CN1065112C - 含苯基羟基亚胺酰基唑衍生物的杀虫组合物 - Google Patents
含苯基羟基亚胺酰基唑衍生物的杀虫组合物 Download PDFInfo
- Publication number
- CN1065112C CN1065112C CN94117855A CN94117855A CN1065112C CN 1065112 C CN1065112 C CN 1065112C CN 94117855 A CN94117855 A CN 94117855A CN 94117855 A CN94117855 A CN 94117855A CN 1065112 C CN1065112 C CN 1065112C
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- group
- alkyl
- compound
- atom
- 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
- SZZLDNXWTQUQHG-UHFFFAOYSA-N N-[phenyl(1H-pyrrol-2-yl)methylidene]hydroxylamine Chemical class C=1C=CC=CC=1C(=NO)C1=CC=CN1 SZZLDNXWTQUQHG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 230000000749 insecticidal effect Effects 0.000 title claims description 7
- 239000000203 mixture Substances 0.000 title description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 17
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 125000000000 cycloalkoxy group Chemical group 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 3
- -1 butyl sulfenyl Chemical group 0.000 claims description 73
- 238000002360 preparation method Methods 0.000 claims description 11
- 150000004820 halides Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 230000000361 pesticidal effect Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 4
- 229920002554 vinyl polymer Polymers 0.000 claims 4
- 239000002671 adjuvant Substances 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 239000002917 insecticide Substances 0.000 abstract description 15
- 125000004414 alkyl thio group Chemical group 0.000 abstract description 3
- 125000004183 alkoxy alkyl group Chemical class 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 125000005353 silylalkyl group Chemical group 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 125000003302 alkenyloxy group Chemical class 0.000 abstract 1
- 125000004981 cycloalkylmethyl group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 99
- 238000006243 chemical reaction Methods 0.000 description 44
- 241000238631 Hexapoda Species 0.000 description 40
- 238000012360 testing method Methods 0.000 description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 238000009472 formulation Methods 0.000 description 11
- 230000006837 decompression Effects 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 241000209094 Oryza Species 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229940072033 potash Drugs 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 235000015320 potassium carbonate Nutrition 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 238000001238 wet grinding Methods 0.000 description 8
- 240000008067 Cucumis sativus Species 0.000 description 7
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 7
- 238000003810 ethyl acetate extraction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000007605 air drying Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 241001364569 Cofana spectra Species 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 5
- 241001556089 Nilaparvata lugens Species 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 231100000225 lethality Toxicity 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 3
- 241001414720 Cicadellidae Species 0.000 description 3
- 241001466044 Delphacidae Species 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 241001600408 Aphis gossypii Species 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241001498622 Cixius wagneri Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000005949 Malathion Substances 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 241001415279 Pseudococcidae Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XWDUMRTZHYADKZ-UHFFFAOYSA-N [O].CC1CCCCC1 Chemical compound [O].CC1CCCCC1 XWDUMRTZHYADKZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000005262 alkoxyamine group Chemical group 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- DIRFUJHNVNOBMY-UHFFFAOYSA-N fenobucarb Chemical compound CCC(C)C1=CC=CC=C1OC(=O)NC DIRFUJHNVNOBMY-UHFFFAOYSA-N 0.000 description 2
- 125000005291 haloalkenyloxy group Chemical group 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 229960000453 malathion Drugs 0.000 description 2
