CN112752751A - 杀昆虫化合物 - Google Patents
杀昆虫化合物 Download PDFInfo
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- CN112752751A CN112752751A CN201980063063.2A CN201980063063A CN112752751A CN 112752751 A CN112752751 A CN 112752751A CN 201980063063 A CN201980063063 A CN 201980063063A CN 112752751 A CN112752751 A CN 112752751A
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- substituted
- alkyl
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- cycloalkyl
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- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000004550 soluble concentrate Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- LOGJGKGBKZOEKZ-UHFFFAOYSA-N sordidin Natural products O1C2(C)CC(C)C1(CC)OC(C)C2 LOGJGKGBKZOEKZ-UHFFFAOYSA-N 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 229960005453 strychnine Drugs 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- XIUROWKZWPIAIB-UHFFFAOYSA-N sulfotep Chemical compound CCOP(=S)(OCC)OP(=S)(OCC)OCC XIUROWKZWPIAIB-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MLGCXEBRWGEOQX-UHFFFAOYSA-N tetradifon Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC(Cl)=C(Cl)C=C1Cl MLGCXEBRWGEOQX-UHFFFAOYSA-N 0.000 description 1
- 229960005199 tetramethrin Drugs 0.000 description 1
- 108010013645 tetranectin Proteins 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 239000004577 thatch Substances 0.000 description 1
- 239000004308 thiabendazole Substances 0.000 description 1
- 235000010296 thiabendazole Nutrition 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 229960004546 thiabendazole Drugs 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- DNVLJEWNNDHELH-UHFFFAOYSA-N thiocyclam Chemical compound CN(C)C1CSSSC1 DNVLJEWNNDHELH-UHFFFAOYSA-N 0.000 description 1
- OPASCBHCTNRLRM-UHFFFAOYSA-N thiometon Chemical compound CCSCCSP(=S)(OC)OC OPASCBHCTNRLRM-UHFFFAOYSA-N 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- QSOHVSNIQHGFJU-UHFFFAOYSA-L thiosultap disodium Chemical compound [Na+].[Na+].[O-]S(=O)(=O)SCC(N(C)C)CSS([O-])(=O)=O QSOHVSNIQHGFJU-UHFFFAOYSA-L 0.000 description 1
- MBNMHBAJUNHZRE-UHFFFAOYSA-M thiosultap monosodium Chemical compound [Na+].OS(=O)(=O)SCC(N(C)C)CSS([O-])(=O)=O MBNMHBAJUNHZRE-UHFFFAOYSA-M 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WPALTCMYPARVNV-UHFFFAOYSA-N tolfenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(OC=3C=CC(C)=CC=3)=CC=2)=C1Cl WPALTCMYPARVNV-UHFFFAOYSA-N 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- DDVNRFNDOPPVQJ-HQJQHLMTSA-N transfluthrin Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=C(F)C(F)=CC(F)=C1F DDVNRFNDOPPVQJ-HQJQHLMTSA-N 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- QQZIUHOKWDFXEY-UHFFFAOYSA-N tribromo(nitro)methane Chemical compound [O-][N+](=O)C(Br)(Br)Br QQZIUHOKWDFXEY-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- IGOWHGRNPLFNDJ-UHFFFAOYSA-N tricos-9t-ene Natural products CCCCCCCCCCCCCC=CCCCCCCCC IGOWHGRNPLFNDJ-UHFFFAOYSA-N 0.000 description 1
- UGCNRZFAUBJVPT-UHFFFAOYSA-N tricyclohexyltin;hydrate Chemical compound O.C1CCCCC1[Sn](C1CCCCC1)C1CCCCC1 UGCNRZFAUBJVPT-UHFFFAOYSA-N 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XAIPTRIXGHTTNT-UHFFFAOYSA-N triflumuron Chemical compound C1=CC(OC(F)(F)F)=CC=C1NC(=O)NC(=O)C1=CC=CC=C1Cl XAIPTRIXGHTTNT-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- FJDHVPHQDPJCHK-UHFFFAOYSA-N trisodium;trioxidoarsane Chemical compound [Na+].[Na+].[Na+].[O-][As]([O-])[O-] FJDHVPHQDPJCHK-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000016788 valerian Nutrition 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 229940057613 veratrum Drugs 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 229960005080 warfarin Drugs 0.000 description 1
- PJVWKTKQMONHTI-UHFFFAOYSA-N warfarin Chemical compound OC=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 PJVWKTKQMONHTI-UHFFFAOYSA-N 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 239000004565 water dispersible tablet Substances 0.000 description 1
- 235000005765 wild carrot Nutrition 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- YEFOAORQXAOVJQ-UHFFFAOYSA-N wuweizischun A Natural products C1C(C)C(C)(O)CC2=CC(OC)=C(OC)C(OC)=C2C2=C1C=C(OC)C(OC)=C2OC YEFOAORQXAOVJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000005943 zeta-Cypermethrin Substances 0.000 description 1
- 229940048462 zinc phosphide Drugs 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
- A01N43/80—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 1,2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/02—Acaricides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Insects & Arthropods (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Catching Or Destruction (AREA)
Abstract
本发明涉及具有式(I)的化合物,其中A1、A2、A3、A4、R1、R2、R3、R4以及n是如在权利要求1中所定义的;或其互变异构体、同分异构体、对映异构体、盐或N‑氧化物;涉及用于制备具有式(I)的化合物的中间体,涉及包含它们的组合物并且涉及使用它们来对抗并且控制昆虫、螨、线虫和软体动物有害生物的方法。
Description
本发明涉及某些异噁唑烷衍生物,涉及用于制备这些衍生物的方法与中间体,涉及包含这些衍生物的杀昆虫、杀螨、杀线虫和杀软体动物的组合物并且涉及使用这些衍生物控制昆虫、螨、线虫和软体动物有害生物的方法。
某些具有杀昆虫特性的异噁唑啉衍生物披露于例如WO2011067272中。
现在已经出人意料地发现某些异噁唑烷衍生物具有高度有效的杀昆虫特性。
因此,在第一方面,作为实施例1,提供了一种具有式(I)的化合物
其中
A1、A2、A3以及A4彼此独立地是C-H、C-R5、或氮;
R1选自-(C0-C4烷基)-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C3-C6环烷基、-R1aOR1aOR1b、-R1aOC(=O)R1b、-R1aOC(=O)OR1b、-R1aN(R1c)C(=O)OR1b、-R1aOC(=O)N(R1b)(R1c)、-R1aC(=O)N(R1b)(R1c)和-S-C(=O)OR1b;
R1a是-(CR1dR1e)m-;
R1b和R1c独立地选自H和C1-C4烷基,其中每个烷基基团是未取代的或被一个至三个卤素原子或被氰基基团取代;
R1d和R1e独立地选自H和C1-C4烷基;
m选自1、2、3和4;
R2是C1-C8烷基,被一个至三个R6a取代的C1-C8烷基,C1-C8卤代烷基,被一个至三个R6a取代的C1-C8卤代烷基,C3-C8环烷基,被一个至三个R6b取代的C3-C8环烷基,其中一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基,C3-C8环烷基-C1-C8烷基,其中环烷基基团中的一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基-C1-C8烷基,C3-C8环烷基-C1-C8卤代烷基,C2-C8烯基,被一个至三个R6a取代的C2-C8烯基,C2-C8卤代烯基,被一个至三个R6a取代的C2-C8卤代烯基,C2-C8炔基,C2-C8卤代炔基,苯基,被一个至三个R7取代的苯基,苯基-C1-C4烷基,其中苯基部分被一个至三个R7取代的苯基-C1-C4烷基,5-6元杂芳基,被一个至三个R7取代的5-6元杂芳基,5-6元杂芳基-C1-C4烷基,其中杂芳基部分被一个至三个R7取代的5-6元杂芳基-C1-C4烷基,-N(R8)(R9),卤素或-OR10;
R3是C1-C8卤代烷基;
R4是芳基、被一个至三个R7取代的芳基、杂芳基或被一个至三个R7取代的杂芳基;
R5独立地是卤素、氰基、硝基、C1-C8烷基、C3-C8环烷基、C1-C8卤代烷基、C2-C8烯基、C2-C8卤代烯基、C2-C8炔基、C2-C8卤代炔基、C1-C8烷氧基、C1-C8卤代烷氧基、或C1-C8烷氧基羰基-,或在相邻碳原子上的两个R5一起形成CH=CH-CH=CH-桥或-N=CH-CH=CH-桥;
R6a独立地是氰基、硝基、氨基、C1-C8烷基氨基、N,N-C1-C8二烷基氨基、羟基、C1-C8烷氧基、或C1-C8卤代烷氧基;
R6b独立地是卤素、氰基、硝基、氧代、C1-C8烷基、C1-C8卤代烷基、氨基、C1-C8烷基氨基、N,N-C1-C8二烷基氨基、羟基、C1-C8烷氧基、C1-C8卤代烷氧基、苯基、被一个至三个R7取代的苯基、5-6元杂芳基、被一个至三个R7取代的5-6元杂芳基;
R7独立地是卤素、氰基、硝基、C1-C8烷基、C1-C8卤代烷基、C1-C8烷氧基、C1-C8卤代烷氧基;
R8和R9独立地是氢,氰基,氰基-C1-C8烷基,C1-C8烷基,被一个至三个R6a取代的C1-C8烷基,C2-C8烯基,被一个至三个R6a取代的C2-C8烯基,C1-C8烷氧基,C1-C8卤代烷氧基,被一个至三个R6a取代的C1-C8卤代烷氧基,被一个至三个R6a取代的C1-C8烷氧基,C1-C8卤代烷基,被一个至三个R6a取代的C1-C8卤代烷基,C3-C8环烷基,被一个至三个R6b取代的C3-C8环烷基,其中一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基,C3-C8环烷基-C1-C8烷基,其中环烷基基团中的一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基-C1-C8烷基,C3-C8环烷基-C1-C8卤代烷基,C2-C8烯基,被一个至三个R6a取代的C2-C8烯基,C2-C8卤代烯基,被一个至三个R6a取代的C2-C8卤代烯基,C2-C8炔基,C2-C8卤代炔基,苯基,被一个至三个R7取代的苯基,苯基-C1-C4烷基,其中苯基部分被一个至三个R7取代的苯基-C1-C4烷基,5-6元杂芳基,被一个至三个R7取代的5-6元杂芳基,5-6元杂芳基-C1-C4烷基,其中杂芳基部分被一个至三个R7取代的5-6元杂芳基-C1-C4烷基,-S(O)R10,-S(O)2R10,COR10,COOR10,或者R8和R9连同氮原子一起通过C3-C8亚烷基链,被一个至三个R6b取代的C3-C8亚烷基链或其中一个碳原子被O、S、S(O)或SO2替换的C3-C8亚烷基链连接;
R10是氢,氰基-C1-C8烷基,C1-C8烷基,被一个至三个R6a取代的C1-C8烷基,C1-C8卤代烷基,被一个至三个R6a取代的C1-C8卤代烷基,C3-C8环烷基,被一个至三个R6b取代的C3-C8环烷基,其中一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基,C3-C8环烷基-C1-C8烷基,其中环烷基基团中的一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基-C1-C8烷基,C3-C8环烷基-C1-C8卤代烷基,C2-C8烯基,被一个至三个R6a取代的C2-C8烯基,C2-C8卤代烯基,被一个至三个R6a取代的C2-C8卤代烯基,C2-C8炔基,C2-C8卤代炔基,苯基,被一个至三个R7取代的苯基,苯基-C1-C4烷基,其中苯基部分被一个至三个R7取代的苯基-C1-C4烷基,5-6元杂芳基,被一个至三个R7取代的5-6元杂芳基,5-6元杂芳基-C1-C4烷基或其中杂芳基部分被一个至三个R7取代的5-6元杂芳基-C1-C4烷基;
n是1或2;
或其互变异构体、盐或N-氧化物。
具有至少一个碱性中心的具有式(I)的化合物可以例如与以下形成例如酸加成盐:强无机酸(如矿物酸,例如高氯酸、硫酸、硝酸、亚硝酸、磷酸或氢卤酸),强有机羧酸(如未取代的或例如被卤素取代的C1-C4烷羧酸,例如乙酸,如饱和或不饱和的二羧酸,例如草酸、丙二酸、琥珀酸、马来酸、富马酸或邻苯二甲酸,如羟基羧酸,例如抗坏血酸、乳酸、苹果酸、酒石酸或柠檬酸,或如苯甲酸),或有机磺酸(如未取代的或例如被卤素取代的C1-C4烷磺酸或芳基磺酸,例如甲烷磺酸或对甲苯磺酸)。具有至少一个酸性基团的具有式(I)的化合物可以例如与碱形成盐,例如矿物盐,如碱金属或碱土金属盐,例如钠盐、钾盐或镁盐;或与氨或有机胺形成盐,如吗啉、哌啶、吡咯烷、单、二或三低碳数烷基胺,例如乙胺、二乙胺、三乙胺或二甲基丙基胺,或单、二或三羟基低碳数烷基胺,例如单乙醇胺、二乙醇胺或三乙醇胺。
在取代基定义中出现的烷基基团是直链的或支链的,并且是例如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基、己基、壬基、癸基以及它们的支链异构体。烷基硫烷基、烷基亚磺酰基、烷基磺酰基、烷氧基、烯基和炔基基团衍生自所提及的烷基基团。烯基和炔基基团是单不饱和的或多不饱和的。
卤素通常是氟、氯、溴或碘。相应地,这也适用于与其他含义结合的卤素,如卤代烷基或卤代苯基。
卤代烷基基团优选地具有从1至6个碳原子的链长。卤代烷基是例如氟甲基、二氟甲基、三氟甲基、氯甲基、二氯甲基、三氯甲基、2,2,2-三氟乙基、2-氟乙基、2-氯乙基、五氟乙基、1,1-二氟-2,2,2-三氯乙基、2,2,3,3-四氟乙基以及2,2,2-三氯乙基。
