CN103833669B - 噻唑基丙烯腈类化合物及其应用 - Google Patents
噻唑基丙烯腈类化合物及其应用 Download PDFInfo
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- CN103833669B CN103833669B CN201210480647.XA CN201210480647A CN103833669B CN 103833669 B CN103833669 B CN 103833669B CN 201210480647 A CN201210480647 A CN 201210480647A CN 103833669 B CN103833669 B CN 103833669B
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- -1 Thiazolyl acrylonitrile compounds Chemical class 0.000 title claims abstract description 20
- 150000001875 compounds Chemical group 0.000 claims abstract description 47
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 239000011630 iodine Chemical group 0.000 claims abstract description 5
- 229910052740 iodine Chemical group 0.000 claims abstract description 5
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000000642 acaricide Substances 0.000 claims description 6
- 241000238631 Hexapoda Species 0.000 claims description 4
- 230000000895 acaricidal effect Effects 0.000 abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 19
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 11
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- 239000007864 aqueous solution Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
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- 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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 4
- ZBELDPMWYXDLNY-UHFFFAOYSA-N methyl 9-(4-bromo-2-fluoroanilino)-[1,3]thiazolo[5,4-f]quinazoline-2-carboximidate Chemical compound C12=C3SC(C(=N)OC)=NC3=CC=C2N=CN=C1NC1=CC=C(Br)C=C1F ZBELDPMWYXDLNY-UHFFFAOYSA-N 0.000 description 4
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- 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
- 238000003756 stirring 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 241000409991 Mythimna separata Species 0.000 description 3
- SFVYRISQVUXLPV-UHFFFAOYSA-N N#CCC(N=C1)=C[S+]1C1=CC=CC=C1 Chemical compound N#CCC(N=C1)=C[S+]1C1=CC=CC=C1 SFVYRISQVUXLPV-UHFFFAOYSA-N 0.000 description 3
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- ZDIACNVYSMNTGL-UHFFFAOYSA-N di(pyrazol-1-yl)methanone Chemical compound C1=CC=NN1C(=O)N1C=CC=N1 ZDIACNVYSMNTGL-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PIDFDZJZLOTZTM-KHVQSSSXSA-N ombitasvir Chemical compound COC(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@H]1C(=O)NC1=CC=C([C@H]2N([C@@H](CC2)C=2C=CC(NC(=O)[C@H]3N(CCC3)C(=O)[C@@H](NC(=O)OC)C(C)C)=CC=2)C=2C=CC(=CC=2)C(C)(C)C)C=C1 PIDFDZJZLOTZTM-KHVQSSSXSA-N 0.000 description 3
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- OSNHWFHVKVBEAC-UHFFFAOYSA-N 2-(2-phenyl-2H-1,3-thiazol-3-yl)acetonitrile Chemical compound C1(=CC=CC=C1)C1SC=CN1CC#N OSNHWFHVKVBEAC-UHFFFAOYSA-N 0.000 description 2
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- SVEGSFSFMLCNFF-UHFFFAOYSA-N 4-(chloromethyl)-2-phenyl-1,3-thiazole Chemical compound ClCC1=CSC(C=2C=CC=CC=2)=N1 SVEGSFSFMLCNFF-UHFFFAOYSA-N 0.000 description 2
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- XFJBGINZIMNZBW-CRAIPNDOSA-N 5-chloro-2-[4-[(1r,2s)-2-[2-(5-methylsulfonylpyridin-2-yl)oxyethyl]cyclopropyl]piperidin-1-yl]pyrimidine Chemical compound N1=CC(S(=O)(=O)C)=CC=C1OCC[C@H]1[C@@H](C2CCN(CC2)C=2N=CC(Cl)=CN=2)C1 XFJBGINZIMNZBW-CRAIPNDOSA-N 0.000 description 2
