CN105939999A - 用于防治无脊椎动物害虫的吡唑类 - Google Patents
用于防治无脊椎动物害虫的吡唑类 Download PDFInfo
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- CN105939999A CN105939999A CN201580006598.8A CN201580006598A CN105939999A CN 105939999 A CN105939999 A CN 105939999A CN 201580006598 A CN201580006598 A CN 201580006598A CN 105939999 A CN105939999 A CN 105939999A
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
- A61P33/14—Ectoparasiticides, e.g. scabicides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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Abstract
本发明涉及式I的新型吡唑类。此外,本发明涉及制备式I的吡唑类的方法和中间体,还涉及包含它们的活性化合物组合,包含它们的组合物以及它们在保护生长的植物以防无脊椎动物害虫侵袭或侵染中的用途。此外,本发明涉及施用该类化合物的方法。本发明还涉及包含该类化合物的种子。
Description
本发明涉及式I的新型吡唑类。此外,本发明涉及制备式I的吡唑类的方法和中间体,还涉及包含它们的活性化合物组合,包含它们的组合物以及它们在保护生长的植物以防无脊椎动物害虫侵袭或侵染中的用途。此外,本发明涉及施用这些化合物的方法。本发明还涉及包含该类化合物的种子。
无脊椎动物害虫以及尤其是节肢动物和线虫破坏生长和收获的作物且袭击木质居住和商业结构体,从而对食物供应和财产造成大的经济损失。仍然需要用于防治无脊椎动物害虫如昆虫、蜘蛛和线虫的新试剂。
WO 2009/027393、WO 2010/034737、WO 2010/034738和WO 2010/112177描述了衍生于吡唑羧酸的N-芳基酰胺的衍生物。这些化合物被提及可以用于防治无脊椎动物害虫。
然而,仍然需要对于防治无脊椎动物害虫高度有效且多功能的试剂。因此,本发明的目的是要提供对大量不同的无脊椎动物害虫,尤其是难以防治的害虫如昆虫具有良好的杀虫活性且显示出宽活性谱的化合物。
已经发现这些目的可以通过如下所示和所定义的式I化合物及其立体异构体、盐、互变异构体和N-氧化物,尤其是其可农用盐实现。
在第一方面,本发明涉及式I化合物及其盐、立体异构体、互变异构体和N-氧化物:
其中
V为O、S或NR1a,其中R1a选自H、C1-C10烷基、C1-C4卤代烷基、C3-C10环烷基、C3-C10环烷基甲基、C3-C10卤代环烷基、C2-C10链烯基、C2-C10卤代链烯基、C2-C10炔基、C1-C10烷氧基-C1-C4烷基、ORa、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的相同或不同取代基,或者
其中R1a和R4与R4所键合的碳原子和R1a所键合的氮原子以及所述碳原子和所述氮原子之间的氮原子一起形成含有2个氮原子作为杂原子且可以进一步含有1或2相互独立地选自NRB、O和S的杂原子的4-8员杂环,其中S可以被氧化,和/或其中该杂环可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代;
D为C1-C8亚烷基、C3-C8亚环烷基、C3-C8亚杂环烷基、C2-C8亚链烯基、C3-C8亚环烯基、C3-C8亚杂环烯基或C2-C8亚炔基,其中D可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代;
U为N或CRU;
T为S、O或NR1b,其中R1b选自H、C1-C10烷基、C1-C4卤代烷基、C3-C10环烷基、C3-C10环烷基甲基、C3-C10卤代环烷基、C2-C10链烯基、C2-C10卤代链烯基、C2-C10炔基、C1-C10烷氧基-C1-C4烷基、ORa、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的相同或不同取代基;
RP1、RP2、RP3和RU相互独立地选自H、卤素、C1-C4烷基、C1-C3卤代烷基、C1-C4烷氧基、C1-C3卤代烷氧基、C1-C4烷硫基、C1-C3卤代烷硫基、C1-C4烷基亚磺酰基、C1-C3卤代烷基亚磺酰基、C1-C4烷基磺酰基、C1-C3卤代烷基磺酰基、C3-C6环烷基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基或C1-C4烷氧基-C1-C4烷基;
R1为H、CN、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C4烷氧基-C1-C4烷基、C2-C10链烯基、C2-C10卤代链烯基、C2-C10炔基、C3-C10卤代炔基、C1-C5亚烷基-CN、ORa、C1-C5亚烷基-ORa、C(Y)Rb、C1-C5亚烷基-C(Y)Rb、C(Y)ORc、C1-C5亚烷基-C(Y)ORc、S(O)2Rd、NReRf、C1-C5亚烷基-NReRf、C(Y)NRgRh、C1-C5亚烷基-C(Y)NRgRh、S(O)nNReRf、C(Y)NRiNReRf、C1-C5亚烷基-S(O)2Rd、C1-C5亚烷基-S(O)nNReRf、C1-C5亚烷基-C(Y)NRiNReRf、苯基、杂环基、杂芳基、苯基-C1-C5烷基、C3-C10环烷基-C1-C5烷基、杂环基-C1-C5烷基和杂芳基-C1-C5烷基,其中后提到的7个基团的环可以未被取代或者可以带有1、2、3、4或5个选自基团Ry和Rx的相同或不同取代基;
R2和R3相互独立地选自H、卤素、CN、NO2、C1-C10烷基、C2-C10链烯基和C2-C10炔基,其中后提到的3个基团可以未被取代、可以部分或完全被卤代或者可以带有1、2或3个相同或不同的取代基Rx,或者其中R2和R3进一步选自ORa、SRa、C(Y)Rb、C(Y)ORc、S(O)Rd、S(O)2Rd、NReRf、C(Y)NRgRh、杂环基、杂芳基、C3-C10环烷基、C5-C10环烯基和苯基,其中后提到的5个基团可以未被取代或者可以带有1、2、3、4或5个选自基团Ry和Rx的相同或不同取代基,并且其中
R4为H、C1-C6烷基、C1-C6烷基-X、C3-C6环烷基或C3-C6环烷基-X,其中X选自O、S或NRB,其中C1-C6烷基或C3-C6环烷基可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代;以及
R5为C1-C6烷基、C1-C6烷基-X、C3-C6环烷基或C3-C6环烷基-X,其中X选自O、S或NRB,其中C1-C6烷基或C3-C6环烷基可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代,或者其中
R4和R5与它们所键合的碳原子一起形成可以含有1、2或3个相互独立地选自NRB、O和S的杂原子的3-8员饱和或不饱和碳环或杂环,其中S可以被氧化和/或该碳环或杂环可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代;
并且其中RA为卤素、NO2、CN、C1-C6烷基、C1-C6烷氧基、C1-C6卤代烷基、C1-C6卤代烷氧基、C3-C6环烷基、C3-C6环烷氧基、C3-C6卤代环烷基、C3-C6卤代环烷氧基、C2-C4链烯基、C2-C4炔基、S(O)nRD、=O、=S、=NRC、=NORC和=NSRC;或者其中
键合于相同碳原子或者相邻碳原子的两个RA与它们所键合的碳原子一起形成可以含有1或2个相互独立地选自NRB、O和S的杂原子的3-6员饱和或不饱和碳环或杂环,其中S可以被氧化;
并且其中RB为H、C1-C2烷基、C1-C2卤代烷基、C1-C2烷基羰基、C1-C2卤代烷基羰基或C1-C2烷氧羰基;
RC为H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6卤代环烷基;
RD为H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6卤代环烷基、C1-C4烷氧基或C1-C4卤代烷氧基;
n为0、1或2;
Y为O或S;
Ra、Rb、Rc相互独立地选自H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基甲基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
Rd选自C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基甲基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;并且其中
Re和Rf相互独立地选自H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基甲基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、C1-C4烷基羰基、C1-C4卤代烷基羰基、C1-C4烷基磺酰基、C1-C4卤代烷基磺酰基、杂环基、杂环基-C1-C4烷基、杂环基羰基、杂环基磺酰基、苯基、苯基羰基、苯基磺酰基、杂芳基、杂芳基羰基、杂芳基磺酰基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的12个基团中的环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;或者
Re和Rf与它们所键合的氮原子一起形成可以带有选自O、S和N的另一杂原子作为环成员原子的5或6员饱和或不饱和杂环并且其中该杂环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
并且其中Rg和Rh相互独立地选自H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
Ri选自H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基甲基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、苯基和苯基-C1-C4烷基,其中后提到的2个基团中的苯基环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
Rx为CN、NO2、C1-C4烷氧基、C1-C4卤代烷氧基、S(O)nRd、S(O)nNReRf、C1-C10烷基羰基、C1-C4卤代烷基羰基、C1-C4烷氧羰基、C1-C4卤代烷氧羰基、C3-C6环烷基、5-7员杂环基、5或6员杂芳基、苯基、C3-C6环烷氧基、3-6员杂环氧基和苯氧基,其中后提到的7个基团可以未被取代或者可以带有1、2、3、4或5个相同或不同的基团Ry;以及
Ry选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、S(O)nRd、S(O)nNReRf、C1-C4烷基羰基、C1-C4卤代烷基羰基、C1-C4烷氧羰基、C1-C4卤代烷氧羰基、C3-C6环烷基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基和C1-C4烷氧基-C1-C4烷基。
在其他方面,本发明涉及一种防治动物害虫的组合物和防治动物害虫的农业组合物,其包含至少一种式I化合物。在仍进一步的方面,本发明涉及一种防治或防除无脊椎动物害虫的方法以及一种保护生长的植物以防无脊椎动物害虫侵袭或侵染的方法。在另一方面,本发明涉及包含式I化合物的种子,并且在再一方面,本发明涉及式I化合物在保护生长的植物以防无脊椎动物害虫侵袭或侵染中的用途。
本发明的其他实施方案可以在权利要求书、说明书和实施例中找到。应理解的是本发明主题的上述特征和下面仍待说明的那些不仅可以以相应的所给组合应用,而且可以以不偏离本发明范围的其他组合应用。
在上述式I化合物中,与取代基R4和R5的波浪线表示R4和R5可以存在于碳-氮双键的碳原子处的两个位置中,即相对于V呈顺式构型或者呈反式构型。因此,如下所示的两种几何异构体GISO-A和GISO-B由本发明的式I化合物覆盖。
出于清楚的原因,在整个说明书中仅提及几何异构体GISO-A,但其描述也包括另一几何异构体GISO-B的公开。
应注意的是本文所用术语“几何异构体”和“几何异构现象”尤其涉及就式I化合物中肟、硫肟或腙基的碳-氮双键而言的“E/Z异构体”和“E/Z异构现象”,其中E和Z构型根据应用Cahn-Ingold-Prelog优先规则的IUPAC确定。
在存在于本发明式I化合物的肟、硫肟和腙基中的碳-氮双键的情况下,E/Z-异构化的能障通常相当低,尤其是若与碳-碳双键的E/Z-异构化能障相比较的话。因此,若例如以溶液提供几何异构体GISO-A和GISO-B,则它们通常平衡存在,其中更稳定的几何异构体比更不稳定的几何异构体以更高比例存在。由于位阻原因,E-异构体通常比Z-异构体稳定并且过量存在。因此,本发明的优选实施方案是在式I化合物中,E-异构体与Z-异构体之比为至少50:50,优选至少70:30,更优选至少90:1,最优选至少99:1。在某些特别优选的实施方案中,式I化合物以E-异构体形式存在。
在一个实施方案中,本发明涉及式I化合物,其中T为O、S或NR1b。这些化合物分别对应于式I.1、式I.2和式I.3。
根据本发明优选I.1化合物。
本发明化合物可以类似于WO 2009/027393和WO 2010/034737中所述合成途径根据有机化学的标准方法制备。
其中T为O的式I.1化合物例如可以通过使式II的活化吡唑羧酸衍生物与式III的3-氨基吡啶或4-氨基哒嗪反应而制备(例如Houben-Weyl:“Methoden der organ.Chemie”[有机化学方法],Georg-Thieme-Verlag,Stuttgart,New York 1985,第E5卷,第941-1045页)。
其中R1不为氢的式I.1化合物还可以通过使用合适的烷基化剂在碱存在下烷基化其中R1为氢的酰胺I.1而制备。烷基化可以在由文献已知的标准条件下进行。
在式II和III中,各基团具有上面对式I所提到的含义,尤其是作为优选提到的含义,X为合适的离去基团如卤素、N3、对硝基苯氧基或五氟苯氧基等。
式II的活化吡唑羧酸衍生物优选为卤化物、活化酯、酸酐、叠氮化物,例如氯化物、氟化物、溴化物、对硝基苯基酯、五氟苯基酯、N-羟基琥珀酰亚胺、羟基苯并三唑-1-基酯。
式II的活化吡唑羧酸衍生物的肟、硫肟或腙基可以通过使式IV的醛或酮与式V的被保护吡唑羧酸衍生物反应而形成,其中PG为保护基团如乙基、叔丁基、苄基等。然后可以将所得产物解保护并转化成式II的活化吡唑羧酸衍生物。制备其中V为O、V为S以及V为NR1a的式II化合物的方法分别描述于WO 2013/072882,J.Org.Chem.48(20),第3531(1983)页以及JP 2013/023476中。
或者式II的活化吡唑羧酸衍生物的肟、硫肟或腙基可以通过使式VI的肟、硫肟或腙与式VII的被保护吡唑羧酸衍生物反应而形成,其中PG为保护基团如乙基、叔丁基、苄基等,并且其中X为离去基团如氯、溴、碘、甲基磺酰氧基、4-甲苯磺酰氧基等。然后可以将所得产物解保护并转化成式II的活化吡唑羧酸衍生物。根据该程序制备肟的方法例如描述于J.Med.Chem,28(7),第896页(1985)中。
式IV和VI的化合物在本领域是已知的或者可以市购或者可以通过文献中已知的方法制备。
式III、V和VII的化合物在本领域是已知的或者可以市购或者可以通过文献中已知的方法制备(参见WO 05/040169;WO 08/074824;Journal of Fluorine chemistry 132(11),第995页(2011))。