烷氧基是例如甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基和叔丁氧基并且还是同分异构的戊氧基以及己氧基基团。
烷氧基烷基基团优选地具有1至6个碳原子的链长。
烷氧基烷基是例如甲氧基甲基、甲氧基乙基、乙氧基甲基、乙氧基乙基、正丙氧基甲基、正丙氧基乙基、异丙氧基甲基或异丙氧基乙基。
烷氧基羰基是例如甲氧基羰基(其为C1烷氧基羰基)、乙氧基羰基、丙氧基羰基、异丙氧基羰基、正丁氧基羰基、叔丁氧基羰基、正戊氧基羰基或己氧基羰基。
环烷基基团优选地具有从3至6个环碳原子,例如环丙基、环丁基、环戊基和环己基。
杂芳基基团优选地是5-6元杂芳基或是被一个至三个R7取代的5-6元杂芳基,其中杂芳基基团含有1至3个选自下组的杂原子,该组由以下各项组成:氮、氧和硫,不可能每个环系统都含有多于2个氧原子以及多于2个硫原子。单环基团的实例包括吡啶基、哒嗪基、嘧啶基、吡嗪基、吡咯基、吡唑基、咪唑基、三唑基(例如,1,2,4-三唑基)、呋喃基、苯硫基、噁唑基、异噁唑基、噁二唑基、噻唑基、异噻唑基、四唑基以及噻二唑基。
根据本发明的具有式(I)的化合物还包括在盐形成期间可以形成的水合物。
关于本发明的每种化合物(包括中间化合物)的A1、A2、A3、A4、R1、R2、R3、R4、R5、R6a、R6b、R7、R8、R9、和R10的优选值在以下实施例中披露。
实施例2:根据实施例1所述的化合物,其中,A1是C-R5;A2是C-H;A3是C-H;并且A4是C-H,其中R5是卤素、氰基、硝基、C1-C8烷基、C3-C8环烷基、C1-C8卤代烷基、或C2-C8烯基。
实施例3:根据实施例1或2所述的化合物,其中,
R1选自-(C0-C4烷基)-C(=O)-C3-C6环烷基和-(C0-C4烷基)-O-C3-C6环烷基。
实施例4:根据实施例1至3中任一项所述的化合物,其中,
R2是C1-C8卤代烷基。
实施例5:根据实施例1至4中任一项所述的化合物,其中,R3是C1-C4卤代烷基。
实施例6:根据实施例1至5中任一项所述的化合物,其中,R4是苯基或被一个至三个R7取代的苯基;其中R7独立地是卤素、氰基、C1-C8烷基、C1-C8卤代烷基、C1-C8烷氧基或C1-C8卤代烷氧基。
实施例7:根据实施例1至6中任一项所述的化合物,其中,A1是CR5并且A2、A3和A4各自是CH;R1选自-(C0-C4烷基)-C(=O)-C3-C6环烷基和-(C0-C4烷基)-O-C3-C6环烷基;R2是C1-C8卤代烷基;R3是C1-C4卤代烷基;R4是芳基或被一个至三个R7取代的芳基;并且n是2;其中R5是C1-C8烷基;并且R7是卤素。
实施例8:根据实施例1所述的化合物,其由具有式(Ia)的化合物表示
其中
R1选自-(C0-C4烷基)-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C3-C6环烷基、-R1aOR1aOR1b、-R1aOC(=O)R1b、-R1aOC(=O)OR1b、-R1aN(R1c)C(=O)OR1b、-R1aOC(=O)N(R1b)(R1c)、-R1aC(=O)N(R1b)(R1c)和-S-C(=O)OR1b;
R1a是-(CR1dR1e)m-;
R1b和R1c独立地选自H和C1-C4烷基,其中每个烷基基团是未取代的或被一个至三个卤素原子或被氰基基团取代;
R1d和R1e独立地选自H和C1-C4烷基;
m选自1、2、3和4。
实施例9:根据实施例8所述的化合物,其中,R1选自
-(C0-C4烷基)-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C(=O)-C3-C6环烷基和-(C0-C4烷基)-O-C3-C6环烷基。
实施例10:根据实施例所述的化合物,其选自:
或其互变异构体、盐或N-氧化物。
如本文所用的术语“具有式(I)的化合物”或“本发明的化合物”具有根据实施例1至10中任一项所述的化合物的含义。
本发明的化合物可以通过如方案1至3中所示的多种方法来制造。
方案1
1)如方案1中所示的,具有式(I)的化合物可以通过使具有式(II)的化合物(其中R是OH、C1-C6烷氧基或Cl、F或Br)与具有式(III)的胺(其中RG是S(O)nR2(其中n是0或1)或保护基团,如-(C=O)O-t-Bu)反应来制备。当R为OH时,此类反应通常是在偶联剂(如N,N’-二环己基碳二亚胺(“DCC”)、1-乙基-3-(3-二甲基氨基-丙基)碳二亚胺盐酸盐(“EDC”)或双(2-氧代-3-噁唑烷基)膦酰氯(“BOP-Cl”))存在下,在碱存在下,以及任选地在亲核性催化剂(如羟基苯并三唑(“HOBT”))的存在下进行。当R为Cl时,此类反应通常是在碱存在下、以及任选地在亲核性催化剂存在下进行。替代性地,有可能在包括有机溶剂(优选为乙酸乙酯)、及水性溶剂(优选为碳酸氢钠溶液)的双相系统中进行此反应。当R为C1-C6烷氧基时,有时有可能通过在热过程中一起加热酯和胺而将酯直接转换成为酰胺。合适的碱包括吡啶,三乙胺,4-(二甲基氨基)-吡啶(“DMAP”)或二异丙基乙基胺(胡宁氏碱(Hunig’s base))。优选的溶剂为N,N-二甲基乙酰胺、四氢呋喃、二噁烷、1,2-二甲氧基乙烷、乙酸乙酯和甲苯。该反应是在从0℃至100℃、优选地从15℃至30℃的温度下、特别是在环境温度下进行的。具有式(III)的胺是文献中已知的,或者可以使用本领域技术人员已知的方法制备。这些方法中的一些描述于制备实例中。
2)具有式(II)的酰卤(其中R是Cl、F或Br)可以在标准条件下由具有式(II)的羧酸(其中R是OH)制备,例如在WO 2009080250中所述的。
3)具有式(II)的羧酸(其中R是OH)可以由具有式(II)的酯(其中R是C1-C6烷氧基)形成,例如在WO 2009080250中所述的。
4)在催化剂(如乙酸钯(II)或双(三苯膦)钯(II)二氯化物)、任选地在配体(如三苯膦)、以及碱(如碳酸钠、吡啶、三乙胺、4-(二甲氨基)-吡啶(“DMAP”)或二异丙基乙胺(胡宁氏碱))的存在下,在溶剂(如水、N,N-二甲基甲酰胺或四氢呋喃)中,具有式(I)的化合物可以通过使具有式(IV)的化合物(其中XB是离去基团,例如卤素(如溴))与一氧化碳和具有式(III)的胺行反应来制备。该反应在从50℃至200℃、优选从100℃至150℃的温度下进行。该反应在从50至200巴,优选地从100至150巴的压力下进行。
5)具有式(IV)的化合物(其中XB是离去基团,例如卤素,如溴)可以通过各种方法来制造,例如在WO 2009080250中所述的。
6)具有式(III)的化合物是已知的化合物,或者可以通过本领域技术人员已知的方法制备。
方案2
7)替代性地,具有式(I)的化合物可以通过不同方法如方案2中所示由具有式(V)的中间体(其中XB是离去基团(例如卤素,如溴),或XB是氰基、甲酰基或乙酰基)根据类似于WO 2009080250中所述的那些的方法制备。具有式(V)的中间体例如可以如在相同参考文献中所述由具有式(VI)的中间体制备。
方案3
8)替代性地,具有式(I)的化合物可以通过不同方法如方案3中所示由具有式(VII)的中间体(其中XC是CH=C(R3)R4、或CH2C(OH)(R3)R4(其中R3和R4是如对于具有式(I)的化合物所定义的))根据类似于WO 2009080250中所述的那些的方法制备。
9)具有式(VII)的化合物(其中XC是CH=C(R3)R4、或CH2C(OH)(R3)R4)可以由具有式(Va)的化合物或由具有式(VII)的化合物(其中XC是CH2-卤素),使用类似于WO 2009080250中所述的那些的方法制备。
10)具有式(VII)的化合物(其中XC是CH2-卤素,如溴或氯)可以通过在从0℃至50℃,优选地从环境温度至40℃的温度下,在溶剂(如乙酸)中使具有式(Va)的甲基酮与卤化剂(例如溴或氯)反应来制备。
方案4
11)具有式(I)的化合物可以通过使具有式(I-H)的化合物与具有式(VIII)的化合物(其中LG是适合的离去基团,例如卤素(如溴或氯)、或咪唑或烷基硫氧基基团或卤代烷基硫氧基基团或芳基硫氧基基团)反应来制备。此类反应通常使用本领域技术人员已知的方法,在碱(如氢氧化钠或氰化钠)的存在下进行。
12)替代性地,在R1是CH2OC1-C6烷基或CH2OC3-C6环烷基的情况下,具有式(I)的化合物可以通过在路易斯酸(如四氯化钛)和碱(如三乙胺)的存在下使具有式(I-H)的化合物与甲醛反应,接着添加醇(如HOC1-C6烷基或HOC3-C6环烷基)来制备。
13)类似地,具有式(V)的化合物可以通过使具有式(V-H)的化合物与具有式(VIII)的化合物反应来制备。类似地,具有式(VII)的化合物可以通过使具有式(VII-H)的化合物与具有式(VIII)的化合物反应来制备。类似地,具有式(Va)的化合物可以通过使具有式(Va-H)的化合物与具有式(VIII)的化合物反应来制备。
反应物可以在碱的存在下进行反应。适合的碱的实例是碱金属或碱土金属氢氧化物、碱金属或碱土金属氢化物、碱金属或碱土金属酰胺、碱金属或碱土金属醇盐、碱金属或碱土金属乙酸盐、碱金属或碱土金属碳酸盐、碱金属或碱土金属二烷基酰胺或碱金属或碱土金属烷基甲硅烷基酰胺、烷基胺、亚烷基二胺、游离的或N-烷基化的饱和或不饱和的环烷基胺、碱性杂环、氢氧化铵以及碳环胺。可以提及的实例是氢氧化钠、氢化钠、氨基钠、甲醇钠、乙酸钠、碳酸钠、叔丁醇钾、氢氧化钾、碳酸钾、氢化钾、二异丙基氨基锂、双(三甲基甲硅烷基)氨基钾、氢化钙、三乙胺、二异丙基乙胺、三亚乙基二胺、环己胺、N-环己基-N,N-二甲基胺、N,N-二乙基苯胺、吡啶、4-(N,N-二甲基氨基)吡啶、奎宁环、N-甲基吗啉、苄基三甲基氢氧化铵和1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)。反应物可以原样相互反应,即不添加溶剂或稀释剂。然而,在大多数情况下,添加惰性溶剂或稀释剂或这些的混合物是有利的。如果反应在碱存在下进行,则过量使用的碱如三乙胺、吡啶、N-甲基吗啉或N,N-二乙基苯胺也可用作溶剂或稀释剂。反应有利地是在从约-80℃至约+140℃、优选从约-30℃至约+100℃的温度范围内,在许多情况下在环境温度与约+80℃之间的范围内进行的。
具有式(I)的化合物能以本身已知的方式转化为另一种具有式(I)的化合物,这是通过以常规方式将具有式(I)的起始化合物的一个或多个取代基用根据本发明的另一个或其他一个或多个取代基的替换来实现的。取决于所选的适合各自情况的反应条件以及起始材料,有可能例如,在一个反应步骤中仅将一个取代基用根据本发明的另一个取代基替换,或者在同一个反应步骤中可以将多个取代基用多个根据本发明的其他取代基来替换。
本发明还提供了可用于制备具有式(I)的化合物的中间体。某些中间体是新颖的并且本身构成本发明的另一个方面。一组新颖中间体是具有式(Int-I)的化合物
其中A1、A2、A3、A4、R1、R2和n是如对于根据实施例1至9中任一项所述的化合物所定义的,并且XB是卤素,如溴,或XB是氰基、甲酰基、CH=N-OH或乙酰基;或其盐或N-氧化物。对于A1、A2、A3、A4、R1、R2和n的优选项和对于具有式(I)的化合物的对应取代基所列出的优选项是相同的。
另一组新颖中间体是具有式(Int-II)的化合物
其中A1、A2、A3、A4、R1、R2和n是如对于根据实施例1至9中任一项所述的化合物所定义的;XC是CH2-卤素,其中卤素优选地是溴或氯、CH=C(R3)R4或CH2C(OH)(R3)R4,其中R3和R4是如对于具有式(I)的化合物所定义的;或其盐或N-氧化物。对于A1、A2、A3、A4、R1、R2和n的优选项和对于具有式(I)的化合物的对应取代基所列出的优选项是相同的。
另一组新颖中间体是具有式(Int-III)的化合物
其中R1、R2和n是如对于根据实施例1至9中任一项所述的化合物所定义的;或其盐或N-氧化物。对于R1、R2和n的优选项和对于具有式(I)的化合物的对应取代基所列出的优选项是相同的。
具有式(I)的化合物包括至少一个手性中心并且可以作为具有式(I*)的化合物或具有式(I**)的化合物存在:
总体上,具有式(I**)的化合物比具有式(I*)的化合物更具生物活性。本发明包括化合物(I*)与化合物(I**)以任何比率的混合物,例如其摩尔比为1:99至99:1,例如10:1至1:10,例如大体上50:50的摩尔比。在富含对映异构体(或差向异构体)的具有式(I**)的混合物中,与两种对映异构体(或差向异构体)的总量相比,具有式(I**)的化合物的摩尔比例是例如大于50%,例如至少55%、60%、65%、70%、75%、80%、85%、90%、95%、96%、97%、98%或至少99%。同样地,在富含对映异构体(或差向异构体)的具有式(I*)的混合物中,与两种对映异构体(或差向异构体)的总量相比,具有式(I*)的化合物的摩尔比例是例如大于50%,例如至少55%、60%、65%、70%、75%、80%、85%、90%、95%、96%、97%、98%或至少99%。富含对映异构体(或差向异构体)的具有式(I**)的混合物是优选的。
根据本发明的具有式(I)的化合物在有害生物控制领域中是有预防和/或治疗价值的活性成分,即使是在低的施用比率下,它们具有有利的杀生物谱并且是温血物种、鱼以及植物良好耐受的。具有式(I)的化合物可以作用于正常敏感的以及还有抗性的动物有害生物(如昆虫或蜱螨目的代表)的所有的或仅个别的发育阶段。这些化合物的杀昆虫的或杀螨的活性可以本身直接显现出来,即对有害生物的破坏,其立即或者只在一段时间之后(例如在蜕皮期间)发生;或间接显现出来,例如减少的产卵和/或孵化率,对应于至少50%至60%的破坏率(死亡率)的良好活性。
上述动物有害生物的实例是:
来自蜱螨目,例如下毛瘿螨属物种(Acalitus spp.)、针刺瘿螨属物种(Aculusspp.)、窄瘿螨属物种(Acaricalus spp.)、瘤瘿螨属物种(Aceria spp.)、粗脚粉螨(Acarussiro)、钝眼蜱属物种(Amblyomma spp.)、锐缘蜱属物种(Argas spp.)、牛蜱属物种(Boophilus spp.)、短须螨属物种(Brevipalpus spp.)、苔螨属物种(Bryobia spp.)、上三脊瘿螨属物种(Calipitrimerus spp.)、皮螨属物种(Chorioptes spp.)、鸡皮刺螨(Dermanyssus gallinae)、表皮螨属物种(Dermatophagoides spp.)、始叶螨属物种(Eotetranychus spp.)、瘿螨属物种(Eriophyes spp.)、半跗线螨属物种(Hemitarsonemusspp.)、璃眼蜱属物种(Hyalomma spp.)、硬蜱属物种(Ixodes spp.)、小爪螨属物种(Olygonychus spp.)、钝缘蜱属物种(Ornithodoros spp.)、侧多食跗线螨(Polyphagotarsone latus)、全爪螨属物种(Panonychus spp.)、桔芸锈螨(Phyllocoptruta oleivora)、植食螨属物种(Phytonemus spp.)、多食跗线螨属物种(Polyphagotarsonemus spp.)、痒螨属物种(Psoroptes spp.)、扇头蜱属物种(Rhipicephalus spp.)、根螨属物种(Rhizoglyphus spp.)、疥螨属物种(Sarcoptesspp.)、狭跗线螨属物种(Steneotarsonemus spp.)、跗线螨属物种(Tarsonemus spp.)以及叶螨属物种(Tetranychus spp.);
来自虱目,例如血虱属物种(Haematopinus spp.)、长颚虱属物种(Linognathusspp.)、人虱属物种(Pediculus spp.)、瘿绵蚜属物种(Pemphigus spp.)以及根瘤蚜属物种(Phylloxera spp.);
来自鞘翅目,例如叩甲属物种(Agriotes spp.)、欧洲鳃角金龟(Amphimallonmajale)、东方异丽金龟(Anomala orientalis)、花象属物种(Anthonomus spp.)、蜉金龟属物种(Aphodius spp.)、玉米拟花萤(Astylus atromaculatus)、金龟属物种(Ataeniusspp.)、甜菜隐食甲(Atomaria linearis)、甜菜胫跳甲(Chaetocnema tibialis)、萤叶甲属物种(Cerotoma spp.)、宽胸叩头虫属物种(Conoderus spp.)、根颈象属物种(Cosmopolites spp.)、绿花金龟(Cotinis nitida)、象虫属物种(Curculio spp.)、圆头犀金龟属物种(Cyclocephala spp.)、皮蠹属物种(Dermestes spp.)、根萤叶甲属物种(Diabrotica spp.)、阿根廷兜虫(Diloboderus abderus)、食植瓢虫属物种(Epilachnaspp.)、Eremnus属物种、黑异爪蔗金龟(Heteronychus arator)、咖啡果小蠹(Hypothenemushampei)、Lagria vilosa、马铃薯甲虫(Leptinotarsa decemLineata)、稻水象属物种(Lissorhoptrus spp.)、Liogenys属物种、Maecolaspis属物种、栗色绒金龟(Maladeracastanea)、美洲叶甲属物种(Megascelis spp.)、油菜花露尾甲(Melighetes aeneus)、鳃金龟属物种(Melolontha spp.)、Myochrous armatus、锯谷盗属物种(Orycaephilusspp.)、耳喙象属物种(Otiorhynchus spp.)、鳃角金龟属物种(Phyllophaga spp.)、斑象属物种(Phlyctinus spp.)、弧丽金龟属物种(Popillia spp.)、蚤跳甲属物种(Psylliodesspp.)、Rhyssomatus aubtilis、劫根蠹属物种(Rhizopertha spp.)、金龟子科(Scarabeidae)、米象属物种(Sitophilus spp.)、麦蛾属物种(Sitotroga spp.)、伪切根虫属物种(Somaticus spp.)、尖隐喙象属物种、大豆茎象(Sternechus subsignatus)、拟步行虫属物种(Tenebrio spp.)、拟谷盗属物种(Tribolium spp.)以及斑皮蠹属物种(Trogoderma spp.);
