llc | Method of inhibiting fruit set on fruit producing plants using an aqueous emulsion of eicosenyl eicosenoate and docosenyl eicosenoate |
DE19948129A1 (de) * | 1999-10-07 | 2001-04-12 | Bayer Ag | Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften |
DE10024934A1 (de) | 2000-05-19 | 2001-11-22 | Bayer Ag | Wirkstoffkombinationen mit insektiziden akariziden Eigenschaften |
US20020103233A1 (en) | 2000-11-30 | 2002-08-01 | Arther Robert G. | Compositions for enhanced acaricidal activity |
DE10117676A1 (de) | 2001-04-09 | 2002-10-10 | Bayer Ag | Dermal applizierbare flüssige Formulierungen zur Bekämpfung von parasitierenden Insekten an Tieren |
US8232261B2 (en) * | 2003-07-18 | 2012-07-31 | Bayer Cropscience Lp | Method of minimizing herbicidal injury |
DE102004006075A1 (de) | 2003-11-14 | 2005-06-16 | Bayer Cropscience Ag | Wirkstoffkombinationen mit insektiziden Eigenschaften |
AU2005290165A1 (en) * | 2004-08-25 | 2006-04-06 | Bayer Cropscience Lp | Method of controlling termites |
DE102004056626A1 (de) | 2004-11-24 | 2006-06-01 | Bayer Cropscience Ag | Substituierte Oxyguanidine |
US9919979B2 (en) | 2005-01-21 | 2018-03-20 | Bayer Cropscience Lp | Fertilizer-compatible composition |
CN114014821B (zh) * | 2021-11-22 | 2022-10-21 | 江苏中旗科技股份有限公司 | 一种噻虫胺的制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07121909B2 (ja) * | 1986-09-10 | 1995-12-25 | 日本バイエルアグロケム株式会社 | 新規複素環式化合物及び殺虫剤 |
IL87250A (en) * | 1987-08-01 | 1993-06-10 | Takeda Chemical Industries Ltd | :-unsaturated amines, process for their preparation, insecticidal/ miticidal compositions containing them |
JP2779403B2 (ja) * | 1988-11-29 | 1998-07-23 | 日本バイエルアグロケム株式会社 | 殺虫性ニトロ化合物 |
IE960441L (en) * | 1988-12-27 | 1990-06-27 | Takeda Chemical Industries Ltd | Guanidine derivatives, their production and insecticides |
EP0418199A3 (en) * | 1989-09-13 | 1991-06-12 | Ciba-Geigy Ag | Guanidine derivatives |
-
1989
- 1989-12-19 JP JP1328888A patent/JPH03200768A/ja active Pending
-
1990
- 1990-10-10 AU AU63964/90A patent/AU6396490A/en not_active Abandoned
- 1990-10-11 US US07/596,039 patent/US5166164A/en not_active Expired - Fee Related
- 1990-10-22 KR KR1019900016913A patent/KR910007880A/ko not_active Application Discontinuation
- 1990-10-23 EP EP19900120294 patent/EP0425978A3/en not_active Withdrawn
- 1990-10-23 CN CN90109217A patent/CN1051728A/zh active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102372700A (zh) * | 2010-04-02 | 2012-03-14 | 上海师范大学 | 1,5-二取代六氢三嗪化合物及制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
US5166164A (en) | 1992-11-24 |
EP0425978A3 (en) | 1991-11-06 |
EP0425978A2 (en) | 1991-05-08 |
KR910007880A (ko) | 1991-05-30 |
AU6396490A (en) | 1991-05-30 |
JPH03200768A (ja) | 1991-09-02 |
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