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- VTWKXBJHBHYJBI-SOFGYWHQSA-N (ne)-n-benzylidenehydroxylamine Chemical compound O\N=C\C1=CC=CC=C1 VTWKXBJHBHYJBI-SOFGYWHQSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ZMESHQOXZMOOQQ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)naphthalene Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZMESHQOXZMOOQQ-UHFFFAOYSA-N 0.000 description 1
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- JUVDEAXMLQQRFP-UHFFFAOYSA-N 1h-imidazol-2-yl(phenyl)methanone Chemical class C=1C=CC=CC=1C(=O)C1=NC=CN1 JUVDEAXMLQQRFP-UHFFFAOYSA-N 0.000 description 1
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 1
- PYRKKGOKRMZEIT-UHFFFAOYSA-N 2-[6-(2-cyclopropylethoxy)-9-(2-hydroxy-2-methylpropyl)-1h-phenanthro[9,10-d]imidazol-2-yl]-5-fluorobenzene-1,3-dicarbonitrile Chemical compound C1=C2C3=CC(CC(C)(O)C)=CC=C3C=3NC(C=4C(=CC(F)=CC=4C#N)C#N)=NC=3C2=CC=C1OCCC1CC1 PYRKKGOKRMZEIT-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- SHBHYINHXNTBRP-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(2-methylsulfonylethyl)benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCCS(=O)(=O)C)C=CC=1 SHBHYINHXNTBRP-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000902805 Aulacophora Species 0.000 description 1
- 241000272639 Brachycaudus mimeuri Species 0.000 description 1
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 235000017647 Brassica oleracea var italica Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- 241000982105 Brevicoryne brassicae Species 0.000 description 1
- AELZBYQHJCEGBO-UHFFFAOYSA-N CC(C)(C)C[O] Chemical compound CC(C)(C)C[O] AELZBYQHJCEGBO-UHFFFAOYSA-N 0.000 description 1
- XVXLNFDATZFSRH-UHFFFAOYSA-N CC(CCCC1)C1OC1CCCC1.[O] Chemical compound CC(CCCC1)C1OC1CCCC1.[O] XVXLNFDATZFSRH-UHFFFAOYSA-N 0.000 description 1
- 241001313742 Callosobruchus chinensis Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241001465977 Coccoidea Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001222563 Empoasca onukii Species 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 241000966204 Lissorhoptrus oryzophilus Species 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000238814 Orthoptera Species 0.000 description 1
- 241000258972 Pentastomida Species 0.000 description 1
- 241000233679 Peronosporaceae Species 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 241000985245 Spodoptera litura Species 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000425037 Toona sinensis Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 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
- 150000003936 benzamides Chemical class 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000021329 brown rice Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004994 halo alkoxy alkyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000005419 hydroxybenzoic acid derivatives Chemical class 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 239000002689 soil Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 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
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (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)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明的杀虫组合物包括上式式表示的苯基羟基亚胺酰基唑衍生物作为活性成分和农业用辅助剂。该活性成分为粉状或粒状制剂时的有效量为0.05-20重量%,在可乳化浓缩或可湿化粉末制剂中的有效量为0.5-80重量%,上式述式中的R、X、Y和Z的含义如说明书所述。
Description
本发明涉及苯基羟基亚胺酰基唑衍生物以及包含它们作为活性组分的杀虫剂。
迄今为止,已知如1-(0-乙基-4-丁基苯基羟基亚胺基)-1H-1,2,4-三唑一类化合物和其类似物具有杀虫活性(如,描述于日本专利申请首次公开No.1-308260)。
公开于上述提及的专利申请中的这些化合物并没有足够的杀虫效果。最近,由于长期和广泛使用常规杀虫剂,已出现许多害虫对其产生抗性,因此,常规杀虫剂的效力也就降低了。尤其是以下这些,半翅目害虫如飞虱科,叶蝉科,蚜科,粉蚧科,粉虱总科,舌形虫纲等,已经对树木以及作物如水稻,麦类,马铃薯等产生很大危害。
因此,人们希望开发一种杀虫剂,它在低剂量使用时具有优异的杀虫效果,而且对上述的具有抗性的害虫也有效。
本发明人合成了多种苯基羟基亚胺酰基唑衍生物,并对其生理活性进行了广泛研究。结果发现,本发明的化合物,其中特别是苯基羟基亚胺酰基唑衍生物的苯环上被取代的某些化合物对多数害虫,尤其是危害性很高的半翅目害虫如飞虱科,叶蝉科,蚜科,舌形虫纲等具有极高的杀虫活性。相应于本发明的化合物的杀虫活性优于日本申请首次公开No.1-308260中描述的化合物。此外,本发明的化合物对上述的具有抗性的害虫显示较高的杀虫活性。
其中R是不少于3个碳原子的支链烷基,不少于2个碳原子的氟代烷基,不少于3个碳原子的支链烷氧基,不少于3个碳原子的卤代烷氧基,环烷基,可被一个或两个烷基取代的环烷基甲基,取代的甲硅烷基烷基,取代的甲硅烷基烷氧基,可被1或2个烷基取代的环烷氧基,烷硫基,卤代烷氧烷基,炔基,或卤代链烯氧基;
X是氢原子,氯原子,或氟原子。
Y是烷基;和
Z是氮原子或次甲基,
在式〔Ⅰ〕中,不少于3个碳原子的支链烷基包括的例子有:异丙基,异丁基,s-丁基,t-丁基,异戊基,1-甲基丁基,2-甲基丁基,新戊基,异己基,1-甲基戊基,2-甲基戊基,3-甲基戊基,2,2-二甲基丁基,2,3-二甲基丁基,3,3-二甲基丁基,5-甲基己基,3,3-二甲基戊基,4,4-二甲基戊基,1,3,3-三甲基丁基,2,3,3-三甲基丁基,3,3-二甲基己基,1,1,3,3-四甲基丁基,等等。