来自双翅目,例如伊蚊属物种(Aedes spp.)、疟蚊属物种(Anopheles spp.)、高梁芒蝇(Antherigona soccata.)、橄榄果实蝇(Bactrocea oleae)、花园毛蚊(Bibiohortulanus)、迟眼蕈蚊属物种(Bradysia spp.)、红头丽蝇(Calliphoraerythrocephala)、小条实蝇属物种(Ceratitis spp.)、金蝇属物种(Chrysomyia spp.)、库蚊属物种(Culex spp.)、黄蝇属物种(Cuterebra spp.)、寡鬃实蝇属物种(Dacus spp.)、地种蝇属物种(Delia spp)、黑腹果蝇(Drosophila melanogaster)、厕蝇属物种(Fanniaspp.)、胃蝇属物种(Gastrophilus spp.)、Geomyza tripunctata、舌蝇属物种(Glossinaspp.)、皮蝇属物种(Hypoderma spp.)、虱蝇属物种(Hyppobosca spp.)、斑潜蝇属物种(Liriomyza spp.)、绿蝇属物种(Lucilia spp.)、黑潜蝇属物种(Melanagromyza spp.)、家蝇属物种(Musca spp.)、狂蝇属物种(Oestrus spp.)、瘿蚊属物种(Orseolia spp.)、瑞典麦秆蝇(Oscinella frit)、藜泉蝇(Pegomyia hyoscyami)、草种蝇属物种(Phorbia spp.)、绕实蝇属物种(Rhagoletis spp)、Rivelia quadrifasciata、Scatella属物种、尖眼蕈蚊属物种(Sciara spp.)、螫蝇属物种(Stomoxys spp.)、虻属物种(Tabanus spp.)、绦虫属物种(Tannia spp.)以及大蚊属物种(Tipula spp.);
来自半翅目,例如瘤缘蝽(Acanthocoris scabrator)、拟缘蝽属物种(Acrosternum spp.)、苜蓿盲蝽(Adelphocoris lineolatus)、土黄缘蝽、海虾盾缘蝽(Bathycoelia thalassina)、土长蝽属物种、臭虫属物种、Clavigralla tomentosicollis、盲蝽属物种(Creontiades spp.)、可可瘤盲蝽、Dichelops furcatus、棉红蝽属物种、埃德萨属物种(Edessa spp.)、美洲蝽属物种(Euchistus spp.)、六斑菜蝽(Eurydemapulchrum)、扁盾蝽属物种、茶翅蝽、具凹巨股长蝽(Horcias nobilellus)、稻缘蝽属物种、草盲蝽属物种、热带硕蚧属物种、卷心菜斑色蝽(Murgantia histrionic)、新长缘蝽属物种、烟盲蝽(Nesidiocoris tenuis)、绿蝽属物种、拟长蝽(Nysius simulans)、海岛蝽象、皮蝽属物种、壁蝽属物种、红猎蝽属物种、可可褐盲蝽、栗土蝽(Scaptocoris castanea)、黑蝽属物种(Scotinophara spp.)、Thyanta属物种、锥鼻虫属物种以及木薯网蝽(Vatigailludens);
来自同翅目,例如豌豆无网长管蚜(Acyrthosium pisum)、Adalges属物种、Agalliana ensigera、塔尔吉隆脉木虱、粉虱属物种(Aleurodicus spp.)、刺粉虱属物种(Aleurocanthus spp.)、甘蔗穴粉虱、软毛粉虱(Aleurothrixus floccosus)、甘蓝粉虱(Aleyrodes brassicae)、棉叶蝉(Amarasca biguttula)、檬果长突叶蝉、肾圆盾蚧属物种、金橙黄肾圆盾蚧(Aonidiella auranti)、蚜科、蚜属物种、圆盾蚧属物种(Aspidiotusspp.)、茄沟无网蚜、马铃薯木虱(Bactericera cockerelli)、小粉虱属物种、短尾蚜属物种(Brachycaudus spp)、甘蓝蚜、喀木虱属物种、双尾蚜(Cavariella aegopodii Scop.)、蜡蚧属物种、黑褐圆盾蚧、橙褐圆盾蚧、大叶蝉属物种、大白叶蝉(Cofana spectra)、隐瘤蚜属物种、叶蝉属物种、褐软蚧、玉米黄翅叶蝉、裸粉虱属物种、柑橘木虱、麦双尾蚜、西圆尾蚜属物种、小绿叶蝉属物种、苹果绵蚜、葡萄斑叶蝉属物种、Gascardia属物种、赤桉木虱(Glycaspis brimblecombei)、菜缢管蚜(Hyadaphis pseudobrassicae)、大尾蚜属物种(Hyalopterus spp.)、超瘤蚜种(Hyperomyzus pallidus)、檬果绿叶蝉(Idioscopusclypealis)、非洲叶蝉、灰飞虱属物种、水土坚蚧、蛎盾蚧属物种、萝卜蚜(Lopaphiserysimi)、Lyogenys maidis、长管蚜属物种、沫蝉属物种、蛾蜡蝉科(Metcalfa pruinosa)、麦无网蚜、麦蜡蝉、瘤蚜属物种、新声蚜属物种(Neotoxoptera sp)、黑尾叶蝉属物种、褐飞虱属物种(Nilaparvata spp.)、梨大绿蚜、Odonaspis ruthae、甘蔗棉蚜、杨梅缘粉虱、考氏木虱、片盾蚧属物种、瘿绵蚜属物种、玉米蜡蝉、扁角飞虱属物种、忽布疣蚜、根瘤蚜属物种(Phylloxera spp)、动性球菌属物种、桑白盾蚧属物种、粉蚧属物种、棉跳盲蝽(Pseudatomoscelis seriatus)、木虱属物种、棉蚧(Pulvinaria aethiopica)、齿盾蚧属物种、Quesada gigas、电光叶蝉(Recilia dorsalis)、缢管蚜属物种、黑盔蚧属物种、带叶蝉属物种、二叉蚜属物种、麦蚜属物种(Sitobion spp.)、白背飞虱、三角苜蓿跳虫(Spissistilus festinus)、条斑飞虱(Tarophagus Proserpina)、声蚜属物种、粉虱属物种、Tridiscus sporoboli、葵粉蚧属物种(Trionymus spp.)、非洲木虱、矢尖蚧、火焰斑叶蝉以及Zyginidia scutellaris;
来自膜翅目,例如顶切叶蚁属(Acromyrmex)、三节叶蜂属物种(Arge spp.)、切叶蚁属物种(Atta spp.)、茎叶蜂属物种(Cephus spp.)、松叶蜂属物种(Diprion spp.)、锯角叶蜂科(Diprionidae)、松叶蜂(Gilpinia polytoma)、实叶蜂属物种(Hoplocampa spp.)、毛蚁属物种(Lasius spp.)、小黄家蚁(Monomorium pharaonis)、新松叶蜂属物种(Neodiprion spp.)、农蚁属物种(Pogonomyrmex spp)、红火蚁、水蚁属物种(Solenopsisspp.)以及胡蜂属物种(Vespa spp.);
来自等翅目,例如乳白蚁属物种(Coptotermes spp)、白蚁(Corniternescumulans)、楹白蚁属物种(Incisitermes spp)、大白蚁属物种(Macrotermes spp)、澳白蚁属物种(Mastotermes spp)、小白蚁属物种(Microtermes spp)、散白蚁属物种(Reticulitermes spp.);热带火蚁(Solenopsis geminate);
来自鳞翅目,例如长翅卷蛾属物种、褐带卷蛾属物种、透翅蛾属物种、地夜蛾属物种、棉叶虫、Amylois属物种、黎豆夜蛾、黄卷蛾属物种、银蛾属物种(Argyresthia spp.)、带卷蛾属物种、丫纹夜蛾属物种、棉潜蛾、玉米楷夜蛾、粉斑螟蛾、桃蛀果蛾、禾草螟属物种、卷叶蛾属物种、越蔓桔草螟(Chrysoteuchia topiaria)、葡萄果蠹蛾、卷叶螟属物种、云卷蛾属物种、纹卷蛾属物种、鞘蛾属物种、磷翅目粉蝶、Cosmophila flava、草螟属物种、大菜螟、苹果异形小卷蛾、黄杨木蛾、小卷蛾属物种、黄杨绢野螟、杆草螟属物种、苏丹棉铃虫、金刚钻属物种、非洲茎螟、粉螟属物种、叶小卷蛾属物种(Epinotia spp)、细斑灯蛾、Etiellazinckinella、花小卷蛾属物种、环针单纹蛾、黄毒蛾属物种、切根虫属物种、Feltiajaculiferia、Grapholita属物种、绿青虫蛾、实夜蛾属物种、菜螟、切叶野螟属物种(Herpetogramma spp)、美国白蛾、番茄蠹蛾、Lasmopalpus lignosellus、旋纹潜叶蛾、潜叶细蛾属物种、葡萄花翅小卷蛾、Loxostege bifidalis、毒蛾属物种、潜蛾属物种、幕枯叶蛾属物种、甘蓝夜蛾、烟草天蛾、Mythimna属物种、夜蛾属物种、秋尺蛾属物种、Orniodesindica、欧洲玉米螟、超小卷蛾属物种、褐卷蛾属物种、小眼夜蛾、蛀茎夜蛾、Pectinophoragossypi-ela、咖啡潜叶蛾、一星黏虫、马铃薯麦蛾、菜粉蝶、粉蝶属物种、小菜蛾、芽蛾属物种、尺叶蛾属物种、薄荷灰夜蛾、西方豆地香(Richia albicosta)、白禾螟属物种(Scirpophaga spp.)、蛀茎夜蛾属物种、长须卷蛾属物种、灰翅夜蛾属物种、棉大卷叶螟、兴透翅蛾属物种、异舟蛾属物种、卷叶蛾属物种、粉纹夜蛾、番茄斑潜蝇、以及巢蛾属物种;
来自食毛目,例如,畜虱属物种和啮毛虱属物种;
来自直翅目,例如蠊属物种、小蠊属物种、蝼蛄属物种、马德拉蜚蠊、飞蝗属物种、北痣蟋蟀(Neocurtilla hexadactyla)、大蠊属物种、痣蟋蟀属物种(Scapteriscus spp)、以及沙漠蝗属物种;
来自啮虫目,例如虱啮属物种(Liposcelis spp.);
来自蚤目,例如角叶蚤属物种(Ceratophyllus spp.)、栉头蚤属物种(Ctenocephalides spp.)以及印鼠客蚤物种(Xenopsylla cheopis);
来自缨翅目,例如Calliothrips phaseoli、花蓟马属物种(Frankliniellaspp.)、阳蓟马属物种(Heliothrips spp)、褐带蓟马属物种(Hercinothrips spp.)、单亲蓟马属物种(Parthenothrips spp.)、橙花苷硬蓟马(Scirtothrips aurantii)、大豆蓟马(Sericothrips variabilis)、带蓟马属物种(Taeniothrips spp.)、蓟马属物种(Thripsspp);和/或
来自缨尾目,例如衣鱼(Lepisma saccharina)。
可在植物发育早期损害作物的土栖有害生物的实例是:
来自鳞翅目,例如长翅卷蛾属(Acleris spp.)、透翅蛾属(Aegeria spp.)、地夜蛾属(Agrotis spp.)、棉叶虫(Alabama argillaceae)、淀粉虫属(Amylois spp.)、丫纹夜蛾属(Autographa spp.)、玉米楷夜蛾(Busseola fusca)、粉斑螟蛾(Cadra cautella)、禾草螟属(Chilo spp.)、大菜螟(Crocidolomia binotalis)、杆草螟属(Diatraea spp.)、苏丹棉铃虫(Diparopsis castanea)、南美玉米苗斑螟属(Elasmopalpus spp.)、实夜蛾属(Heliothis spp.)、甘蓝夜蛾(Mamestra brassicae)、马铃薯麦蛾(Phthorimaeaoperculella)、小菜蛾(Plutella xylostella)、白禾螟属(Scirpophaga spp.)、蛀茎夜蛾属(Sesamia spp.)、灰翅夜蛾属(Spodoptera spp.)、以及卷叶蛾属(Tortrix spp.);
来自鞘翅目(Coleoptera),例如,缺隆叩甲属(Agriotes spp.)、花象属(Anthonomus spp.)、甜菜隐食甲(Atomaria linearis)、甜菜胫跳甲(Chaetocnematibialis)、鳄梨象属(Conotrachelus spp.)、根颈象属(Cosmopolites spp.)、象虫属(Curculio spp.)、皮蠹属(Dermestes spp.)、根萤叶甲属(Diabrotica spp.)、Dilopoderus属、食植瓢虫属(Epilachna spp.)、Eremnus属、异爪犀金龟属(Heteronychusspp.)、稻水象属(Lissorhoptrus spp.)、鳃金龟属(Melolontha spp.)、锯谷盗属(Orycaephilus spp.)、耳喙象属(Otiorhynchus spp.)、斑象属(Phlyctinus spp.)、丽金龟属(Popillia spp.)、油菜跳甲属(Psylliodes spp.)、劫根蠹属(Rhizopertha spp.)、金龟子科(Scarabeidae)、麦蛾属(Sitotroga spp.)、伪切根虫属(Somaticus spp.)、纤毛象属(Tanymecus spp.)、拟步行虫属(Tenebrio spp.)、拟谷盗属(Tribolium spp.)、斑皮蠹属(Trogoderma spp.)以及距步甲属(Zabrus spp.);
来自直翅目,例如蝼蛄属(Gryllotalpa spp.);
来自等翅目(Isoptera),例如散白蚁属;
来自啮虫目,例如虱啮属物种(Liposcelis spp.);
来自虱目,例如血虱属物种(Haematopinus spp.)、长颚虱属物种(Linognathusspp.)、人虱属物种(Pediculus spp.)、瘿绵蚜属物种(Pemphigus spp.)以及根瘤蚜属物种(Phylloxera spp.);
来自同翅目,例如苹果棉蚜(Eriosoma larigerum);
来自膜翅目,例如,顶切叶蚁属、布切叶白蚁属、茎叶蜂属、毛蚁属、小黄家蚁、新松叶蜂属、火蚁属以及胡蜂属;
来自双翅目,例如大蚊属(Tipula spp.);
十字花科植物跳甲(条跳甲属)、根蛆(地种蝇属)、卷心菜心皮象鼻虫(龟象属)以及蚜虫。
具有式(I)的化合物可以用于控制线虫。因此,在另一个方面中,本发明还涉及一种控制由植物寄生线虫(内寄生线虫、半内寄生线虫和外寄生线虫)对植物及其部分的损害的方法,尤其是以下植物寄生线虫,如根结线虫(root knot nematode)、北方根结线虫(Meloidogyne hapla)、南方根结线虫(Meloidogyne incognita)、爪哇根结线虫(Meloidogyne javanica)、花生根结线虫(Meloidogyne arenaria)以及其他根结线虫物种;孢囊形成线虫(cyst-forming nematodes)、马铃薯金线虫(Globodera rostochiensis)以及其他球孢囊线虫属(Globodera)物种;禾谷孢囊线虫(Heterodera avenae)、大豆孢囊线虫(Heterodera glycines)、甜菜孢囊线虫(Heterodera schachtii)、红三叶异皮线虫(Heterodera trifolii)、以及其他异皮线虫属(Heterodera)物种;种瘿线虫(Seed gallnematodes)、粒线虫属(Anguina)物种;茎及叶面线虫(Stem and foliar nematodes)、滑刃线虫属(Aphelenchoides)物种;刺毛线虫(Sting nematode)、长尾刺线虫(Eelonolaimuslongicaudatus)以及其他刺线虫属(Belonolaimus)物种;松树线虫(Pine nematodes)、松材线虫(Bursaphelenchus xylophilus)以及其他伞滑刃属(Bursaphelenchus)物种;环形线虫(Ring nematodes)、环线虫属(Criconema)物种、小环线虫属(Criconemella)物种、轮线虫属(Criconemoides)物种、中环线虫属(Mesocriconema)物种;茎及鳞球茎线虫(Stemand bulb nematodes)、腐烂茎线虫(Ditylenchus destructor)、鳞球茎茎线虫(Ditylenchus dipsaci)以及其他茎线虫属(Ditylenchus)物种;维线虫(Awl nematodes)、锥线虫属(Dolichodorus)物种;螺旋线虫(Spiral nematodes)、多头螺旋线虫(Heliocotylenchus multicinctus)以及其他螺旋线虫属(Helicotylenchus)物种;鞘及鞘形线虫(Sheath and sheathoid nematodes)、鞘线虫属(Hemicycliophora)物种以及半轮线虫属(Hemicriconemoides)物种;潜根线虫属(Hirshmanniella)物种;支线虫(Lancenematodes)、冠线虫属(Hoploaimus)物种;假根结线虫(false rootknot nematodes)、珍珠线虫属(Nacobbus)物种;针状线虫(Needle nematodes)、横带长针线虫(Longidoruselongatus)以及其他长针线虫属(Longidorus)物种;大头针线虫(Pin nematodes)、短体线虫属(Pratylenchus)物种;腐线虫(Lesion nematodes)、花斑短体线虫(Pratylenchusneglectus)、穿刺短体线虫(Pratylenchus penetrans)、弯曲短体线虫(Pratylenchuscurvitatus)、古氏短体线虫(Pratylenchus goodeyi)以及其他短体线虫属(Pratylenchus)物种;柑桔穿孔线虫(Burrowing nematodes)、香蕉穿孔线虫(Radopholussimilis)以及其他内侵线虫属(Radopholus)物种;肾状线虫(Reniform nematodes)、罗柏氏盘旋线虫(Rotylenchus robustus)、肾形盘旋线虫(Rotylenchus reniformis)以及其他盘旋线虫属(Rotylenchus)物种;盾线虫属(Scutellonema)物种;短粗根线虫(Stubby rootnematodes)、原始毛刺线虫(Trichodorus primitivus)以及其他毛刺线虫属(Trichodorus)物种、拟毛刺线虫属(Paratrichodorus)物种;矮化线虫(Stuntnematodes)、马齿苋矮化线虫(Tylenchorhynchus claytoni)、顺逆矮化线虫(Tylenchorhynchus dubius)以及其他矮化线虫属(Tylenchorhynchus)物种;柑桔线虫(Citrus nematodes)、穿刺线虫(Tylenchulus)物种;短剑线虫(Dagger nematodes)、剑线虫属(Xiphinema)物种;以及其他植物寄生线虫物种,如亚粒线虫属物种(Subanguinaspp.)、根结线虫属物种(Hypsoperine spp.)、大刺环线虫属物种(Macroposthonia spp.)、Melinius属物种、刻点胞囊属物种(Punctodera spp.)和五沟线虫属物种(Quinisulciusspp.)。
特别地,通过本发明的化合物可以控制这些线虫物种:根结线虫属物种(Meloidogyne spp.)、异皮线虫属物种(Heterodera spp.)、盘旋线虫属物种(Rotylenchusspp.)以及短体线虫属物种(Pratylenchus spp.)。
根据本发明的活性成分可用于控制、也就是遏制或破坏上述类型的有害生物,这些有害生物特别出现在植物上,尤其是在农业中、在园艺中以及在林业中的有用的植物和观赏植物上,或者在这些植物的器官上,例如果实、花、叶、茎、块茎或根,并且在一些情况下,甚至在一个随后的时间点形成的植物器官仍保持受保护以抵抗这些有害生物。