其中T为S的式I.2化合物例如可以通过使式I.1化合物与2,4-二(4-甲氧基苯基)-1,3,2,4-二硫杂二磷杂丁环-2,4-二硫化物或PS5根据Synthesis 2003,第1929页中所述方法反应而制备。
其中T为NR1b的式I.3化合物例如可以经由亚胺形成而由式I.1化合物开始制备。
在一个实施方案中,本发明涉及式I化合物,其中U为CRU,优选CH,或N。其中U为CH和U为N的化合物分别对应于式I.A和式I.B。
根据本发明特别优选式I.B化合物。
若R1为H,则式I化合物取决于U的含义可以以两种或三种互变异构形式存在。例如,若选择U为CH,正如式I.A化合物中那样,则可以形成两种互变异构体T-A和T-B。
若选择U为N,正如式I.B化合物中那样,则可以形成三种互变异构体T-A、T-B和T-C。
出于清楚的原因,在整个说明书中仅提及互变异构体T-A,但其描述也包括其他互变异构体的公开。
若R1不为H,则式I化合物取决于U的含义可以以两种或三种异构形式存在。例如,若选择U为CH,正如式I.A化合物中那样,则可以形成两种结构异构体ISO-A和ISO-B。
若选择U为N,正如式I.B化合物中那样,则可以形成三种结构异构体ISO-A、ISO-B和ISO-C。
根据本发明优选式I化合物以结构异构体ISO-A的形式存在。然而,式I化合物还可以以结构异构体ISO-B或ISO-C的形式或者以两种或更多种结构异构体ISO-A、ISO-B和ISO-C的混合物的形式存在。出于清楚的原因,在整个说明书中仅提及结构异构体ISO-A,但其描述也包括其他结构异构体的公开。
异构体ISO-C可以通过将其中R1为氢的化合物I.B烷基化而得到。该反应可以通过类似于哒嗪类的已知N-烷基化而进行。哒嗪类的N-烷基化在文献中是已知的且例如可以在J.Chem.Soc.,Perkin Trans.第1卷,第401页(1988)以及J.Org.Chem.第46卷,第2467页(1981)中找到。例如,可以将下列化合物I.B用作原料。
在另一实施方案中,本发明涉及式I化合物,其中V为O、S或NR1a。这些化合物分别对应于式I.X、式I.Y和式I.Z。取决于V的含义,这些化合物可以分别作为肟、硫肟和腙化合物提及。
根据本发明制备式I.X和I.Y化合物。特别优选式I.X化合物。
式I化合物由于取决于V的含义产生的肟、硫肟和腙结构部分而可以形成其他互变异构体。例如,若R4或R5中任一个在α-碳原子处提供氢原子,则在式I.X、I.Y和I.Z化合物中可能存在亚胺-烯胺互变异构现象,和/或若选择R1a为H,则在式I.Z化合物中可能存在偶氮-腙互变异构现象。由于肟、硫肟和腙结构部分而形成的互变异构体也由本发明式I化合物覆盖。
式I化合物的N-氧化物可以通过根据制备杂芳族N-氧化物的标准方法氧化化合物I,例如通过Journal of Organometallic Chemistry 1989,370,17-31种所述方法制备。
若各化合物不能经由上述途径制备,则可以通过衍生其他化合物I或通过所述合成途径的常规改性而制备它们。例如,在单独情况下,某些化合物I可以有利地通过酯水解、酰胺化、酯化、醚裂解、烯烃化、还原、氧化等而由其他化合物I制备。
反应混合物以常规方式后处理,例如通过与水混合、分离各相并且合适的话通过层析,例如在矾土或硅胶上层析而提纯粗产物。一些中间体和终产物可以以无色或浅棕色粘稠油形式得到,将它们在减压和温和升高的温度下除去或提纯挥发性组分。若中间体和终产物以固体得到,则它们可以通过重结晶或研制进行提纯。
术语“本发明化合物”或“式I化合物”包括本文所定义的化合物及其立体异构体、盐、互变异构体或N-氧化物。术语“本发明的化合物”应理解为等同于“本发明化合物”,因此也包括其立体异构体、盐、互变异构体或N-氧化物。
连接于式I的骨架的基团可以含有一个或多个手性中心。此时式I化合物取决于取代基以不同对映体或非对映体形式存在。本发明涉及式I的每一可能立体异构体,即单一对映体或非对映体,以及其混合物。
如上所示,式I化合物取决于肟、硫肟或腙基的碳-氮双键处的取代基构型而可能以不同几何异构体形式存在。本发明涉及式I化合物的E-和Z-异构体二者。在本发明的优选实施方案中,式I化合物以E-异构体形式存在。
如上所示,式I化合物取决于R1的位置而可能以不同结构异构体的形式存在,条件是R1不为H。本发明涉及如式I.A(R1≠H):ISO-A化合物、式I.A(R1≠H):ISO-B化合物、式I.B(R1≠H):ISO-A化合物、式I.B(R1≠H):ISO-B化合物、式I.B(R1≠H):ISO-C化合物中所示每一可能结构异构体及其混合物。
如上所示,若R1为H,若V为NR1a,其中R1a为H,和/或若R4或R5中任一个在α-碳原子处提供氢原子,则式I化合物还可以以不同互变异构体的形式存在。本发明涉及式I的每一可能互变异构体。
式I化合物可以是无定形的或者可以以一种或多种可能具有不同宏观性能如稳定性或显示不同生物学性能如活性的不同结晶状态(多晶形)存在。本发明涉及无定形和结晶的式I化合物、相应化合物I的不同结晶状态的混合物及其无定形或结晶盐。
式I化合物的盐优选为可兽用盐和/或可农用盐,优选可兽用盐。它们可以以常规方式形成,例如若式I化合物具有碱性官能团,则通过使该化合物与所述阴离子的酸反应。
式I化合物的可兽用和/或可农用盐尤其包括其阳离子和阴离子分别对式I化合物的杀害虫作用没有不利影响的那些酸的酸加成盐。
有用酸加成盐的阴离子主要是氯离子、溴离子、氟离子、硫酸氢根、硫酸根、磷酸二氢根、磷酸氢根、磷酸根、硝酸根、碳酸氢根、碳酸根、六氟硅酸根、六氟磷酸根、苯甲酸根和C1-C4链烷酸的阴离子,优选甲酸根、乙酸根、丙酸根和丁酸根。它们可以通过使式I化合物与对应阴离子的酸,优选盐酸、氢溴酸、硫酸、磷酸或硝酸反应而形成。
术语“N-氧化物”包括具有至少一个被氧化成N-氧化物结构部分的叔氮的任何式I化合物。
在各变量的上述定义中提到的有机结构部分象术语卤素一样为各基团成员的各次列举的集合性术语。前缀Cn-Cm在每种情况下表示该基团中可能的碳原子数。
术语“卤素”在每种情况下表示氟、溴、氯或碘,尤其是氟、氯或溴。
本文所用以及在烷基氨基、烷基羰基、烷硫基、烷基亚磺酰基、烷基磺酰基和烷氧基烷基的烷基结构部分中的术语“烷基”在每种情况下表示通常具有1-10个碳原子,常常是1-6个碳原子,优选1-4个碳原子,更优选1-3个碳原子的直链或支化烷基。烷基的实例为甲基、乙基、正丙基、异丙基、正丁基、2-丁基、异丁基、叔丁基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、正己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基和1-乙基-2-甲基丙基。
本文所用以及在卤代烷基羰基、卤代烷氧羰基、卤代烷硫基、卤代烷基磺酰基、卤代烷基亚磺酰基、卤代烷氧基和卤代烷氧基烷基的卤代烷基结构部分中的术语“卤代烷基”在每种情况下表示通常具有1-10个碳原子,常常是1-6个碳原子,优选1-4个碳原子的直链或支化烷基,其中该基团的氢原子部分或全部被卤原子替代。优选的卤代烷基结构部分选自C1-C4卤代烷基,更优选C1-C3卤代烷基或C1-C2卤代烷基,尤其是C1-C2氟烷基,如氟甲基、二氟甲基、三氟甲基、1-氟乙基、2-氟乙基、2,2-二氟乙基、2,2,2-三氟乙基、五氟乙基等。
本文所用术语“烷氧基”在每种情况下表示经由氧原子键合且通常具有1-10个碳原子,常常是1-6个碳原子,优选1-4个碳原子的直链或支化烷基。烷氧基的实例是甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、2-丁氧基、异丁氧基、叔丁氧基等。
本文所用术语“烷氧基烷基”是指通常包含1-10个,常常是1-4个,优选1-2个碳原子的烷基,其中1个碳原子带有如上所定义的通常包含1-4个,优选1或2个碳原子的烷氧基。实例是CH2OCH3、CH2-OC2H5、2-甲氧基乙基和2-乙氧基乙基。
本文所用术语“卤代烷氧基”在每种情况下表示具有1-10个碳原子,常常是1-6个碳原子,优选1-4个碳原子的直链或支化烷氧基,其中该基团的氢原子部分或全部被卤原子,尤其是氟原子替代。优选的卤代烷氧基结构部分包括C1-C4卤代烷氧基,尤其是C1-C2氟烷氧基,如氟甲氧基、二氟甲氧基、三氟甲氧基、1-氟乙氧基、2-氟乙氧基、2,2-二氟乙氧基、2,2,2-三氟乙氧基、2-氯-2-氟乙氧基、2-氯-2,2-二氟乙氧基、2,2-二氯-2-氟乙氧基、2,2,2-三氯乙氧基、五氟乙氧基等。
本文所用术语“烷硫基(烷基硫基:烷基-S-)”是指经由硫原子连接的具有1-10个碳原子,优选1-4个碳原子(=C1-C4烷硫基),更优选1-3个碳原子的直链或支化饱和烷基。
本文所用术语“卤代烷硫基”是指如上所述的烷硫基,其中氢原子部分或全部被氟、氯、溴和/或碘替代。
本文所用术语“烷基亚磺酰基(烷基次硫酸基:C1-C6烷基-S(=O)-)”是指通过亚磺酰基的硫原子在烷基中的任何位置键合的具有1-10个碳原子,优选1-4个碳原子(=C1-C4烷基亚磺酰基),更优选1-3个碳原子的直链或支化饱和烷基(如上所述)。
本文所用术语“卤代烷基亚磺酰基”是指如上所述的烷基亚磺酰基,其中氢原子部分或全部被氟、氯、溴和/或碘替代。
本文所用术语“烷基磺酰基(烷基-S(=O)2-)”是指经由磺酰基的硫原子在烷基中的任何位置键合的具有1-10个碳原子,优选1-4个碳原子(=C1-C4烷基磺酰基),更优选1-3个碳原子的直链或支化饱和烷基(如上所述)。
本文所用术语“卤代烷基磺酰基”是指如上所述的烷基磺酰基,其中氢原子部分或全部被氟、氯、溴和/或碘替代。
术语“烷基羰基”是指如上所定义的烷基,其经由羰基(C=O)的碳原子与该分子的其余部分键合。
术语“卤代烷基羰基”是指如上所述的烷基羰基,其中氢原子部分或全部被氟、氯、溴和/或碘替代。
术语“烷氧羰基”是指如上所定义的烷基,其经由氧原子与该分子的其余部分键合。
术语“卤代烷氧羰基”是指如上所述的烷氧羰基,其中氢原子部分或全部被氟、氯、溴和/或碘替代。
本文所用术语“链烯基”在每种情况下表示通常具有2-10个,常常是2-6个,优选2-4个碳原子的单不饱和烃基,例如乙烯基、烯丙基(2-丙烯-1-基)、1-丙烯-1-基、2-丙烯-2-基、甲代烯丙基(2-甲基丙-2-烯-1-基)、2-丁烯-1-基、3-丁烯-1-基、2-戊烯-1-基、3-戊烯-1-基、4-戊烯-1-基、1-甲基丁-2-烯-1-基、2-乙基丙-2-烯-1-基等。
本文所用术语“卤代链烯基”是指如上所定义的链烯基,其中氢原子部分或全部被卤原子替代。
本文所用术语“炔基”在每种情况下表示通常具有2-10个,常常是2-6个,优选2-4个碳原子的单不饱和烃基,例如乙炔基、炔丙基(2-丙炔-1-基)、1-丙炔-1-基、1-甲基丙-2-炔-1-基)、2-丁炔-1-基、3-丁炔-1-基、1-戊炔-1-基、3-戊炔-1-基、4-戊炔-1-基、1-甲基丁-2-炔-1-基、1-乙基丙-2-炔-1-基等。
本文所用术语“卤代炔基”是指如上所定义的炔基,其中氢原子部分或全部被卤原子替代。
本文所用以及在环烷氧基和环烷基甲基的环烷基结构部分中的术语“环烷基”在每种情况下表示通常具有3-10个或3-6个碳原子的单环脂环族基团,如环丙基、换丁基、环戊基、环己基、环庚基、环辛基、环壬基和环癸基或环丙基、环丁基、环戊基和环己基。
本文所用以及在卤代环烷氧基的卤代环烷基结构部分中的术语“卤代环烷基”在每种情况下表示通常具有3-10个碳原子或3-6个碳原子的单环脂环族基团,其中至少一个,例如1、2、3、4或5个氢原子被卤素,尤其是氟或氯替代。实例是1-和2-氟环丙基,1,2-、2,2-和2,3-二氟环丙基,1,2,2-三氟环丙基,2,2,3,3-四氟环丙基,1-和2-氯环丙基,1,2-、2,2-和2,3-二氯环丙基,1,2,2-三氯环丙基,2,2,3,3-四氯环丙基,1-、2-和3-氟环戊基,1,2-、2,2-、2,3-、3,3-、3,4-、2,5-二氟环戊基,1-、2-和3-氯环戊基,1,2-、2,2-、2,3-、3,3-、3,4-、2,5-二氯环戊基等。
术语“环烷氧基”是指如上所定义的环烷基,其经由氧原子与该分子的其余部分键合。
术语“卤代环烷氧基”是指如上所定义的卤代环烷基,其经由氧原子与该分子的其余部分键合。
术语“环烷基烷基”是指如上所定义的环烷基,其经由烷基如C1-C5烷基或C1-C4烷基,尤其是甲基(=环烷基甲基)与该分子的其余部分键合。
本文所用术语“环烯基”在每种情况下表示通常具有5-10个或3-8个碳原子的单环单不饱和非芳族基团,例如包括环庚烯基或环辛烯基。
术语“杂环基”通常包括5或6员,尤其是6员单环杂环非芳族基团。杂环非芳族基团通常包含1、2或3个选自N、O和S的杂原子作为环成员,其中作为环成员的S原子可以作为S、SO或SO2存在。5或6员杂环基团的实例包括饱和或不饱和非芳族杂环,如环氧乙烷基、氧杂环丁烷基、硫杂环丁烷基、硫杂环丁烷基-S-氧化物(S-氧代硫杂环丁烷基)、硫杂环丁烷基-S-二氧化物(S-二氧代硫杂环丁烷基)、吡咯烷基、吡咯啉基、吡唑啉基、四氢呋喃基、二氢呋喃基、1,3-二氧戊环基、四氢噻吩基、S-氧代四氢噻吩基、S-二氧代四氢噻吩基、二氢噻吩基、S-氧代二氢噻吩基、S-二氧代二氢噻吩基、唑烷基、唑啉基、噻唑啉基、氧杂四氢噻吩基、哌啶基、哌嗪基、吡喃基、二氢吡喃基、四氢吡喃基、1,3-和1,4-二烷基、噻喃基、S-氧代噻喃基、S-二氧代噻喃基、二氢噻喃基、S-氧代二氢噻喃基、S-二氧代二氢噻喃基、四氢噻喃基、S-氧代四氢噻喃基、S-二氧代四氢噻喃基、吗啉基、硫吗啉基、S-氧代硫吗啉基、S-二氧代硫吗啉基、噻嗪基等。还包含1或2个羰基作为环成员的杂环的实例包括吡咯烷-2-酮基、吡咯烷-2,5-二酮基、咪唑烷-2-酮基、唑烷-2-酮基、噻唑烷-2-酮基等。
术语“杂芳基”包括包含1、2、3或4个选自N、O和S的杂原子作为环成员的5或6员单环杂芳族基团。5或6员杂芳族基团的实例包括吡啶基,即2-、3-或4-吡啶基,嘧啶基,即2-、4-或5-嘧啶基,吡嗪基,哒嗪基,即3-或4-哒嗪基,噻吩基,即2-或3-噻吩基,呋喃基,即2-或3-呋喃基,吡咯基,即2-或3-吡咯基,唑基,即2-、3-或5-唑基,异唑基,即3-、4-或5-异唑基,噻唑基,即2-、3-或5-噻唑基,异噻唑基,即3-、4-或5-异噻唑基,吡唑基,即1-、3-、4-或5-吡唑基,即1-、2-、4-或5-咪唑基,二唑基,例如2-或5-[1,3,4]二唑基,4-或5-(1,2,3-二唑)基,3-或5-(1,2,4-二唑)基,2-或5-(1,3,4-噻二唑)基,噻二唑基,例如2-或5-(1,3,4-噻二唑)基,4-或5-(1,2,3-噻二唑)基,3-或5-(1,2,4-噻二唑)基,三唑基,例如1H-、2H-或3H-1,2,3-三唑-4-基,2H-三唑-3-基,1H-、2H-或4H-1,2,4-三唑基,以及四唑基,即1H-或2H-四唑基。术语“杂芳基”还包括包含1、2或3个选自N、O和S的杂原子作为环成员的8-10员双环杂芳族基团,其中5或6员杂芳族环稠合于苯基环或5或6员杂芳族基团。稠合于苯基环或5或6员杂芳族基团5或6员杂芳族环的实例包括苯并呋喃基、苯并噻吩基、吲哚基、吲唑基、苯并咪唑基、苯并噻唑基、苯并二唑基、苯并噻二唑基、苯并嗪基、喹啉基、异喹啉基、嘌呤基、1,8-二氮杂萘基、蝶啶基、吡啶并[3,2-d]嘧啶基或吡啶并咪唑基等。这些稠合杂芳基可以经由5或6员杂芳族环的任何环原子或者经由稠合苯基结构部分的碳原子键合于该分子的其余部分。
术语“杂环氧基”和“苯氧基”是指如上所定义的杂环基和苯基,其经由氧原子与该分子的其余部分键合。
术语“杂环基磺酰基”、“苯基磺酰基”和“杂芳基磺酰基”分别是指如上所定义的杂环基、苯基和如上所定义的杂芳基,其经由磺酰基的硫原子与该分子的其余部分键合。
术语“杂环基羰基”、“苯基羰基”和“杂芳基羰基”分别是指如上所定义的杂环基、苯基和如上所定义的杂芳基,其经由羰基(C=O)的碳原子与该分子的其余部分键合。
术语“杂环基烷基”和“杂芳基烷基”分别是指如上所定义的杂环基或杂芳基,其经由C1-C5烷基或C1-C4烷基,尤其是甲基(=杂环基甲基或杂芳基甲基)与该分子的其余部分键合。
