CN103833743B - 噻唑基吡唑基丙烯腈类化合物及其应用 - Google Patents
噻唑基吡唑基丙烯腈类化合物及其应用 Download PDFInfo
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- CN103833743B CN103833743B CN201210483661.5A CN201210483661A CN103833743B CN 103833743 B CN103833743 B CN 103833743B CN 201210483661 A CN201210483661 A CN 201210483661A CN 103833743 B CN103833743 B CN 103833743B
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- -1 Thiazolyl pyrazolyl acrylonitrile compound Chemical class 0.000 title claims abstract description 20
- 150000001875 compounds Chemical group 0.000 claims abstract description 46
- 230000002147 killing effect Effects 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 241001124076 Aphididae Species 0.000 claims description 8
- 230000036541 health Effects 0.000 claims description 3
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 claims 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- 239000001963 growth medium Substances 0.000 claims 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 claims 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims 1
- 230000000895 acaricidal effect Effects 0.000 abstract description 13
- 244000045947 parasite Species 0.000 abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052794 bromium Inorganic materials 0.000 abstract description 6
- 125000005843 halogen group Chemical group 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011630 iodine Chemical group 0.000 abstract description 4
- 229910052740 iodine Chemical group 0.000 abstract description 4
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 abstract description 3
- 241000607479 Yersinia pestis Species 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000749 insecticidal effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
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- 239000000243 solution Substances 0.000 description 8
- 208000035126 Facies Diseases 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 241000272639 Brachycaudus mimeuri Species 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 0 Cc1c(C(CCCI)=O)[s]c(*)n1 Chemical compound Cc1c(C(CCCI)=O)[s]c(*)n1 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000004083 survival effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- IJNRBGYVKVGQMR-UHFFFAOYSA-N 2-(1-phenylpyrazol-3-yl)acetonitrile Chemical compound N1=C(CC#N)C=CN1C1=CC=CC=C1 IJNRBGYVKVGQMR-UHFFFAOYSA-N 0.000 description 3