特别地,适合的目标作物是,谷物,如小麦、大麦、黑麦、燕麦、稻、玉米或高梁;甜菜,如糖用甜菜或饲料甜菜;果实,例如梨果、核果或无核小果,如苹果、梨、李子、桃、杏、樱桃或浆果,例如草莓、覆盆子或黑莓;豆科作物,如菜豆、小扁豆、豌豆或大豆;油料作物,如油菜、芥菜、罂粟、橄榄、向日葵、椰子、蓖麻、可可豆或落花生;瓜类作物,如南瓜、黄瓜或甜瓜;纤维植物,如棉花、亚麻、大麻或黄麻;柑橘类果实,如橙子、柠檬、葡萄柚或橘子;蔬菜,如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、番茄、马铃薯或灯笼椒;樟科,如鳄梨、肉桂或樟脑;以及还有烟草、坚果、咖啡、茄子、甘蔗、荼、胡椒、葡萄藤、蛇麻草、车前草科以及乳胶植物。
本发明的组合物和/或方法还可以用在任何观赏植物和/或蔬菜作物(包括花、灌木、阔叶树和常绿植物)上。
例如,本发明可以用于任何以下观赏植物物种:藿香蓟属物种、假面花属物种(Alonsoa spp.)、银莲花属物种、南非葵(Anisodontea capsenisis)、春黄菊属物种、金鱼草属物种、紫菀属物种、秋海棠属物种(例如丽格海棠、四季秋海棠、球根秋海棠(B.tubéreux))、叶子花属物种、雁河菊属物种(Brachycome spp.)、芸苔属物种(观赏植物)、蒲包草属物种、辣椒、长春花、美人蕉属物种、矢车菊属物种、菊属物种、瓜叶菊属物种(银叶菊(C.maritime))、金鸡菊属物种、红景天(Crassula coccinea)、火红萼距花(Cupheaignea)、大丽花属物种、翠雀属物种、荷包牡丹、彩虹菊属物种(Dorotheantus spp.)、洋桔梗、连翘属物种、倒挂金钟属物种、老鹳草属鼠麹草属(Geranium gnaphalium)、大丁草属物种、千日红、天芥菜属物种、向日葵属物种、木槿属物种、绣球花属物种、绣球属物种、嫣红蔓、凤仙花属物种(非洲凤仙花)、血苋属物种(Iresines spp.)、伽蓝菜属物种、马缨丹、三月花葵、狮耳花、百合属物种、松叶菊属物种、沟酸浆属物种、美国薄荷属物种、龙面花属物种、万寿菊属物种、石竹属物种(康乃馨)、美人蕉属物种、酢浆草属物种、雏菊属物种、天竺葵属物种(盾叶天竺葵、马蹄纹天竺葵)、堇菜属物种(三色堇)、碧冬茄属物种、草夹竹桃属物种、香茶菜属物种(Plecthranthus spp.)、一品红属物种、爬山虎属物种(五叶爬山虎、爬山虎)、报春花属物种、毛茛属物种、杜鹃花属物种、蔷薇属物种(玫瑰)、黄雏菊属物种、非洲堇属物种、鼠尾草属物种、紫扇花(Scaevola aemola)、蛾蝶花(Schizanthuswisetonensis)、景天属物种、茄属物种、苏非尼亚矮牵牛属物种(Surfinia spp.)、万寿菊属物种、烟草属物种、马鞭草属物种、百日草属物种以及其他花坛植物。
例如,本发明可以用于任何以下蔬菜物种:葱属物种(大蒜、洋葱、A.oschaninii、韭葱、火葱、大葱)、茴香芹、旱芹(Apium graveolus)、芦笋、甜菜、芸苔属物种(甘蓝、大白菜、芜菁)、辣椒、鹰嘴豆、苦苣、菊苣属物种(菊苣、苦苣)、西瓜(Citrillus lanatus)、黄瓜属物种(黄瓜、甜瓜)、南瓜属物种(西葫芦、印度南瓜)、菜蓟属物种(Cyanara spp.)(朝鲜蓟、刺苞菜蓟)、野胡萝卜、茴香、金丝桃属物种、莴苣、番茄属物种(番茄、圣女果番茄)、薄荷属物种、罗勒、香芹、菜豆属物种(菜豆、荷包豆)、豌豆、萝卜、食用大黄、迷迭香属物种、鼠尾草属物种、黑婆罗门参(Scorzonera hispanica)、茄子、菠菜、新缬草属物种(莴苣缬草、V.eriocarpa)以及蚕豆。
优选的观赏植物物种包括非洲堇(African violet)、秋海棠属、大丽花属、大丁草属、绣球属、马鞭草属、蔷薇属、伽蓝菜属、一品红属、紫菀属、矢车菊属、金鸡菊属、翠雀属、美国薄荷属、草夹竹桃属、黄雏菊属、景天属、碧冬茄属、堇菜属、凤仙花属、老鹳草属、菊属、毛茛属、倒挂金钟属、鼠尾草属、绣球花属、迷迭香、鼠尾草、圣约翰草(St.Johnswort)、薄荷(mint)、甜椒(sweet pepper)、番茄和黄瓜(cucumber)。
根据本发明的活性成分尤其适合于控制棉花、蔬菜、玉米、水稻以及大豆作物上的扁豆蚜、黄瓜条叶甲、烟芽夜蛾、桃蚜、小菜蛾以及海灰翅夜蛾。根据本发明的活性成分另外尤其适合于控制甘蓝夜蛾(优选地在蔬菜上)、苹果蠹蛾(优选地在苹果上)、小绿叶蝉(优选地在蔬菜、葡萄园里)、马铃薯叶甲(Leptinotarsa)(优选地在马铃薯上)以及二化螟(优选地在水稻上)。
根据本发明的活性成分尤其适合于控制棉花、蔬菜、玉米、水稻以及大豆作物上的扁豆蚜、黄瓜条叶甲、烟芽夜蛾、桃蚜、小菜蛾以及海灰翅夜蛾。根据本发明的活性成分另外尤其适合于控制甘蓝夜蛾(优选地在蔬菜上)、苹果蠹蛾(优选地在苹果上)、小绿叶蝉(优选地在蔬菜、葡萄园里)、马铃薯叶甲(Leptinotarsa)(优选地在马铃薯上)以及二化螟(优选地在水稻上)。
在另一方面中,本发明还可涉及一种控制由植物寄生线虫(内寄生的-、半内寄生的-和外寄生线虫)对植物及其部分的损害的方法,尤其是以下植物寄生线虫,如根结线虫(root knot nematodes)、北方根结线虫(Meloidogyne hapla)、南方根结线虫(Meloidogyne incognita)、爪哇根结线虫(Meloidogyne javanica)、花生根结线虫(Meloidogyne arenaria)以及其他根结线虫物种;孢囊形成线虫(cyst-formingnematodes)、马铃薯金线虫(Globodera rostochiensis)以及其他球孢囊线虫属(Globodera)物种;禾谷孢囊线虫(Heterodera avenae)、大豆孢囊线虫(Heteroderaglycines)、甜菜孢囊线虫(Heterodera schachtii)、红三叶异皮线虫(Heteroderatrifolii)、以及其他异皮线虫属(Heterodera)物种;种瘿线虫(Seed gall nematodes)、粒线虫属(Anguina)物种;茎及叶面线虫(Stem and foliar nematodes)、滑刃线虫属(Aphelenchoides)物种;刺毛线虫(Sting nematodes)、长尾刺线虫(Belonolaimuslongicaudatus)以及其他刺线虫属(Belonolaimus)物种;松树线虫(Pine nematodes)、松材线虫(Bursaphelenchus xylophilus)以及其他伞滑刃属(Bursaphelenchus)物种;环形线虫(Ring nematodes)、环线虫属(Criconema)物种、小环线虫属(Criconemella)物种、轮线虫属(Criconemoides)物种、中环线虫属(Mesocriconema)物种;茎及鳞球茎线虫(Stemand bulb nematodes)、腐烂茎线虫(Ditylenchus destructor)、鳞球茎茎线虫(Ditylenchus dipsaci)以及其他茎线虫属(Ditylenchus)物种;维线虫(Awl nematodes)、锥线虫属(Dolichodorus)物种;螺旋线虫(Spiral nematodes)、多头螺旋线虫(Heliocotylenchus multicinctus)以及其他螺旋线虫属(Helicotylenchus)物种;鞘及鞘形线虫(Sheath and sheathoid nematodes)、鞘线虫属(Hemicycliophora)物种以及半轮线虫属(Hemicriconemoides)物种;潜根线虫属(Hirshmanniella)物种;支线虫(Lancenematodes)、冠线虫属(Hoploaimus)物种;假根结线虫(false rootknot nematodes)、珍珠线虫属(Nacobbus)物种;针状线虫(Needle nematodes)、横带长针线虫(Longidoruselongatus)以及其他长针线虫属(Longidorus)物种;大头针线虫(Pin nematodes)、短体线虫属(Pratylenchus)物种;腐线虫(Lesion nematodes)、花斑短体线虫(Pratylenchusneglectus)、穿刺短体线虫(Pratylenchus penetrans)、弯曲短体线虫(Pratylenchuscurvitatus)、古氏短体线虫(Pratylenchus goodeyi)以及其他短体线虫属(Pratylenchus)物种;柑桔穿孔线虫(Burrowing nematodes)、香蕉穿孔线虫(Radopholussimilis)以及其他内侵线虫属(Radopholus)物种;肾状线虫(Reniform nematodes)、罗柏氏盘旋线虫(Rotylenchus robustus)、肾形盘旋线虫(Rotylenchus reniformis)以及其他盘旋线虫属(Rotylenchus)物种;盾线虫属(Scutellonema)物种;短粗根线虫(Stubby rootnematodes)、原始毛刺线虫(Trichodorus primitivus)以及其他毛刺线虫属(Trichodorus)物种、拟毛刺线虫属(Paratrichodorus)物种;矮化线虫(Stuntnematodes)、马齿苋矮化线虫(Tylenchorhynchus claytoni)、顺逆矮化线虫(Tylenchorhynchus dubius)以及其他矮化线虫属(Tylenchorhynchus)物种;柑桔线虫(Citrus nematodes)、穿刺线虫(Tylenchulus)物种;短剑线虫(Dagger nematodes)、剑线虫属(Xiphinema)物种;以及其他植物寄生线虫物种,如亚粒线虫属物种(Subanguinaspp.)、根结线虫属物种(Hypsoperine spp.)、大刺环线虫属物种(Macroposthonia spp.)、矮化线虫属物种(Melinius spp.)、刻点胞囊属物种(Punctodera spp.)、以及五沟线虫属物种(Quinisulcius spp.)。
本发明的化合物还具有针对软体动物的活性。其实例包括例如福寿螺科;蛞蝓科(Arion)(黑蛞蝓(A.ater)、环状蛞蝓(A.circumscriptus)、棕阿勇蛞蝓(A.hortensis)、红蛞蝓(A.rufus));巴蜗牛科(Bradybaenidae)(灌木巴蜗牛(Bradybaena fruticum));葱蜗牛属(Cepaea)(花园葱蜗牛(C.hortensis)、森林葱蜗牛(C.Nemoralis));ochlodina;野蛞蝓属(Deroceras)(野灰蛞蝓(D.agrestis)、D.empiricorum、光滑野蛞蝓(D.laeve)、网纹野蛞蝓(D.reticulatum));圆盘螺属(Discus)(圆形圆盘蜗牛(D.rotundatus));Euomphalia;土蜗属(Galba)(截口土蜗(G.trunculata));小蜗牛属(Helicelia)(伊塔拉小蜗牛(H.itala)、布维小蜗牛(H.obvia));大蜗牛科(Helicidae)Helicigona arbustorum);Helicodiscus;大蜗牛(Helix)(开口大蜗牛(H.aperta));蛞蝓属(Limax)(利迈科斯蛞蝓(L.cinereoniger)、黄蛞蝓(L.flavus)、边缘蛞蝓(L.marginatus)、大蛞蝓(L.maximus)、柔蛞蝓(L.tenellus));椎实螺属(Lymnaea);Milax(小蛞蝓科)(黑色小蛞蝓(M.gagates)、边缘小蛞蝓(M.marginatus)、硕氏小蛞蝓(M.sowerbyi));钻螺属(Opeas);瓶螺属(Pomacea)(福寿螺(P.canaticulata));瓦娄蜗牛属(Vallonia)和Zanitoides。
作物应被理解为还包括已经被赋予对除草剂(像溴草腈)或多种类别的除草剂(如ALS-、EPSPS-、GS-、HPPD-和PPO-抑制剂)的耐受性的那些作物。通过常规的育种方法已经被赋予了对咪唑啉酮(例如,甲氧咪草烟)的耐受性的作物的实例是夏季卡诺拉。通过遗传工程方法而被赋予了对除草剂的耐受性的作物的实例包括例如草甘膦和草铵膦抗性玉米品种,这些玉米品种以商标名和是可商购的。
作物还应被理解为天然地是或已经赋予对害虫的抗性的那些作物。这包括通过使用重组DNA技术转化从而例如能够合成一种或多种选择性作用毒素的植物,这些毒素如是从如产毒素的细菌已知的。可以被表达的毒素的实例包括δ-内毒素,营养期杀虫蛋白(Vip),细菌定殖线虫的杀虫蛋白,以及由蝎子、蛛形纲动物、黄蜂和真菌产生的毒素。
已经被修饰为表达苏云金杆菌毒素的作物的实例是Bt maize(先正达种子公司(Syngenta Seeds))。包括编码杀昆虫抗性并且由此表达多于一种毒素的多于一种基因的作物的实例是(先正达种子公司)。作物或其种子材料还可以是对多种类型的有害生物具有抗性(当通过遗传修饰产生时的所谓的叠加转基因事件)。例如,植物可以具有表达杀昆虫蛋白而同时耐受除草剂的能力,例如Herculex(陶氏益农公司(Dow AgroSciences),先锋良种国际公司(Pioneer Hi-Bred International))。
根据本发明的组合物的其他使用范围是保护所储存的物品和储存室以及保护原材料,如木材、纺织品、地板或建筑物,以及还在卫生领域中,尤其是保护人类、家畜以及多产的牲畜免遭所提及类型的有害生物的侵害。
本发明还提供了用于控制有害生物(如蚊和其他的疾病媒介物;同样参见http://www.who.int/malaria/vector_control/irs/en/)的方法。在一个实施例中,用于控制有害生物的方法包括通过涂刷、轧制、喷雾、涂布或浸渍,向目标有害生物、它们的场所或表面或基底施用本发明的组合物。通过举例,通过本发明的方法考虑到了表面(如墙、天花板或地板表面)的IRS(室内滞留喷雾)施用。在另一个实施例中,考虑了将此类组合物施用于如下基底,如无纺或织物材料,该基底呈网织品、被覆物、被褥、窗帘以及帐篷的形式(或可以在这些物品的制造中使用)。
在一个实施例中,用于控制此类有害生物的方法包括向目标有害生物、它们的场所或表面或基底施用杀有害生物有效量的本发明的组合物,以便于在该表面或基底上提供有效的滞留的杀有害生物活性。这样的施用可以通过涂刷、轧制、喷雾、涂布或浸渍本发明的杀有害生物组合物来进行。通过举例,通过本发明的方法考虑到了表面(如墙、天花板或地板表面)的IRS施用,以便于在该表面上提供有效的滞留的杀有害生物活性。在另一个实施例中,考虑了施用此类组合物以用于在基底如织物材料上的有害生物的残留控制,该基底呈网织品、被覆物、被褥、窗帘以及帐篷的形式(或可以在这些物品的制造中使用)的。
有待处理的基底(包括无纺物、织物或网织品)可以由天然纤维,如棉花、拉菲亚树叶纤维、黄麻、亚麻、剑麻、粗麻布或羊毛,或者合成纤维,如聚酰胺、聚酯、聚丙烯、聚丙烯腈等等制成。聚酯是特别适合的。纺织品处理的方法是已知的,例如WO 2008151984、WO2003034823、US5631072、WO 2005064072、WO 2006128870、EP1724392、WO 2005113886或WO 2007090739。
根据本发明的组合物的其他使用范围是针对所有观赏树木连同所有种类的果树和坚果树的树木注射/树干处理领域。
在树木注射/树干处理领域中,根据本发明的化合物特别适合于对抗来自上述的鳞翅目和来自鞘翅目的钻木昆虫,尤其是对抗下表X和Y中列出的钻木虫:
表X.具有经济重要性的外来钻木虫的实例。
表Y.具有经济重要性的本地钻木虫的实例。
本发明也可以用于控制任何可以存在于草坪草中的昆虫有害生物,包括例如甲虫、毛虫、火蚁、地面珍珠(ground pearl)、千足虫、潮虫、螨虫、蝼蛄、介壳虫、粉蚧蜱、沫蝉、南方麦小蝽以及蛴螬。本发明可以用于控制处于其生命周期的各个阶段的昆虫有害生物,包括卵、幼虫、若虫和成虫。
特别地,本发明可用于控制用草坪草的根部喂养的昆虫有害生物,所述昆虫有害生物包括蛴螬(如圆头犀金龟属物种(Cyclocephala spp.)(例如标记的金龟子、C.lurida)、Rhizotrogus属物种(例如欧洲金龟子,欧洲切根鳃金龟(R.majalis))、黄栌属物种(Cotinus spp.)(例如绿六月甲虫(Green June beetle)、绿六月花金龟(C.nitida))、弧丽金龟属物种(Popillia spp.)(例如日本甲虫、日本弧丽金龟(P.japonica))、鳃角金龟属物种(Phyllophaga spp.)(例如五月/六月甲虫)、金龟属物种(例如草坪草黑金龟(Blackturfgrass ataenius)、黑绒金龟)、绒毛金龟属物种(Maladera spp.)(例如亚洲花园甲虫(Asiatic garden beetle)、栗色绒金龟)以及Tomarus属物种)、地面珍珠(硕蚧属物种(Margarodes spp.))、蝼蛄(褐黄色的、南方的、以及短翅的;痣蟋蟀属物种(Scapteriscusspp.)、非洲蝼蛄(Gryllotalpa africana))以及大蚊幼虫(leatherjackets)(欧洲大蚊(European crane fly)、大蚊属物种(Tipula spp.))。
本发明还可以用于控制茅草住宅的草坪草的昆虫有害生物,这些昆虫有害生物包括粘虫(如秋夜蛾(fall armyworm)草地贪夜蛾(Spodoptera frugiperda),和常见粘虫一星黏虫(Pseudaletia unipuncta))、切根虫,象鼻虫(尖隐喙象属物种(Sphenophorusspp.),如S.venatus verstitus和牧草长喙象(S.parvulus))以及草地螟(如草螟属物种(Crambus spp.)和热带草地螟,Herpetogramma phaeopteralis)。
本发明还可以用于控制在地上生活并取食草坪草叶子的草坪草中的昆虫有害生物,这些昆虫有害生物包括麦小蝽(如南方麦小蝽,南方杆长蝽(Blissus insularis))、狗牙根螨(Bermudagrass mite)(Eriophyes cynodoniensis)、盖氏虎尾草粉蚧(草竹粉蚧(Antonina graminis))、两线沫蝉(Propsapia bicincta)、叶蝉、切根虫(夜蛾科)、以及麦二叉蚜。
本发明还可以用于控制草坪草中的其他有害生物,如在草坪中创建蚁巢的外引红火蚁(红火蚁(Solenopsis invicta))。
在卫生领域中,根据本发明的组合物有效地对抗外寄生虫如硬蜱、软蜱、疥螨、秋螨、蝇(叮咬和舔舐)、寄生性蝇幼虫,虱、发虱、鸟虱和跳蚤。
此类寄生虫的实例是:
虱目:血虱属物种、长颚虱属物种(Linognathus spp.)、人虱属物种以及阴虱属物种(Phtirus spp.)、管虱属物种。
食毛目:毛羽虱属物种、短羽虱属物种、鸭虱属物种、牛羽虱属物种、Werneckiella属物种、Lepikentron属物种、畜虱属物种、啮毛虱属物种以及猫羽虱属物种(Felicolaspp.)。