术语“苯基烷基”是指苯基,其经由C1-C5烷基或C1-C4烷基,尤其是甲基(=苯基甲基)与该分子的其余部分键合,实例包括苄基、1-苯基乙基、2-苯基乙基、2-苯氧基乙基等。
术语“杂环基烷基”通常包括3-8员,尤其是6员单环饱和非芳族杂环基团。非芳族杂环基团通常包含1、2或3个选自N、O和S的杂原子作为环成员,其中作为环成员的S原子可以作为S、SO或SO2存在。
术语“杂环烯基”通常包括3-8员,尤其是6员单环单不饱和非芳族杂环基团。非芳族杂环基团通常包含1、2或3选自N、O和S的杂原子作为环成员,其中作为环成员的S原子可以作为S、SO或SO2存在。
术语“亚烷基”、“亚环烷基”、“亚杂环烷基”、“亚链烯基”、“亚环烯基”、“亚杂环烯基”和“亚炔基”分别是指如上所定义的烷基、环烷基、杂环烷基、链烯基、环烯基、杂环烯基和炔基,它们经由相应基团的两个原子,优选经由两个碳原子键合于该分子的其余部分。
术语“碳环”通常包括包含3-8个或5-8个,优选5或6个碳原子的3-8员或5-8员,优选5或6员单环非芳族环。
术语“杂环”通常包括如上面对“碳环”所述的3-8员或5-8员,优选5或6员单环非芳族环,其包含1、2或3个选自N、O和S的杂原子作为环成员,其中作为环成员的S原子可以作为S、SO或SO2存在。
对于各变量,中间体的特别优选实施方案对应于式I化合物的那些。
在特殊实施方案中,式I化合物的各变量具有下列含义,其中这些含义单独和相互组合均为式I化合物的特殊实施方案:
在优选实施方案中,本发明涉及其中T为O的式I化合物,即如上所示的式I.1化合物。
在另一优选实施方案中,本发明涉及其中U为CH或N的式I化合物,即如上所示的式I.A和I.B化合物。根据本发明特别优选其中U为N的式I化合物,即式I.B化合物。
在另一优选实施方案中,本发明涉及其中V为O或S的式I化合物,即如上所示的式I.X和I.Y化合物。
在式I化合物的优选实施方案中,RP1、RP2和RP3为H。这些化合物对应于式I*。
式I*化合物还可以由下式I*表示,其中RN表示在吡唑环的氮原子处的(R5)(R4)C=N-V-D-取代基。
在式I化合物的另一优选实施方案中,R1为H、C1-C2烷基或C1-C2烷氧基-C1-C2烷基,优选C1-C2烷基。
在式I化合物的另一优选实施方案中,R2和R3相互独立地选自H、卤素、CN、C1-C4烷基、C1-C4卤代烷基、C3-C4环烷基、C3-C4卤代环烷基、ORa和SRa,其中Ra为C1-C4烷基、C1-C4卤代烷基、C3-C4环烷基或C3-C4卤代环烷基。优选R2为C1-C2烷基、C1-C2卤代烷基、C3环烷基或C3卤代环烷基,更优选R2为CH3或卤代甲基。优选R3为H。
在式I化合物的第一优选实施方案中,R4为H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6环烷基甲基,并且R5为C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6环烷基甲基,其中在每种情况下C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6环烷基甲基可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代。
在式I化合物的第二优选实施方案中,R4和R5均独立地选自C1-C4烷基-X,其中X选自O、S或NRB。
在式I化合物的第三优选实施方案中,R4和R5与它们所键合的碳原子一起形成可以含有1或2个相互独立地选自NRB、O和S的杂原子的非芳族5-6员碳环或杂环,其中S可以被氧化,和/或其中该碳环或杂环可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代。
在式I化合物的另一优选实施方案中,D为C1-C8亚烷基、C3-C8亚环烷基或C3-C8亚杂环烷基,优选C2-C8亚烷基,其中D可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代。优选D为支化C2-C8亚烷基,更优选α-支化C2-C8亚烷基,其中C2-C8亚烷基可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代。特别优选D为CH(CH3)CH2,其中优选CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀。
在第一优选实施方案中,RA为卤素、CN、C1-C2烷基、C1-C2卤代烷基、C1-C2烷氧基、C1-C2卤代烷氧基、C3-C4环烷基、C3-C4卤代环烷基、C3-C4环烷氧基或C3-C4卤代环烷氧基。
在第二优选实施方案中,两个RA键合于相同碳原子且与它们所键合的碳原子一起形成环丙烷。
在优选实施方案中,RB为H、C1-C2烷基、C1-C2卤代烷基或C3-C6环烷基。
鉴于上面情况,本发明优选涉及式I化合物,
·其中T为O,U为CH,V为O且RP1、RP2和RP3为H,即式I*.1.A.X化合物;
·其中T为O,U为N,V为O且RP1、RP2和RP3为H,即式I*.1.B.X化合物;
·其中T为O,U为CH,V为S且RP1、RP2和RP3为H,即式I*.1.A.Y化合物;或者
·其中T为O,U为N,V为S且RP1、RP2和RP3为H,即式I*.1.A.Y化合物。
尤其考虑到其用途,优选汇编在下表中的式I化合物,这些化合物对应于式I.1,尤其分别为式I*.1.A.X、I*.1.B.X、I*.1.A.Y和I*.1.B.Y化合物(表1-9覆盖式I*.1.A.X,表10-18覆盖式I*.1.B.X化合物,表19-27覆盖式I*.1.A.Y化合物以及表28-36覆盖式I*.1.B.Y化合物)。此外,对表中取代基所提到的基团各自本身为所述取代基的特别优选实施方案,与其中提到它的组合无关。
表1
其中U为CH,V为O,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表2
其中U为CH,V为O,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表3
其中U为CH,V为O,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表4
其中U为CH,V为O,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表5
其中U为CH,V为O,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表6
其中U为CH,V为O,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表7
其中U为CH,V为O,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表8
其中U为CH,V为O,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表9
其中U为CH,V为O,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表10
其中U为N,V为O,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表11
其中U为N,V为O,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表12
其中U为N,V为O,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表13
其中U为N,V为O,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表14
其中U为N,V为O,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表15
其中U为N,V为O,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表16
其中U为N,V为O,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表17
其中U为N,V为O,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表18
其中U为N,V为O,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表19
其中U为CH,V为S,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表20
其中U为CH,V为S,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表21
其中U为CH,V为S,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表22
其中U为CH,V为S,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表23
其中U为CH,V为S,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表24
其中U为CH,V为S,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表25
其中U为CH,V为S,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表26
其中U为CH,V为S,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表27
其中U为CH,V为S,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表28
其中U为N,V为S,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表29
其中U为N,V为S,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表30
其中U为N,V为S,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表31
其中U为N,V为S,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表32
其中U为N,V为S,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表33
其中U为N,V为S,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2CH2且R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表34
其中U为N,V为S,RP1、RP2和RP3为H,R1为H,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表35
其中U为N,V为S,RP1、RP2和RP3为H,R1为CH3,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表36
其中U为N,V为S,RP1、RP2和RP3为H,R1为CH2CH3,R3为H,D为CH2CH(CH3),其中CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀,并且其中R2、R4和R5的组合对化合物而言在每种情况下对应于表A的一行的式I.1化合物
表A
本发明还涉及至少一种本发明化合物与至少一种下文所定义的混合配对的混合物。优选一种作为组分I的本发明化合物与一种作为组分II的下文所定义的混合配对的二元混合物。该二元混合物的优选重量比为5000:1-1:5000,优选1000:1-1:1000,更优选100:1-1:100,特别优选10:1-1:10。在该二元混合物中,组分I和II可以等量使用,或者可以使用过量的组分I或过量的组分II。
混合配对可以选自农药,尤其是杀虫剂、杀线虫剂和杀螨剂,杀真菌剂,除草剂,植物生长调节剂,肥料等。优选的混合配对是杀虫剂、杀线虫剂和杀真菌剂。
根据the Mode of Action Classification of the Insecticide ResistanceAction Committee(IRAC)分类和编号的本发明化合物可以与其一起使用并且可能产生潜在的协同增效效果的农药的下列列举M用来说明可能的组合,而不施加任何限制:
M.1选自如下的乙酰胆碱酯酶(AChE)抑制剂:
M.1A氨基甲酸酯类,例如涕灭威(aldicarb)、棉铃威(alanycarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、丁酮威(butocarboxim)、丁酮氧威(butoxycarboxim)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、苯虫威(ethiofencarb)、仲丁威(fenobucarb)、抗螨脒(formetanate)、呋线威(furathiocarb)、异丙威(isoprocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、速灭威(metolcarb)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、久效威(thiofanox)、混杀威(trimethacarb)、XMC、灭杀威(xylylcarb)和唑蚜威(triazamate);或者
M.1B有机磷酸酯类,例如高灭磷(acephate)、唑啶磷(azamethiphos)、乙基谷硫磷(azinphos-ethyl)、谷硫磷(azinphosmethyl)、硫线磷(cadusafos)、氯氧磷(chlorethoxyfos)、毒虫畏(chlorfenvinphos)、氯甲硫磷(chlormephos)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、蝇毒磷(coumaphos)、杀螟腈(cyanophos)、甲基内吸磷(demeton-S-methyl)、二嗪农(diazinon)、敌敌畏(dichlorvos/DDVP)、百治磷(dicrotophos)、乐果(dimethoate)、甲基毒虫畏(dimethylvinphos)、乙拌磷(disulfoton)、EPN、乙硫磷(ethion)、丙线磷(ethoprophos)、伐灭磷(famphur)、苯线磷(fenamiphos)、杀螟松(fenitrothion)、倍硫磷(fenthion)、噻唑硫磷(fosthiazate)、庚烯磷(heptenophos)、新烟碱类(imicyafos)、异丙胺磷(isofenphos)、O-(甲氧基氨基硫代磷酰基)水杨酸异丙酯、异唑磷(isoxathion)、马拉硫磷(malathion)、灭蚜磷(mecarbam)、甲胺磷(methamidophos)、杀扑磷(methidathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、二溴磷(naled)、氧乐果(omethoate)、砜吸磷(oxydemeton-methyl)、一六零五(parathion)、甲基对硫磷(parathion-methyl)、稻丰散(phenthoate)、甲拌磷(phorate)、伏杀磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、巴胺磷(propetamphos)、丙硫磷(prothiofos)、吡唑硫磷(pyraclofos)、哒嗪硫磷(pyridaphenthion)、喹硫磷(quinalphos)、治螟磷(sulfotep)、丁基嘧啶磷(tebupirimfos)、双硫磷(temephos)、特丁磷(terbufos)、杀虫威(tetrachlorvinphos)、甲基乙拌磷(thiometon)、三唑磷(triazophos)、敌百虫(trichlorfon)和蚜灭磷(vamidothion);