- VDOVQUQCWWQDKL-UHFFFAOYSA-N 3-(bromomethyl)-1-phenylpyrazole Chemical class N1=C(CBr)C=CN1C1=CC=CC=C1 VDOVQUQCWWQDKL-UHFFFAOYSA-N 0.000 description 3
- ZXTYXRDIZUQHEV-UHFFFAOYSA-N C1(=CC=CC=C1)N1N=CC=C1.CC1(CC(C(=O)O)=CC=C1)C(=O)O Chemical class C1(=CC=CC=C1)N1N=CC=C1.CC1(CC(C(=O)O)=CC=C1)C(=O)O ZXTYXRDIZUQHEV-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000409991 Mythimna separata Species 0.000 description 3
- 241000500437 Plutella xylostella Species 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000003810 ethyl acetate extraction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
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- 240000007124 Brassica oleracea Species 0.000 description 2
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- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 2
- 241001498622 Cixius wagneri Species 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 2
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
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- LDJUYMIFFNTKOI-UHFFFAOYSA-N 2,2-dimethylbutanoyl chloride Chemical class CCC(C)(C)C(Cl)=O LDJUYMIFFNTKOI-UHFFFAOYSA-N 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 235000009973 maize Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
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- 230000003020 moisturizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910000104 sodium hydride Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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Abstract
本发明公开了一种结构新颖的噻唑基吡唑基丙烯腈类化合物或其立体异构体，化合物结构如通式I所示：式中：R选自C1‑C6烷基、卤代C1‑C6烷基、C3‑C8环烷基、C1‑C6烷氧基或苯基，苯环上的氢还可进一步被如下取代基取代：卤素、氰基、硝基、甲基或卤代甲基；X选自氯、溴或碘。通式I化合物具有优异的杀虫、杀螨活性，可用于防治害虫、害螨。
Description
技术领域
本发明属于杀虫、杀螨剂领域。具体涉及一种噻唑基吡唑基丙烯腈类化合物及其应用。
背景技术
由于杀虫、杀螨剂在使用一段时间后，害虫、害螨会对其产生抗性，因此，需要不断发明新型的和改进的具杀虫、杀螨活性的化合物和组合物。同时，随着人们对农畜产品等日益增长的需要和对环境保护的日益重视，也一直需要使用成本更低、对环境友好的新的杀虫、杀螨剂。