双翅目及长角亚目(Nematocerina)和短角亚目(Brachycerina),例如伊蚊属物种(Aedes spp.)、疟蚊属物种、库蚊属物种(Culex spp.)、蚋属物种(Simulium spp.)、真蚋属物种(Eusimulium spp.)、白蛉属物种(Phlebotomus spp.)、罗蛉属物种(Lutzomyiaspp.)、库蠓属物种(Culicoides spp.)、斑虻属物种(Chrysops spp.)、驼背虻属物种(Hybomitra spp.)、黄虻属物种(Atylotus spp.)、虻属物种(Tabanus spp.)、麻虻属物种(Haematopota spp.)、Philipomyia属物种、蜂虱蝇属物种(Braula spp.)、家蝇属物种(Musca spp.)、齿股蝇属物种(Hydrotaea spp.)、螫蝇属物种、黑角蝇属物种(Haematobiaspp.)、莫蝇属物种(Morellia spp.)、厕蝇属物种(Fannia spp.)、舌蝇属物种(Glossinaspp.)、丽蝇属物种(Calliphora spp.)、绿蝇属物种(Lucilia spp.)、金蝇属物种(Chrysomyia spp.)、污蝇属物种(Wohlfahrtia spp.)、麻蝇属物种(Sarcophaga spp.)、狂蝇属物种(Oestrus spp.)、皮蝇属物种(Hypoderma spp.)、胃蝇属物种(Gasterophilusspp.)、虱蝇属物种(Hippobosca spp.)、羊虱蝇属物种(Lipoptena spp.)和蜱蝇属物种(Melophagus spp.)。
蚤目(Siphonapterida),例如蚤属物种(Pulex spp.)、栉头蚤属物种、客蚤属物种(Xenopsylla spp.)、角叶蚤属物种。
异翅目(Heteropterida),例如臭虫属物种、锥鼻虫属物种、红猎蝽属物种、锥蝽属物种(Panstrongylus spp.)。
蜚蠊目(Blattarida),例如东方蜚蠊(Blatta orientalis)、美洲大蠊(Periplaneta americana)、德国小蠊(Blattelagermanica)以及夏柏拉蟑螂属物种(Supella spp.)。
蜱螨(Acaria)亚纲(螨科(Acarida))和后气门目(Meta-stigmata)和中气门目(Meso-stigmata),例如锐缘蜱属物种(Argas spp.)、钝缘蜱属物种(Ornithodorus spp.)、耳蜱属物种(Otobius spp.)、硬蜱属物种(Ixodes spp.)、钝眼蜱属物种(Amblyommaspp.)、牛蜱属物种(Boophilus spp.)、革蜱属物种(Dermacentor spp.)、血蜱属物种(Haemophysalis spp.)、璃眼蜱属物种(Hyalomma spp.)、扇头蜱属物种(Rhipicephalusspp.)、皮刺螨属物种(Dermanyssus spp.)、刺利螨属物种(Raillietia spp.)、肺刺螨属物种(Pneumonyssus spp.)、胸刺螨属物种(Sternostoma spp.)和瓦螨属物种(Varroaspp.)。
轴螨目(Actinedida)(前气门亚目(Prostigmata))和粉螨目(Acaridida)(无气门亚目(Astigmata)),例如蜂盾螨属(Acarapis spp.)、姬螯属(Cheyletiella spp.)、禽螯螨属(Ornithocheyletia spp.)、肉螨属(Myobia spp.)、疮螨属(Psorergates spp.)、蠕形螨属(Demodex spp.)、恙螨属(Trombicula spp.)、牦螨属(Listrophorus spp.)、粉螨属(Acarus spp.)、食酪螨属(Tyrophagus spp.)、嗜木螨属(Caloglyphus spp.)、颈下螨属(Hypodectes spp.)、翅螨属(Pterolichus spp.)、痒螨属、皮螨属、耳疥螨属(Otodectesspp.)、疥螨属、耳螨属(Notoedres spp.)、鸟疥螨属(Knemidocoptes spp.)、胞螨属(Cytodites spp.)以及鸡雏螨属(Laminosioptes spp.)。
根据本发明的组合物还适用于保护在如木材、纺织品、塑料、粘合剂、胶、漆料、纸张和卡片、皮革、地板和建筑等情况下的材料免受昆虫侵染。
根据本发明的组合物可以用于,例如,对抗下列有害生物:甲虫,如北美家天牛、多毛绿虎天牛、家具窃蠹、报死窃蠹、Ptilinuspecticornis、Dendrobium pertinex、细齿叉尾长蠹、Priobium carpini、褐粉蠹、非洲粉蠹、南方粉蠹、抱扁蠹、软毛粉蠹、扁腿粉蠹、鳞毛粉蠹、材小蠹属、木小蠹属、黑长蠹、红腹槲长蠹、棕异翅长蠹、双棘长蠢属以及竹蠹,并且还有膜翅目,如蓝黑树蜂、大树蜂、泰加大树蜂和Urocerus augu,以及白蚁类,如黄颈木白蚁、麻头堆砂白蚁、印巴结构木异白蚁、黄肢散白蚁、桑特散白蚁、欧洲散白蚁、达氏澳白蚁、内华达动白蚁和台湾家白蚁,以及无翼昆虫类,如衣鱼。
根据本发明的化合物可以按未改性的形式用作杀有害生物剂,但它们通常以多种方式使用配制佐剂(如载体、溶剂以及表面活性物质)被配制成组合物。这些配制品可以处于不同的实体形式,例如,处于以下形式:撒粉剂、凝胶、可湿性粉剂、水可分散性颗粒剂、水可分散性片剂、泡腾压缩片剂、可乳化的浓缩物、微可乳化浓缩物、水包油乳剂、可流动油、水性分散体、油性分散体、悬乳剂、胶囊悬浮液、可乳化的颗粒剂、可溶性液体、水可溶性浓缩物(以水或水混溶性有机溶剂作为载体)、浸渍的聚合物膜或处于已知的其他形式,例如从Manual on Development and Use of FAO and WHO Specifications for Pesticides[关于杀有害生物剂的FAO和WHO标准的发展和使用的手册],联合国,第1版,二次修订(2010)中已知的。此类配制品可以直接使用或者可以在使用前稀释。可以用例如水、液体肥料、微量营养素、生物有机体、油或溶剂来进行稀释。
可以通过例如将活性成分与配制佐剂混合来制备这些配制品以便获得处于精细分散固体、颗粒、溶液、分散体或乳剂形式的组合物。这些活性成分还可以与其他佐剂(如精细分散固体、矿物油、植物或动物来源的油、改性的植物或动物来源的油、有机溶剂、水、表面活性物质或它们的组合)来一起配制。
这些活性成分还可以被包含于非常精细的微胶囊中。微胶囊在多孔载体中含有活性成分。这使活性成分能以受控的量值释放(例如,缓慢释放)到环境中。微胶囊通常具有从0.1到500微米的直径。它们包含的活性成分的量按重量计是胶囊重量的约从25%至95%。这些活性成分可以处于整块固体的形式、处于固体或液体分散体中的精细颗粒的形式或处于合适溶液的形式。包囊的膜可以包括例如天然的或合成的橡胶、纤维素、苯乙烯/丁二烯共聚物、聚丙烯腈、聚丙烯酸酯、聚酯、聚酰胺、聚脲、聚氨酯或化学改性的聚合物以及淀粉黄原酸酯、或本领域的技术人员已知的其他聚合物。替代性地,可以形成非常精细的微胶囊,其中活性成分在基础物质的固体基质中是以精细分散颗粒的形式被包含的,但这些微胶囊本身未经包裹。
适合于制备根据本发明的组合物的配制佐剂本身是已知的。作为液体载体可以使用:水、甲苯、二甲苯、石油醚、植物油、丙酮、甲基乙基酮、环己酮、酸酐、乙腈、乙酰苯、乙酸戊酯、2-丁酮、碳酸丁烯酯、氯苯、环己烷、环己醇、乙酸烷基酯、二丙酮醇、1,2-二氯丙烷、二乙醇胺、对-二乙基苯、二甘醇、松脂酸二乙二醇酯、二甘醇丁基醚、二甘醇乙基醚、二甘醇甲醚、N,N-二甲基甲酰胺、二甲基亚砜、1,4-二噁烷、二丙二醇、二丙二醇甲基醚、双丙甘醇二苯甲酸酯、二丙二醇、烷基吡咯烷酮、乙酸乙酯、2-乙基己醇、碳酸乙烯酯、1,1,1-三氯乙烷、2-庚酮、α-蒎烯、d-苧烯、乳酸乙酯、乙二醇、乙二醇丁基醚、乙二醇甲基醚、γ-丁内酯、丙三醇、乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯、十六烷、己二醇、乙酸异戊基酯、乙酸异冰片基酯、异辛烷、异佛尔酮、异丙苯、肉豆蔻酸异丙酯、乳酸、月桂胺、异亚丙基丙酮、甲氧基丙醇、甲基异戊基酮、甲基异丁基酮、月桂酸甲酯、辛酸甲酯、油酸甲酯、二氯甲烷、间二甲苯、正己烷、正辛胺、十八烷酸、辛胺乙酸酯、油酸、油烯基胺、邻二甲苯、苯酚、聚乙二醇、丙酸、乳酸丙酯、碳酸亚丙酯、丙二醇、丙二醇甲基醚、对-二甲苯、甲苯、磷酸三乙酯、三乙二醇、二甲苯磺酸、石蜡、矿物油、三氯乙烯、全氯乙烯、乙酸乙酯、乙酸戊酯、乙酸丁酯、丙二醇甲基醚、二乙二醇甲基醚、甲醇、乙醇、异丙醇以及更高分子量的醇,例如戊醇、四氢呋喃醇、己醇、辛醇、乙二醇、丙二醇、甘油、N-甲基-2-吡咯烷酮等。
适合的固体载体是例如滑石、二氧化钛、叶蜡石黏土、硅石、凹凸棒石黏土、硅藻土、石灰石、碳酸钙、膨润土、钙蒙脱土、棉籽壳、小麦粉、大豆粉、浮石、木粉、经研磨的胡桃壳、木质素和类似的物质。
许多表面活性物质可以有利地用在固体和液体配制品两者中,尤其是在使用前可以被载体稀释的那些配制品中。表面活性物质可以是阴离子的、阳离子的、非离子的或聚合的并且它们可以用作乳化剂、湿润剂或悬浮剂或用于其他目的。典型的表面活性物质包括例如烷基硫酸酯的盐,如十二烷基硫酸二乙醇铵;烷基芳基磺酸酯的盐,如十二烷基苯磺酸钙;烷基酚/氧化烯加成产物,如乙氧基化壬基苯酚;醇/氧化烯加成产物,如乙氧基化十三烷醇;皂,如硬脂酸钠;烷基萘磺酸酯的盐,如二丁基萘磺酸钠;磺基琥珀酸二烷基酯的盐,如二(2-乙基己基)磺基琥珀酸钠;山梨糖醇酯,如山梨糖醇油酸酯;季铵,如氯化十二烷基三甲基铵;脂肪酸的聚乙二醇酯,如聚乙二醇硬脂酸酯;环氧乙烷和环氧丙烷的嵌段共聚物;以及磷酸单烷基酯和二烷基酯的盐;以及还有其他物质,例如描述于:McCutcheon'sDetergents and Emulsifiers Annual[麦卡琴清洁剂和乳化剂年鉴],MC出版公司(MCPublishing Corp.),里奇伍德,新泽西州(Ridgewood New Jersey)(1981)。
可以用于杀有害生物配制品的其他佐剂包括结晶抑制剂、粘度改性剂、悬浮剂、染料、抗氧化剂、发泡剂、光吸收剂、混合助剂、消泡剂、络合剂、中和或改变pH的物质和缓冲液、腐蚀抑制剂、香料、湿润剂、吸收增强剂、微量营养素、增塑剂、助流剂、润滑剂、分散剂、增稠剂、防冻剂、杀微生物剂、以及液体和固体肥料。
根据本发明的组合物可以包括添加剂,该添加剂包括植物或动物来源的油、矿物油、此类油的烷基酯或此类油与油衍生物的混合物。在根据本发明的组合物中的油添加剂的量通常是基于有待施用的混合物的从0.01%至10%。例如,可以在喷雾混合物已经制备以后将油添加剂以所希望的浓度添加到喷雾罐中。优选的油添加剂包括矿物油或植物来源的油,例如菜籽油、橄榄油或葵花籽油;乳化的植物油;植物来源的油的烷基酯,例如甲基衍生物;或动物来源的油,如鱼油或牛脂。优选的油添加剂包括C8-C22脂肪酸的烷基酯,尤其是C12-C18脂肪酸的甲基衍生物,例如月桂酸、棕榈酸以及油酸的甲基酯(分别为月桂酸甲酯、棕榈酸甲酯和油酸甲酯)。许多油衍生物获知于以下文献:Compendium of HerbicideAdjuvants,10th Edition,Southern Illinois University,2010[除草剂佐剂纲要,第10版,南伊利诺伊大学,2010]。
这些本发明组合物总体上包括按重量计从0.1%至99%,尤其是按重量计从0.1%至95%的本发明的化合物以及按重量计从1%至99.9%的配制佐剂,该配制佐剂优选地包括按重量计从0至25%的表面活性物质。而商用产品可以优选地被配制为浓缩物,最终使用者将通常使用稀释配制品。
施用比率在宽范围之内变化并且取决于土壤的性质、施用方法、作物植物、待控制的有害生物、主要气候条件、以及受施用方法、施用时间以及目标作物支配的其他因素。一般来讲,可以将化合物以从1l/ha至2000l/ha、尤其是从10l/ha到1000l/ha的比率施用。
通过添加其他具有杀昆虫、杀螨和/或杀真菌活性的成分,根据本发明的组合物的活性可以显著地加宽,并且适合于普遍情况。具有式(I)的化合物与其他具有杀昆虫、杀螨和/或杀真菌活性的成分的混合物还可以具有进一步地、令人惊讶的优点,这些优点还可以在更宽的含义上描述为协同活性。例如,植物的更好的耐受性、降低的植物毒性、昆虫可以在它们的不同发育阶段得到控制、或者在它们的生产期间(例如,在研磨或者混合期间,在它们的储存期间或它们的使用期间)的更好的行为。
在这里,适当添加的活性成分是例如以下类别的活性成分的代表:有机磷化合物、硝基苯酚衍生物、硫脲、保幼激素、甲脒、二苯甲酮衍生物、脲类、吡咯衍生物、氨基甲酸酯、拟除虫菊酯、氯化烃、酰基脲、吡啶基亚甲基氨基衍生物、大环内酯类、新烟碱以及苏芸金芽孢杆菌制剂。
优选的混合物如下所示,其中根据实施例1至10中任一项所述的化合物用“I”进行表示。具体地,“I”表示根据实施例10的化合物。
包括佐剂的组合物包括I+选自由石油组成的物质组中的化合物;
包含杀螨剂的组合物包括I+1,1-双(4-氯苯基)-2-乙氧基乙醇、I+2,4-二氯苯基苯磺酸酯、I+2-氟-N-甲基-N-1-萘乙酰胺、I+4-氯苯基苯基砜、I+阿维菌素、I+灭螨醌、I+乙酰虫腈、I+氟丙菊酯、I+涕灭威、I+涕灭砜威、I+α-氯氰菊酯、I+赛硫磷、I+磺胺螨酯、I+氨基硫代盐、I+胺吸磷、I+胺吸磷草酸氢盐、I+双甲脒、I+杀螨特、I+三氧化二砷、I+AVI 382、I+AZ 60541、I+益棉磷、I+保棉磷(azinphos-methyl)、I+偶氮苯、I+三唑锡(azacyclotin)、I+偶氮磷(azothoate)、I+苯茵灵、I+苯诺沙磷(benoxafos)、I+苯螨特(benzoximate)、I+苯甲酸苄酯、I+联苯肼酯、I+氟氯菊酯、I+乐杀螨、I+溴灭菊酯、I+溴烯杀(bromocyclen)、I+溴硫磷、I+乙基溴硫磷、I+溴螨酯(bromopropylate)、I+噻嗪酮、I+丁酮威、I+丁酮砜威、I+丁酮威(butylpyridaben)、I+石硫合剂(calcium polysulfide)、I+毒杀芬(campheechlor)、I+氯灭杀威(carbanolate)、I+甲萘威、I+克百威(carbofuran)、I+卡波硫磷、I+CGA 50’439、I+灭螨猛(chinomethionat)、I+杀螨醚(chlorbenside)、I+杀虫脒、I+杀虫脒盐酸盐、I+溴虫腈、I+敌螨、I+杀螨酯(chlorfenson)、I+敌螨特(chlorfensulfide)、I+氯芬磷、I+乙酯杀螨醇(chlorobenzilate)、I+伊托明(chloromebuform)、I+灭虫脲(chloromethiuron)、I+丙酯杀螨醇(chloropropylate)、I+毒死蜱、I+甲基毒死蜱、I+虫螨磷(chlorthiophos)、I+瓜菊酯(cinerin)I、I+瓜菊酯II、I+瓜叶菊素(cinerins)、I+四螨嗪、I+氯氰碘柳胺、I+库马磷、I+克罗米通、I+巴毒磷(crotoxyphos)、I+硫杂灵、I+果虫磷(cyanthoate)、I+丁氟螨酯、I+三氯氟氰菊酯、I+三环锡、I+氯氰菊酯、I+DCPM、I+DDT、I+田乐磷(demephion)、I+田乐磷-O、I+田乐磷-S、I+内吸磷(demeton)、I+甲基内吸磷、I+内吸磷-O、I+甲基内吸磷-O、I+内吸磷-S、I+甲基内吸磷-S、I+内吸磷-S-甲基砜(demeton-S-methylsulfon)、I+杀螨隆、I+氯亚胺硫磷(dialifos)、I+二嗪磷、I+苯氟磺胺、I+敌敌畏、I+迪克力弗斯(dicliphos)、I+开乐散、I+百治磷、I+遍地克、I+甲氟磷(dimefox)、I+乐果、I+二甲杀螨霉素(dinactin)、I+消螨酚(dinex)、I+消螨酚(dinex-diclexine)、I+消螨通(dinobuton)、I+敌螨普(dinocap)、I+敌螨普-4、I+敌螨普-6、I+二硝酯、I+硝戊酯(dinopenton)、I+硝辛酯(dinosulfon)、I+硝丁酯(dinoterbon)、I+敌恶磷、I+二苯砜、I+双硫仑、I+乙拌磷、I+DNOC、I+苯氧炔螨(dofenapyn)、I+多拉克汀、I+硫丹、I+因毒磷(endothion)、I+EPN、I+依立诺克丁、I+乙硫磷、I+益硫磷(ethoate-methyl)、I+乙螨唑(etoxazole)、I+乙嘧硫磷(etrimfos)、I+抗螨唑(fenazaflor)、I+喹螨醚、I+苯丁锡(fenbutatin oxide)、I+苯硫威(fenothiocarb)、I+甲氰菊酯、I+吡螨胺(fenpyrad)、I+唑螨酯(fenpyroximate)、I+芬螨酯(fenson)、I+氟硝二苯胺(fentrifanil)、I+氰戊菊酯、I+氟虫腈、I+嘧螨酯(fluacrypyrim)、I+氟佐隆、I+氟螨噻(flubenzimine)、I+氟螨脲、I+氟氰戊菊酯(flucythrinate)、I+联氟螨(fluenetil)、I+氟虫脲、I+氟氯苯菊酯(flumethrin)、I+氟杀螨(fluorbenside)、I+氟胺氰菊酯(fluvalinate)、I+FMC 1137、I+抗螨脒、I+抗螨脒盐酸盐、I+安硫磷(formothion)、I+胺甲威(formparanate)、I+γ-HCH、I+果绿啶(glyodin)、I+苄螨醚(halfenprox)、I+庚烯醚(heptenophos)、I+十六碳烷基环丙烷羧酸酯、I+噻螨酮、I+碘甲烷、I+水胺硫磷(isocarbophos)、I+异丙基O-(甲氧基氨基硫代磷酰基)水杨酸酯、I+伊维菌素、I+茉莉菊酯(jasmolin)I、I+茉莉菊酯II、I+碘硫磷(jodfenphos)、I+林丹、I+虱螨脲、I+马拉硫磷、I+苄丙二腈(malonoben)、I+灭蚜磷(mecarbam)、I+地胺磷(mephosfolan)、I+甲硫芬、I+虫螨畏(methacrifos)、I+甲胺磷、I+杀扑磷、I+灭虫威、I+灭多虫、I+溴甲烷、I+速灭威(metolcarb)、I+速灭磷、I+自克威(mexacarbate)、I+米尔螨素、I+杀螨茵素肟(milbemycinoxime)、I+丙胺氟磷(mipafox)、I+久效磷、I+茂硫磷(morphothion)、I+莫昔克丁、I+二溴磷(naled)、I+NC-184、I+NC-512、I+氟蚊灵(nifluridide)、I+尼柯霉素、I+戊氰威(nitrilacarb)、I+戊氰威(nitrilacarb)1:1氯化锌络合物、I+NNI-0101、I+NNI-0250、I+氧乐果(氧乐果)、I+杀线威、I+亚异砜磷(oxydeprofos)、I+砜拌磷(oxydisulfoton)、I+pp’-DDT、I+对硫磷、I+氯菊酯、I+石油、I+芬硫磷、I+稻丰散、I+甲拌磷、I+伏杀硫磷、I+硫环磷(phosfolan)、I+亚胺硫磷、I+磷胺、I+辛硫磷、I+甲基嘧啶磷、I+氯化松节油(polychloroterpenes)、I+杀螨霉素(polynactins)、I+丙氯诺、I+丙溴磷、I+蜱虱威(promacyl)、I+克螨特、I+胺丙畏(propetamphos)、I+残杀威、I+乙噻唑磷(prothidathion)、I+发硫磷(prothoate)、I+除虫菊酯I、I+除虫菊酯II、I+除虫菊素(pyrethrins)、I+哒螨灵、I+哒嗪硫磷(pyridaphenthion)、I+嘧螨醚(pyrimidifen)、I+嘧硫磷、I+喹硫磷(quinalphos)、I+喹硫磷(quintiofos)、I+R-1492、I+RA-17、I+鱼藤酮、I+八甲磷(schradan)、I+硫线磷(sebufos)、I+塞拉菌素(selamectin)、I+SI-0009、I+苏硫磷(sophamide)、I+季酮螨酯、I+螺甲螨酯、I+SSI-121、I+舒非仑、I+氟虫胺(sulfluramid)、I+治螟磷(sulfotep)、I+硫黄、I+SZI-121、I+τ-氟胺氰菊酯、I+吡螨胺、I+TEPP、I+叔丁威(terbam)、I+司替罗磷、I+三氯杀螨砜(tetradifon)、I+杀螨霉素(tetranactin)、I+杀螨硫醚(tetrasul)、I+久效威(thiafenox)、I+抗虫威(thiocarboxime)、I+久效威(thiofanox)、I+甲基乙拌磷(thiometon)、I+克杀螨、I+苏力菌素(thuringiensin)、I+威茵磷(triamiphos)、I+苯噻螨(triarathene)、I+三唑磷、I+唑呀威(triazuron)、I+敌百虫、I+氯苯乙丙磷(trifenofos)、I+甲杀螨霉素(trinactin)、I+灭蚜硫磷、I+氟吡唑虫(vaniliprole)和I+YI-5302;