M.2.GABA门控氯离子通道拮抗剂,如
M.2A环二烯有机氯化合物,例如硫丹(endosulfan)或氯丹(chlordane);或
M.2B fiproles(苯基吡唑类),例如乙虫腈(ethiprole)、锐劲特(fipronil)、丁烯氟虫腈(flufiprole)、pyrafluprole和pyriprole;
M.3选自如下的钠通道调节剂:
M.3A合成除虫菊酯类,例如氟丙菊酯(acrinathrin)、丙烯除虫菊(allethrin)、右旋丙烯菊酯(d-cis-trans allethrin)、右旋反式丙烯菊酯(d-trans allethrin)、氟氯菊酯(bifenthrin)、生物烯丙菊酯(bioallethrin)、2-环戊烯基生物烯丙菊酯(bioallethrinS-cyclopentenyl)、生物苄呋菊酯(bioresmethrin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、高效氟氯氰菊酯(beta-cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、氯氟氰菊酯(lambda-cyhalothrin)、精高效氯氟氰菊酯(gamma-cyhalothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、高效反式氯氰菊酯(theta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、苯醚氰菊酯(cyphenothrin)、溴氰菊酯(deltamethrin)、烯炔菊酯(empenthrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、氟氰戊菊酯(flucythrinate)、氟氯苯菊酯(flumethrin)、氟胺氰菊酯(tau-fluvalinate)、溴氟醚菊酯(halfenprox)、heptafluthrin、咪炔菊酯(imiprothrin)、氯氟醚菊酯(meperfluthrin)、甲氧苄氟菊酯(metofluthrin)、momfluorothrin、氯菊酯(permethrin)、苯醚菊酯(phenothrin)、炔酮菊酯(prallethrin)、丙氟菊酯(profluthrin)、除虫菊酯(pyrethrin(除虫菊(pyrethrum)))、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、七氟菊酯(tefluthrin)、四氟醚菊酯(tetramethylfluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)和四氟菊酯(transfluthrin);或
M.3B钠通道调节剂如DDT或甲氧滴滴涕(methoxychlor);
M.4选自如下的烟碱型乙酰胆碱受体激动剂(nAChR):
M.4A新烟碱类,例如吡虫清(acetamiprid)、噻虫胺(chlothianidin)、环氧虫啶(cycloxaprid)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、硝胺烯啶(nitenpyram)、噻虫啉(thiacloprid)和噻虫嗪(thiamethoxam);或化合物
M.4A.2:(2E-)-1-[(6-氯吡啶-3-基)甲基]-N'-硝基-2-亚戊基氨基胍;或
M.4A.3:1-[(6-氯吡啶-3-基)甲基]-7-甲基-8-硝基-5-丙氧基-1,2,3,5,6,7-六氢咪唑并[1,2-a]吡啶;或
M.4B:烟碱(nicotine)类;
M.5选自多杀菌素类别的烟碱型乙酰胆碱受体变构活化剂,例如艾克敌105(spinosad)或乙基多杀菌素(spinetoram);
M.6选自阿维菌素和米尔倍霉素类别的氯离子通道活化剂,例如齐墩螨素(abamectin)、甲氨基阿维菌素苯甲酸盐(emamectin benzoate)、伊维菌素(ivermectin)、lepimectin或米尔螨素(milbemectin);
M.7保幼激素模拟物,如
M.7A保幼激素类似物,如蒙512(hydroprene)、烯虫炔酯(kinoprene)和蒙五一五(methoprene);或其他如
M.7B双氧威(fenoxycarb),或
M.7C蚊蝇醚(pyriproxyfen);
M.8其他非特异性(多位点)抑制剂,例如
M.8A烷基卤化物如溴甲烷和其他烷基卤化物,或
M.8B氯化苦(chloropicrin),或
M.8C磺酰氟(sulfuryl fluoride),或
M.8D硼砂,或
M.8E酒石酸氧锑钾(tartar emetic);
M.9选择性同翅目昆虫进食阻断剂,例如
M.9B拒嗪酮(pymetrozine),或
M.9C氟啶虫酰胺(flonicamid);
M.10螨虫生长抑制剂,例如
M.10A四螨嗪(clofentezine)、噻螨酮(hexythiazox)和氟螨嗪(diflovidazin),或
M.10B特苯唑(etoxazole);
M.11昆虫中肠膜的微生物干扰剂,例如苏云金芽孢杆菌(bacillusthuringiensis)或球形芽孢杆菌(bacillus sphaericus)以及它们产生的杀虫蛋白如苏云金芽孢杆菌以色列亚种(bacillus thuringiensis subsp.Israelensis)、球形芽孢杆菌、苏云金芽胞杆菌鲇泽亚种(bacillus thuringiensis subsp.aizawai)、苏云金芽胞杆菌库尔斯塔克亚种(bacillus thuringiensis subsp.kurstaki)和苏云金芽胞杆菌拟步行甲亚种菌株(bacillus thuringiensis subsp.tenebrionis),或Bt作物蛋白:Cry1Ab,Cry1Ac,Cry1Fa,Cry2Ab,mCry3A,Cry3Ab,Cry3Bb和Cry34/35Ab1;
M.12线粒体ATP合成酶抑制剂,如
M.12A杀螨硫隆(diafenthiuron),或
M.12B有机锡杀螨剂,如三唑锡(azocyclotin)、三环锡(cyhexatin)或杀螨锡(fenbutatin oxide),或
M.12C克螨特(propargite),或
M.12D三氯杀螨砜(tetradifon);
M.13经由质子梯度干扰的氧化磷酸化去偶剂,例如氟唑虫清(chlorfenapyr)、二硝酚(DNOC)或氟虫胺(sulfluramid);
M.14烟碱型乙酰胆碱受体(nAChR)通道阻断剂,例如沙蚕毒素类似物,如杀虫磺(bensultap)、杀螟丹(cartap hydrochloride)、杀虫环(thiocyclam)或杀虫双(thiosultap sodium);
M.15类型0几丁质生物合成抑制剂如苯甲酰脲类,如双三氟虫脲(bistrifluron)、定虫隆(chlorfluazuron)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、多氟虫酰脲(noviflumuron)、伏虫隆(teflubenzuron)或杀虫隆(triflumuron);
M.16类型1几丁质生物合成抑制剂如噻嗪酮(buprofezin);
M.17双翅目昆虫蜕皮干扰剂,例如灭蝇胺(cyromazine);
M.18蜕皮素受体激动剂如二酰肼类,例如甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、特丁苯酰肼(halofenozide)、呋喃虫酰肼(fufenozide)或环虫酰肼(chromafenozide);
M.19章鱼胺受体激动剂(Octopamin receptor agonsit),例如双甲脒(amitraz);
M.20线粒体配合物III电子传输抑制剂,例如
M.20A灭蚁腙(hydramethylnon),或
M.20B灭螨醌(acequinocyl),或
M.20C嘧螨酯(fluacrypyrim);
M.21线粒体配合物I电子传输抑制剂,例如
M.21A METI杀螨剂和杀虫剂,如喹螨醚(fenazaquin)、唑螨酯(fenpyroximate)、嘧螨醚(pyrimidifen)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)或唑虫酰胺(tolfenpyrad),或
M.21B鱼藤酮(rotenone);
M.22电压依赖性钠通道阻断剂,例如
M.22A二唑虫(indoxacarb),或
M.22B氰氟虫胺(metaflumizone);或
M.22B.1:2-[2-(4-氰基苯基)-1-[3-三氟甲基苯基]亚乙基]-N-[4-(二氟甲氧基)苯基]氨基脲;或
M.22B.2:N-(3-氯-2-甲基苯基)-2-[(4-氯苯基)[4-[甲基(甲基磺酰基)氨基]苯基]亚甲基]氨基脲;
M.23乙酰CoA羧化酶抑制剂,如季酮酸和四氨基酸(Tetramic acid)衍生物,例如螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)或螺虫乙酯(spirotetramat);
M.24线粒体配合物IV电子传输抑制剂,例如
M.24A膦类如磷化铝、磷化钙、膦或磷化锌,或
M.24B氰化物;
M.25线粒体配合物II电子传输抑制剂,如β-酮腈衍生物,例如腈吡螨酯(cyenopyrafen)或丁氟螨酯(cyflumetofen);
M.28选自二酰胺类的鱼尼汀(Ryanodine)受体调节剂,例如氟虫酰胺(flubendiamide)、氯虫酰胺(chlorantraniliprole)氰虫酰胺(cyantraniliprole)氟氰虫酰胺(tetraniliprole)或邻苯二甲酰胺化合物
M.28.1:(R)-3-氯-N1-{2-甲基-4-[1,2,2,2-四氟-1-三氟甲基乙基]苯基}-N2-(1-甲基-2-甲基磺酰基乙基)邻苯二甲酰胺,和
M.28.2:(S)-3-氯-N1-{2-甲基-4-[1,2,2,2-四氟-1-三氟甲基乙基]苯基}-N2-(1-甲基-2-甲基磺酰基乙基)邻苯二甲酰胺,或化合物
M.28.3:3-溴-N-{2-溴-4-氯-6-[(1-环丙基乙基)氨基甲酰基]苯基}-1-(3-氯吡啶-2-基)-1H-吡唑-5-甲酰胺(建议的ISO名:cyclaniliprole),或化合物
M.28.4:2-[3,5-二溴-2-({[3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基]羰基}氨基)苯甲酰基]-1,2-二甲基肼甲酸甲酯;或选自M.28.5a)-M.28.5d)和M.28.5h)-M.28.5l)的化合物:
M.28.5a)N-[4,6-二氯-2-[(二乙基-λ-4-亚硫烷基(sulfanylidene))氨基甲酰基]苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;
M.28.5b)N-[4-氯-2-[(二乙基-λ-4-亚硫烷基)氨基甲酰基]-6-甲基苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;
M.28.5c)N-[4-氯-2-[(二-2-丙基-λ-4-亚硫烷基)氨基甲酰基]-6-甲基苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;
M.28.5d)N-[4,6-二氯-2-[(二-2-丙基-λ-4-亚硫烷基)氨基甲酰基]苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;
M.28.5h)N-[4,6-二溴-2-[(二乙基-λ-4-亚硫烷基)氨基甲酰基]苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;
M.28.5i)N-[2-(5-氨基-1,3,4-噻二唑-2-基)-4-氯-6-甲基苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺;
M.28.5j)3-氯-1-(3-氯-2-吡啶基)-N-[2,4-二氯-6-[[(1-氰基-1-甲基乙基)氨基]羰基]苯基]-1H-吡唑-5-甲酰胺;
M.28.5k)3-溴-N-[2,4-二氯-6-(甲基氨基甲酰基)苯基]-1-(3,5-二氯-2-吡啶基)-1H-吡唑-5-甲酰胺;
M.28.5l)N-[4-氯-2-[[(1,1-二甲基乙基)氨基]羰基]]-6-甲基苯基]-1-(3-氯-2-吡啶基)-3-(氟甲氧基)-1H-吡唑-5-甲酰胺;
或选自如下的化合物:
M.28.6:N-(2-氰基丙-2-基)-N-(2,4-二甲基苯基)-3-碘苯-1,2-二甲酰胺;或
M.28.7:3-氯-N-(2-氰基丙-2-基)-N-(2,4-二甲基苯基)-苯-1,2-二甲酰胺;
M.29.未知或不确定作用模式的杀虫活性化合物,例如afidopyropen、afoxolaner、印楝素(azadirachtin)、磺胺螨酯(amidoflumet)、苯螨特(benzoximate)、联苯肼酯(bifenazate)、broflanilide、溴螨酯(bromopropylate)、喹菌酮(chinomethionat)、冰晶石(cryolite)、dicloromezotiaz、三氯杀螨醇(dicofol)、嘧虫胺(flufenerim)、flometoquin、氟噻虫砜(fluensulfone)、fluhexafon、氟吡菌酰胺(fluopyram)、flupyradifurone、fluralaner、虫酮(metoxadiazone)、增效醚(piperonyl butoxide)、pyflubumide、啶虫丙醚(pyridalyl)、pyrifluquinazon、氟啶虫胺腈(sulfoxaflor)、tioxazafen、triflumezopyrim,或化合物
M.29.3:11-(4-氯-2,6-二甲基苯基)-12-羟基-1,4-二氧杂-9-氮杂二螺[4.2.4.2]十四碳-11-烯-10-酮,或化合物
M.29.4:3-(4'-氟-2,4-二甲基联苯-3-基)-4-羟基-8-氧杂-1-氮杂螺[4.5]癸-3-烯-2-酮,或化合物
M.29.5:1-[2-氟-4-甲基-5-[(2,2,2-三氟乙基)亚磺酰基]苯基]-3-三氟甲基-1H-1,2,4-三唑-5-胺或基于坚强芽孢杆菌(bacillus firmus)的活性物(Votivo,I-1582);或选自M.29.6组的化合物,其中该化合物选自M.29.6a)至M.29.6k):
M.29.6a)(E/Z)-N-[1-[(6-氯-3-吡啶基)甲基]-2-亚吡啶基]-2,2,2-三氟乙酰胺;
M.29.6b)(E/Z)-N-[1-[(6-氯-5-氟-3-吡啶基)甲基]-2-亚吡啶基]-2,2,2-三氟乙酰胺;
M.29.6c)(E/Z)-2,2,2-三氟-N-[1-[(6-氟-3-吡啶基)甲基]-2-亚吡啶基]乙酰胺;
M.29.6d)(E/Z)-N-[1-[(6-溴-3-吡啶基)甲基]-2-亚吡啶基]-2,2,2-三氟乙酰胺;
M.29.6e)(E/Z)-N-[1-[1-(6-氯-3-吡啶基)乙基]-2-亚吡啶基]-2,2,2-三氟乙酰胺;
M.29.6f)(E/Z)-N-[1-[(6-氯-3-吡啶基)甲基]-2-亚吡啶基]-2,2-二氟乙酰胺;
M.29.6g)(E/Z)-2-氯-N-[1-[(6-氯-3-吡啶基)甲基]-2-亚吡啶基]-2,2-二氟乙酰胺;
M.29.6h)(E/Z)-N-[1-[(2-氯嘧啶-5-基)甲基]-2-亚吡啶基]-2,2,2-三氟乙酰胺;
M.29.6i)(E/Z)-N-[1-[(6-氯-3-吡啶基)甲基]-2-亚吡啶基]-2,2,3,3,3-五氟丙酰胺;