不少于3个碳原子的支链烷氧基的例子包括:异丙氧基,异丁氧基,s-丁氧基,t-丁氧基,i-戊氧基,新戊氧基,1-甲基丁氧基,2-甲基丁氧基,1,2-二甲基丙氧基,2-乙基丁氧基,2,2-二甲基丁氧基,3,3-二甲基丁氧基,2,3,3-三甲基丙氧基,2,2-二甲基戊氧基,1,3,3-三甲基丁氧基,1-乙基-2,2-二甲基丙氧基,1-异丙氧基-2-甲基丙氧基,等等。
不少于2个碳原子的氟代烷基的例子包括:全氟乙基,全氟丙基,全氟异丙基,金氟丁基,全氟异戊基,4,4,4-三氟-3,3-双(三氟甲基)丁基,等等。
不少于3个碳原子的卤代烷氧基的例子包括:4,4,4-三氟丁氧基,3-氯-2,2-二甲基丙氧基,1,1,2,3,3,3-六氟丙氧基,2,2-双(三氟甲基)丙氧基,3,3,3-三氟-2,2一双(三氟甲基)丙氧基,2,2,3,3,4,4,4-七氟-1-甲基丁氧基,等。
作为环烷基使用的有,环丙基,环戊基,环己基,或环庚基。
可被1或2个烷基取代的环烷基甲基包括:环丙基甲基,环戊基甲基,2-甲基环戊基甲基,3-甲基环戊基甲基,环己基甲基,或3,5-二甲基环己基甲基。
三烷基甲硅基烷基可作为取代的甲硅基烷基使用。
取代的甲硅烷基烷氧基包括三烷基甲硅基烷氧基,二烷基单链烯基甲硅基烷氧基,或二烷基-氯取代的烷基甲硅烷基烷氧基。
可被1个或2个烷基取代的环烷氧基包括环丙氧基,环戊氧基,2-甲基环己氧基,3-甲基环己氧基,4-甲基环己氧基,2,3-二甲基环己氧基,或2,5-二甲基环己氧基。
可应用的烷硫基如2-甲基丙硫基或其类似物。
卤代烷氧基烷基包括1,1-双(三氟甲基)乙氧基甲基或其类似物。
可使用的炔基为3,3-二甲基-1-丁炔基或其类似物。
链烯基包括3,3-二甲基-1-丁烯基或1-己烯基。
卤代链烯氧基包括2-溴-1-氯乙烯氧基或其类似基团。
此外,用于Y中的烷基包括1到4个碳原子的直链或支链烷基,如,甲基,乙基,丙基,异丙基,丁基,异丁基,s-丁基,t-丁基,或类似基团。
在式〔Ⅰ〕中,优选的R为一具有3到8个碳原子的支链烷基,
3到7个碳原子的支链烷氧基,或3到7个碳原子的卤代烷氧基;Y
为乙基,丙基,异丙基,或s-丁基;z为氮原子。
式〔Ⅰ〕代表的苯基羟基亚胺酰基唑衍生物包括两种异构体:顺式和反式构型。根据本发明的化合物不仅包括每种异构体而且包括任意比例的两种异构体的混合体。
此外,当式〔Ⅰ〕中的x具有饱和或不饱和的环链烷烃基或脂族烃基取代基时,式〔Ⅰ〕代表的化合物可能至少含有两种异构体,本发明包括这些异构体。
其次,对应于本发明的化合物列于表1。表1中给出的化合物序号和以后描述中的相对应。
相应于本发明的化合物可用下列A到D方法制备方法A(反应式1)
化合物序号 | R | X | Y | Z | 熔点(℃)或折光率〔nD 20〕 |
1234567891011121314151617181920 | 3-C3H11-i3-OC3H7-i3-OC4H3-i3-OC4H3-s3-OCH(CH3)CH3CH2CH33-OCH3CH(CH3)CH2CH33-OC3E13-i3-C4H3-i3-C3H33-i3-C4H3-s3-CH2CH(CH3)CH3CH33-C3H7-i3-C4H3-i3-OCH2CH(C2H3)33-CH(CH2)CH3CH2CH33-CH3CH(CH3)CH3CH2CH33-CH(CH3)CH2CH2CH7CH33-CH3CH2CH(CH3)CH2CH33-OCH2CH2C(CH3)33-CH3CH(CH3)CH(CH3)3 | 4-FHHHHHHHHHHHHHHHHHHH | C3H3-iC3H3-iC3H3-iC2E3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC2H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-i | NNNNNNNNNNNNNNNNNNNN | 1.52531.53901.53411.53201.53121.51771.53411.53601.53171.53381.53701.53981.53121.53281.53171.53091.52051.52931.52891.5304 |
2122232425262728293031323334353637383940414243444546474849 | 3-C3H11-i3-C3H11-i5-C3H12-i3-C6H13-i5-C3H13-i3-OCH(CH3)CF2CF3CF35-OCH(CH3)CF2CF2CF35-C3H13-i3-OCH(CH3)CH2C(CH3)33-C(CH3)2CH2C(CH3)33-C3H33-i3-C3H33-i3-C6H13-i3-C6H13-i3-OC4H3-i3-OC3H21-i3-CH3C(CH2)33-OC4H3-t5-C4H13-i5-C4H23-i3-C4H23-i3-C3H23-i3-C3H23-i3-OCH2C(CH3)33-C3H23-i3-CH3CH2C(CH3)33-OCH2C(CH3)2CH2CH33-C3H23-i3-OCF3CHFCF3 | 2-F4-F2-FH2-ClH2-Cl2-ClHH4-F4-F4-F4-FHHHH2-F2-FHHHHHHHHH | C3H3-iC3H2-iC3H3-iC3H2-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iC3H3-iCH3C4H3-sC2H3C2H3-iC4H3C3H3-iC3H3-iC3H3C3H3-i | NNNNNNNNNNNCHNCHCHCHNNNCHNNNNNNNNN | 1.52021.52111.52021.51981.53601.47601.49191.52521.51081.52301.51471.52581.51321.52301.54001.53581.52481.53081.51621.52251.54221.52931.53261.52021.52901.52581.52691.53201.4809 |
5051525354555657585960616263646566676869707172737475767778 | 3-OCH2C(CH3)33-OCH(CH3)C(CH3)33-OCH2C(CH3)33-OCH2C(CH3)33-C6H23-i3-CH2CH2CH2C(CH3)33-OCH2CH2CH2CF33-C3H11-i3-CH2CH2CH2C(CH3)33-CH2CH2CH2C(CH3)33-OCH2C(CH3)2CH2CE2CH33-OCH2C(CH3)33-CH2CH2C(CH3)33-CH2CH2C(CH3)33-CH2CH2C(CH3)33-CH2CH3C(CH2)33-OCH2C(CH3)2CH2Ci3-CH2CH2C(CH3)33-CH2CH2C(CH3)33-CH2CH2C(CH3)33-OCH2C(CH3)3CH2CH33-CH2CH2C(CH3)33-OCH2C(CH3)2CH2CH2CH33-OCH(CH3)C(CH3)33-CH2CH2C(CH3)3CH2CH2CH35-CH2CH3C(CH3)2CH3CH33-CH3CH2C(CH3)33-OCH2C(CH3)33-CH2C(CH3)2CH2CH2 | HHHH2-FHHHHHHHHHHHHHH4-FHHHHHH2-F4-F4-FH | C3H3-iC3H3-iC2H3C4H3-sC3H7-iC3H7-iC3H7-iC4H3-iC4H3-sC3H3C3H3-iC3H3C4H3-sC2H5C4H3-sC3H5C3H7-iC3H7C3H2-iC4H3-tC3H3C3H2-iC3H3C3H3C3H3C3H3C3H3C3E3C3H3-i | CHNNNNNNNNNNNNNNCHCHNNNNNCHNNNNNNN | 1.53401.52731.53721.52761.51731.52551.50881.52881.52291.52681.527145-461.52611.53471.53131.54011.54401.53051.51831.52381.52901.53261.53001.53271.52491.52331.51711.52031.5306 |
798081828384858687888990919293949596979899100101102103104105106107 | 5-CH3CH2C(CH3)33-C3H13-i3-C3H12-i3-OCH2C(CH3)35-CH2CH2C(CH3)33-OCH(CH3)CH2CH(CH3)23-OCH(CH3)CH2CH(CH3)33-OCH(CH3)CH(CH3)25-CH2CH3C(CH3)35-CH3CH3C(CH3)33-OCH(CH3)CH(CH3)33-CH2CH2C(CH3)35-CH2CH2C(CH3)33-CH(CH3)CH2C(CH3)33-CH(CH3)CH2C(CH3)33-CH2CH(CH3)C(CH3)33-CH2CH(CH3)C(CH3)33-CH2CH2C(CH3)2CH3CH33-CH2CH2C(CF3)35-CH2CH2C(CF3)33-OCH(C2H3)C(CH3)33-OCH(C2H3)C(CH3)33-OCH2C(CH3)(CF3)23-OCH2C(CH3)(CF3)33-OCH2C(CF3)33-OCH2C(CF3)35-OCH2C(CH3)35-OCH2C(CH3)35-OCH2C(CH3)(CF3)3 | 2-F4-F4-F4-F2-FHHH2-Cl2-ClH4-Cl2-FHHHHHH2-FHHHHHH2-F2-F2-F | C3H3-iC3H3C2H3C3H3-iC3H2C3H3-iC3H3C3H3-iC3H3-iC3H3C3H2C3H3-iC3H3C3H3-iC3H3C3H3-iC2H3C3H2-iC3H2-iC3H3-iC3H3C3H3-iC3Hi3C3H3-iC3H3C3H3-iC3H3C3H3-iC3H3 | NNNNNNNNNCHNNCHNNNNNNNNNNNNNNNN | 1.51681.52141.52621.51981.50681.52621.52931.53271.52921.53601.53521.53381.52331.53051.52741.4952 |