包括驱蠕虫剂的组合物包括:I+阿巴美丁、I+克芦磷酯、I+多拉克汀、I+依马克丁、I+依马克丁苯甲酸酯、I+依立诺克丁、I+伊维菌素、I+米尔倍霉素、I+莫昔克丁、I+哌嗪、I+塞拉菌素(selamectin)、I+多杀菌素和I+硫菌灵(thiophanate);
包括杀鸟剂的组合物包括:I+氯醛糖、I+异狄氏剂、I+倍硫磷、I+吡啶-4-胺和I+士的宁;
包含生物控制剂的组合物包括:I+棉褐带卷蛾颗粒体病毒(Adoxophyes oranaGV)、I+放射形土壤杆菌、I+钝绥螨属物种(Amblyseius spp.)、I+芹菜夜蛾核多角体病毒(Anagrapha falcifera NPV)、I+Anagrus atomus、I+蚜虫寄生蜂(Aphelinusabdominalis)、I+棉蚜寄生蜂(Aphidius colemani)、I+食蚜瘿蚊(Aphidoletesaphidimyza)、I+苜蓿银纹夜蛾核多角体病毒(Autographa californica NPV)、I+坚强芽孢杆菌(Bacillus firmus)、I+球形芽孢杆菌(Bacillus sphaericus Neide)、I+苏云金芽孢杆菌(Bacillus thuringiensis Berliner)、I+苏云金芽胞杆菌鲇泽亚种(Bacillusthuringiensis subsp.aizawai)、I+苏云金芽孢杆菌以色列亚种(Bacillusthuringiensis subsp.israelensis)、I+苏云金芽孢杆菌日本亚种(Bacillusthuringiensis subsp.japonensis)、I+苏云金芽孢杆菌k.(Bacillus thuringiensissubsp.kurstaki)、I+苏云金芽孢杆菌t.(Bacillus thuringiensis subsp.tenebrionis)、I+球孢白僵茵(Beauveria bassiana)、I+布氏白僵茵(Beauveria brongniartii)、I+草蜻蛉(Chrysoperla carnea)、I+孟氏隐唇瓢虫(Cryptolaemus montrouzieri)、I+苹果蠹蛾颗粒体病毒(Cydia pomonella Gv)、I+西伯利亚离颚茧蜂(Dacnusa sibirica)、I+豌豆潜叶蝇姬小蜂(Diglyphus isaea)、I+丽蚜小蜂(Encarsia formosa)、I+桨角蚜小蜂(Eretmocerus eremicus)、I+玉米穗夜蛾核多角体病毒(Helicoverpa zea NPV)、I+嗜茵异小杆线虫(Heterorhabditis bacteriophora)和H.megidis、I+会聚长足瓢虫(Hippodamiaconvergens)、I+橘粉介壳虫寄生蜂(Leptomastix dactylopii)、I+盲蝽(Macrolophuscaliginosus)、I+甘蓝夜蛾核多角体病毒(Mamestra brassicae NPV)、I+Metaphycushelvolus、I+黄绿绿僵茵(Metarhizium anisopliae var.acridum)、I+金龟子绿僵菌小孢变种(Metarhizium anisopliae var.anisopliae)、I+松黄叶蜂(Neodiprion sertifer)核多角体病毒和红头松树叶蜂(N.Lecontei)核多角体病毒、I+小花蝽属物种、I+玫烟色拟青霉(Paecilomyces fumosoroseus)、I+淡紫拟青霉(I+Paecilomyces lilacinus)、I+智利捕植螨(Phytoseiulus persimilis)、I+甜菜夜蛾(Spodoptera exigua multicapsid)多核衣壳核多角体病毒、I+毛蚊线虫(Steinernema bibionis)、I+小卷蛾斯氏线虫(Steinernemacarpocapsae)、I+夜蛾斯氏线虫、I+Steinernema glaseri、I+Steinernema riobrave、I+Steinernema riobravis、I+Steinernema scapterisci、I+斯氏线虫属物种(Steinernemaspp.)、I+赤眼蜂属物种、I+西方盲走螨(Typhlodromus occidentalis)、I+皂皮树(I+Quillaja saponaria.)、I+基于印楝树的产品(I+Neem tree based products)、I+颗粒体病毒(I+Granulovirus)和I+蜡蚧轮枝茵(Verticillium lecanii);
包括土壤消毒剂的组合物包括:I+碘甲烷和甲基溴;
包括化学不育剂的组合物包括:I+唑磷嗪、I+双(氮丙啶)甲氨基膦硫化物(bisazir)、I+白消安、I+除虫脲、I+迪麦替夫(dimatif)、I+六甲蜜胺、I+六甲磷、I+甲基涕巴、I+甲硫涕巴、I+不育特(methyl apholate)、I+不孕啶(morzid)、I+氟幼脲、I+涕巴(tepa)、I+硫代六甲磷(thiohempa)、I+硫涕巴、I+曲他胺和I+尿烷亚胺;
包括昆虫信息素的组合物包括:I+(E)-癸-5-烯-1-基乙酸酯与(E)-癸-5-烯-1-醇、I+(E)-十三碳-4-烯-1-基乙酸酯、I+(E)-6-甲基庚-2-烯-4-醇、I+(E,Z)-十四碳-4,10-二烯-1-基乙酸酯、I+(Z)-十二碳-7-烯-1-基乙酸酯、I+(Z)-十六碳-11-烯醛、I+(Z)-十六碳-11-烯-1-基乙酸酯、I+(Z)-十六碳-13-烯-11-炔-1-基乙酸酯、I+(Z)-二十-13-烯-10-酮、I+(Z)-十四碳-7-烯-1-醛、I+(Z)-十四碳-9-烯-1-醇、I+(Z)-十四碳-9-烯-1-基乙酸酯、I+(7E,9Z)-十二碳-7,9-二烯-1-基乙酸酯、I+(9Z,11E)-十四碳-9,11-二烯-1-基乙酸酯、I+(9Z,12E)-十四碳-9,12-二烯-1-基乙酸酯、I+14-甲基十八-1-烯、I+4-甲基壬醛-5-醇与4-甲基壬醛-5-酮、I+α-多纹素(multistriatin)、I+西部松小蠹集合信息素(brevicomin)、I+十二碳二烯醇(codlelure)、I+十二碳二烯醇(codlemone)、I+诱蝇酮(cuelure)、I+环氧十九烷(disparlure)、I+十二碳-8-烯-1基乙酸酯、I+十二碳-9-烯-1-基乙酸酯、I+十二碳-8、I+10-二烯-1-基乙酸酯、I+dominicalure、I+4-甲基辛酸乙酯、I+丁香酚、I+南部松小蠹集合信息素(frontalin)、I+诱虫十六酯(gossyplure)、I+诱杀烯混剂(grandlure)、I+诱杀烯混剂I、I+诱杀烯混剂II、I+诱杀烯混剂III、I+诱杀烯混剂IV、I+醋酸十六烯酯(hexalure)、I+齿小蠹二烯醇(ipsdienol)、I+小蠢烯醇(ipsenol)、I+金龟子性诱剂(japonilure)、I+里尼汀(lineatin)、I+利特乐(litlure)、I+粉纹夜蛾性诱剂(looplure)、I+诱杀酯(medlure)、I+蒙托么克酸(megatomoic acid)、I+诱虫醚(methyleugenol)、I+诱虫烯(muscalure)、I+十八-2,13-二烯-1-基乙酸酯、I+十八-3,13-二烯-1-基乙酸酯、I+贺康彼(orfralure)、I+oryctalure、I+非乐康(ostramone)、I+诱虫环(siglure)、I+索地丁(sordidin)、I+食菌甲诱醇(sulcatol)、I+十四-11-烯-1-基乙酸酯、I+特诱酮、I+特诱酮A、I+特诱酮B1、I+特诱酮B2、I+特诱酮C和I+创科尔(trunc-call);
包含昆虫驱避剂的组合物包括:I+2-(辛基硫代)乙醇、I+避蚊酮(butopyronoxyl)、I+丁氧基(聚丙二醇)、I+己二酸二丁酯、I+邻苯二甲酸二丁酯、I+丁二酸二丁酯、I+避蚊胺、I+驱蚊酯(dimethyl carbate)、I+邻苯二甲酸二甲酯、I+乙基己二醇、I+己酰胺、I+甲喹丁(methoquin-butyl)、I+甲基新癸酰胺、I+草氨酸酯(oxamate)和I+羟哌酯;
包含杀昆虫剂的组合物包括:I+1-二氯-1-硝基乙烷、I+1,1-二氯-2,2-双(4-乙基苯基)乙烷、I+,I+1,2-二氯丙烷、I+1,2-二氯丙烷与1,3-二氯丙烯、I+1-溴-2-氯乙烷、I+乙酸2,2,2-三氯-1-(3,4-二氯苯基)乙基酯、I+2,2-二氯乙烯基2-乙基亚磺酰基乙基甲基磷酸酯、I+二甲基氨基甲酸2-(1,3-二硫戊环-2-基)苯基酯、I+硫氰酸2-(2-丁氧基乙氧基)乙基酯、I+甲基氨基甲酸2-(4,5-二甲基-1,3-二氧戊环-2-基)苯基酯、I+2-(4-氯-3,5-二甲苯基氧基)乙醇、I+2-氯乙烯基二乙基磷酸酯、I+2-咪唑啉酮、I+2-异戊酰基茚满-1,3-二酮、I+甲基氨基甲酸2-甲基(丙-2-炔基)氨基苯基酯、I+月桂酸2-硫氰基乙基酯、I+3-溴-1-氯丙-1-烯、I+二甲基氨基甲酸3-甲基-1-苯基吡唑-5-基酯、I+甲基氨基甲酸4-甲基(丙-2-炔基)氨基-3,5-二甲苯基酯、I+二甲基氨基甲酸5,5-二甲基-3-氧代环己-1-烯基酯、I+阿维菌素、I+乙酰甲胺磷、I+啶虫脒、I+家蝇磷、I+乙酰虫腈、I+氟丙菊酯、I+丙烯腈、I+棉铃威、I+涕灭威、I+涕灭砜威、I+氯甲桥萘、I+烯丙菊酯、I+阿洛氨菌素、I+除害威、I+α-氯氰菊酯、I+α-蜕皮激素、I+磷化铝、I+赛硫磷、I+硫代酰胺、I+灭害威、I+胺吸磷、I+胺吸磷草酸氢盐、I+双甲脒、I+新烟碱、I+乙基杀扑磷、I+AVI382、I+AZ 60541、I+印楝素、I+甲基吡啶磷、I+谷硫磷-乙基、I+谷硫磷-甲基、I+偶氮磷、I+苏云金芽孢杆菌δ内毒素类、I+六氟硅酸钡、I+多硫化钡、I+熏菊酯、I+Bayer 22/190、I+Bayer22408、I+噁虫威、I+丙硫克百威、I+杀虫磺、I+β-氟氯氰菊酯、I+β-氯氰菊酯、I+联苯菊酯、I+生物烯丙菊酯、I+生物烯丙菊酯S-环戊烯基异构体、I+戊环苄呋菊酯(bioethanomethrin)、I+生物氯菊酯、I+除虫菊酯、I+双(2-氯乙基)醚、I+双三氟虫脲、I+硼砂、I+溴灭菊酯、I+溴苯烯磷、I+溴杀烯、I+溴-DDT、I+溴硫磷、I+溴硫磷-乙基、I+合杀威、I+噻嗪酮、I+畜虫威、I+脱甲基丁嘧啶磷、I+丁酮威、I+丁酯膦、I+丁酮砜威、I+丁基哒螨灵、I+硫线磷、I+砷酸钙、I+氰化钙、I+多硫化钙、I+毒杀芬、I+氯灭杀威、I+甲萘威、I+克百威、I+二硫化碳、I+四氯化碳、I+三硫磷、I+丁硫克百成、I+杀螟丹、I+杀螟丹盐酸盐、I+西伐丁、I+冰片丹、I+氯丹、I+开蓬、I+杀虫脒、I+杀虫脒盐酸盐、I+氯氧磷、I+溴虫腈、I+毒虫畏、I+定虫隆、I+氯甲磷、I+氯仿、I+三氯硝基甲烷、I+氯辛硫磷、I+灭虫吡啶、I+毒死蜱、I+毒死蜱-甲基、I+虫螨磷、I+环虫酰肼、I+灰菊素I、I+灰菊素II、I+灰菊素类、I+顺式苄呋菊酯(cis-resmethrin)、I+顺式苄呋菊酯(cismethrin)、I+功夫菊酯、I+除线威、I+氯氰碘柳胺、I+噻虫胺、I+乙酰亚砷酸铜、I+砷酸铜、I+油酸铜、I+蝇毒磷、I+畜虫磷、I+克罗米通、I+巴毒磷、I+克芦磷酯、I+冰晶石、I+CS 708、I+苯腈膦、I+杀螟睛、I+果虫磷、I+环虫菊酯、I+乙氰菊酯、I+氟氯氰菊酯、I+三氯氟氰菊酯、I+氯氰菊酯、I+苯氰菊酯、I+环丙马秦、I+畜蜱磷、I+d-柠檬烯、I+d-四甲菊酯、I+DAEP、I+棉隆、I+DDT、I+单甲基克百威(decarbofuran)、I+溴氰菊酯、I+田乐磷、I+田乐磷-O、I+田乐磷-S、I+内吸磷、I+内吸磷-甲基、I+内吸磷-O、I+内吸磷-O-甲基、I+内吸磷-S、I+内吸磷-S-甲基、I+内吸磷-S-甲基砜、I+丁醚脲、I+氯亚胺硫磷、I+二胺磷、I+二嗪磷、I+异氯磷、I+除线磷、I+敌敌畏、I+迪克力弗斯、I+迪克莱赛尔(dicresyl)、I+百治磷、I+地昔尼尔、I+狄氏刑、I+二乙基5-甲基吡唑-3-基磷酸酯、I+除虫脲、I+二羟丙茶碱(dilor)、I+四氟甲醚菊酯、I+甲氟磷、I+地麦威、I+乐果、I+苄菊酯、I+甲基毒虫畏、I+敌蝇威、I+消螨酚(dinex)、I+消螨酚(dinex-diclexine)、I+丙硝酚、I+戊硝酚、I+达诺杀、I+呋虫胺、I+苯虫醚、I+蔬果磷、I+二氧威、I+敌恶磷、I+乙拌磷、I+苯噻乙双硫磷(dithicrofos)、I+DNOC、I+多拉克汀、I+DSP、I+蜕皮激素、I+EI 1642、I+甲氨基阿维菌素、I+甲氨基阿维菌素苯甲酸盐、I+EMPC、I+烯炔菊酯、I+硫丹、I+因毒磷、I+异狄氏剂、I+EPBP、I+EPN、I+保幼醚、I+依立诺克丁、I+高氰戊菊酯、I+牛津郡丙硫磷(etaphos)、I+乙硫苯威、I+乙硫磷、I+乙虫腈、I+益硫磷-甲基、I+灭线磷、I+甲酸乙酯、I+乙基-DDD、I+二溴化乙烯、I+二氯化乙烯、I+环氧乙烷、I+醚菊酯、I+乙嘧硫磷、I+EXD、I+氨磺磷、I+苯线磷、I+抗螨唑、I+皮蝇磷、I+苯硫威、I+芬氟司林、I+杀螟硫磷、I+丁苯威、I+嘧酰虫胺(fenoxacrim)、I+苯氧威、I+吡氯氰菊酯、I+甲氰菊酯、I+吡螨胺、I+丰索磷、I+倍硫磷、I+倍硫磷-乙基、I+氰戊菊酯、I+氟虫腈、I+氟啶虫酰胺、I+氟虫酰胺、I+氟氯双苯隆(flucofuron)、I+氟环脲、I+氟氰戊菊酯、I+联氟螨、I+嘧虫胺、I+氟虫脲、I+三氟醚菊酯、I+氟氯苯菊酯、I+氟胺氰菊酯、I+FMC 1137、I+地虫磷、I+伐虫脒、I+伐虫脒盐酸盐、I+安硫磷、I+藻螨威、I+丁苯硫磷、I+福司吡酯、I+噻唑酮磷、I+丁硫环磷、I+呋线威、I+抗虫菊、I+γ-氯氟氰菊酯、I+γ-HCH、I+双胍盐、I+双胍乙酸盐、I+GY-81、I+苄螨醚、I+氯虫酰肼、I+HCH、I+HEOD、I+飞布达、I+庚烯磷、I+速杀硫磷、I+氟铃脲、I+HHDN、I+氟蚁腙、I+氢氰酸、I+烯虫乙酯、I+海驱威、I+吡虫啉、I+炔咪菊酯、I+茚虫威、I+碘甲烷、I+IPSP、I+氯唑磷、I+碳氯灵、I+水胺硫磷、I+异艾氏剂、I+异柳磷、I+移栽灵、I+异丙威、I+O-(甲氧基氨基硫代磷酰基)水杨酸异丙酯、I+稻瘟灵、I+异拌磷、I+噁唑磷、I+伊维菌素、I+茉莉菊酯I、I+茉莉菊酯II、I+碘硫磷、I+保幼激素I、I+保幼激素II、I+保幼激素III、I+氯戊环、I+烯虫炔酯、I+λ-氯氟氰菊酯、I+砷酸铅、I+雷皮菌素、I+对溴磷、I+林旦、I+丙嘧硫磷、I+虱螨脲、I+噻唑磷、I+甲基氨基甲酸间异丙苯基酯、I+磷化镁、I+马拉硫磷、I+特螨腈、I+叠氮磷、I+灭蚜磷、I+四甲磷、I+灭蚜硫磷、I+地安磷、I+氯化亚汞、I+倍硫磷亚砜、I+氰氟虫腙、I+威百亩、I+威百亩钾、I+威百亩钠、I+虫螨畏、I+甲胺磷、I+甲烷磺酰氟、I+杀扑磷、I+灭虫威、I+杀虫乙烯磷、I+灭多威、I+烯虫酯、I+甲喹丁、I+甲醚菊酯、I+甲氧滴滴涕、I+甲氧苯酰、I+溴甲烷、I+异硫氰酸甲酯、I+甲基氯仿、I+二氯甲烷、I+甲氧苄氟菊酯、I+速灭威、I+恶虫酮、I+速灭磷、I+兹克威、I+密灭汀、I+米尔贝肟、I+丙胺氟、I+灭蚁灵、I+久效磷、I+茂硫磷、I+莫昔克丁、I+萘酞磷、I+二溴磷、I+萘、I+NC-170、I+NC-184、I+烟碱、I+硫酸烟碱、I+氟蚁灵、I+烯啶虫胺、I+硝乙脲噻唑、I+戊氰威、I+戊氰威1:1氯化锌络合物、I+NNI-0101、I+NNI-0250、I+降烟碱、I+双苯氟脲、I+多氟脲、I+O-5-二氯-4-碘苯基O-乙基乙基硫代膦酸酯、I+O,O-二乙基O-4-甲基-2-氧代-2H-色烯-7-基硫代膦酸酯、I+O,O-二乙基O-6-甲基-2-丙基嘧啶-4-基硫代膦酸酯、I+O,O,O',O'--四丙基二硫代焦磷酸酯、I+油酸、I+氧化乐果、I+杀线威、I+砜吸磷-甲基、I+异亚砜磷、I+砜拌磷、I+pp'-DDT、I+对-二氯苯、I+对硫磷、I+对硫磷-甲基、I+氟幼脲、I+五氯苯酚、I+月桂酸五氯苯基酯、I+氯菊酯、I+石油油料、I+PH 60-38、I+芬硫磷、I+苯醚菊酯、I+稻丰散、I+甲拌磷+TX、I+伏杀硫磷、I+硫环磷、I+亚胺硫磷、I+对氯硫磷、I+磷胺、I+磷化氢、I+辛硫磷、I+辛硫磷-甲基、I+甲胺嘧磷、I+抗蚜威、I+乙基嘧啶磷、I+甲基嘧啶磷、I+聚氯二环戊二烯异构体类、I+聚氯萜类、I+亚砷酸钾、I+硫氰酸钾、I+丙炔菊酯、I+早熟素I、I+早熟素II、I+早熟素III、I+乙酰嘧啶磷、I+丙溴磷、I+丙氟菊酯、I+蜱虱威、I+猛杀威、I+丙虫磷、I+胺丙畏、I+残杀威、I+乙噻唑磷、I+丙硫磷、I+发硫磷、I+丙苯烃菊酯、I+吡蚜酮、I+吡唑硫磷、I+定菌磷、I+苄呋菊酯、I+除虫菊酯I、I+除虫菊酯II、I+除虫菊酯类、I+哒螨灵、I+啶虫丙醚、I+哒嗪硫磷、I+嘧螨醚、I+嘧硫磷、I+吡丙醚、I+苦木提取物、I+喹硫磷(quinalphos)、I+喹硫磷-甲基、I+畜宁磷、I+喹硫磷(quintiofos)、I+R-1492、I+雷复尼特、I+苄呋菊酯、I+鱼藤酮、I+RU 15525、I+RU 25475、I+尼亚那、I+利阿诺定、I+沙巴藜芦、I+八甲磷、I+硫线磷、I+塞拉菌素、I+SI-0009、I+SI-0205、I+SI-0404、I+SI-0405、I+氟硅菊酯、I+SN 72129、I+亚砷酸钠、I+氰化钠、I+氟化钠、I+六氟硅酸钠、I+五氯酚钠、I+硒酸钠、I+硫氰酸钠、I+苏硫磷、I+多杀菌素、I+螺甲螨酯、I+螺虫乙酯、I+萨尔科福隆、I+萨尔科福隆钠、I+氟虫胺、I+治螟磷、I+磺酰氟、I+硫丙磷、I+焦油、I+τ-氟胺氰菊酯、I+噻螨威、I+TDE、I+虫酰肼、I+吡螨胺、I+丁基嘧啶磷、I+氟苯脲、I+七氟菊酯、I+双硫磷、I+TEPP、I+环戊烯丙菊酯、I+叔丁威、I+特丁硫磷、I+四氯乙烷、I+杀虫畏、I+四甲菊酯、I+θ氯氰菊酯、I+噻虫啉、I+塞芬诺克斯、I+噻虫嗪、I+苯噻硫磷、I+克虫威、I+杀虫环、I+杀虫环草酸氢盐、I+硫双威、I+久效威、I+甲基乙拌磷、I+虫线磷、I+杀虫单、I+杀虫双、I+苏云金素、I+唑虫酰胺、I+四溴菊酯、I+四氟苯菊酯、I+反式苄氯菊酯、I+威菌磷、I+唑蚜威、I+三唑磷、I+唑呀威、I+敌百虫、I+三氯偏磷酸-3、I+毒壤膦、I+三氯丙氧磷、I+杀铃脲、I+混杀威、I+烯虫硫酯、I+蚜灭磷、I+甲烯氟虫腈、I+藜芦定、I+藜芦碱、I+XMC、I+灭杀威、I+YI-5302、I+ζ-氯氰菊酯、I+泽塔米林、I+磷化锌、I+丙硫恶唑磷和ZXI 8901、I+氰虫酰胺、I+氯虫酰胺、I+唑螨氰、I+丁氟螨酯、I+氟虫吡喹、I+乙基多杀菌素、I+螺虫乙酯、I+砜虫啶、I+丁虫腈、I+氯氟醚菊酯、I+四氟醚菊酯、I+三氟苯嘧啶、I+双丙环虫酯、I+flupyrimin、I+溴虫氟苯双酰胺、I+氯氟氰虫酰胺、I+Fluxametamide、I+Momfluorothrin、I+κ-联苯菊酯、I+κ-七氟菊酯、I+Dichloromezotiaz、I+ε-甲氧苄氟菊酯、I+ε-momfluorothrin、I+环溴虫酰胺、I+Tetrachloraniliprole、Ibenzpyrimoxan;