M.29.6j)N-[1-[(6-氯-3-吡啶基)甲基]-2-亚吡啶基]-2,2,2-三氟硫代乙酰胺;或
M.29.6k)N-[1-[(6-氯-3-吡啶基)甲基]-2-亚吡啶基]-2,2,2-三氟-N'-异丙基乙酰胺;或化合物
M.29.8:8-氯-N-[2-氯-5-甲氧基苯基)磺酰基]-6-三氟甲基)-咪唑并[1,2-a]吡啶-2-甲酰胺;或化合物
M.29.9a):4-[5-(3,5-二氯苯基)-5-三氟甲基-4H-异唑-3-基]-2-甲基-N-(1-氧代硫杂丁环-3-基)苯甲酰胺;或
M.29.9.b):4-[5-(3,5-二氯苯基)-5-三氟甲基-4H-二氢异唑-3-基]-N-[(甲氧亚氨基)甲基]-2-甲基苯甲酰胺;或
M.29.10:5-[3-[2,6-二氯-4-(3,3-二氯烯丙氧基)苯氧基]丙氧基]-1H-吡唑;或选自M.29.11组的化合物,其中该化合物选自M.29.11b)至M.29.11p):
M.29.11.b)3-(苯甲酰基甲基氨基)-N-[2-溴-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]-6-三氟甲基苯基]-2-氟苯甲酰胺;
M.29.11.c)3-(苯甲酰基甲基氨基)-2-氟-N-[2-碘-4-[1,2,2,2-四氟-1-三氟甲基乙基]-6-三氟甲基苯基]苯甲酰胺;
M.29.11.d)N-[3-[[[2-碘-4-[1,2,2,2-四氟-1-三氟甲基乙基]-6-三氟甲基苯基]氨基]羰基]苯基]-N-甲基苯甲酰胺;
M.29.11.e)N-[3-[[[2-溴-4-[1,2,2,2-四氟-1-三氟甲基乙基]-6-三氟甲基苯基]氨基]羰基]]-2-氟苯基]-4-氟-N-甲基苯甲酰胺;
M.29.11.f)4-氟-N-[2-氟-3-[[[2-碘-4-[1,2,2,2-四氟-1-三氟甲基乙基]-6-三氟甲基苯基]氨基]羰基]苯基]-N-甲基苯甲酰胺;
M.29.11.g)3-氟-N-[2-氟-3-[[[2-碘-4-[1,2,2,2-四氟-1-三氟甲基乙基]-6-三氟甲基苯基]氨基]羰基]苯基]-N-甲基苯甲酰胺;
M.29.11.h)2-氯-N-[3-[[[2-碘-4-[1,2,2,2-四氟-1-三氟甲基乙基]-6-三氟甲基苯基]氨基]羰基]苯基]-3-吡啶甲酰胺;
M.29.11.i)4-氰基-N-[2-氰基-5-[[2,6-二溴-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]氨基甲酰基]苯基]-2-甲基苯甲酰胺;
M.29.11.j)4-氰基-3-[(4-氰基-2-甲基苯甲酰基)氨基]-N-[2,6-二氯-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]-2-氟苯甲酰胺;
M.29.11.k)N-[5-[[2-氯-6-氰基-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]氨基甲酰基]-2-氰基苯基]-4-氰基-2-甲基苯甲酰胺;
M.29.11.l)N-[5-[[2-溴-6-氯-4-[2,2,2-三氟-1-羟基-1-三氟甲基乙基]苯基]氨基甲酰基]-2-氰基苯基]-4-氰基-2-甲基苯甲酰胺;
M.29.11.m)N-[5-[[2-溴-6-氯-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]氨基甲酰基]-2-氰基苯基]-4-氰基-2-甲基苯甲酰胺;
M.29.11.n)4-氰基-N-[2-氰基-5-[[2,6-二氯-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]氨基甲酰基]苯基]-2-甲基苯甲酰胺;
M.29.11.o)4-氰基-N-[2-氰基-5-[[2,6-二氯-4-[1,2,2,2-四氟-1-三氟甲基乙基]苯基]氨基甲酰基]苯基]-2-甲基苯甲酰胺;
M.29.11.p)N-[5-[[2-溴-6-氯-4-[1,2,2,2-四氟-1-三氟甲基乙基]苯基]氨基甲酰基]-2-氰基苯基]-4-氰基-2-甲基苯甲酰胺;
或选自M.29.12组的化合物,其中该化合物选自M.29.12a)至M.29.12m):
M.29.12.a)2-(1,3-二烷-2-基)-6-[2-(3-吡啶基)-5-噻唑基]吡啶;
M.29.12.b)2-[6-[2-(5-氟-3-吡啶基)-5-噻唑基]-2-吡啶基]嘧啶;
M.29.12.c)2-[6-[2-(3-吡啶基)-5-噻唑基]-2-吡啶基]嘧啶;
M.29.12.d)N-甲基磺酰基-6-[2-(3-吡啶基)噻唑-5-基]吡啶-2-甲酰胺
M.29.12.e)N-甲基磺酰基-6-[2-(3-吡啶基)噻唑-5-基]吡啶-2-甲酰胺
M.29.12.f)N-乙基-N-[4-甲基-2-(3-吡啶基)噻唑-5-基]-3-甲硫基丙酰胺
M.29.12.g)N-甲基-N-[4-甲基-2-(3-吡啶基)噻唑-5-基]-3-甲硫基丙酰胺
M.29.12.h)N,2-二甲基-N-[4-甲基-2-(3-吡啶基)噻唑-5-基]-3-甲硫基丙酰胺
M.29.12.i)N-乙基-2-甲基-N-[4-甲基-2-(3-吡啶基)噻唑-5-基]-3-甲硫基丙酰胺
M.29.12.j)N-[4-氯-2-(3-吡啶基)噻唑-5-基]-N-乙基-2-甲基-3-甲硫基丙酰胺
M.29.12.k)N-[4-氯-2-(3-吡啶基)噻唑-5-基]-N,2-二甲基-3-甲硫基丙酰胺
M.29.12.l)N-[4-氯-2-(3-吡啶基)噻唑-5-基]-N-甲基-3-甲硫基丙酰胺
M.29.12.m)N-[4-氯-2-(3-吡啶基)噻唑-5-基]-N-乙基-3-甲硫基丙酰胺;或化合物
M.29.14a)1-[(6-氯-3-吡啶基)甲基]-1,2,3,5,6,7-六氢-5-甲氧基-7-甲基-8-硝基咪唑并[1,2-a]吡啶;或
M.29.14b)1-[(6-氯吡啶-3-基)甲基]-7-甲基-8-硝基-1,2,3,5,6,7-六氢咪唑并[1,2-a]吡啶-5-醇;或化合物
M.29.16a)1-异丙基-N,5-二甲基-N-哒嗪-4-基吡唑-4-甲酰胺;或
M.29.16b)1-(1,2-二甲基丙基)-N-乙基-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;
M.29.16c)N,5-二甲基-N-哒嗪-4-基-1-(2,2,2-三氟-1-甲基乙基)吡唑-4-甲酰胺;
M.29.16d)1-[1-(1-氰基环丙基)乙基]-N-乙基-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;
M.29.16e)N-乙基-1-(2-氟-1-甲基丙基)-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;
M.29.16f)1-(1,2-二甲基丙基)-N,5-二甲基-N-哒嗪-4-基吡唑-4-甲酰胺;
M.29.16g)1-[1-(1-氰基环丙基)乙基]-N,5-二甲基-N-哒嗪-4-基吡唑-4-甲酰胺;
M.29.16h)N-甲基-1-(2-氟-1-甲基丙基]-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;
M.29.16i)1-(4,4-二氟环己基)-N-乙基-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;或
M.29.16j)1-(4,4-二氟环己基)-N,5-二甲基-N-哒嗪-4-基吡唑-4-甲酰胺。
上面所列M组市售化合物尤其可以在The Pesticide Manual,第16版,C.MacBean,British Crop Protection Council(2013)中找到。在线农药手册定期更新且可以通过http://bcpcdata.com/pesticide-manual.html获取。
提供ISO通用名的另一农药在线数据库是http://www.alanwood.net/pesticides。
M.4新烟碱类环氧虫啶由WO 20120/069266和WO 2011/06946已知,新烟碱类M.4A.2—有时也称为戊吡虫胍(guadipyr)—由WO 2013/003977已知且新烟碱类M.4A.3(在中国被批准为哌虫啶)由WO 2010/069266已知。氰氟虫胺类似物M.22B.1描述于CN10171577中且类似物M.22B.2描述于CN102126994中。邻苯二甲酰胺类M.28.1和M.28.2均由WO 2007/101540已知。邻氨基苯甲酰胺M.28.3描述于WO 2005/077943中。酰肼化合物M.28.4描述于WO 2007/043677中。邻氨基苯甲酰胺M.28.5a)-M.28.5d)和M.28.5h)描述于WO 2007/006670、WO 2013/024009和WO 2013/024010中,邻氨基苯甲酰胺化合物M.28.5i)描述于WO 2011/085575中,M.28.5j)描述于WO 2008/134969中,M.28.5k)描述于US2011/046186中且M.28.5l)描述于WO 2012/034403中。二酰胺化合物M.28.6和M.28.7可以在CN102613183中找到。螺缩酮取代的环状酮-烯醇衍生物M.29.3由WO 2006/089633已知,且联苯基取代的螺环酮-烯醇衍生物M.29.4由WO 2008/067911已知。三唑基苯基硫化物M.29.5描述于WO 2006/043635中且基于坚强芽孢杆菌的生物控制剂描述于WO 2009/124707中。列于M.29.6下的化合物M.29.6a)-M.29.6i)描述于WO2012/029672中,并且M.29.6j)和M.29.6k)描述于WO2013/129688中。杀线虫剂M.29.8由WO2013/055584已知。异唑啉M.29.9.a)描述于WO2013/050317中。异唑啉M.29.9.b)描述于WO2014/126208中。啶虫丙醚型类似物M.29.10由WO2010/060379已知。羧酰胺broflanilide和M.29.11.b)-M.29.11.h)描述于WO2010/018714中并且羧酰胺M.29.11i)-M.29.11.p)描述于WO2010/127926中。吡啶基噻唑类M.29.12.a)-M.29.12.c)由WO2010/006713已知,M.29.12.d)和M.29.12.e)由WO2012/000896已知,并且M.29.12.f)-M.29.12.m)由WO2010/129497已知。化合物M.29.14a)和M.29.14b)由WO2007/101369已知。吡唑类M.29.16.a)-M.29.16h)分别描述于WO2010/034737,WO2012/084670和WO2012/143317中,并且吡唑类M.29.16i)和M.29.16j)描述于US 61/891437中。
根据本发明的化合物可以与其联合使用的杀真菌剂的下列列举用于说明可能的组合,但不限制它们:
A)呼吸抑制剂
-Qo位点的配合物III抑制剂(例如嗜球果伞素类):腈嘧菌酯(azoxystrobin)(A.1.1)、甲香菌酯(coumethoxystrobin)(A.1.2)、丁香菌酯(coumoxystrobin)(A.1.3)、醚菌胺(dimoxystrobin)(A.1.4)、烯肟菌酯(enestroburin)(A.1.5)、烯肟菌胺(fenaminstrobin)(A.1.6)、fenoxystrobin/氟菌螨酯(flufenoxystrobin)(A.1.7)、氟嘧菌酯(fluoxastrobin)(A.1.8)、亚胺菌(kresoxim-methyl)(A.1.9)、mandestrobin(A.1.10)、叉氨苯酰胺(metominostrobin)(A.1.11)、肟醚菌胺(orysastrobin)(A.1.12)、啶氧菌酯(picoxystrobin)(A.1.13)、唑菌胺酯(pyraclostrobin)(A.1.14)、pyrametostrobin(A.1.15)、唑菌酯(pyraoxystrobin)(A.1.16)、肟菌酯(trifloxystrobin)(A.1.17)、2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧甲基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺(A.1.18)、pyribencarb(A.1.19)、triclopyricarb/chlorodincarb(A.1.20)、唑酮菌(famoxadone)(A.1.21)、咪唑菌酮(fenamidone)(A.1.21);N-[2-[(1,4-二甲基-5-苯基吡唑-3-基)氧基甲基]苯基]-N-甲氧基氨基甲酸甲酯(A.1.22),1-[3-氯-2-[[1-(4-氯苯基)-1H-吡唑-3-基]氧基甲基]苯基]-4-甲基四唑-5-酮(A.1.23),1-[3-溴-2-[[1-(4-氯苯基)吡唑-3-基]氧基甲基]苯基]-4-甲基四唑-5-酮(A.1.24),1-[2-[[1-(4-氯苯基)吡唑-3-基]氧基甲基]-3-甲基苯基]-4-甲基四唑-5-酮(A.1.25),1-[2-[[1-(4-氯苯基)吡唑-3-基]氧基甲基]-3-氟苯基]-4-甲基四唑-5-酮(A.1.26),1-[2-[[1-(2,4-二氯苯基)吡唑-3-基]氧基甲基]-3-氟苯基]-4-甲基四唑-5-酮(A.1.27),1-[2-[[4-(4-氯苯基)噻唑-2-基]氧基甲基]-3-甲基苯基]-4-甲基四唑-5-酮(A.1.28),1-[3-氯-2-[[4-对甲苯基噻唑-2-基]氧基甲基]苯基]-4-甲基四唑-5-酮(A.1.29),1-[3-环丙基-2-[[2-甲基-4-(1-甲基吡唑-3-基)苯氧基]甲基]苯基]-4-甲基四唑-5-酮(A.1.30),1-[3-二氟甲氧基-2-[[2-甲基-4-(1-甲基吡唑-3-基)苯氧基]甲基]苯基]-4-甲基四唑-5-酮(A.1.31),1-甲基-4-[3-甲基-2-[[2-甲基-4-(1-甲基吡唑-3-基)苯氧基]甲基]苯基]四唑-5-酮(A.1.32),1-甲基-4-[3-甲基-2-[[1-[3-三氟甲基苯基]亚乙氨基]氧基甲基]苯基]四唑-5-酮(A.1.33),(Z,2E)-5-[1-(2,4-二氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯胺(A.1.34),(Z,2E)-5-[1-(4-氯苯基)吡唑-3-基]oxy-2-甲氧亚氨基-N,3-二甲基戊-3-烯胺(A.1.35),(Z,2E)-5-[1-(4-氯-2-氟苯基)吡唑-3-基]oxy-2-甲氧亚氨基-N,3-二甲基戊-3-烯胺(A.1.36);
-Qi位点的配合物III抑制剂:氰霜唑(cyazofamid)(A.2.1)、amisulbrom(A.2.2)、2-甲基丙酸[(3S,6S,7R,8R)-8-苄基-3-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]-6-甲基-4,9-二氧代-1,5-二氧壬环-7-基]酯(A.2.3)、2-甲基丙酸[(3S,6S,7R,8R)-8-苄基-3-[[3-乙酰氧基甲氧基-4-甲氧基吡啶-2-羰基]氨基]-6-甲基-4,9-二氧代-1,5-二氧壬环-7-基]酯(A.2.4)、2-甲基丙酸[(3S,6S,7R,8R)-8-苄基-3-[(3-异丁氧基羰氧基-4-甲氧基吡啶-2-羰基)氨基]-6-甲基-4,9-二氧代-1,5-二氧壬环-7-基]酯(A.2.5)、2-甲基丙酸[(3S,6S,7R,8R)-8-苄基-3-[[3-(1,3-苯并间二氧杂环戊烯-5-基甲氧基)-4-甲氧基吡啶-2-羰基]氨基]-6-甲基-4,9-二氧代-1,5-二氧壬环-7-基]酯(A.2.6);2-甲基丙酸(3S,6S,7R,8R)-3-[[(3-羟基-4-甲氧基-2-吡啶基)羰基]氨基]-6-甲基-4,9-二氧代-8-(苯基甲基)-1,5-二氧壬环-7-基酯(A.2.7)、异丁酸(3S,6S,7R,8R)-8-苄基-3-[3-[(异丁酰氧基)甲氧基]-4-甲氧基吡啶酰胺基]-6-甲基-4,9-二氧代-1,5-二氧壬环-7-基酯(A.2.8);