108109110111112113114115116117118119120121122123124125126127128129130131132133134135 | 5-OCH2C(CH3)(CF3)25-OCH2C(CF3)35-OCH2C(CF3)33-OCH3C(CH3)(CF3)33-OCH2C(CH3)(CF3)33-OCH2C(CF3)23-OCH2C(CF3)33-CH2CH2C(CH3)33-CH2CH2C(CH3)3CH(CH3)23-OCH<CH(CH3)23-OCH2C(CH3)33-CH2CH2C(CH3)33-OC4H3-i3-OC4H3-i5-CH2CH2CH(CH3)CH2CH33-C2F33-C3F73-C4F35-CH2CH2C(CH3)35-CH2CH2C(CH3)35-CH2CH2C(CH3)35-CH2CH2C(CH3)35-CH2C(CH3)35-C4H3-t5-(CH2)3C(CH3)35-C4H3-t5-CH2C(CH3)35-(CH2)3C(CH3)3 | 2-F2-F2-F4-F4-F4-F4-FHHHHH4-F4-F2-FHHH2-F2-F2-F2-F2-F2-F2-F2-F2-F2-F | C3H3-iC3H3C3H3-iC3H3C3H3-iC3H3C3H3-iC4H3-iC3H3-iC3H3C3H3CH3C3H3-iC3H3C4H3-iC3H3-iC3H3-iC3H3-iCH3C2H3C4H3-iC4H3-tC3H3-iC3H3-iC3H3-iC3H3C3H3C3H3 | NNNNNNNNNCHCHNNNNNHNNNNNNNNNNN | 1.52481.52221.53011.53391.539844~4561~631.51521.59211.47381.4633 |
其中A为卤原子;R,X,Y,和Z如上述。
式〔Ⅰ〕代表的化合物可由式〔Ⅱ〕代表的苯基羟基亚胺唑化合物与式〔Ⅲ〕代表的卤化物或磺酸酯化合物在碱存在下反应制得。在此反应中,卤化物或磺酸酯化合物使用的量可是等当量或过量。此外,反应中使用的碱包括无机碱,例如碱金属氢氧化物如氢氧化钠,氢氧化钾等;碱金属碳酸盐如碳酸钠,碳酸钾等;碱金属碳酸氢盐如碳酸氢钠,碳酸氢钾,等,或有机碱如三乙胺,N,N-二甲基苯胺,吡啶,1,8-二氮杂环〔5,4,0〕十一烷-7-烯,等。
如需要,反应可在稀释剂存在下进行。稀释剂包括水或非活性有机溶剂。例如,酮类如丙酮,丁酮,等等;可被卤代的芳香烃如苯,甲苯,二甲苯,氯苯等,脂肪烃如石油醚,轻汽油等;醚类如乙醚,四氢呋喃,二噁烷等;腈类如乙腈,丙腈等;或酰胺类如N,N-二甲基甲酰胺,N,N-二甲基乙酰胺,N-甲基吡咯烷酮等都可使用。
合成反应的温度从0℃到反应体系的回流温度,优选的是在40°-100℃。反应时间依赖于反应化合物的类型。反应通常在1到6小时完成。
方法B
其中B为卤原子,R,X,Y和Z意义同上。
式〔Ⅰ〕代表的化合物可在碱存在下,用式〔Ⅳ〕代表的苯基羟基亚胺酰基卤化物与式〔Ⅴ〕代表的唑或三唑化合物反应制得。在此反应中,唑或三唑可以等量或过量和碱或溶剂使用。此外,可用如方法A中描述同样的碱。
如需要,反应可在适宜的稀释剂存在下进行。上述的同样稀释剂在此适用。
此合成反应温度范围在室温到回流温度,优选的在80°-130℃。反应时间依赖于反应化合物类型。反应通常在2-5小时完成,可获得好收率。
方法C
其中D为不少于3个碳原子的支链烷基,不少于3个碳原子的卤代烷基,取代的甲硅基烷基,可被1个或2个烷基取代的环烷基,或卤代链烯基;A'为卤原子,烷基磺酰氧基,可被取代的苯基磺酰氧基,X,Y,Z同上述。
式〔Ⅷ〕代表的化合物可在碱存在下,通过式〔Ⅵ〕代表的在其苯环上具有羟基的化合物与式〔Ⅶ〕代表的卤化物或磺酸酯化合物反应而得。在此反应中,卤化物和磺酸酯化合物可以等量或过量使用。此外,方法A中描述的碱可用于此反应。
如需要,反应可在适宜稀释剂存在下进行。这里可使用如上述的稀释剂。
所进行的合成反应温度范围可在0℃到反应体系的回流温度,优选的是在40°到120℃。反应时间代赖于反应化合物的类型。反应通常在1到8个小时完成。
方法D
其中E为不少于3个碳原子的支链烷基,不少于3个碳原子的氟代烷基,取代的甲硅基烷基,可被1个或2个烷基取代的环烷基,或卤代链烯基;X,Y,和Z同上描述。
式〔Ⅹ〕代表的化合物可通过式〔Ⅵ〕代表的其中苯环上具有羟基的化合物与式〔Ⅸ〕代表的醇化合物在三苯基膦和偶氮二羧酸二乙酯或偶氮二羧酸二甲酯存在下反应制得,在此反应中,醇化合物可以等量或过量使用。
如需要,此反应可于适宜的稀释剂存在下进行。此外,方法A中描述的稀释剂可用于此。优选地,乙腈或四氢呋喃是适当的
合成反应温度范围宜在0℃到回流温度,优选地在30°-120℃。反应时间依赖于化合物的类型。反应通常在0.5到72小时内完成。
制备相应于本发明化合物的方法将于以下的实施例中具体描述。
例1
1-〔0-异丙基-3-(3,3-二甲基丁氧基)苯基羟基亚胺酰基〕-1H-1,2,4-三唑(化合物19)的合成
向1.6g(5.6mmol)1-〔3-(3,3-二甲基丁氧基)苯基羟基亚胺酰基〕-1H-1,2,4-三唑溶于100ml N,N-二甲基甲酰胺的溶液中加入0.16g(6.7mmol)氢化钠,混合物在80℃搅拌20分钟,然后放置,自然冷却到约50℃。向此混合物中加入1.1g(6.5mmol)的2-碘丙烷,在约50℃下搅拌1小时。反应混合物放置,自然冷却至室温。冷却的混合物倾入水中,以乙酸乙酯萃取。用水洗后,有机层以无水硫酸镁干燥。减压下去掉有机层中的溶剂。残留物用柱色谱纯化,得1.4g(产率:87%)的预想产物,其折光率在20℃时为
1.5289c
例2
1-(0-异丙基-3-异戊基苯基羟基亚胺酰基)-1H-1,2,4-三唑(化合物9)的合成
向100ml的N,N-二甲基甲酰胺中加入1.5g(5.6mmol)的0-异丙基-3-异戊基苯基羟基亚胺酰氯,0.8g(11.6mmol)的1,2,4-三唑,和1.6g(11.6mmol)的碳酸钾。所得混合物在120℃下搅拌3小时完成反应。反应混合物放置,自然冷至室温。冷却的反应混合物倾入水中,以乙酸乙酯提取。有机层以水洗后,以无水硫酸镁干燥。其中的溶剂减压下去掉。残留物以柱色谱纯化,得1.4g(产率:71%)的预想产物,其折光率在20℃下为
1.5317。
例3
1-(0-异丙基-3-异丁氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑(化合物3)的合成
向100ml的N,N-二甲基甲酰胺中加入1.2g(4.9mmol)的1-(0-异丙基-3-羟基苯基羟基亚胺酰基)-1H-1,2,4-三唑,0.7g(5.1mmol)的异丁基溴,0.8g(5.8mmol)的碳酸钾。将所得的混合物在80℃下搅拌1小时完成反应。反应混合物静置自然冷却。冷却的混合物倾入水中,以乙酸乙酯提取。有机层以无水硫酸镁干燥。减压下移去有机层中的溶剂。残物通过柱色谱纯化而获得1.1g(产率:73%)的预想产物,在20℃下其折光率为
1.5341。
例4
1-(0-异丙基-3-新戊氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑(化合物44)的合成
将2.5g(0.010mol)的1-(0-异丙基-3-羟基苯基羟基亚胺酰基)-1H-1,2,4-三唑,0.9g(10.0mmol)的2,2-二甲基-1-丙醇,2.6g(10.0mmol)的三苯膦溶于40ml的四氢呋喃中。溶液在水浴中冷却到不超过10℃。向此溶液中逐滴加入1.7g(10.0mmol)的偶氮二羧酸二乙酯,以使溶液的温度不超过20℃。混合物搅拌过夜,加热至60℃。反应混合物然后浓缩。残留物通过柱色谱纯化得到0.8g(产率:25%)的预想产物,其在20℃下的折光率为
1.5202。
例5
1-(0-乙基-3-三甲基硅基甲氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑(化合物147)的合成
将1。5g的1-(3-三甲基硅基甲氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑溶于50ml干燥过的四氢呋喃(THF)和50毫升二甲基甲酰胺(DMF)的混合溶剂中。向此溶液中加入0.15g的氢化钠.将所得的混合物在室温下搅拌10分钟。溶有2.0克碘乙烷的10ml THF溶液滴加入上述混合物中,历时15分钟。反应混合物然后于50℃搅拌3小时完成反应。所得的混合物于减压下凝缩至其体积的一半。凝缩混合物放置冷却后.将其倾入大量水中。有机层以乙酸乙酯提取.硫酸镁干燥。减压下移去有机层的溶剂。残物以柱色谱(淋洗剂:己烷/乙酸乙酯=4/1)纯化,得到1.2g(产率:75%)的预想产物,其在20℃下的折光率为
1.5385。
例6
1-(0-异丙基-3-环己基苯基羟基亚胺酰基)-1H-1,2,4-三唑(化合物153)的合成