日产化学工业株式会社在WO9740009申请中，公开了具有杀虫、杀螨或杀菌活性的乙烯衍生物的制备及其杀虫活性，其中的化合物KC（专利中编号II-63）化合物在500ppm的浓度下对桃蚜的防效在80%以上。
在现有技术中，如本发明所示的噻唑基吡唑基丙烯腈类化合物及其杀虫、杀螨活性未见公开。
发明内容
本发明的目的在于提供一种结构新颖的噻唑基吡唑基丙烯腈类化合物，它可应用于农业、林业或非治疗目的的卫生上害虫、害螨的防治。
本发明的技术方案如下：
本发明提供了一种噻唑基吡唑基丙烯腈类化合物，如通式I所示：
式中：
R选自C1-C6烷基、卤代C1-C6烷基、C3-C8环烷基、C1-C6烷氧基或苯基，苯环上的氢还可进一步被如下取代基取代：卤素、氰基、硝基、甲基或卤代甲基；
X选自氯、溴或碘；
或其立体异构体。
本发明进一步优选的化合物为，通式I中：
R选自C1-C6烷基、卤代C1-C6烷基、C3-C8环烷基、C1-C6烷氧基或苯基；
X选自氯、溴或碘；
或其立体异构体。
本发明更进一步优选的化合物为，通式I中：
R选自C3-C6烷基、卤代C3-C6烷基或C1-C4烷氧基；
X选自氯；
或其立体异构体。
上面给出的通式I化合物的定义中，汇集所用术语一般定义如下：
烷基是指直链或支链形式，例如甲基、乙基、正丙基、异丙基等。环烷基包括环丙基、环丁基、环丙基甲基、甲基环丙基等。卤代烷基是指烷基被一个或多个卤原子取代的基团，如氯乙基、三氟甲基等。烷氧基是指烷基末端连有氧原子的基团，例如甲氧基、乙氧基、正丙氧基、异丙氧基等。卤素是指氟、氯、溴、碘。立体异构体是指在式I中，碳碳双键B上的取代基CN和OCOR在B键的同一侧（Z构型）或两侧（E构型）。
本发明的通式I化合物可由如下方法制备，反应式中各基团定义同前。
式中：L代表合适的离去基团，如氯、溴或对甲苯磺酰氧基等。
通式II化合物与通式III化合物在适宜的溶剂中、温度为-10℃到回流温度下反应0.5-48小时制得目标化合物I。
适宜的溶剂选自二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、四氢呋喃、二氧六环、N,N-二甲基甲酰胺或二甲基亚砜等。
加入适宜的碱类物质对反应有利。适宜的碱可以选自有机碱，例如三乙胺、N,N-二甲基苯胺、吡啶、甲醇钠、叔丁醇钠或叔丁醇钾等；或无机碱如氢氧化钠、氢氧化钾、碳酸氢钠、碳酸钠或氢化钠等。
根据反应条件的差异或起始原料的不同，通式I化合物存在立体异构现象。例如碳碳双键B上的取代基CN和OCOR1在B键的同一侧（Z构型）或两侧（E构型）。通过选择适当的起始原料或控制反应条件，可以得到一种异构体过量的产物或单一异构体。也可以通过对粗产物进行常规手段的分离，例如通过柱色谱、重结晶等方法，得到单一异构体。这些异构体的结构可通过X-射线单晶衍射，核磁共振等常规分析方法确定。
通式III化合物有市售。
通式II化合物的制备方法如下：
式中：L1代表合适的离去基团，如氯、溴、吡唑基、咪唑基、酯基或对甲苯磺酰氧基等。
通式IV化合物与通式V化合物在适宜的溶剂中、在碱的存在下、温度为-10℃到沸点下反应0.5-48小时制得通式化合物II。
适宜的溶剂主要选自：二氯甲烷、氯仿、四氯化碳、苯、甲苯、甲醇、乙醇、乙酸乙酯、乙腈、四氢呋喃、二氧六环、N,N-二甲基甲酰胺、二甲基亚砜、2-甲基戊烷、甲基环戊烷、己烷、环己烷、甲基环己烷、庚烷、辛烷、壬烷、丁醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丁基醚等，或者如上两种或三种不同溶剂的混合物。
加入适宜的碱类物质对反应有利。适宜的碱选自有机碱如三乙胺、N,N-二甲基苯胺、吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、5-乙基-2-甲基吡啶、2,3-二甲基吡啶、2,4-二甲基吡啶、3,5-二甲基吡啶、2,6-二甲基吡啶、2,4,6-三甲基吡啶、喹啉、甲醇钠、乙醇钠、叔丁醇钠或叔丁醇钾等，或无机碱如氢氧化钠、氢氧化钾、碳酸钠或碳酸钾等。
通式IV化合物的制备参见DE2633992中描述的操作方法。
通式V化合物的具体制备参见Tetrahedron Lett.,2005,46,2251，J.Med.Chem.,1973,16,978，US 6096898。
表1列出了部分通式I化合物的结构和物理性质。
表1
部分化合物的1H NMR(300MHz,CDCl3)数据如下：
化合物8：7.95(d,1H),7.70(m,2H),7.48(m,1H),7.36(m,2H),6.74(d,1H),2.61(s,3H),1.29(s,9H)。
化合物9：7.96(d,1H),7.69(m,2H),7.47(m,1H),7.35(m,2H),6.77(d,1H),2.63(s,3H),1.65(q,2H),1.24(s,6H),0.79(t,3H)。
化合物25：7.99(d,1H),7.72(m,2H),7.48(m,1H),7.35(m,2H),6.81(d,1H),3.90(s,3H),2.59(s,3H)。