-配合物II抑制剂(例如羧酰胺类):麦锈灵(benodanil)(A.3.1)、benzovindiflupyr(A.3.2)、bixafen(A.3.3)、啶酰菌胺(boscalid)(A.3.4)、萎锈灵(carboxin)(A.3.5)、呋菌胺(fenfuram)(A.3.6)、氟吡菌酰胺(fluopyram)(A.3.7)、氟酰胺(flutolanil)(A.3.8)、氟唑菌酰胺(fluxapyroxad)(A.3.9)、呋吡唑灵(furametpyr)(A.3.10)、isofetamid(A.3.11)、isopyrazam(A.3.12)、丙氧灭绣胺(mepronil)(A.3.13)、氧化萎锈灵(oxycarboxin)(A.3.14)、penflufen(A.3.14)、吡噻菌胺(penthiopyrad)(A.3.15)、sedaxane(A.3.16)、叶枯酞(tecloftalam)(A.3.17)、溴氟唑菌(thifluzamide)(A.3.18)、N-(4'-三氟甲硫基联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺(A.3.19)、N-(2-(1,3,3-三甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺(A.3.20)、3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺(A.3.21)、3-(三氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺(A.3.22)、1,3-二甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺(A.3.23)、3-(三氟甲基)-1,5-二甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺(A.3.24)、1,3,5-三甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺(A.3.25)、N-(7-氟-1,1,3-三甲基-2,3-二氢化茚-4-基)-1,3-二甲基-吡唑-4-甲酰胺(A.3.26)、N-[2-(2,4-二氯苯基)-2-甲氧基-1-甲基乙基]-3-(二氟甲基)-1-甲基-吡唑-4-甲酰胺(A.3.27);
-其他呼吸抑制剂(例如配合物I,去偶剂):二氟林(diflumetorim)(A.4.1)、(5,8-二氟喹唑啉-4-基)-{2-[2-氟-4-(4-三氟甲基吡啶-2-基氧基)苯基]乙基}胺(A.4.2);硝基苯基衍生物:乐杀螨(binapacryl)(A.4.3)、敌螨通(dinobuton)(A.4.4)、敌螨普(dinocap)(A.4.5)、氟啶胺(fluazinam)(A.4.6);嘧菌腙(ferimzone)(A.4.7);有机金属化合物:三苯锡基盐,如薯瘟锡(fentin-acetate)(A.4.8)、三苯锡氯(fentin chloride)(A.4.9)或毒菌锡(fentin hydroxide)(A.4.10);ametoctradin(A.4.11);以及硅噻菌胺(silthiofam)(A.4.12);
B)甾醇生物合成抑制剂(SBI杀真菌剂)
-C14脱甲基酶抑制剂(DMI杀真菌剂):三唑类:戊环唑(azaconazole)(B.1.1)、双苯三唑醇(bitertanol)(B.1.2)、糠菌唑(bromuconazole)(B.1.3)、环唑醇(cyproconazole)(B.1.4)、醚唑(difenoconazole)(B.1.5)、烯唑醇(diniconazole)(B.1.6)、烯唑醇M(diniconazole-M)(B.1.7)、氧唑菌(epoxiconazole)(B.1.8)、腈苯唑(fenbuconazole)(B.1.9)、喹唑菌酮(fluquinconazole)(B.1.10)、氟硅唑(flusilazole)(B.1.11)、粉唑醇(flutriafol)(B.1.12)、己唑醇(hexaconazole)(B.1.13)、酰胺唑(imibenconazole)(B.1.14)、环戊唑醇(ipconazole)(B.1.15)、环戊唑菌(metconazole)(B.1.17)、腈菌唑(myclobutanil)(B.1.18)、oxpoconazole(B.1.19)、多效唑(paclobutrazole)(B.1.20)、戊菌唑(penconazole)(B.1.21)、丙环唑(propiconazole)(B.1.22)、丙硫菌唑(prothioconazole)(B.1.23)、硅氟唑(simeconazole)(B.1.24)、戊唑醇(tebuconazole)(B.1.25)、氟醚唑(tetraconazole)(B.1.26)、三唑酮(triadimefon)(B.1.27)、唑菌醇(triadimenol)(B.1.28)、戊叉唑菌(triticonazole)(B.1.29)、烯效唑(uniconazole)(B.1.30)、1-[rel-(2S;3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷基甲基]-5-氰硫基-1H-[1,2,4]三唑(B.1.31)、2-[rel-(2S;3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷基甲基]-2H-[1,2,4]三唑-3-硫醇(B.1.32)、2-[2-氯-4-(4-氯苯氧基)苯基]-1-(1,2,4-三唑-1-基)戊-2-醇(B.1.33)、1-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-环丙基-2-(1,2,4-三唑-1-基)乙醇(B.1.34)、2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丁-2-醇(B.1.35)、2-[2-氯-4-(4-氯苯氧基)苯基]-1-(1,2,4-三唑-1-基)丁-2-醇(B.1.36)、2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-3-甲基-1-(1,2,4-三唑-1-基)丁-2-醇(B.1.37)、2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丙-2-醇(B.1.38)、2-[2-氯-4-(4-氯苯氧基)苯基]-3-甲基-1-(1,2,4-三唑-1-基)丁-2-醇(B.1.39)、2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)戊-2-醇(B.1.40)、2-[4-(4-氟苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丙-2-醇(B.1.41)、2-[2-氯-4-(4-氯苯氧基)苯基]-1-(1,2,4-三唑-1-基)戊-3-炔-2-醇(B.1.51);咪唑类:抑霉唑(imazalil)(B.1.42)、稻瘟酯(pefurazoate)(B.1.43)、丙氯灵(prochloraz)(B.1.44)、氟菌唑(triflumizol)(B.1.45);嘧啶类、吡啶类和哌嗪类:异嘧菌醇(fenarimol)(B.1.46)、氟苯嘧啶醇(nuarimol)(B.1.47)、啶斑肟(pyrifenox)(B.1.48)、嗪氨灵(triforine)(B.1.49)、[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)异唑-4-基]-(3-吡啶基)甲醇(B.1.50);
-Δ14-还原酶抑制剂:4-十二烷基-2,6-二甲基吗啉(aldimorph)(B.2.1)、吗菌灵(dodemorph)(B.2.2)、吗菌灵乙酸酯(dodemorph-acetate)(B.2.3)、丁苯吗啉(fenpropimorph)(B.2.4)、克啉菌(tridemorph)(B.2.5)、苯锈啶(fenpropidin)(B.2.6)、粉病灵(piperalin)(B.2.7)、螺茂胺(spiroxamine)(B.2.8);
-3-酮基还原酶抑制剂:环酰菌胺(fenhexamid)(B.3.1);
C)核酸合成抑制剂
-苯基酰胺类或酰基氨基酸类杀真菌剂:苯霜灵(benalaxyl)(C.1.1)、精苯霜灵(benalaxyl-M)(C.1.2)、kiralaxyl(C.1.3)、甲霜灵(metalaxyl)(C.1.4)、精甲霜灵(metalaxyl-M)(mefenoxam,C.1.5)、甲呋酰胺(ofurace)(C.1.6)、霜灵(oxadixyl)(C.1.7);
-其他:土菌消(hymexazole)(C.2.1)、异噻菌酮(octhilinone)(C.2.2)、恶喹酸(oxolinic acid)(C.2.3)、磺嘧菌灵(bupirimate)(C.2.4)、5-氟胞嘧啶(C.2.5)、5-氟-2-(对甲苯基甲氧基)嘧啶-4-胺(C.2.6)、5-氟-2-(4-氟苯基甲氧基)嘧啶-4-胺(C.2.7);
D)细胞分裂和细胞骨架抑制剂
-微管蛋白抑制剂,如苯并咪唑类、托布津类(thiophanate):苯菌灵(benomyl)(D1.1)、多菌灵(carbendazim)(D1.2)、麦穗宁(fuberidazole)(D1.3)、涕必灵(thiabendazole)(D1.4)、甲基托布津(thiophanate-methyl)(D1.5);三唑并嘧啶类:5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶(D1.6);
-其他细胞分裂抑制剂:乙霉威(diethofencarb)(D2.1)、噻唑菌胺(ethaboxam)(D2.2)、戊菌隆(pencycuron)(D2.3)、氟吡菌胺(fluopicolide)(D2.4)、苯酰菌胺(zoxamide)(D2.5)、苯菌酮(metrafenone)(D2.6),pyriofenone(D2.7);
E)氨基酸和蛋白质合成抑制剂
-蛋氨酸合成抑制剂(苯胺基嘧啶类):环丙嘧啶(cyprodinil)(E.1.1)、嘧菌胺(mepanipyrim)(E.1.2)、二甲嘧菌胺(pyrimethanil)(E.1.3);
-蛋白质合成抑制剂:灭瘟素(blasticidin-S)(E.2.1)、春雷素(kasugamycin)(E.2.2)、水合春雷素(kasugamycin hydrochloride-hydrate)(E.2.3)、米多霉素(mildiomycin)(E.2.4)、链霉素(streptomycin)(E.2.5)、土霉素(oxytetracyclin)(E.2.6)、多氧霉素(polyoxine)(E.2.7)、井冈霉素(validamycin A)(E.2.8);
F)信号转导抑制剂
-MAP/组氨酸蛋白激酶抑制剂:氟菌安(fluoroimid)(F.1.1)、异丙定(iprodione)(F.1.2)、杀菌利(procymidone)(F.1.3)、烯菌酮(vinclozolin)(F.1.4)、拌种咯(fenpiclonil)(F.1.5)、氟菌(fludioxonil)(F.1.6);
-G蛋白抑制剂:喹氧灵(quinoxyfen)(F.2.1);
G)类脂和膜合成抑制剂
-磷脂生物合成抑制剂:克瘟散(edifenphos)(G.1.1)、异稻瘟净(iprobenfos)(G.1.2)、定菌磷(pyrazophos)(G.1.3)、稻瘟灵(isoprothiolane)(G.1.4);
-类脂过氧化:氯硝胺(dicloran)(G.2.1)、五氯硝基苯(quintozene)(G.2.2)、四氯硝基苯(tecnazene)(G.2.3)、甲基立枯磷(tolclofos-methyl)(G.2.4)、联苯(G.2.5)、地茂散(chloroneb)(G.2.6)、氯唑灵(etridiazole)(G.2.7);
-磷脂生物合成和细胞壁沉积:烯酰吗啉(dimethomorph)(G.3.1)、氟吗啉(flumorph)(G.3.2)、双炔酰菌胺(mandipropamid)(G.3.3)、丁吡吗啉(pyrimorph)(G.3.4)、苯噻菌胺(benthiavalicarb)(G.3.5)、异丙菌胺(iprovalicarb)(G.3.6)、valifenalate(G.3.7)和N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯(G.3.8);
-影响细胞膜渗透性的化合物和脂肪酸:百维灵(propamocarb)(G.4.1);
-脂肪酸酰胺水解酶抑制剂:oxathiapiprolin(G.5.1)、甲磺酸2-{3-[2-(1-{[3,5-二(二氟甲基-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氢-1,2-唑-5-基}苯基酯(G.5.2)、甲磺酸2-{3-[2-(1-{[3,5-二(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氢-1,2-唑-5-基}-3-氯苯基酯(G.5.3);
H)具有多位点作用的抑制剂
-无机活性物质:波尔多液(Bordeaux混合物)(H.1.1)、醋酸铜(H.1.2)、氢氧化铜(H.1.3)、王铜(copper oxychloride)(H.1.4)、碱式硫酸铜(H.1.5)、硫(H.1.6);
-硫代-和二硫代氨基甲酸酯类:福美铁(ferbam)(H.2.1)、代森锰锌(mancozeb)(H.2.2)、代森锰(maneb)(H.2.3)、威百亩(metam)(H.2.4)、代森联(metiram)(H.2.5)、甲基代森锌(propineb)(H.2.6)、福美双(thiram)(H.2.7)、代森锌(zineb)(H.2.8)、福美锌(ziram)(H.2.9);
-有机氯化合物(例如邻苯二甲酰亚胺类、硫酰胺类、氯代腈类):敌菌灵(anilazine)(H.3.1)、百菌清(chlorothalonil)(H.3.2)、敌菌丹(captafol)(H.3.3)、克菌丹(captan)(H.3.4)、灭菌丹(folpet)(H.3.5)、抑菌灵(dichlofluanid)(H.3.6)、双氯酚(dichlorophen)(H.3.7)、六氯苯(H.3.8)、五氯酚(pentachlorphenole)(H.3.9)及其盐、四氯苯酞(phthalide)(H.3.10)、对甲抑菌灵(tolylfluanid)(H.3.11)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯苯磺酰胺(H.3.12);
-胍类及其他:胍(H.4.1)、多果定(H.4.2)、多果定游离碱(H.4.3)、双胍盐(guazatine)(H.4.4)、双胍辛胺(guazatine-acetate)(H.4.5)、双胍辛醋酸盐(iminoctadine)(H.4.6)、双胍辛胺三乙酸盐(iminoctadine-triacetate)(H.4.7)、双八胍盐(iminoctadine-tris(albesilate))(H.4.8)、二噻农(dithianon)(H.4.9)、2,6-二甲基-1H,5H-[1,4]二噻二烯并[2,3-c:5,6-c']联吡咯-1,3,5,7(2H,6H)-四酮(H.4.10);
I)细胞壁合成抑制剂
-葡聚糖合成抑制剂:井冈霉素(validamycin)(I.1.1)、多氧霉素(polyoxin B)(I.1.2);
-黑素合成抑制剂:咯喹酮(pyroquilon)(I.2.1)、三环唑(tricyclazole)(I.2.2)、氯环丙酰胺(carpropamid)(I.2.3)、双氯氰菌胺(dicyclomet)(I.2.4)、氰菌胺(fenoxanil)(I.2.5);