将3.3g的(0-异内基-3-环已基苯基羟基亚胺酰氯,1.6g的1,2,4-三唑,和3.3g的碳酸钾溶于100ml的N,N-二甲基乙酰胺(DMAC)中。上述混合物于130℃下搅拌2小时。反应混合物静置自然冷却后,将其倾入水中。有机层用乙酸乙酯提取.以硫酸镁干燥。减压下去掉有机层中的溶剂。残留物以柱色谱(淋洗剂:己烷/乙酸乙酯=4/1)纯化而得到3.1g(产率:84%),熔点为49°-51℃的预想产物(白色固体)
例7
1-〔0-异丙基-(3-(1,1,1,3,3,3-六氟-2-甲基-2-丙氧基)甲基)苯基羟基亚胺酰基〕-1H-1,2,4-三唑(化合物162)的合成
将1.2g的0-异丙基-{3-(1,1,1,3,3,3-六氟-2-甲基-2-丙氧基)甲基}苯基羟基亚胺酰氯,0.4g的1,2,4-三唑,和0.9g的碳酸钾加入到50ml的DMAC中。上述混合物于130℃搅拌3小时。所得的混合物放置自然冷却后,倾入水中。有机层以乙酸乙酯提取,硫酸镁干燥。减压下去掉有机层中的溶剂。残余物通过柱色谱(洗脱剂:己烷/乙酸乙酯=4/1纯化,得到0.9g(产率:69%)的预想产物(透明粘性液体),20℃时的折光率为
1.4821。
例8
1-(0-异丙基-3-3甲基硅基甲氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑(化合物140)的合成
将2.7g的1-(0-异丙基-3-羟基苯基羟基亚胺酰基)-1H-1,2,4-三唑,1.5g的三甲基氯硅烷,1.8g的碳酸钾,少量碘化钾催化剂加入到100ml的DMF中。混合物于90℃搅拌2小时。所得混合物放置自然冷却后,将其倾入水中。有机层以乙酸乙酯提取,硫酸镁干燥。减压下去掉有机层中的溶剂。残留物通过柱色谱(洗脱液:己烷/乙酸乙酯=4/1)纯化,得到3.2g(产率:89%)的具有在20℃时折光率为
1.5310的预想产物(透明粘性液体)。
例9
1-(0-异丙基-3-环己氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑(化合物158)的合成
将2.0g的1-(0-异丙基-3-羟基苯基羟基亚胺酰基)-1H-1,2,4-三唑,1.6g的环己醇,和4.3g的三苯基膦溶于100ml的THF中。上述混合物保持在5℃。30分钟内,向此溶液中逐滴加入10ml溶有2.8g偶氮二羧酸二乙酯的THF溶液。所得混合物于室温下搅拌8小时。减压下去掉此混合物中的溶剂。残留物通过柱色谱(洗脱剂:己烷/乙酸乙酯=4/1)纯化,得到2.1g(产率:78%)的预想产物(透明粘性液体),在20℃时的折光率为
1.5490
式〔Ⅱ〕,〔Ⅳ〕和〔Ⅵ〕代表的化合物系相应为本发明化合物的原料,它们可由方法a到c制得。
方法a
其中R,X,Z,和B同上述。
式〔Ⅱ〕代表的苯基羟基亚胺酰基唑化合物可在如乙腈等溶剂中,于碱如碳酸钾等存在下,通过式〔Ⅺ〕代表的苯基羟基亚胺酰卤化合物和式〔Ⅴ〕代表的唑或三唑化合物反应合成。
所进行合成反应的温度范围从0℃到反应体系的回流温度,优选的是50°~80℃。反应时间有赖于反应化合物的类型。通常,反应于1到6小时完成。
方法b
其中R,X,Z和B的定义同上。
式〔Ⅳ〕代表的苯基羟基亚胺酰卤化物可通过在有或没有惰性溶剂如芳香烃(如苯、甲苯等),卤代烃(如氯仿,四氯化碳等)等存在下,以式〔Ⅻ〕代表的苯甲酰胺与卤化试剂如五氧化二磷,二氯亚砜等反应合成。此外,式〔Ⅳ代表的苯基羟基亚胺酰卤化物也可以在非活性溶剂腈如乙腈、丙腈等,或芳香烃如苯,氯苯等存在下,通过式〔Ⅻ〕代表的苯甲酰胺化合物与三苯基膦和四氯化碳,或三苯基膦和四溴化碳组成的卤化剂反应合成。这种情况下,四氯化碳和四溴化碳可用作溶剂。
此合成反应进行的温度范围从0℃到反应体系的回流温度,优选的为50℃到80℃,反应时间要依赖于反应化合物的类型。通常反应在1-6小时完成。
方法c
其中X,Y,和Z的定义同上。
式〔Ⅵ〕代表的化合物可在非活性质子偶极溶剂如水,乙酸,乙醇,乙酸乙酯,N,N-二甲基乙酰胺,N,N-二甲基甲酰胺等中,在碳-钯催化剂存在下,通过氢化裂解相应于式〔ⅩⅢ〕代表的苄氧基化合物合成。而且,式〔Ⅵ〕代表的化合物也可以在非活性溶剂芳香烃如苯,氯苯等,或卤代烃如二氯甲烷,1,2-二氯乙烷等中,用三溴化硼或三氯化硼将式〔ⅩⅢ〕代表的相应的苄氧化合物去苄基而合成。
合成反应温度范围从-60℃到40℃,优选地为-30℃到室温。反应时间依赖于反应化合物的类型。通常,反应在1到8小时完成。
此外,式〔Ⅺ〕,〔Ⅻ〕,和〔ⅩⅢ〕代表的化合物可用下列方法制得。
式〔Ⅺ〕代表的化合物可用以已知方法从相应的苯甲醛化合物和羟胺盐酸反应制得的苯甲醛肟和卤化剂如N-溴琥珀酰亚胺,N-氯琥珀酰亚胺,氯等反应合成得到。
式〔Ⅻ〕代表的化合物可用从相应的苯甲酸衍生物衍生的苯甲酰卤或苯甲酰基咪唑与烷氧基胺反应合成。
此外,式〔ⅩⅢ〕代表的苄氧基化合物可由苄化的羟基苯甲酸衍生物经下列系列步骤合成:以已知方法从苄基化合物合成苯甲酰卤;以烷氧基胺与苯甲酰卤反应;根据方法b进行卤化;进行方法B中的步骤。
参考下述实例,对制备相应于本发明原料的方法进行详细描述。
例10
1-〔3-(3,3-二甲基丁氧基)苯基羟基亚胺酰基〕-1H-1,2,4-三唑的合成
向100ml的1,2-二甲氧基乙烷中加入2.0g(7.8mmol)的3-(3,3-二甲基丁氧基)苯基羟基亚胺酰氯,1.9g(27.5mmol)1,2,4-三唑,和1.5g(10.9mmol)的碳酸钾。混合物在约50℃下搅拌8小时。所得的混合物放置自然冷却后,将其中的溶剂脱去。残留物经过柱色谱纯化,得到预想的产物1.2g(产率:46%)
例11
0-异丙基-3-异戊基苯基羟基亚胺酰氯的合成
向200ml乙腈中加入5.4g(23.5mmol)的0-异丙基3-异戊基苯基异羟肟酸,9.9g(37.8mmol)三苯基膦,和11.6g(75.3mmol)四氯化碳。混合物回流1小时。经回流的混合物放置自然冷却,其中的溶剂减压除去。残留物经柱色谱纯化,得到预想产物5.1g(产率:88%)
例12
1-(0-异丙基-3-羟基苯基羟基亚胺酰基)-1H-1,2,4-三唑的合成
室温下,向150ml的乙酸乙酯中加入5.0g 1-(0-异丙基-3-苯甲氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑(溶点:62°-67℃)和1g 10%的钯-碳。连通混合物,进行加氢反应。8小时后,去掉钯-碳。滤液然后浓缩。残留物用柱色谱纯化,得到3.2g(产率:89%)00的预想产物,其熔点为160℃到163℃。
根据本发明的杀虫剂包括以式〔Ⅰ〕代表的苯基羟基亚胺酰基唑衍生物作为活性成分。
对应于本发明的化合物作为杀虫剂使用时,这些化合物可以单独使用或用已知方法按配方与载体,表面活性剂,分散剂,助剂等制成如粉剂,可湿粉,乳化提缩物,细粒,颗粒等。
配方中使用的载体适宜的例子是固体载体如羟铝石(Zirclite),滑石,膨润土,粘土,高岭土,硅藻土,白碳,蛭石,熟石灰,硅砂,硫酸铝,和尿素;液体载体如异丙醇,二甲苯,环己酮,甲萘,等。表面活性剂和分散剂的应用例子包括烷基苯磺酸的金属盐和二萘基甲烷二磺酸,硫酸酯的醇盐,烷基芳基磺酸盐,木质素磺酸盐,聚氧乙烯乙二醇醚,聚氧乙烯烷基芳基醚,聚氧乙烯脱水山梨醇单烷化物等。
助剂的适宜例子包括羧甲基纤维素,聚乙烯乙二醇,阿拉伯树胶等等。
这些制剂可以直接使用,或将其稀释成适宜的浓度后使用。
活性成分的比例根据需要选定。当制成粉剂或颗粒时,活性成分比较好的占重量的0.05%到20%(优选的占0.1%到10%重量化)。对乳油或可湿性粉剂,活性成分占重量的0.5-80%(优选的占重量的1-80%)是适宜的。
根据本发明的杀虫剂可用于多种目的。例如,对茎和叶部位喷洒,注入灌溉水,以及在播种前,播种时,移植时,以及植物成熟时注入土壤。本发明的杀虫剂也具有杀菌性能。
根据本发明的杀虫剂的应用比例依赖于所用的活性化合物的种类,要控制的害虫或病害的种类,害虫或病害的性质,伤害程度,环境条件,使用的制剂方式等而变化。
当直接以粉剂或颗粒使用本发明的杀虫剂时,活性成分的使用比例宜选择每10公亩0.05g到5kg,优选地为每10公亩0.1g到1kg。此外,当以液体形式如乳油或可湿性粉剂使用本发明杀虫剂时,活性成分的应用比例适宜选择在0.1ppm到5000ppm,优选地为1ppm到1000ppm。
相应于本发明的杀虫剂可以单独使用或和其它杀虫剂或杀菌剂结合使用。
根据下面的配方实施例对代表性配方进行说明。其中给出的“%”都指重量百分比。没有限制下面实例中描述的助剂和化合物的种类和比例。
配方例1:乳油
将30%的化合物(9),20%的环己酮,11%的聚氧乙烯烷基芳基醚,4%的烷基苯磺酸钙,35%的甲萘均匀溶解,得到乳油。
配方例2:可湿性粉剂
将40%的化合物(10),15%的硅藻土,15%的粘土,25%的白碳,2%的二萘甲烷磺酸钠,和3%的木质素磺酸钠均匀混合,研磨成可湿粉。
配方例3:粉剂
将2%的化合物(17),5%的硅藻土,93%的粘土均匀混合,研磨成粉剂。
配方例4:颗粒
将5%的化合物(1),2%的月桂醇的酯钠盐,5%的木质素磺酸钠,2%的羰甲基纤维素,86%的粘土混合研磨。100份重量的磨碎混合物加入到20份重量的水中。将所得的混合物提和,通过挤压成粒机形成14目到32目的颗粒。将形成的颗粒干燥成预想的颗粒。
相应于本发明的苯基羟基亚胺酰基唑衍生物和日本专利申请首次公开No.1-308260中描述的化合物相比对半翅目害虫显示较好的控制,这些半翅目害虫如飞虱科包括稻褐飞虱,向背飞虱,稻灰飞虱等,叶蝉科包括黑尾叶蝉,Empoasca onukii等,蚜科包括棉蚜,桃蚜,甘蓝蚜等,粉虱总科包括温室自粉虱等,粉蚧科包括康氏粉蚧等,蝽科包括缘椿(Leptocorixa Corbetti)等。此外,本发明的苯基羟基亚胺酰基唑衍生物对下列害虫亦有效,鳞翅目包括小菜蛾,斜纹夜蛾等,双翅目包括家蝇等,鞘翅目包括稻象甲,绿豆象,黄守瓜等,直翅目包括德国小蠊等,叶螨科包括棉红叶螨,拮全瓜螨等。