本发明的噻唑基吡唑基丙烯腈类化合物具有高的杀虫、杀螨活性，可防治小菜蛾、甜菜夜蛾、斜纹夜蛾、棉铃虫、草地粘虫、粉纹夜蛾、豌蚜、豆蚜、甜菜蚜、棉蚜、苹果蚜、桃蚜、玉米蚜、粉虱、叶蝉、飞虱、稻飞虱、粉蚧、棉网蝽、番茄盲蝽、稻绿蝽、稻臭蝽、棉蓟马、苜蓿蓟马、黄豆蓟马、马铃薯甲虫、叩甲、蝇、蚊、螨等多种害虫。同已知的丙烯腈类化合物相比，本发明的噻唑基吡唑基丙烯腈类化合物具有意想不到的高杀虫、杀螨活性，尤其具有高的杀蚜虫活性。因此，本发明还包括通式I化合物用于控制害虫、害螨的用途。
本发明还包括以通式I化合物作为活性组分的杀虫、杀螨组合物。该杀虫、杀螨组合物中活性组分的重量百分含量在1-99%之间。该杀虫、杀螨组合物中还包括农业、林业或卫生上可接受的载体。
本发明的组合物可以制剂的形式施用。通式I化合物作为活性组分溶解或分散于载体中或配制成制剂以便作为杀虫、杀螨剂使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油。在这些组合物中，至少加入一种液体或固体载体，并且当需要时可以加入适当的表面活性剂。
本发明的技术方案还包括防治害虫、害螨的方法：将本发明的杀虫、杀螨组合物施于需要控制的害虫、害螨或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克，优选有效量为每公顷50克到500克。
对于某些应用，例如在农业上可在本发明的杀虫、杀螨组合物中加入一种或多种其它的杀菌剂、杀虫剂、除草剂、植物生长调节剂或肥料等，由此可产生附加的优点和效果。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
具体实施方式
下列合成实例及生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
合成实施例
实施例1、化合物8的制备
(1)3-甲基-1-苯基-1H-吡唑的制备
向反应瓶内加入苯肼（5.00克，0.046摩尔），4,4-二甲氧基-2-丁酮（7.30克，0.055摩尔），乙醇40毫升，升温至回流，回流2小时。向反应液中滴加浓盐酸（0.5毫升），继续回流2小时。反应结束后降温至30℃以下，反应液倾入200毫升水中，用3×150毫升乙酸乙酯萃取，所得有机相用饱和氯化钠水溶液（150毫升）洗涤后，用无水硫酸镁干燥，减压浓缩后，残余物通过柱色谱分离（淋洗液：乙酸乙酯:石油醚＝1:10）得5.00克3-甲基-1-苯基-1H-吡唑，黄色油，收率68％。
(2)3-溴甲基-1-苯基-1H-吡唑的制备
向反应瓶内加入3-甲基-1-苯基-1H-吡唑（0.50克，0.003摩尔），甲苯5毫升，升温至70℃，向反应液加入N-溴代丁二酰亚胺（0.40克，0.003摩尔），偶氮二异丁腈（催化量），加毕，反应液升温至回流，回流反应1小时。反应结束后降温至30℃以下，反应液倾入50毫升水中，用3×50毫升乙酸乙酯萃取，所得有机相用饱和碳酸氢钠水溶液（50毫升）、饱和氯化钠水溶液（50毫升）洗涤后，用无水硫酸镁干燥，减压浓缩后，残余物通过柱色谱分离（淋洗液：乙酸乙酯:石油醚＝1:100）得0.40克3-溴甲基-1-苯基-1H-吡唑，黄色油，收率56％。
(3)2-(1-苯基-1H-吡唑-3-基)乙腈的制备
向反应瓶内加入3-溴甲基-1-苯基-1H-吡唑（0.55克，0.003摩尔），二甲基亚砜5毫升，氰化钠（0.15克，0.003摩尔），室温反应6小时。反应结束后将反应液倾入100毫升水中，用3×100毫升乙酸乙酯萃取，所得有机相用饱和氯化钠水溶液（100毫升）洗涤后，用无水硫酸镁干燥，减压浓缩后，残余物通过柱色谱分离（淋洗液：乙酸乙酯:石油醚＝1:20）得0.20克2-(1-苯基-1H-吡唑-3-基)乙腈，黄色油，收率36％。
(4)3-(2-氯-4-甲基噻唑-5-基)-3-羟基-2-(1-苯基-1H-吡唑-3-基)丙烯腈的制备
在冰水浴下，向反应瓶内加入2-(1-苯基-1H-吡唑-3-基)乙腈（3.00克，0.016摩尔），(2-氯-4-甲基噻唑-5-基)(1H-吡唑-1-基)甲酮（4.33克，0.019摩尔），四氢呋喃40毫升，搅拌约1小时，分批加入叔丁醇钾（3.59克，0.032摩尔），加料结束，反应液升温至室温，室温反应6小时。反应液倾入150毫升水中，用100毫升乙酸乙酯萃取，所得水相用浓盐酸调酸至pH值为2~3，用3×150毫升乙酸乙酯萃取，有机相经饱和碳酸氢钠水溶液（150毫升）、饱和氯化钠水溶液（150毫升）洗涤后，用无水硫酸镁干燥，浓缩后得2.70克3-(2-氯-4-甲基噻唑-5-基)-3-羟基-2-(1-苯基-1H-吡唑-3-基)丙烯腈，黄色固体，收率61％。
(5)化合物8的制备
在冰水浴下，向反应瓶内加入3-(2-氯-4-甲基噻唑-5-基)-3-羟基-2-(1-苯基-1H-吡唑-3-基)丙烯腈（0.34克，0.001摩尔），乙腈5毫升，三乙胺（0.10克，0.001摩尔），再将新戊酰氯（0.12克，0.001摩尔）滴加到反应瓶内，滴加结束，升温至室温搅拌反应2小时，反应液倾入50毫升水中，用乙酸乙酯100毫升萃取，所得有机相用饱和碳酸氢钠水溶液（100毫升）、饱和氯化钠水溶液洗涤后（100毫升），用无水硫酸镁干燥，减压浓缩后，残余物通过柱色谱分离（淋洗液：乙酸乙酯:石油醚＝1:15），得到0.15克化合物8，白色固体，收率38%。