J)植物防御诱发剂
-噻二唑素(acibenzolar-S-methyl)(J.1.1)、噻菌灵(probenazole)(J.1.2)、异噻菌胺(isotianil)(J.1.3)、噻酰菌胺(tiadinil)(J.1.4)、调环酸钙(prohexadione-calcium)(J.1.5);膦酸酯类:藻菌磷(fosetyl)(J.1.6)、乙磷铝(fosetyl-aluminum)(J.1.7)、亚磷酸及其盐(J.1.8)、碳酸氢钾或钠(J.1.9);
K)未知作用模式
-拌棉醇(bronopol)(K.1.1)、灭螨蜢(chinomethionat)(K.1.2)、环氟菌胺(cyflufenamid)(K.1.3)、清菌脲(cymoxanil)(K.1.4)、棉隆(dazomet)(K.1.5)、咪菌威(debacarb)(K.1.6)、哒菌清(diclomezine)(K.1.7)、野燕枯(difenzoquat)(K.1.8)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)(K.1.9)、二苯胺(K.1.10)、胺苯吡菌酮(fenpyrazamine)(K.1.11)、氟联苯菌(flumetover)(K.1.12)、磺菌胺(flusulfamide)(K.1.13)、flutianil(K.1.14)、磺菌威(methasulfocarb)(K.1.15)、氯定(nitrapyrin)(K.1.16)、异丙消(nitrothal-isopropyl)(K.1.18)、oxathiapiprolin(K.1.19)、tolprocarb(K.1.20)、喹啉铜(oxin-copper)(K.1.21)、丙氧喹啉(proquinazid)(K.1.22)、tebufloquin(K.1.23)、叶枯酞(K.1.24)、唑菌嗪(triazoxide)(K.1.25)、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮(K.1.26)、2-[3,5-二(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-(丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮(K.1.27)、2-[3,5-二(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氟-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮(K.1.28)、2-[3,5-二(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氯-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮(K.1.29)、N-(环丙基甲氧亚氨基-(6-二氟甲氧基-2,3-二氟苯基)甲基)-2-苯基乙酰胺(K.1.30)、N'-(4-(4-氯-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒(K.1.31)、N'-(4-(4-氟-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒(K.1.32)、N'-(2-甲基-5-三氟甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒(K.1.33)、N'-(5-二氟甲基-2-甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒(K.1.34)、甲氧基乙酸6-叔丁基-8-氟-2,3-二甲基喹啉-4-基酯(K.1.35)、3-[5-(4-甲基苯基)-2,3-二甲基异唑烷-3-基]吡啶(K.1.36)、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶(pyrisoxazole)(K.1.37)、N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺(K.1.38)、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑(K.1.39)、2-(4-氯氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔氧基乙酰胺、(Z)-3-氨基-2-氰基-3-苯基丙-2-烯酸乙酯(K.1.40)、picarbutrazox(K.1.41)、N-[6-[[(Z)-[(1-甲基四唑-5-基)苯基亚甲基]氨基]氧基甲基]-2-吡啶基]氨基甲酸戊酯(K.1.42)、2-[2-[(7,8-二氟-2-甲基-3-喹啉基)氧基]-6-氟-苯基]丙-2-醇(K.1.43)、2-[2-氟-6-[(8-氟-2-甲基-3-喹啉基)氧基]苯基]丙-2-醇(K.1.44)、3-(5-氟-3,3,4,4-四甲基-3,4-二氢异喹啉-1-基)喹啉(K.1.45)、3-(4,4-二氟-3,3-二甲基-3,4-二氢异喹啉-1-基)喹啉(K.1.46)、3-(4,4,5-三氟-3,3-二甲基-3,4-二氢异喹啉-1-基)喹啉(K.1.47)、9-氟-2,2-二甲基-5-(3-喹啉基)-3H-1,4-苯并氧氮杂(K.1.48)。
由通用名描述的杀真菌剂、其制备及其例如对有害真菌的活性是已知的(参见http://www.alanwood.net/pesticides/);这些物质可以市购。
由IUPAC命名法描述的化合物、其制备及其农药活性也是已知的(参见Can.J.Plant Sci.48(6),587-94,1968;EP-A 141 317;EP-A 152 031;EP-A 226 917;EP-A243 970;EP-A 256 503;EP-A 428 941;EP-A 532 022;EP-A 1 028 125;EP-A 1 035 122;EP-A 1 201 648;EP-A 1 122 244,JP 2002316902;DE 19650197;DE 10021412;DE102005009458;US 3,296,272;US 3,325,503;WO 98/46608;WO 99/14187;WO 99/24413;WO99/27783;WO 00/29404;WO 00/46148;WO 00/65913;WO 01/54501;WO 01/56358;WO 02/22583;WO 02/40431;WO 03/10149;WO 03/11853;WO 03/14103;WO 03/16286;WO 03/53145;WO 03/61388;WO 03/66609;WO 03/74491;WO 04/49804;WO 04/83193;WO 05/120234;WO 05/123689;WO 05/123690;WO 05/63721;WO 05/87772;WO 05/87773;WO 06/15866;WO 06/87325;WO 06/87343;WO 07/82098;WO 07/90624,WO 11/028657,WO 2012/168188,WO 2007/006670,WO 2011/77514;WO 13/047749,WO 10/069882,WO 13/047441,WO03/16303,WO 09/90181,WO 13/007767,WO 13/010862,WO 13/127704,WO 13/024009,WO13/024010和WO 13/047441,WO 13/162072,WO 13/092224,WO 11/135833)。
本发明化合物的合适混合配对也包括生物农药。
已经将生物农药定义为基于微生物(细菌、真菌、病毒、线虫等)或天然产物(化合物,如代谢物、蛋白质或来自生物或其他天然源的提取物)的农药形式(U.S.EnvironmentalProtection Agency:http://www.epa.gov/pesticides/biopesticides/)。生物农药主要分为两类,即微生物农药和生物化学农药:
(1)微生物农药由细菌、真菌或病毒构成(并且通常包括细菌和真菌产生的代谢物)。昆虫病原线虫也被人类为微生物农药,尽管它们是多细胞的。
(2)生物化学农药是防治有害物或提供如下所定义的其他作物保护用途,但具有无毒作用模式(如生长或发育调节,引诱剂,驱除剂或防御活化剂(例如诱发的耐受性)且对哺乳动物相对无毒的天然物质或结构上类似于天然物质且功能上等同于天然物的来自生物来源的提取物。
用于作物病害的生物农药已经本身对多种作物确认。例如,生物农药在防治霜霉病中起重要作用。其益处包括:0天安全间隔期,能够在温和至严重病害压力下使用以及能够以与其他注册农药的混合物或以轮流方案使用。
生物农药的主要生长领域是种子处理和土壤改良领域。生物农药种子处理例如用于控制引起种子腐烂病、立枯病、根腐病和苗枯病的土传真菌病原体。它们还可以用于控制内部种子传播的真菌病原体以及在种子表面上的真菌病原体。许多生物农药产品也显示出刺激植物宿主防御和其他生理过程的能力,这可以使得被处理作物更耐受许多生物和非生物应力或者可以调节植物生长。许多生物农药产品也显示出刺激植物健康、植物生长和/或产量提高活性的能力。
根据本发明的化合物可以与其联合使用的生物农药的下列列举用于说明可能的组合,但不限制它们:
L)生物农药
L1)具有杀真菌、杀细菌、杀病毒和/或植物防御活化剂活性的微生物农药:白粉寄生孢(Ampelomyces quisqualis)、黄曲霉(Aspergillus flavus)、出芽短梗霉(Aureobasidium pullulans)、高地芽孢杆菌(Bacillus altitudinis)、解淀粉芽孢杆菌(B.amyloliquefaciens)、巨大芽孢杆菌(B.megaterium)、莫海威芽孢杆菌(B.mojavensis)、蕈状芽孢杆菌(B.mycoides)、短小芽孢杆菌(B.pumilus)、简单芽孢杆菌(B.simplex)、盐土芽孢杆菌(B.solisalsi)、枯草芽孢杆菌(B.subtilis)、解淀粉枯草芽孢杆菌变种(B.subtilis var.amyloliquefaciens)、橄榄假丝酵母(Candida oleophila)、拮抗酵母(C.saitoana)、番茄细菌性溃疡病(Clavibacter michiganensis)(噬菌体)、盾壳霉(Coniothyrium minitans)、寄生隐丛赤壳菌(Cryphonectria parasitica)、白色隐球菌(Cryptococcus albidus)、Dilophosphora alopecuri、尖镰孢(Fusarium oxysporum)、Clonostachys rosea f.catenulate(也称为链孢粘帚菌(Gliocladium catenulatum))、粉红粘帚霉(Gliocladium roseum)、抗生素溶杆菌(Lysobacter antibioticus)、产霉溶杆菌(L.enzymogenes)、核果梅奇酵母(Metschnikowia fructicola)、Microdochium dimerum、小球壳孢(Microsphaeropsis ochracea)、白色产气霉(Muscodor albus)、蜂房芽孢杆菌(Paenibacillus alvei)、多粘类芽孢杆菌(Paenibacillus polymyxa)、成团泛菌(Pantoeavagans)、大伏革菌(Phlebiopsis gigantea)、假单胞菌属(Pseudomonas sp.)、Pseudomonas chloraphis、Pseudozyma flocculosa、异常毕赤酵母(Pichia anomala)、寡雄腐霉(Pythium oligandrum)、Sphaerodes mycoparasitica、灰绿链霉菌(Streptomycesgriseoviridis)、利迪链霉菌(S.lydicus)、紫黑链霉菌(S.violaceusniger)、黄蓝状菌(Talaromyces flavus)、Trichoderma asperelloides、棘孢木霉(T.asperellum)、深绿木霉(T.atroviride)、顶孢木霉(T.fertile)、盖姆斯木霉(T.gamsii)、T.harmatum、哈茨木霉(T.harzianum)、多孔木霉(T.polysporum)、钩木霉(T.stromaticum)、绿木霉(T.virens)、绿色木霉(T.viride)、Typhula phacorrhiza、奥德曼细基格孢(Ulocladium oudemansii)、大丽轮枝菌(Verticillium dahlia)、小西葫芦黄花叶病毒(无毒菌株);
L2)具有杀真菌、杀细菌、杀病毒和/或植物防御活化剂活性的生物化学农药:Harpin蛋白、Reynoutria sachalinensis提取物;
L3)具有杀虫、杀螨、杀螺和/或杀线虫活性的微生物农药:放射形土壤杆菌(Agrobacterium radiobacter),蜡样芽孢杆菌(Bacillus cereus),坚强芽孢杆菌(B.firmus),苏云金芽孢杆菌(B.thuringiensis),苏云金芽孢杆菌鲇泽亚种(B.thuringiensis ssp.aizawai),苏云金芽孢杆菌以色列亚种(B.t.ssp.israelensis),苏云金芽孢杆菌蜡螟亚种(B.t.ssp.galleriae),苏云金芽孢杆菌库斯塔克亚种(B.t.ssp.kurstaki),苏云金芽孢杆菌拟步行甲亚种(B.t.ssp.tenebrionis),球孢白僵菌(Beauveria bassiana),布氏白僵菌(B.brongniartii),伯克霍尔德氏菌(Burkholderiaspp.),Chromobacterium subtsugae,苹果蠹蛾颗粒体病毒(Cydia pomonellagranovirus)(CpGV),伪苹果蠹蛾颗粒体病毒(Cryptophlebia leucotreta granulovirus)(CrleGV),黄杆菌属(Flavobacterium spp.),棉铃虫核型多角体病毒(Helicoverpaarmigera nucleopolyhedrovirus)(HearNPV),棉铃虫核型多角体病毒(Helicoverpa zeanucleopolyhedrovirus)(HzNPV),棉铃虫单核衣壳核型多角体病毒(Helicoverpa zeasingle capsid nucleopolyhedrovirus)(HzSNPV),嗜菌异小杆线虫(Heterorhabditisbacteriophora),玫烟色棒束孢(Isaria fumosorosea),Lecanicillium longisporum,L.muscarium,金龟子绿僵菌(Metarhizium anisopliae),金龟子绿僵菌变种(Metarhiziumanisopliae var.anisopliae),金龟子绿僵菌蝗变种(M.anisopliae var.acridum),莱氏野村菌(Nomuraea rileyi),玫烟色拟青毒(Paecilomyces fumosoroseus),淡紫色拟青霉(P.lilacinus),日本甲虫类芽孢杆菌(Paenibacillus popilliae),巴氏杆菌属(Pasteuria spp.),拟斯扎瓦巴氏杆菌(P.nishizawae),穿刺巴氏杆菌(P.penetrans),P.ramosa,P.thornea,P.usgae,荧光假单胞菌(Pseudomonas fluorescens),灰翅夜蛾核型多角体病毒(Spodoptera littoralis nucleopolyhedrovirus)(SpliNPV),斯氏小卷蛾线虫(Steinernema carpocapsae),斯氏夜蛾线虫(S.feltiae),锯蜂线虫(S.kraussei),Streptomyces galbus,细黄链霉菌(S.Microflavus);