此外,本发明化合物对引起下列病害的病原菌有杀菌活性,且能有效的控制,这些病害有:稻瘟病,水稻纹枯病,黄瓜霜霉病,黄瓜花腐病,黄瓜白粉病,黄瓜细菌性角斑病,以及甘兰黑斑病。
现根据下列试验实施例说明本发明化合物的效果。
试验例1:
对商品药剂显示杀虫抗性的黑尾叶蝉死亡率试验。
根据配方2制得的可湿粉用水稀释至20ppm的浓度。将稻类植物的叶和茎浸入所制得的水溶液中。空气干燥后,将上述茎和叶放入一试验管内。在此管中加进10只黑尾叶蝉幼虫。用脱脂棉封住试管开口。封闭的试管放入25℃的恒温箱内6天,数一下害虫死亡的数目,计算害虫的死亡百分率。其结果见表2。
重复此试验。作比较试验的化合物列于下,它们公开于日本专利申请首次公开No.1-308260,以及仲丁威,马拉硫磷。对比(较)试验是以商用试验的1000ppm浓度下进行的。对比化合物1:
1-(0-乙基-4-丁基苯基羟基亚胺酰基)-1H-1,2,4-三唑对比化合物2:
1-(0-异丙基-4-丁基苯基羟基亚胺酰基)-1H-1,2,4-三唑。对比化合物3:
1-(0-异丙基-4-丁氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑对比化合物4:
1-(0-异丙基-4-己基苯基羟基亚胺酰基)-1H-1,2,4-三唑对比化合物5:
1-(0-丙基-3-(2,2,2-三氟乙氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑对比化合物6
1-(0-异丙基-2-氯-5-甲氧基苯基羟基亚胺酰基)-1H-1,2,4-三唑。对比化合物7
仲丁威,(通用名,由Kumiai ChemicalIndustries,Co.,Ltd.生产)对比化合物8
马拉硫磷(俗名,由Kumiai ChemicalIndustries.,CO.,Ltd.生产)。
表2化合物序号 死亡的害虫(%)
1 100
2 100
3 100
4 100
5 100
6 100
7 100
8 100
9 100
10 100
11 100
12 100
13 100
14 100
15 100
16 100
17 100
18 100
19 100
20 100
21 100
22 100续于后页
表2(续)化合物序号 死亡的害虫(%)
23 100
24 100
25 100
26 100
27 100
28 100
29 100
30 100
31 100
32 100
33 100
34 100
35 100
36 100
37 100
38 100
39 100
40 100
41 100
42 100
43 100
44 100续于后页
45 100
表2(续)化合物序号 死亡的害虫(%)
46 100
47 100
48 100
49 100
50 100
51 100
52 100
53 100
54 100
55 100
56 100
57 100
58 100
59 100
60 100
61 100
62 100
63 100
64 100
65 100
66 100
67 100
68 100续于后页
表2(续)化合物序号 死亡的害虫(%)
69 100
70 100
71 100
72 100
73 100
74 100
75 100
76 100
77 100
78 100
79 100
80 100
81 100
82 100
83 100
84 100
85 100
86 100
87 100
88 100
89 100
90 100
115 100续于后页
表2(续)化合物序号 死亡的害虫(%)
116 100
117 100
118 100
119 100
120 100
121 100
122 100
123 100
124 100
125 100列比化合物1 30对比化合物2 60对比化合物3 50对比化合物4 40对比化合物5 30对比化合物6 20对比化合物7 30(商品试剂)对比化合物8 40(商品试剂)
试验例2
稻褐飞虱死亡率试验。
将按配方例2制得的可湿粉用水稀释到预定浓度。将稻类植物的茎和叶浸入得到的水溶液制剂中。空气干燥后,将上述的茎和叶置于一式管中。再向其中放入10只稻褐飞虱的幼虫,用脱脂棉封住试管的开口。将封闭的试管置于25℃下的恒室箱内6天后,数数害虫的死亡数而计算其死亡百分率,其结果见表3。
用试验例1描述的化合物进行对比试验。
表3
死亡的害虫(%)化合物序号 20ppm 4ppm
1 100 100
2 100 100
3 100 100
4 100 100
5 100 100
6 100 100
7 100 100
8 100 100
9 100 100
10 100 100
11 100 100
12 100 100
13 100 100
14 100 100
15 100 100
16 100 100
17 100 100
18 100 100
19 100 100
20 100 100
21 100 100续于后页
表3(续)化合物序号 死亡的害虫(%)
20ppm 4ppm
22 100 100
23 100 100
24 100 100
25 100 100
26 100 100
27 100 100
28 100 100
29 100 100
30 100 100
31 100 100
32 100 100
33 100 100
34 100 100
35 100 100
36 100 100
37 100 100
38 100 100
39 100 100
40 100 100
41 100 100
42 100 100续于后页
表3(续)
死亡的害虫(%)化合物序号 20ppm 4ppm
43 100 100
44 100 100
45 100 100
46 100 100
47 100 100
48 100 100
49 100 100
50 100 100
51 100 100
52 100 100
53 100 100
54 100 100
55 100 100
56 100 100
57 100 100
58 100 100
59 100 100
60 100 100
61 100 100
62 100 100
63 100 100续于后页
表3(续)
死亡的害虫(%)化合物序号 20ppm 4ppm
64 100 100
65 100 100
66 100 100
67 100 100
68 100 100
69 100 100
70 100 100
71 100 100
72 100 100
73 100 100
74 100 100
75 100 100
76 100 100
77 100 100
78 100 100
79 100 100
80 100 100
81 100 100
82 100 100
83 100 100
84 100 100续于后页
表3(续)
死亡的害虫(%)化合物序号 20ppm 4ppm
85 100 100
86 100 100
87 100 100
88 100 100
89 100 100
90 100 100
91 100 100
115 100 100
117 100 100
118 100 100
119 100 100
120 100 100
121 100 100
122 100 100对比化合物1 90 50对比化合物2 90 70对比化合物3 90 70对比化合物4 60 30对比化合物5 90 50对比化合物6 100 70
试验例3
棉蚜死亡率试验。
根据配方例2制得的可湿粉用水稀释至浓度为100ppm。将黄瓜的幼秧浸入所得的水溶液制剂中。空气干燥后,将其置于直径为55mm的聚乙烯杯中,10只棉蚜的幼虫放在杯中幼秧的叶上。将杯在置于25℃的恒温箱内3天后。数数害虫的死亡数,从而计算其死亡百分率。重复这样的实验。其结果见表4。
表4化合物序号 死亡的害虫(%)
1 100
2 100
3 100
4 100
5 100
6 100
7 100
8 100
9 100
10 100
11 100
12 100
13 100
14 100
15 100
16 100
17 100
18 100
19 100
20 100
21 100
22 100续于后页
表4(续)化合物序号 死亡的害虫(%)
23 100
24 100
25 100
26 100
27 100
28 100
29 100
30 100
31 100
32 100
33 100
34 100
35 100
36 100
37 100
38 100
39 100
40 100
41 100
42 100
43 100
44 100续于后页
表4(续)化合物序号 死亡的害虫(%)
45 100
46 100
47 100
48 100
49 100
50 100
51 100
52 100
53 100
54 100
55 100
56 100
57 100
58 100
59 100
60 100
61 100
62 100
63 100
64 100
65 100
66 100
表4(续)化合物序号 死亡的害虫(%)
67 100
68 100
69 100
70 100
71 100
72 100
73 100
74 100
75 100
76 100
77 100
78 100
79 100
80 100
81 100
82 100
83 100
84 100
85 100
86 100
87 100
88 100续于后页
表4(续)
化合物序号 死亡的害虫(%)
89 100
90 100
91 100
115 100
117 100
118 100
119 100
试验例4
稻褐飞虱的死亡率试验。