包括杀软体动物剂的组合物包括:I+二(三丁基锡)氧化物、I+溴乙酰胺、I+砷酸钙、I+除线威(cloethocarb)、I+乙酰亚砷酸铜、I+硫酸铜、I+三苯锡、I+磷酸铁、I+四聚乙醛、I+灭虫威、I+氯硝柳胺、I+氯硝柳胺乙醇胺盐、I+五氯苯酚、I+五氯苯氧化钠、I+噻螨威(tazimcarb)、I+硫双威、I+三丁基氧化锡、I+杀螺吗啉(trifenmorph)、I+混杀威(trimethacarb)、I+乙酸三苯基锡和三苯基氢氧化锡、I+皮瑞普(pyriprole);
包含杀线虫剂的组合物包括:I+AKD-3088、I+1,2-二溴-3-氯丙烷、I+1,2-二氯丙烷、I+1,2-二氯丙烷与1,3-二氯丙烯、I+1,3-二氯丙烯、I+3,4-二氯四氢噻吩1,1-二氧化物、I+3-(4-氯苯基)-5-甲基绕丹宁、I+5-甲基-6-硫代-1,3,5-噻二嗪烷-3-基乙酸、I+6-异戊烯基氨基嘌呤、I+阿巴美丁、I+乙酰虫腈、I+棉铃威、I+涕灭威、I+涕灭砜威、I+AZ 60541、I+苯氯噻唑、I+苯茵灵、I+丁基哒螨酮(butylpyridaben)、I+硫线磷(cadusafos)、I+克百威(carbofuran)、I+二硫化碳、I+丁硫克百威、I+氯化苦、I+毒死蜱、I+除线威(cloethocarb)、I+细胞分裂素(cytokinins)、I+棉隆、I+DBCP、I+DCIP、I+除线特(diamidafos)、I+除线磷(dichlofenthion)、I+迪克力弗斯、I+乐果、I+多拉克汀、I+依马克丁、I+依马克丁苯甲酸酯、I+依立诺克丁、I+灭线磷、I+二溴乙烷、I+苯线磷(fenamiphos)、I+吡螨胺(fenpyrad)、I+丰索磷、I+噻唑磷(fosthiazate)、I+丁硫环磷(fosthietan)、I+糠醛、I+GY-81、I+速杀硫磷(heterophos)、I+碘甲烷、I+氯唑磷(isamidofos)、I+氯唑磷(isazofos)、I+伊维菌素、I+激动素、I+甲基灭蚜磷(mecarphon)、I+威百亩、I+威百亩钾盐、I+威百亩钠盐、I+甲基溴、I+异硫氰酸甲酯、I+杀螨菌素肟(milbemycin oxime)、I+莫昔克丁、I+疣孢漆斑茵(Myrothecium verrucaria)组分、I+NC-184、I+杀线威、I+甲拌磷、I+磷胺、I+磷虫威(phosphocarb)、I+硫线磷(sebufos)、I+塞拉菌素(selamectin)、I+多杀菌素、I+叔丁威(terbam)、I+特丁磷(terbufos)、I+四氯噻吩、I+噻菲农、I+虫线磷(thionazin)、I+三唑磷、I+唑呀威(triazuron)、I+二甲苯酚、I+YI-5302和玉米素、I+氟噻虫砜(fluensulfone)、I+氟吡菌酰胺、I+异菌脲、I+替奥沙芬(Tioxazafen)、I+三氟咪啶酰胺(Fluazaindolizine);
包含增效剂的组合物包括:I+2-(2-丁氧基乙氧基)乙基胡椒基酯、I+5-(1,3-苯并二氧杂环戊烯-5-基)-3-己基环己-2-烯酮、I+具有橙花叔醇的法呢醇、I+MB-599、I+MGK264、I+增效醚(piperonyl butoxide)、I+增效醛(piprotal)、I+增效酯(propyl isomer)、I+S421、I+增效散(sesamex)、I+芝麻林素(sesasmolin)和I+亚砜;
包含动物驱避剂的组合物包括:I+蒽醌、I+氯醛糖、I+环烷酸铜、I+王铜、I+二嗪磷、I+二环戊二烯、I+双胍盐(guazatine)、I+双胍醋酸盐、I+灭虫威、I+吡啶-4-胺、I+塞仑、I+混杀威(trimethacarb)、I+环烷酸锌和I+福美锌;
另外的组合物包括:I+溴氟菊酯(Brofluthrinate)、I+环氧虫啶(Cycloxaprid)、I+Diflovidazine、I+Flometoquin、I+Fluhexafon、I+戊吡虫胍(Guadipyr)、I+小菜蛾颗粒体病毒(Plutella xylostella Granulosis virus)、I+苹果蠹蛾颗粒体病毒(Cydiapomonella Granulosis virus)、I+正康壮素(Harpin)、I+咪唑环磷(Imicyafos)、I+烟芽夜蛾核型多角体病毒(Heliothis virescens Nucleopolyhedrovirus)、I+实夜蛾属punctigera核型多角体病毒(Heliothis punctigera Nucleopolyhedrovirus)、I+棉铃虫核型多角体病毒(Helicoverpa armigera Nucleopolyhedrovirus)、I+谷实夜蛾核型多角体病毒(Helicoverpa zea Nucleopolyhedrovirus)、I+草地贪夜蛾核型多角体病毒(Spodoptera frugiperda Nucleopolyhedrovirus)、I+小菜蛾核型多角体病毒(Plutellaxylostella Nucleopolyhedrovirus)、I+拟斯扎瓦巴氏杆菌(Pasteuria nishizawae)、I+对-伞花烃(p-cymene)、I+吡氟丁酰胺(Pyflubumide)、I+吡嗪氟虫腈(Pyrafluprole)、I+除虫菊(pyrethrum)、I+QRD 420、I+QRD 452、I+QRD 460、I+萜类混合物(Terpenoid blends)、I+萜类化合物(Terpenoids)、I+氟氰虫酰胺(Tetraniliprole)、以及I+α-松油烯;
组合物还包括具有式(I)的化合物与由以下代码引用的活性物质的混合物,如I+代码AE 1887196(BSC-BX60309)、I+代码NNI-0745GR、I+代码IKI-3106、I+代码JT-L001、I+代码ZNQ-08056、I+代码IPPA152201、I+代码HNPC-A9908(CAS:[660411-21-2])、I+代码HNPC-A2005(CAS:[860028-12-2])、I+代码JS118、I+代码ZJ0967、I+代码ZJ2242、I+代码JS7119(CAS:[929545-74-4])、I+代码SN-1172、I+代码HNPC-A9835、I+代码HNPC-A9955、I+代码HNPC-A3061、I+代码Chuanhua 89-1、I+代码IPP-10、I+代码ZJ3265、I+代码JS9117、I+代码ZJ3757、I+代码ZJ4042、I+代码ZJ4014、I+代码ITM-121、I+代码DPX-RAB55(DKI-2301)、I+代码NA-89、I+代码MIE-1209、I+代码MCI-8007、I+代码BCS-CL73507、I+代码S-1871、I+代码DPX-RDS63、以及I+代码AKD-1193。
在活性成分之后的括号中的参考,例如[3878-19-1]是指化学文摘登记号。上文描述的混合配伍物是已知的。当活性成分包括在“The Pesticide Manual[杀有害生物剂手册]”[The Pesticide Manual-A World Compendium[杀有害生物剂手册-全球概览];第13版;编辑:C.D.S.TomLin;The British Crop Protection Coimcil[英国农作物保护委员会]]中的情况下,它们在其中以上文对于特定化合物的圆括号中所给出的条目编号来描述;例如化合物“阿巴美丁”以条目编号(1)来描述。在“[CCN]”在上文添加到特定化合物的情况下,所述的化合物包括在“Compendium of Pesticide Common Names[杀有害生物剂通用名纲要]”中,其可以在互联网[A.Wood;Compendium of Pesticide Common Names,Copyright1995-2004]上获得;例如,化合物“乙酰虫腈”描述于互联网地址http://www.alanwood.net/pesticides/acetoprole.html。
在活性成分之后的括号中的参考,例如[3878-19-1]是指化学文摘登记号。上文描述的混合配伍物是已知的。当活性成分包括在“The Pesticide Manual[杀有害生物剂手册]”[The Pesticide Manual-A World Compendium[杀有害生物剂手册-全球概览];第13版;编辑:C.D.S.TomLin;The British Crop Protection Coimcil[英国农作物保护委员会]]中的情况下,它们在其中以上文对于特定化合物的圆括号中所给出的条目编号来描述;例如化合物“阿巴美丁”以条目编号(1)来描述。在“[CCN]”在上文添加到特定化合物的情况下,所述的化合物包括在“Compendium of Pesticide Common Names[杀有害生物剂通用名纲要]”中,其可以在互联网[A.Wood;Compendium of Pesticide Common Names,Copyright1995-2004]上获得;例如,化合物“乙酰虫腈”描述于互联网地址http://www.alanwood.net/pesticides/acetoprole.html。
多数活性成分通过上文中所谓的“通用名”来表示,在不同的情形中使用相应的“ISO通用名”或另一“通用名”。若名称不是“通用名”,则所使用的名称种类以特定化合物的圆括号中所给出的名称来代替;在这种情况下,使用IUPAC名称、IUPAC/化学文摘名、“化学名称”、“惯用名”、“化合物名称”或“开发代码”,或若既不使用那些名称之一也不使用“通用名”,则使用“别名”。“CAS登记号”意指化学文摘登记号。
具有式(I)的化合物与上述活性成分的活性成分混合物包含具有式(I)的化合物和上述活性成分,优选地是处于从100:1至1:6000的混合比率,尤其是从50:1至1:50,更尤其是处于从20:1至1:20的比率,甚至更尤其从10:1至1:10,非常尤其是从5:1和1:5,尤其优选的是从2:1至1:2的比率,并且从4:1至2:1的比率同样是优选的,特别是处于1:1、或5:1、或5:2、或5:3、或5:4、或4:1、或4:2、或4:3、或3:1、或3:2、或2:1、或1:5、或2:5、或3:5、或4:5、或1:4、或2:4、或3:4、或1:3、或2:3、或1:2、或1:600、或1:300、或1:150、或1:35、或2:35、或4:35、或1:75、或2:75、或4:75、或1:6000、或1:3000、或1:1500、或1:350、或2:350、或4:350、或1:750、或2:750、或4:750的比率。那些混合比率是按重量计的。
如上所述的混合物可以被用于控制有害生物的方法中,该方法包括将包含如上所述的混合物的组合物施用于有害生物或其环境中,除了通过手术或疗法用于治疗人或动物体的方法以及在人或动物体上实施的诊断方法之外。
包含具有式(I)的化合物以及一种或多种如上所述的活性成分的混合物可以例如以单一的“掺水即用”的形式施用,以组合的喷雾混合物(该混合物由单一活性成分组分的单独配制品构成)(如“桶混制剂”)施用,并且当以顺序的方式(即,一个在另一个适当短的时期之后,如几小时或几天)施用时组合使用这些单一活性成分来施用。施用具有式(I)的化合物与如上所述的活性成分的顺序对于实施本发明并不是至关重要的。
根据本发明的组合物还可以包含其他固体或液体助剂,例如稳定剂,例如未环氧化的或环氧化的植物油(例如环氧化的椰子油、菜籽油或大豆油),消泡剂(例如硅酮油),防腐剂,粘度调节剂,粘合剂和/或增粘剂,肥料或其他用于获得特定效果的活性成分,例如杀细菌剂、杀真菌剂、杀线虫剂、植物活化剂、杀软体动物剂或除草剂。
根据本发明的组合物是以本身已知的方式,在不存在助剂的情况下,例如通过研磨、筛选和/或压缩固体活性成分;和在至少一种助剂的存在下,例如通过紧密混合活性成分与一种或多种助剂和/或将活性成分与一种或多种助剂一起研磨来制备。用于制备组合物的这些方法和用于制备这些组合物的化合物(I)的用途也是本发明的主题。
这些组合物的施用方法,即控制上述类型的有害生物的方法,如喷雾、雾化、撒粉、刷涂、包衣、撒播或浇灌-它们被选择以适于普遍情况的预期目的-以及这些组合物用于控制上述类型的有害生物的用途是本发明的其他主题。典型的浓度比是在0.1与1000ppm之间、优选在0.1与500ppm之间的活性成分。每公项的施用比率总体上是每公项1g至2000g活性成分、尤其是10g/ha至1000g/ha、优选地是10g/ha至600g/ha。
在作物保护领域中,优选的施用方法是施用至这些植物的叶(叶施用),可能的是选择施用的频率和比率以符合所讨论的有害生物的侵染风险。可替代地,该活性成分可以通过根系统(内吸作用)到达植物,这是通过用液体组合物将这些植物的场所浸透或者通过将呈固体形式的活性成分引入植物的场所(例如引入土壤,例如以颗粒的形式(土施))来实现的。在水稻作物的情况下,此类颗粒剂可以被计量地加入淹水的稻田中。
本发明的这些化合物及其组合物还适合于植物繁殖材料的保护(例如种子,像果实、块茎或籽粒,或者苗圃植物),以对抗上述类型的有害生物。可以用该化合物在种植前对繁殖材料进行处理,例如可以在播种前对种子进行处理。替代性地,该化合物可以施用至种子籽粒(包衣),这是通过将籽粒浸渍入液体组合物中或通过施加固体组合物层实现的。还可能在该繁殖材料被种植在施用处时施用这些组合物,例如在条播期间将这些组合物施入种子犁沟。这些用于植物繁殖材料的处理方法和如此处理的植物繁殖材料是本发明另外的主题。典型的处理比率将取决于有待控制的植物以及有害生物/真菌,并且通常在每100kg种子1克至200克之间、优选在每100kg种子5克至150克之间,如在每100kg种子10克至100克之间。
术语种子包括所有种类的种子以及植物繁殖体,包括但并不限于真正的种子、种子块、吸盘、谷粒、鳞球茎、果实、块茎、谷物、根茎、插条、切割枝条以及类似物并且在优选实施例中意指真正的种子。
本发明还包括用具有式(I)的化合物包衣或处理的种子或含有具有式(I)的化合物的种子。尽管取决于施用的方法成分的更多或更少的部分可以渗透到种子材料中,术语“包衣或处理和/或含有”通常表示在施用的时候,在大多数情况下,活性成分在种子的表面。当所述种子产品被(再)种植时,它可以吸收活性成分。在实施例中,本发明使得其上粘附有具有式(I)的化合物的植物繁殖材料可得。此外,由此可得包含用具有式(I)的化合物处理过的植物繁殖材料的组合物。
种子处理包括本领域中已知的所有合适的种子处理技术,如拌种、种子包衣、种子撒粉、浸种以及种子造粒。根据实施例1至9中任一项所述的化合物的种子处理施用可以通过任何已知的方法进行,如在播种前或播种/种植种子期间对种子进行喷雾或撒粉。
本发明进一步涉及一种用于控制有害生物的方法,该方法包括将根据本发明的组合物施用于有害生物或其环境中,优选地除了通过手术或疗法用于治疗人或动物体的方法以及在人或动物体上实施的诊断方法之外。
本发明进一步涉及一种用于保护植物繁殖材料免受有害生物攻击的方法,该方法包括用包含根据本发明的化合物的组合物或用根据本发明的化合物处理该繁殖材料或该繁殖材料所种植的场所。本发明进一步涉及用包含根据本发明的化合物的杀有害生物组合物或用根据本发明的化合物处理过的植物繁殖材料。
接下来的实例用来阐明本发明。本发明的化合物与已知化合物的区别可以在于在低施用比率下更大的功效,这可以由本领域技术人员使用在实例中概述的实验程序,使用更低的施用比率(如果必要的话),例如50ppm、12.5ppm、6ppm、3ppm、1.5ppm或0.8ppm来证实。温度以摄氏度给出;溶剂的混合比以体积份给出。
制备实例:
“Mp”是指以℃计的熔点。自由基表示甲基基团。在Brucker400MHz光谱仪上记录1HNMR测量值,化学位移相对于TMS标准物以ppm给出。光谱在如指定的氘代溶剂中测量。
实例1:N-(环丙氧基甲基)-4-[(5S)-5-(3,5-二氯-4-氟-苯基)-5-(三氟甲基)-
4H-异噁唑-3-基]-N-[(4R)-2-(二氟甲基磺酰基)异噁唑烷-4-基]-2-甲基-苯甲酰胺(化合
物A2)的制备
在0℃下,在氩气氛下向4-[(5S)-5-(3,5-二氯-4-氟-苯基)-5-(三氟甲基)-4H-异噁唑-3-基]-N-[(4R)-2-(二氟甲基磺酰基)异噁唑烷-4-基]-2-甲基-苯甲酰胺(1.5g)和多聚甲醛(300mg)在二氯甲烷(12mL)中的混合物中添加三乙胺(1.02mL),并且将混合物搅拌15分钟。然后在0℃下向混合物中逐滴添加氯化钛(IV)(7.25mL,在甲苯中1mol/L),并且使反应混合物升温至环境温度并搅拌5小时30分钟。之后,将此反应混合物分为4个等体积的反应介质并转移到新的反应小瓶中。然后,在环境温度下向4个单独的反应小瓶中的每一个中引入环丙醇(0.394mL),并且将内容物搅拌45分钟。之后,添加额外量的环丙醇(0.4mL)并且将反应混合物在环境温度下再搅拌2小时。然后将反应混合物用水和乙酸乙酯稀释。将水层分离并用乙酸乙酯萃取两次。将总的合并的有机层经硫酸钠干燥,过滤并在真空下浓缩以得到粗残余物,将其通过Combiflash色谱法(洗脱液:梯度环己烷/乙酸乙酯1:0至60:40)纯化,以得到141mg的所希望的产物A2。1H NMR(400MHz,CDCl3)δppm 7.50-7.65(m,4H)7.32(d,1H)6.48(t,1H)5.48-5.56(m,1H)4.53(br s,2H)4.29-4.50(m,3H)4.10(d,1H)3.84(brdd,1H)3.71(d,1H)2.97(m,1H)2.32(s,3H)0.24-0.41(m,4H)。19F NMR(377MHz,CDCl3)δppm-79.55(s,3F)-113.45(s,1F)-121.02(d,1F)-123.62(d,1F)
实例2:N-(环丙烷羰基)-4-[(5S)-5-(3,5-二氯-4-氟-苯基)-5-(三氟甲基)-4H-
异噁唑-3-基]-N-[(4R)-2-(二氟甲基磺酰基)异噁唑烷-4-基]-2-甲基-苯甲酰胺(化合物
A1)的制备