实施例2、化合物9的制备
在冰水浴下，向反应瓶内加入3-(2-氯-4-甲基噻唑-5-基)-3-羟基-2-(1-苯基-1H-吡唑-3-基)丙烯腈（0.34克，0.001摩尔），乙腈5毫升，三乙胺（0.10克，0.001摩尔），再将2,2-二甲基丁酰氯（0.13克，0.001摩尔）滴加到反应瓶内，滴加结束，升温至室温搅拌反应2小时，反应液倾入50毫升水中，用乙酸乙酯100毫升萃取，所得有机相用饱和碳酸氢钠水溶液（100毫升）、饱和氯化钠水溶液洗涤后（100毫升），用无水硫酸镁干燥，减压浓缩后，残余物通过柱色谱分离（淋洗液：乙酸乙酯:石油醚＝1:15），得到0.20克化合物9，黄色固体，收率45%。
实施例3、化合物29的制备
在冰水浴下，向反应瓶内加入3-(2-氯-4-甲基噻唑-5-基)-3-羟基-2-(1-苯基-1H-吡唑-3-基)丙烯腈（0.34克，0.001摩尔），乙腈5毫升，三乙胺（0.10克，0.001摩尔），再将氯甲酸异丁酯（0.14克，0.001摩尔）滴加到反应瓶内，滴加结束，升温至室温搅拌反应2小时，反应液倾入50毫升水中，用乙酸乙酯100毫升萃取，所得有机相用饱和碳酸氢钠水溶液（100毫升）、饱和氯化钠水溶液洗涤后（100毫升），用无水硫酸镁干燥，减压浓缩后，残余物通过柱色谱分离（淋洗液：乙酸乙酯:石油醚＝1:20），得到0.20克化合物29为一组立体异构体混合物（E:Z=3:2），黄色油，收率45%。
生物活性测定
根据待测化合物的溶解性，原药用丙酮或二甲亚砜溶解，然后用1‰的吐温80溶液配制成所需浓度的待测液50毫升，丙酮或二甲亚砜在溶液中的含量不超过10％。杀虫、杀螨死亡率活性分级如下：A：100%；B：99%-80%；C：79%-60%；D：59%-0。
实施例4、杀虫活性的测定
4.1杀桃蚜活性的测定
取直径6厘米培养皿，皿底覆一层滤纸，并滴加适量自来水保湿。从培养桃蚜的甘蓝植株上剪取大小适宜（直径约3厘米）且长有15～30头蚜虫的甘蓝叶片，去除有翅蚜及叶片正面的蚜虫，调查基数后，叶背向上置于培养皿内，用手持式Airbrush喷雾器进行喷雾处理，压力为10psi(约合0.7kg/cm2)，喷液量为0.5mL，每处理3次重复，处理后置于标准观察室内，48小时后调查存活虫数，计算死亡率并分级。
按照以上方法，部分测试化合物与已知化合物KC（WO9740009中的II-63号化合物）进行了杀桃蚜活性的平行测定。试验结果见表2。
表2：噻唑基吡唑基丙烯腈与已知化合物KC杀桃蚜活性的平行比较
4.2杀小菜蛾活性的测定
将甘蓝叶片用打孔器打成直径2厘米的叶碟，用Airbrush喷雾处理，压力为10psi(约合0.7kg/cm2)，每叶碟正反面喷雾，喷液量为0.5mL。阴干后每处理接入10头2龄试虫，每处理3次重复。处理后放入25℃、相对湿度60～70%观察室内培养，72小时后调查存活虫数，计算死亡率并分级。
部分供试的化合物中，下列化合物在浓度为600ppm时对小菜蛾的防治效果较好，死亡率达到B级以上：9。
4.3杀粘虫活性的测定
将玉米叶片剪成长2厘米的叶段，用Airbrush喷雾处理，压力为10psi(约合0.7kg/cm2)，每叶段正反面喷雾，喷液量为0.5mL。阴干后每处理接入10头2龄试虫，每处理3次重复。处理后放入25℃、相对湿度60～70%观察室内培养，72小时后调查存活虫数，计算死亡率并分级。
部分供试的化合物中，下列化合物在浓度为600ppm时对粘虫的防治效果较好，死亡率达到B级以上：8、25、28。
实施例5、杀螨活性的测定
对朱砂叶螨成螨活性的测定
测定方法：取两片真叶菜豆苗，接上朱砂叶螨成螨并调查基数后，用Airbrush喷雾器进行整株喷雾处理，压力为10psi(约合0.7kg/cm2)，喷液量为0.5mL。每处理3次重复，处理后置于标准观察室，72小时后调查存活螨数，计算死亡率并分级。
部分供试的化合物中，下列化合物在浓度为100ppm时对螨的防治效果较好，死亡率达到B级以上：8、9、25、28、29。
部分供试的化合物中，下列化合物在浓度为10ppm时对螨的防治效果较好，死亡率达到B级以上：28。
Claims (5)
1.一种噻唑基吡唑基丙烯腈类化合物，如通式I所示：
式中：
R选自叔丁基、2-甲基-2-丁基、甲氧基、异丙氧基或异丁氧基；
X选自氯。
2.按照权利要求1所述的化合物，其特征在于，通式I中：
R选自叔丁基或2-甲基-2-丁基；
X选自氯。
3.一种按照权利要求1所述的通式I化合物控制蚜虫的用途。
4.一种杀蚜虫组合物，含有如权利要求1所述的通式I所示化合物为活性组分和农业、林业或卫生上可接受的载体，组合物中活性组分的重量百分含量为1-99％。
5.一种控制蚜虫的方法，其特征在于：将权利要求4所述的组合物以每公顷10克到1000克的有效剂量施于需要控制的蚜虫或其生长的介质上。
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