按配方例2制得的可湿粉以水稀释到预定浓度。将水稻的茎和叶用得到的水溶液制剂浸渍。空气干燥后,将上述的茎和叶置于试管中。再向其中放入10只稻褐飞虱幼虫,用脱脂棉封住试管的开口。将封闭的试管置于25℃的恒温箱6天后,数一数害虫的死亡数目从而计算其死亡百分率。重复此实验。所得结果见表5。
表5
死亡的害虫(%)化合物序号 2ppm 4ppm
140 100 100
141 100 100
142 100 100
143 100 100
144 100 100
145 100 100
146 100 100
147 100 100
148 100 100
149 100 100
150 100 100
151 100 100
152 100 100
153 100 100
154 100 100
155 100 100
156 100 100
157 100 100
158 100 100
159 100 100
160 100 100续于后页
表5(续)
死亡的害虫(%)化合物序号 2ppm 4ppm
161 100 100
162 100 100
163 100 100
164 100 100
165 100 100
166 100 100
167 100 100
168 100 100
169 100 100
170 100 100
171 100 100
172 100 100
173 100 100
174 100 100
175 100 100
176 100 100
177 100 100
178 100 100
179 100 100
180 100 100
181 100 100续于后页
表5(续)
死亡的害虫(%)化合物序号 2ppm 4pmm
182 100 100
183 100 100
184 100 100
185 100 100
试验例5
对商品试剂显示杀虫抗性的黑尾叶蝉的死亡率试验。
按配方例2制得的可湿粉用水稀释剂500ppm浓度。将水稻的茎和叶用此水溶液制剂浸渍。空气干燥后,将茎和叶置于一试管中。再加入五只黑尾叶蝉幼虫,试管开口用脱脂棉封住。将封闭的试管置于25℃的恒温箱内6天后,数数害虫的死亡数目,计算其死亡百分率。重复此实验。其结果见表6。
表6化合物序号 死亡的害虫(%)
140 100
141 100
142 100
143 100
144 100
145 100
146 100
147 100
148 100
149 100
150 100
151 100
152 100
153 100
154 100
155 100
156 100
157 100
158 100
159 100
160 100
161 100续于后页
表6(续)化合物序号 死亡的害虫(%)
162 100
163 100
164 100
165 100
166 100
167 100
168 100
169 100
170 100
171 100
172 100
173 100
174 100
175 100
176 100
177 100
178 100
179 100
180 100
181 100
182 100
183 100
184 100
185 100
试验例6
棉蚜死亡率试验。
按配方例2制得的可湿粉用水稀释到100ppm浓度。用此水溶液制剂浸渍黄瓜的幼秧。空气干燥后,将幼秧置于直径55mm的聚乙烯杯中。10只棉蚜幼虫置于黄瓜的叶上。将此杯置于25℃的恒温箱3天后,数数害虫的死亡数,计算其死亡百分率。然后重复此试验,其结果见表7。
表7化合物序号 死亡的害虫(%)
140 100
141 100
142 100
143 100
144 100
145 100
146 100
147 100
148 100
149 100
150 100
151 100
152 100
153 100
154 100
155 100
156 100
157 100
158 100
159 100
160 100
161 100续于后页
表7(续)化合物序号 死亡的害虫(%)
162 100
163 100
164 100
165 100
166 100
167 100
168 100
169 100
170 100
171 100
172 100
173 100
174 100
175 100
176 100
177 100
178 100
179 100
180 100
181 100
182 100
183 100
184 100
Claims (4)
1.一种杀虫组合物,它包括式(Ⅰ)表示的,杀虫有效量的苯基羟基亚胺酰基唑衍生物,以及选自载体、表面活性剂、分散剂和辅助剂的至少一种农业用辅助剂,
所述苯基羟基亚胺酰基唑衍生物的化学式(Ⅰ)如下式中:R为5至8个碳原子的支链烷基,
2至6个碳原子的氟代烷基,
3至7个碳原子的支链烷氧基,
3至5个碳原子的卤代烷氧基,
3至7个碳原子的环烷基、
4至7个碳原子的环烷基甲基,它可被1或2个甲基取代,
三甲基甲硅烷基乙基,
1至2个碳原子的甲硅烷基烷氧基,它可各自独立地被1至2个碳原子的烷基、乙烯基、氯甲基三取代,
3至6个碳原子的环烷氧基,它可被1或2个烷基取代,
丁基硫基,
卤代丁氧基甲基,
5至6个碳原子的链烯基,
6个碳原子的炔基,或
卤代乙烯氧基;X为氢原子、氯原子,或氟原子;Y为1至4个碳原子的烷基;Z为氮原子或次甲基;
所述有效组分的量,
在粉状或粒状制剂中,为0.05-20重量%,
在乳油或可湿性粉剂中为0.5-80重量%。
2.根据权利1所述的杀虫组合物,其中,所述式(Ⅰ)的R为5至8个碳原子的支链烷基或为3至7个碳原子的支链烷氧基,Z为氮原子。
3.根据权利要求1所述的杀虫组合物,其中,所述式(Ⅰ)的R为3至7个碳原子的环烷基、
4至7个碳原子的环烷基甲基,它可被1或2个甲基取代,
三甲基甲硅烷基乙基,
1至2个碳原子的甲硅烷基烷氧基,它可各自独立地被1至2个碳原子的烷基、乙烯基、氯甲基三取代,
3至6个碳原子的环烷氧基,它可被1或2个烷基取代,
丁基硫基,
卤代丁氧基甲基,
6个碳原子的炔基,或
卤代乙烯氧基;
4.根据权利要求1所述的杀虫组合物,其中,所述式(Ⅰ)的R为4至7个碳原子的环烷甲基,Z为氮原子。
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP331896/90 | 1990-11-29 | ||
JP331896/1990 | 1990-11-29 | ||
JP33189690 | 1990-11-29 | ||
JP159834/91 | 1991-06-05 | ||
JP3159834A JP3051967B2 (ja) | 1991-06-05 | 1991-06-05 | ベンゾヒドロキシモイルアゾール誘導体及び殺虫剤 |
JP159834/1991 | 1991-06-05 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN91107579A Division CN1030913C (zh) | 1990-11-29 | 1991-11-29 | 制备苯基羟基亚胺酰基唑衍生物的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1101221A CN1101221A (zh) | 1995-04-12 |
CN1065112C true CN1065112C (zh) | 2001-05-02 |
Family
ID=26486512
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN91107579A Expired - Lifetime CN1030913C (zh) | 1990-11-29 | 1991-11-29 | 制备苯基羟基亚胺酰基唑衍生物的方法 |
CN94117855A Expired - Lifetime CN1065112C (zh) | 1990-11-29 | 1994-11-09 | 含苯基羟基亚胺酰基唑衍生物的杀虫组合物 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN91107579A Expired - Lifetime CN1030913C (zh) | 1990-11-29 | 1991-11-29 | 制备苯基羟基亚胺酰基唑衍生物的方法 |
Country Status (8)
Country | Link |
---|---|
US (2) | US5366988A (zh) |
EP (1) | EP0513397B1 (zh) |
KR (1) | KR950013854B1 (zh) |
CN (2) | CN1030913C (zh) |
AT (1) | ATE178895T1 (zh) |
BR (1) | BR9106026A (zh) |
DE (1) | DE69131125T2 (zh) |
WO (1) | WO1992009581A1 (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9307247D0 (en) * | 1993-04-07 | 1993-06-02 | Zeneca Ltd | Fungicidal compounds |
EP0633252A1 (en) * | 1993-07-09 | 1995-01-11 | Shionogi & Co., Ltd. | Benzaldehyde oxime derivatives, production and use thereof |
CA2186947A1 (en) * | 1994-04-01 | 1995-10-12 | Kazuo Ueda | Oxime derivative and bactericide containing the same as active ingredients |