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- QIOZLISABUUKJY-UHFFFAOYSA-N Thiobenzamide Chemical compound NC(=S)C1=CC=CC=C1 QIOZLISABUUKJY-UHFFFAOYSA-N 0.000 description 1
- 241000255993 Trichoplusia ni Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 235000009508 confectionery Nutrition 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[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
- 238000005516 engineering process 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
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 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
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 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
- 229940072033 potash Drugs 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
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Classifications
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—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
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
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- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明公开了一种结构新颖的噻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。在WO2007100160和WO2007100161申请中，进一步公开了化合物KC（专利中编号1）的制备、杀虫活性及合成工艺研究，化合物KC在25ppm的浓度下对桃蚜具有高的防治效果。
在现有技术中，如本发明所示的噻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选自氯或溴；
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OCOR1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、甲氧基、乙氧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化合物的具体制备参见WO9740009。
通式V化合物的具体制备参见TetrahedronLett.,2005,46,2251，J.Med.Chem.,1973,16,978，US6096898。
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1HNMR(300MHz,CDCl3)数据如下：
化合物8：7.95-7.91(m,2H),7.66(s,1H),7.48-7.46(m,3H),2.63(s,3H),1.26(s,9H)。
化合物9：7.69-7.65(m,2H),7.52(s,2H),7.43-7.40(m,3H),2.19(s,3H),1.37(s,9H)。
化合物10：7.95-7.93(m,2H),7.66(s,1H),7.48-7.46(m,3H),2.63(s,3H),1.62-1.59(m,2H),1.21(s,6H),0.77(t,3H)。
化合物28：7.98-7.95(m,2H),7.75(s,1H),7.48-7.46(m,3H),4.32-4.25(m,2H),2.60(s,3H),1.34(m,3H)。
化合物38：7.95-7.91(m,2H),7.65(s,2H),7.48-7.45(m,3H),2.63(s,3H),1.25(s,9H)。
化合物39：7.69-7.65(m,2H),7.52(s,2H),7.43-7.40(m,3H),2.19(s,3H),1.37(s,9H)。
化合物40：7.95-7.93(m,2H),7.67(s,1H),7.48-7.45(m,3H),2.63(s,3H),1.62-1.59(m,2H),1.21(s,6H),0.77(t,3H)。
化合物68：7.95-7.92(m,2H),7.66(s,1H),7.48-7.46(m,3H),2.63(s,3H),1.26(s,9H)。
本发明的噻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、9的制备
(1)4-(氯甲基)-2-苯基噻唑的制备
向三口瓶内加入硫代苯甲酰胺（20.00克，0.146摩尔），甲醇200毫升，1,3-二氯丙酮（22.21克，0.157摩尔），升温至回流，回流反应3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＝1:10）得21.00克4-(氯甲基)-2-苯基噻唑，黄色油，收率：69%。
(2)2-(2-苯基噻唑-3-基)乙腈的制备
向反应瓶内加入氰化钠（4.91克，0.100摩尔），水100毫升，滴加4-(氯甲基)-2-苯基噻唑（21.00克，0.100摩尔）的乙醇（100毫升）溶液，滴加完毕，升温至回流，回流16小时。反应结束后将反应液倾入200毫升水中，用3×200毫升乙酸乙酯萃取，所得有机相用饱和氯化钠水溶液（200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13.22克2-(2-苯基噻唑-3-基)乙腈，黄色油，收率66％。
(3)3-(2-氯-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈的制备
在冰水浴下，向反应瓶内加入2-（1-苯基噻唑-4-基）乙腈（3.00克，0.015摩尔），（2-氯-4-甲基噻唑-5-基）（1H-吡唑-1-基）甲酮（3.72克，0.018摩尔），四氢呋喃40毫升，搅拌约1小时，分批加入叔丁醇钾（3.36克，0.030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2.63克3-(2-氯-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈，黄色固体，收率51％。