向4-[(5S)-5-(3,5-二氯-4-氟-苯基)-5-(三氟甲基)-4H-异噁唑-3-基]-N-[(4R)-2-(二氟甲基磺酰基)异噁唑烷-4-基]-2-甲基-苯甲酰胺(150mg)和N,N-二甲基氨基吡啶(6mg)在干燥二氯甲烷(3.2mL)中的混合物中添加三乙胺(0.12mL),接着添加环丙烷甲酰氯(77mg),并且将反应混合物在环境温度下搅拌3天。之后,将反应混合物用水和乙酸乙酯稀释。将水层分离,用乙酸乙酯萃取两次,并且将总的合并的有机层经硫酸钠干燥,过滤并在真空下浓缩以得到粗残余物,将其通过Combiflash色谱法(洗脱液:梯度环己烷/乙酸乙酯100:0至75:25)和反相制备型HPLC纯化以得到72mg的所希望的产物A1。1H NMR(400MHz,CDCl3)δppm 7.53-7.62(m,4H)7.37(d,1H)6.27-6.65(m,1H)5.52-5.59(m,1H)4.48(t,1H)4.25-4.34(m,2H)4.10(d,1H)3.96(br dd,1H)3.70(d,1H)2.50(s,3H)1.22-1.30(m,1H)1.03(br d,2H)0.62(br d,2H)。19F NMR(377MHz,CDCl3)δppm-79.55(s,3F)-113.24(s,1F)-120.83(d,1F)-124.31(d,1F)。
生物学实例:
这些实例展示了具有式(I)的化合物的杀有害生物/杀昆虫特性。
如下进行试验:
实例B1:黄瓜条叶甲(玉米根虫)
将24孔微量滴定板中的置于琼脂层上的玉米芽通过喷雾用从10'000ppm DMSO储备溶液制备的水性测试溶液进行处理。在干燥之后,用L2期幼虫对板进行侵染(6至10只/孔)。侵染4天之后,相比于未处理样品,针对死亡率和生长抑制对这些样品进行评估。
以下化合物在200ppm施用比率下给出了两个类别(死亡率或生长抑制)中至少一个的至少80%的效果:A1
实例B2:英雄美洲蝽(Euschistus heros)(新热带区褐蝽象)
将24孔微量滴定板中的琼脂上的大豆叶片用从10'000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。在干燥之后,用N2期若虫对叶片进行侵染。侵染5天之后,相比于未处理样品,针对死亡率和生长抑制对这些样品进行评估。
以下化合物在200ppm施用比率下给出了两个类别(死亡率或生长抑制)中至少一个的至少80%的效果:A1、A2。
实例B3:小菜蛾(Plutella xylostella)(小菜蛾(Diamond back moth))
将具有人工饲料的24孔微量滴定板用从10'000ppm DMSO储备溶液制备的水性测试溶液通过移液进行处理。在干燥之后,将菜蛾属卵吸移穿过塑料模板到凝胶印迹纸上并且用其封闭板。侵染8天之后,相比于未处理样品,针对死亡率和生长抑制对这些样品进行评估。
以下化合物在200ppm施用比率下给出了两个类别(死亡率或生长抑制)中至少一个的至少80%的效果:A2
实例B4:小菜蛾(Plutella xylostella)(小菜蛾(Diamond back moth))
将具有人工饲料的24孔微量滴定板用从10'000ppm DMSO储备溶液制备的水性测试溶液通过移液进行处理。在干燥之后,用L2期幼虫对板进行侵染(10至15只/孔)。侵染5天之后,相比于未处理样品,针对死亡率和生长抑制对这些样品进行评估。
以下化合物在200ppm施用比率下给出了两个类别(死亡率或生长抑制)中至少一个的至少80%的效果:A1
实例B5:桃蚜(Myzus persicae)(绿桃蚜):摄食/接触活性
将向日葵叶圆片置于24孔微量滴定板中的琼脂上并且用从10'000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用混合年龄的蚜虫种群进行侵染。侵染6天之后,针对死亡率对这些样品进行评估。
以下化合物在200ppm施用比率下产生至少80%的死亡率:A1
实例B6:海灰翅夜蛾(埃及棉叶虫)
将棉花叶圆片置于24孔微量滴定板中的琼脂上并且用从10'000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用五只L1期幼虫进行侵染。侵染3天之后,相比于未处理样品,针对死亡率、拒食效果以及生长抑制对这些样品进行评估。当这些类别(死亡率、拒食效果和生长抑制)中的至少一个高于未处理的样品时,实现测试样品对海灰翅夜蛾的控制。
以下化合物在200ppm施用比率下产生至少80%的控制:A1、A2
实例B7:二点叶螨(Tetranychus urticae)(二斑叶螨):摄食/接触活性
将24孔微量滴定板中的琼脂上的豆叶圆片用从10'000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用混合年龄的螨种群进行侵染。侵染8天之后,针对混合种群(活动阶段)的死亡率对这些样品进行评估。
以下化合物在200ppm施用比率下产生至少80%的死亡率:A1
实例B8:烟蓟马(葱蓟马)摄食/接触活性
将向日葵叶圆片置于24孔微量滴定板中的琼脂上并且用从10'000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用混合年龄的蓟马种群进行侵染。侵染6天之后,针对死亡率对这些样品进行评估。
以下化合物在200ppm施用比率下产生至少80%的死亡率:A1。
Claims (14)
1.一种具有式(I)的化合物
其中
A1、A2、A3以及A4彼此独立地是C-H、C-R5、或氮;
R1选自-(C0-C4烷基)-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C3-C6环烷基、-R1aOR1aOR1b、-R1aOC(=O)R1b、-R1aOC(=O)OR1b、-R1aN(R1c)C(=O)OR1b、-R1aOC(=O)N(R1b)(R1c)、-R1aC(=O)N(R1b)(R1c)和-S-C(=O)OR1b;
R1a是-(CR1dR1e)m-;
R1b和R1c独立地选自氢和C1-C4烷基,其中每个烷基基团是未取代的或被一个至三个卤素原子或被氰基基团取代;
R1d和R1e独立地选自氢和C1-C4烷基;
m选自1、2、3和4;
R2是C1-C8烷基,被一个至三个R6a取代的C1-C8烷基,C1-C8卤代烷基,被一个至三个R6a取代的C1-C8卤代烷基,C3-C8环烷基,被一个至三个R6b取代的C3-C8环烷基,其中一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基,C3-C8环烷基-C1-C8烷基,其中环烷基基团中的一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基-C1-C8烷基,C3-C8环烷基-C1-C8卤代烷基,C2-C8烯基,被一个至三个R6a取代的C2-C8烯基,C2-C8卤代烯基,被一个至三个R6a取代的C2-C8卤代烯基,C2-C8炔基,C2-C8卤代炔基,苯基,被一个至三个R7取代的苯基,苯基-C1-C4烷基,其中苯基部分被一个至三个R7取代的苯基-C1-C4烷基,5-6元杂芳基,被一个至三个R7取代的5-6元杂芳基,5-6元杂芳基-C1-C4烷基,其中杂芳基部分被一个至三个R7取代的5-6元杂芳基-C1-C4烷基,-N(R8)(R9),卤素或-OR10;
R3是C1-C8卤代烷基;
R4是芳基、被一个至三个R7取代的芳基、杂芳基或被一个至三个R7取代的杂芳基;
R5独立地是卤素、氰基、硝基、C1-C8烷基、C3-C8环烷基、C1-C8卤代烷基、C2-C8烯基、C2-C8卤代烯基、C2-C8炔基、C2-C8卤代炔基、C1-C8烷氧基、C1-C8卤代烷氧基、或C1-C8烷氧基羰基-,或在相邻碳原子上的两个R5一起形成CH=CH-CH=CH-桥或-N=CH-CH=CH-桥;
R6a独立地是氰基、硝基、氨基、C1-C8烷基氨基、N,N-C1-C8二烷基氨基、羟基、C1-C8烷氧基、或C1-C8卤代烷氧基;
R6b独立地是卤素、氰基、硝基、氧代、C1-C8烷基、C1-C8卤代烷基、氨基、C1-C8烷基氨基、N,N-C1-C8二烷基氨基、羟基、C1-C8烷氧基、C1-C8卤代烷氧基、苯基、被一个至三个R7取代的苯基、5-6元杂芳基、被一个至三个R7取代的5-6元杂芳基;
R7独立地是卤素、氰基、硝基、C1-C8烷基、C1-C8卤代烷基、C1-C8烷氧基、C1-C8卤代烷氧基;
R8和R9独立地是氢,氰基,氰基-C1-C8烷基,C1-C8烷基,被一个至三个R6a取代的C1-C8烷基,C2-C8烯基,被一个至三个R6a取代的C2-C8烯基,C1-C8烷氧基,C1-C8卤代烷氧基,被一个至三个R6a取代的C1-C8卤代烷氧基,被一个至三个R6a取代的C1-C8烷氧基,C1-C8卤代烷基,被一个至三个R6a取代的C1-C8卤代烷基,C3-C8环烷基,被一个至三个R6b取代的C3-C8环烷基,其中一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基,C3-C8环烷基-C1-C8烷基,其中环烷基基团中的一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基-C1-C8烷基,C3-C8环烷基-C1-C8卤代烷基,C2-C8烯基,被一个至三个R6a取代的C2-C8烯基,C2-C8卤代烯基,被一个至三个R6a取代的C2-C8卤代烯基,C2-C8炔基,C2-C8卤代炔基,苯基,被一个至三个R7取代的苯基,苯基-C1-C4烷基,其中苯基部分被一个至三个R7取代的苯基-C1-C4烷基,5-6元杂芳基,被一个至三个R7取代的5-6元杂芳基,5-6元杂芳基-C1-C4烷基,其中杂芳基部分被一个至三个R7取代的5-6元杂芳基-C1-C4烷基,-S(O)R10,-S(O)2R10,COR10,COOR10,或者R8和R9连同氮原子一起可以通过C3-C8亚烷基链,被一个至三个R6b取代的C3-C8亚烷基链或其中一个碳原子被O、S、S(O)或SO2替换的C3-C8亚烷基链连接;
R10是氢,氰基-C1-C8烷基,C1-C8烷基,被一个至三个R6a取代的C1-C8烷基,C1-C8卤代烷基,被一个至三个R6a取代的C1-C8卤代烷基,C3-C8环烷基,被一个至三个R6b取代的C3-C8环烷基,其中一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基,C3-C8环烷基-C1-C8烷基,其中环烷基基团中的一个碳原子被O、S、S(O)或SO2替换的C3-C8环烷基-C1-C8烷基,C3-C8环烷基-C1-C8卤代烷基,C2-C8烯基,被一个至三个R6a取代的C2-C8烯基,C2-C8卤代烯基,被一个至三个R6a取代的C2-C8卤代烯基,C2-C8炔基,C2-C8卤代炔基,苯基,被一个至三个R7取代的苯基,苯基-C1-C4烷基,其中苯基部分被一个至三个R7取代的苯基-C1-C4烷基,5-6元杂芳基,被一个至三个R7取代的5-6元杂芳基,5-6元杂芳基-C1-C4烷基或其中杂芳基部分被一个至三个R7取代的5-6元杂芳基-C1-C4烷基;
n是1或2;
或其互变异构体、同分异构体、对映异构体、盐或N-氧化物。
2.根据权利要求1所述的化合物,其中,
A1是C-R5;A2是C-H;A3是C-H;并且A4是C-H,其中R5是卤素、氰基、硝基、C1-C8烷基、C3-C8环烷基、C1-C8卤代烷基、或C2-C8烯基。
3.根据权利要求1至3中任一项所述的化合物,其中,
R1选自-(C0-C4烷基)-C(=O)-C3-C6环烷基和-(C0-C4烷基)-O-C3-C6环烷基。
4.根据权利要求1至3中任一项所述的化合物,其中,R2是C1-C8卤代烷基。
5.根据权利要求1至4中任一项所述的化合物,其中,R3是C1-C4卤代烷基。
6.根据权利要求1至5中任一项所述的化合物,其中,R4是苯基或被一个至三个R7取代的苯基;其中R7独立地是卤素、氰基、C1-C8烷基、C1-C8卤代烷基、C1-C8烷氧基、或C1-C8卤代烷氧基。
7.根据权利要求1至6中任一项所述的化合物,其中,A1是CR5,并且A2、A3和A4各自是CH;R1选自-(C0-C4烷基)-C(=O)-C3-C6环烷基和-(C0-C4烷基)-O-C3-C6环烷基;R2是C1-C8卤代烷基;R3是C1-C4卤代烷基;R4是芳基或被一个至三个R6b取代的芳基;并且n是2;其中R5是C1-C8烷基;并且R6b独立地是卤素、氰基、硝基、C1-C4烷基、或C1-C4卤代烷基、C1-C4烷氧基、或C1-C4卤代烷氧基。
8.根据权利要求1所述的化合物,其由具有式(Ia)的化合物表示
其中
R1选自-(C0-C4烷基)-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C(=O)-C3-C6环烷基、-(C0-C4烷基)-O-C3-C6环烷基、-R1aOR1aOR1b、-R1aOC(=O)R1b、-R1aOC(=O)OR1b、-R1aN(R1c)C(=O)OR1b、-R1aOC(=O)N(R1b)(R1c)、-R1aC(=O)N(R1b)(R1c)和-S-C(=O)OR1b;
R1a是-(CR1dR1e)m-;
R1b和R1c独立地选自H和C1-C4烷基,其中每个烷基基团是未取代的或被一个至三个卤素原子或被氰基基团取代;
R1d和R1e独立地选自H和C1-C4烷基;
m选自1、2、3和4。
9.一种具有式(Int-I)的化合物
其中A1、A2、A3、A4、R1和R2是如根据权利要求1至8中任一项所定义的,并且XB是离去基团,或XB是氰基、甲酰基、CH=N-OH或乙酰基;或其互变异构体、同分异构体、对映异构体、盐或N-氧化物;或者
一种具有式(Int-II)的化合物
其中A1、A2、A3、A4、R1和R2是如根据权利要求1至8中任一项所定义的,并且XC是CH2-卤素、CH=C(R3)R4、或CH2C(OH)(R3)R4,其中R3和R4是如对于根据权利要求1至9中任一项所述的具有式(I)的化合物所定义的;或其互变异构体、同分异构体、对映异构体、盐或N-氧化物;或者
一种具有式(Int-III)的化合物
其中R1和R2是如对于根据权利要求1至8中任一项所述的具有式(I)的化合物所定义的;或其互变异构体、同分异构体、对映异构体、盐或N-氧化物。
10.一种对抗和/或控制无脊椎动物有害生物的方法,所述方法包括向所述有害生物、所述有害生物的场所、或易受所述有害生物攻击的植物施用杀有害生物有效量的如权利要求1至8中任一项所定义的具有式(I)的化合物。
11.一种杀有害生物组合物,其包含至少一种根据权利要求1至8中任一项所述的具有式(I)的化合物,或适当时其互变异构体作为活性成分,所述化合物在每种情况下呈游离形式或呈农用化学上可利用的盐形式。
12.一种用于控制有害生物的方法,所述方法包括将根据权利要求11所述的组合物施用于所述有害生物或其环境,除了通过手术或疗法用于治疗人或动物体的方法以及在人或动物体上实施的诊断方法之外。
13.一种用于保护植物繁殖材料免受有害生物攻击的方法,所述方法包括用根据权利要求11所述的组合物处理所述繁殖材料或所述繁殖材料所种植的场所。
14.一种植物繁殖材料,其是用根据权利要求11所述的杀有害生物组合物处理过的。
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DE102004023894A1 (de) | 2004-05-12 | 2005-12-08 | Basf Ag | Verfahren zur Behandlung von flexiblen Substraten |
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WO2006128870A2 (en) | 2005-06-03 | 2006-12-07 | Basf Aktiengesellschaft | Composition for the impregnation of fibers, fabrics and nettings imparting a protective activity against pests |
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- 2019-09-20 CA CA3119299A patent/CA3119299A1/en active Pending
- 2019-09-20 AU AU2019348401A patent/AU2019348401A1/en not_active Abandoned
- 2019-09-20 CN CN201980063063.2A patent/CN112752751A/zh active Pending
- 2019-09-20 EP EP19783220.7A patent/EP3856728A1/en not_active Withdrawn
- 2019-09-20 WO PCT/EP2019/075389 patent/WO2020064565A1/en unknown
- 2019-09-20 JP JP2021516740A patent/JP2022502386A/ja not_active Abandoned
- 2019-09-20 BR BR112021005763-3A patent/BR112021005763A2/pt not_active Application Discontinuation
- 2019-09-20 US US17/278,822 patent/US20220033364A1/en not_active Abandoned
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CN103221395A (zh) * | 2010-11-23 | 2013-07-24 | 先正达参股股份有限公司 | 杀虫化合物 |
CN103354811A (zh) * | 2011-02-09 | 2013-10-16 | 先正达参股股份有限公司 | 杀虫化合物 |
TW201330773A (zh) * | 2011-10-03 | 2013-08-01 | Syngenta Participations Ag | 殺昆蟲化合物 |
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TW201726662A (zh) * | 2015-10-02 | 2017-08-01 | 先正達合夥公司 | 殺有害生物活性吡唑衍生物 |
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US20220033364A1 (en) | 2022-02-03 |
WO2020064565A1 (en) | 2020-04-02 |
EP3856728A1 (en) | 2021-08-04 |
AU2019348401A1 (en) | 2021-04-01 |
JP2022502386A (ja) | 2022-01-11 |
CA3119299A1 (en) | 2020-04-02 |
BR112021005763A2 (pt) | 2021-06-29 |
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