US6268312B1 (en) | 1994-04-01 | 2001-07-31 | Shionogi & Co., Ltd. | Oxime derivative and bactericide containing the same as active ingredient |
ATE339514T1 (de) * | 1996-07-16 | 2006-10-15 | Gen Probe Inc | Verfahren zum nachweis und amplifikation von nukleinsäuresequenzen unter verbrauch von modifizierten oligonukleotiden mit erhöhter zielschmelztemperatur (tm) |
DE19828257A1 (de) * | 1998-06-25 | 1999-12-30 | Bayer Ag | Werkstoffe zur Konstruktion und Isolation, ein Verfahren zur Herstellung und deren Verwendung sowie ein Bindemittel zur Herstellung von Werkstoffen |
US8981111B2 (en) * | 2008-04-22 | 2015-03-17 | Bayer Cropscience Ag | Fungicide hydroximoyl-heterocycles derivatives |
KR200486248Y1 (ko) * | 2017-05-08 | 2018-04-20 | 주식회사 쁘레베베 | 보온기능을 갖는 안전쿠션 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0142653A1 (de) * | 1983-09-22 | 1985-05-29 | Bayer Ag | 1-Azolyl-substituierte Oximether |
JPH01308260A (ja) * | 1988-02-10 | 1989-12-12 | Kumiai Chem Ind Co Ltd | ベンゾヒドロキシモイルアゾール誘導体及び殺虫剤 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2723942C2 (de) * | 1977-05-27 | 1982-11-11 | Basf Ag, 6700 Ludwigshafen | ω-(1,2,4-Triazol-1-yl) acetophenonoximäther |
DE3310830A1 (de) * | 1983-03-24 | 1984-09-27 | Bayer Ag, 5090 Leverkusen | Substituierte phenethyl-triazolyl-derivate, verfahren zu ihrer herstellung sowie ihre verwendung als fungizide |
-
1991
- 1991-11-25 KR KR1019920701799A patent/KR950013854B1/ko not_active IP Right Cessation
- 1991-11-25 DE DE69131125T patent/DE69131125T2/de not_active Expired - Lifetime
- 1991-11-25 WO PCT/JP1991/001614 patent/WO1992009581A1/ja active IP Right Grant
- 1991-11-25 EP EP92902483A patent/EP0513397B1/en not_active Expired - Lifetime
- 1991-11-25 AT AT92902483T patent/ATE178895T1/de active
- 1991-11-25 BR BR919106026A patent/BR9106026A/pt not_active Application Discontinuation
- 1991-11-25 US US07/915,817 patent/US5366988A/en not_active Expired - Lifetime
- 1991-11-29 CN CN91107579A patent/CN1030913C/zh not_active Expired - Lifetime
-
1994
- 1994-07-27 US US08/281,039 patent/US5512551A/en not_active Expired - Lifetime
- 1994-11-09 CN CN94117855A patent/CN1065112C/zh not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0142653A1 (de) * | 1983-09-22 | 1985-05-29 | Bayer Ag | 1-Azolyl-substituierte Oximether |
JPH01308260A (ja) * | 1988-02-10 | 1989-12-12 | Kumiai Chem Ind Co Ltd | ベンゾヒドロキシモイルアゾール誘導体及び殺虫剤 |
Also Published As
Publication number | Publication date |
---|---|
US5366988A (en) | 1994-11-22 |
ATE178895T1 (de) | 1999-04-15 |
EP0513397A4 (en) | 1993-04-07 |
WO1992009581A1 (en) | 1992-06-11 |
KR927003538A (ko) | 1992-12-18 |
EP0513397B1 (en) | 1999-04-14 |
DE69131125D1 (de) | 1999-05-20 |
CN1101221A (zh) | 1995-04-12 |
DE69131125T2 (de) | 1999-09-30 |
CN1030913C (zh) | 1996-02-07 |
CN1062725A (zh) | 1992-07-15 |
KR950013854B1 (ko) | 1995-11-17 |
EP0513397A1 (en) | 1992-11-19 |
US5512551A (en) | 1996-04-30 |
BR9106026A (pt) | 1993-01-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1163130C (zh) | 杀真菌组合物 | |
CN1036304C (zh) | 以苯基三唑衍生物作为活性成份的杀虫剂组合物 | |
CN1221532C (zh) | 吡咯甲酰胺和吡咯硫代甲酰胺及其在农药上的应用 | |
CN1027069C (zh) | 噁唑烷二酮衍生物的制造方法 | |
CN1248255A (zh) | 3-杂环基取代的苯甲酰类衍生物 | |
CN1082318A (zh) | 杀真菌的吲哚衍生物 | |
CN1079735A (zh) | 芳基吡唑杀真菌剂 | |
CN1028714C (zh) | 含嘧啶衍生物作为活性成分的除草剂组合物 | |
CN1025470C (zh) | 含新型硅烷衍生物的农药,杀虫剂和杀螨剂组合物 | |
CN1105179A (zh) | 三唑衍生物、杀虫剂、杀螨剂及其制备方法 | |
CN1030419A (zh) | 6,7-二氢-吡唑并[1,5-a][1,3,5]三嗪-2-磺酰胺其制备方法和用其作为除莠剂和植物生长调节剂的用途 | |
CN1014240B (zh) | 哒嗪酮衍生物的制备方法 | |
CN1065112C (zh) | 含苯基羟基亚胺酰基唑衍生物的杀虫组合物 | |
CN86100884A (zh) | 制备三嗪衍生物及含有该衍生物作为有效成分的除草剂的方法 | |
CN1052856A (zh) | 哌啶衍生物 | |
CN1129893A (zh) | 除草组合物 | |
CN1058968A (zh) | 植物保护剂、其制备方法及应用 | |
CN1603299A (zh) | 新型羧酸酯类除草剂 | |
CN85107078A (zh) | 含吡啶衍生物的花粉生成抑制组合物 | |
CN1027032C (zh) | 种子消毒组合物 | |
CN1024317C (zh) | 杀真菌剂组合物 | |
CN88102112A (zh) | 杂环新芬烷类似物,其制备方法及其作为杀虫剂的应用 | |
CN85104330A (zh) | 胺衍生物的制备方法和含胺衍生物的杀真菌剂 | |
CN1560058A (zh) | 具有除草活性的氟取代苯氧乙酰氧基烃基膦酸酯和盐及制备 | |
CN1012575B (zh) | N-链烷酰苯胺的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CX01 | Expiry of patent term |
Expiration termination date: 20111129 Granted publication date: 20010502 |