(4)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-(2-苯基噻唑-4-基)丙烯腈（0.36克，0.001摩尔），乙腈10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＝1:20），得到化合物8，黄色油0.21克，收率49%。
(5)化合物9的制备
向反应瓶内加入3-(2-氯-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈（0.72克，0.002摩尔），碳酸氢钠（0.34克，0.004摩尔），甲苯20毫升，4-二甲氨基吡啶(催化量)，四丁基溴化铵(催化量)，升温至100℃，再将新戊酰氯（0.24克，0.002摩尔）滴加到反应瓶内，滴加结束，继续反应2小时。反应液降温至30℃以下，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＝1:30），得到化合物9，黄色油0.30克，收率41%。
实施例2、化合物38的制备
(1)3-(2-溴-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈的制备
在冰水浴下，向反应瓶内加入2-（1-苯基噻唑-4-基）乙腈（1.00克，0.005摩尔），（2-溴-4甲基噻唑-5-基）（1H-吡唑-1-基）甲酮（1.36克，0.005摩尔），四氢呋喃20毫升，搅拌约1小时，分批加入叔丁醇钾（1.12克，0.010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3×100毫升乙酸乙酯萃取，有机相经饱和碳酸氢钠水溶液（100毫升）、饱和氯化钠水溶液（100毫升）洗涤后，用无水硫酸镁干燥，浓缩后得1.27克3-(2-溴-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈，黄色固体，收率79％。
(2)化合物38的制备
在冰水浴下，向反应瓶内加入3-(2-溴-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈（0.40克，0.001摩尔），乙腈10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3×100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），得到化合物38，黄色油0.31克，收率63%。
实施例3、化合物58的制备
在冰水浴下，向反应瓶内加入3-(2-溴-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈（0.40克，0.001摩尔），乙腈10毫升，三乙胺（0.10克，0.001摩尔），再将氯甲酸乙酯（0.11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3×100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），得到化合物58为一组立体异构体混合物（E:Z=2:5），黄色油0.29克，收率60%。
实施例4、化合物68的制备
(1)3-(2-碘-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈的制备
在冰水浴下，向反应瓶内加入2-（1-苯基噻唑-4-基）乙腈（0.60克，0.003摩尔），（2-碘-4-甲基噻唑-5-基）（1H-吡唑-1-基）甲酮（0.96克，0.003摩尔），四氢呋喃10毫升，搅拌约1小时，分批加入叔丁醇钾（0.67克，0.006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100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3×100毫升乙酸乙酯萃取，有机相经饱和碳酸氢钠水溶液（100毫升）、饱和氯化钠水溶液（100毫升）洗涤后，用无水硫酸镁干燥，浓缩后得0.52克3-(2-碘-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈，黄色固体，收率39％。
(2)化合物68的制备
在冰水浴下，向反应瓶内加入3-(2-碘-4-甲基噻唑-5-基)-3-羟基-2-(2-苯基噻唑-4-基)丙烯腈（0.45克，0.001摩尔），乙腈10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3×100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68，黄色油，收率40%。
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5、杀虫活性的测定
5.1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（WO2007100160中的1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：噻唑基丙烯腈与已知化合物KC杀桃蚜活性的平行比较
5.2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：8、9、10、28、39、40、41、58、68、69、70。
5.3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100ppm时对粘虫的防治效果较好，死亡率达到B级以上：8、9、10、11、40、41、58、68、69、70。
实施例6、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、10、11、38、39、40、41、58、68、69、70。
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：9、39、41、58、68、69、70。
Claims (5)
1.一种噻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环烷基或C1-C6烷氧基；
X选自氯、溴或碘；
或其顺/反异构体。
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C3-C6烷基；
X选自氯或溴；
或其顺/反异构体。
3.一种按照权利要求1所述的通式I化合物控制农业害虫、害螨的用途。
4.一种杀虫、杀螨组合物，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％。
5.一种控制害虫、害螨的方法，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害虫、害螨或其生长的介质上。
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