L4)具有杀虫、杀螨、杀螺、信息素和/或杀线虫活性的生物化学农药:L-香芹酮、柠檬醛、乙酸(E,Z)-7,9-十二碳二烯-1-基酯、甲酸乙酯、(E,Z)-2,4-癸二烯酸乙酯(梨酯)、(Z,Z,E)-7,11,13-十六碳三烯醛、丁酸庚酯、肉豆蔻酸异丙酯、千里酸熏衣草酯、顺式-茉莉酮、2-甲基-1-丁醇、甲基丁香酚、茉莉酮酸甲酯、(E,Z)-2,13-十八碳二烯-1-醇、(E,Z)-2,13-十八碳二烯-1-醇乙酸酯、(E,Z)-3,13-十八碳二烯-1-醇、R-1-辛烯-3-醇、白蚁信息素(pentatermanone)、乙酸(E,Z,Z)-3,8,11-十四碳三烯基酯、乙酸(Z,E)-9,12-十四碳二烯-1-基酯、Z-7-十四碳烯-2-酮、乙酸Z-9-十四碳烯-1-基酯、Z-11-十四碳烯醛、Z-11-十四碳烯-1-醇、Chenopodium ambrosiodae提取物、印度楝树油、皂树(Quillay)提取物;
L5)具有植物应力降低、植物生长调节剂、植物生长促进和/或产量提高活性的微生物农药:无乳固氮螺菌(Azospirillum amazonense),巴西固氮螺菌(A.brasilense),生脂固氮螺菌(A.lipoferum),伊拉克固氮螺菌(A.irakense),高盐固氮螺菌(A.halopraeferens),慢生根瘤菌属(Bradyrhizobium spp.),埃氏慢生根瘤菌(B.elkanii),日本慢生根瘤菌(B.japonicum),辽宁慢生根瘤菌(B.liaoningense),慢生羽扇豆根瘤菌(B.lupini),食酸戴尔福特菌(Delftia acidovorans),丛枝菌根真菌(Glomusintraradices),中生根瘤菌属(Mesorhizobium spp.),豌豆根瘤菌菜豆生物型(Rhizobiumleguminosarum bv.phaseoli),豌豆根瘤菌三叶草生物型(R.l.bv.trifolii),R.l.bv.viciae,R.tropici,Sinorhizobium meliloti。
选自L1)和/或L2)组的生物农药也可以具有杀虫、杀螨、杀螺、信息素、杀线虫、植物应力降低、植物生长调节剂、植物生长促进和/或产量提高活性。选自L3)和/或L4)组的生物农药也可以具有杀真菌、杀细菌、杀病毒、植物防御活化剂、植物应力降低、植物生长调节剂、植物生长促进和/或产量提高活性。选自L5)组的生物农药也可以具有杀真菌、杀细菌、杀病毒、植物防御活化剂、杀虫、杀螨、杀螺、信息素和/或杀线虫活性。
许多这些生物农药已经在本文所述保藏号下保藏(前缀如ATCC或DSM是指相应菌种保藏的首字母缩略词,详情在这里例如见http://www.wfcc.info/ccinfo/collection/by_acronym/))、在文献中提及、被注册和/或可市购:1989年在德国Konstanz分离的出芽短梗霉DSM 14940和DSM 14941的混合物(例如芽生孢子,来自bio-ferm GmbH,奥地利),至少在1980年以前最初在巴西南部(Passo Fundo)的小麦地带分离的巴西固氮螺菌Sp245(BR 11005;例如Gramíneas,来自巴西BASFAgricultural Specialties Ltd.),巴西固氮螺菌菌株Ab-V5和Ab-V6(例如AzoMax,来自Novozymes BioAg Produtos papra Agricultura Ltda.,Quattro Barras,巴西或来自Simbiose-Agro,巴西;Plant Soil 331,413-425,2010),解淀粉芽孢杆菌菌株AP-188(NRRL B-50615和B-50331;US 8,445,255);在日本Kikugawa-shi由空气分离的解淀粉芽孢杆菌植物亚种D747(US 20130236522 A1;FERM BP-8234;例如DoubleNickelTM 55 WDG,来自Certis LLC,USA),在德国Brandenburg由土壤分离的解淀粉芽孢杆菌植物亚种FZB24(也称SB3615;DSM 96-2;J.Plant Dis.Prot.105,181-197,1998;例如来自Novozyme Biologicals,Inc.,USA),在德国Brandenburg由土壤分离的解淀粉芽孢杆菌植物亚种FZB42(DSM 23117;J.Plant Dis.Prot.105,181-197,1998;例如42,来自德国AbiTEP GmbH),至少在1988年以前在Sutton Bonington,Nottinghamshire,U.K.由蚕豆分离的解淀粉芽孢杆菌植物亚种MBI600(也称1430;NRRL B-50595;US 2012/0149571 A1;例如来自BASF Corp.,USA),在California,U.S.A.于1995年由桃园分离的解淀粉芽孢杆菌植物亚种QST-713(NRRL B-21661;例如MAX,来自Bayer Crop Science LP,USA),在South Dakoda,U.S.A.于1992年分离的解淀粉芽孢杆菌植物亚种TJ1000(也称1BE;ATCC BAA-390;CA 2471555 A1;例如QuickRootsTM,来自TJ Technologies,Watertown,SD,USA),坚强芽孢杆菌CNCM I-1582,由以色列中部平原地区的土壤分离的亲代菌株EIP-N1(CNCM I-1556)的变体(WO 2009/126473,US 6,406,690;例如来自Bayer CropScience LP,USA),在墨西哥由苹果树根围分离的短小芽孢杆菌GHA 180(IDAC 260707-01;例如BX,来自加拿大Quebec的Premier Horticulture),至少在1993年以前由被Erwinia tracheiphila侵染的黄瓜分离的也称为BU-F22和BU-F33的短小芽孢杆菌INR-7(NRRL B-50185、NRRL B-50153;US 8,445,255),至少在2008年以前在南非由禾草根围分离的短小芽孢杆菌KFP9F(NRRL B-50754;WO 2014/029697;例如BAC-UP或FUSION-P,来自南非BASF AgriculturalSpecialities(Pty)Ltd.),在1998年由在Pohnpei,Federated States of Micronesia收集的土壤分离的短小芽孢杆菌QST 2808(NRRL B-30087;例如或Plus,来自Bayer Crop Science LP,USA),简单芽孢杆菌ABU 288(NRRL B-50304;US 8,445,255),在北美由红甜菜根分离的枯草芽孢杆菌FB17,也称UD 1022或UD10-22(ATCC PTA-11857;System.Appl.Microbiol.27,372-379,2004;US 2010/0260735;WO 2011/109395);在1987年由取自Ephraim,Wisconsin,U.S.A.的草坪的土壤分离的苏云金芽胞杆菌鲇泽亚种ABTS-1857(也称ABG-6346;ATCC SD-1372;例如来自BioFa AG,Münsingen,德国),在Brownsville,Texas,U.S.A.于1967年由患病棉红铃虫黑色幼虫分离的苏云金芽胞杆菌库尔斯塔克亚种ABTS-351,等同于HD-1(ATCC SD-1275;例如DF,来自Valent BioSciences,IL,USA),由E.saccharina幼虫尸体分离的苏云金芽胞杆菌库尔斯塔克亚种SB4(NRRL B-50753;例如Beta来自BASF Agricultural Specialities(Pty)Ltd.,南非),苏云金芽胞杆菌拟步行甲亚种NB-176-1,菌株NB-125的突变体,在1982年由甲虫黄粉虫(Tenebrio molitor)的死蛹分离的野生型菌株(DSM 5480;EP 585 215 B1;例如来自瑞士Valent BioSciences),球孢白僵菌GHA(ATCC 74250;例如22WGP,来自Laverlam Int.Corp.,USA),球孢白僵菌JW-1(ATCC 74040;例如来自意大利CBC(Europe)S.r.l.),由龟甲虫Conchyloctenia punctata的幼虫分离的球孢白僵菌PPRI 5339(NRRL 50757;例如来自南非BASFAgricultural Specialities(Pty)Ltd.),在巴西Rio de Janeiro分离的埃氏慢生根瘤菌菌株SEMIA 5019(也称29W)和在the State of Rio Grande do Sul于1967年分离的SEMIA587,来自以前接种北美分离物的区域并自1968年开始用于商业接种体(Appl.Environ.Microbiol.73(8),2635,2007;例如GELFIX 5,来自巴西BASFAgricultural Specialties Ltd.),在美国由Wisconsin大田分离的日本慢生根瘤菌532c(Nitragin 61A152;Can.J.Plant.Sci.70,661-666,1990;例如Super,来自加拿大BASF AgriculturalSpecialties Ltd.),菌株USDA 138的日本慢生根瘤菌E-109变体(INTA E109,SEMIA 5085;Eur.J.Soil Biol.45,28-35,2009;Biol.Fertil.Soils 47,81-89,2011);保藏于SEMIA的日本慢生根瘤菌菌株,由Appl.Environ.Microbiol.73(8),2635,2007已知:由Embrapa-Cerrados从巴西Cerrados地区的土壤分离的SEMIA 5079,自1992年起用于商业接种体(CPAC 15;例如GELFIX 5或ADHERE 60,来自巴西BASF Agricultural Specialties Ltd.),在巴西由Embrapa-Cerrados在实验室条件下得到的日本慢生根瘤菌SEMIA 5080,自1992年起用于商业接种体,为最初在U.S.A.分离的SEMIA 586(CB1809)的天然变体(CPAC 7;例如GELFIX 5或ADHERE 60,来自巴西BASF Agricultural Specialties Ltd.);在日本Nikko于2008年由土壤分离的伯克霍尔德氏菌A396(NRRL B-50319;WO 2013/032693;Marrone BioInnovations,Inc.,USA),由油籽油菜分离的盾壳霉CON/M/91-08(WO 1996/021358;DSM9660;例如WG,WG,来自德国Bayer CropScience AG),harpin(α-β)蛋白(Science 257,85-88,1992;例如MessengerTM或HARP-N-Tek,来自Plant HealthCare plc,U.K.),棉铃虫核型多角体病毒(Helicoverpa armigeranucleopolyhedrovirus)(HearNPV)(J.Invertebrate Pathol.107,112-126,2011;例如来自瑞士Adermatt Biocontrol;来自巴西Koppert;Max,来自澳大利亚Queensland的AgBiTech Pty Ltd.),棉铃虫单核衣壳核型多角体病毒(Helicoverpa zea single capsid nucleopolyhedrovirus)(HzSNPV)(例如来自Certis LLC,USA),棉铃虫核型多角体病毒(Helicoverpa zeanucleopolyhedrovirus)ABA-NPV-U(例如来自澳大利亚Queensland的AgBiTech Pty Ltd.),嗜菌异小杆线虫(例如G,来自BASF AgriculturalSpecialities Limited,UK),在Apopka,Florida,U.S.A.由紫背天葵上的粉蚧分离的玫烟色棒束孢Apopka-97(ATCC 20874;Biocontrol Science Technol.22(7),747-761,2012;例如PFR-97TM或来自Certis LLC,USA),在奥地利由苹果小卷蛾分离的金龟子绿僵菌变种F52,也称275或V275(DSM 3884,ATCC 90448;例如加拿大NovozymesBiologicals BioAg Group),在以色列中部由葡萄分离的核果梅奇酵母277(US 6,994,849;NRRL Y-30752;例如以前的来自以色列Agrogreen),在菲律宾由感染的线虫卵分离的淡紫色拟青霉(Paecilomyces ilacinus)251(AGAL 89/030550;WO1991/02051;Crop Protection 27,352-361,2008;例如来自德国Bayer CropScience AG,以及来自Certis,USA),至少在2008年以前在南非由禾草根围分离的蜂房芽孢杆菌NAS6G6(WO 2014/029697;NRRL B-50755;例如BAC-UP,来自南非BASF AgriculturalSpecialities(Pty)Ltd.),在Illinois,U.S.A.于二十一世纪零零年代中期由大豆田分离的拟斯扎瓦巴氏杆菌Pn1(ATCC SD-5833;Federal Register 76(22),5808,2011年2月2日;例如ClarivaTM PN,来自Syngenta Crop Protection,LLC,USA),比莱青霉(也称P.bilaii)菌株ATCC 18309(=ATCC 74319),ATCC 20851和/或ATCC 22348(=ATCC 74318),最初在加拿大Alberta由土壤分离(Fertilizer Res.39,97-103,1994;Can.J.Plant Sci.78(1),91-102,1998;US 5,026,417,WO 1995/017806;例如Jump来自加拿大Novozymes Biologicals BioAg Group),Reynoutria sachalinensis提取物(EP 0307510B1;例如SC,来自Marrone BioInnovations,Davis,CA,USA或来自德国BioFa AG),斯氏小卷蛾线虫(例如来自BASF AgriculturalSpecialities Limited,UK),斯氏夜蛾线虫(例如来自BioWorks,Inc.,USA;来自BASF Agricultural Specialities Limited,UK),细黄链霉菌NRRLB-50550(WO 2014/124369;德国Bayer CropScience),在南非分离的Trichodermaasperelloides JM41R(NRRL 50759;也称顶孢木霉;例如来自南非BASFAgricultural Specialities(Pty)Ltd.),哈茨木霉T-22,也称KRL-AG2(ATCC 20847;BioControl 57,687-696,2012;例如来自BioWorks Inc.,USA或SabrExTM,来自Advanced Biological Marketing Inc.,Van Wert,OH,USA)。
根据本发明,生物农药(诸如印度楝树油的油除外)的固体材料(干物质)被认为是活性组分(例如在干燥或蒸发提取介质或在微生物农药的液体配制剂情况下悬浮介质之后得到)。
按照本发明,本文用于生物提取物如皂树提取物的重量比和百分数基于相应提取物的干含量(固体材料)的总重量。
包含至少一种呈活的微生物细胞形式—包括休眠形式—的微生物农药的组合物的总重量比可以使用相应微生物的CFU量来计算相应活性组分的总重量而确定,使用下列等式:1×1010CFU等于1克相应活性组分总重量。菌落形成单位为活的微生物细胞,尤其是真菌和细菌细胞的度量。此外,这里“CFU”在(昆虫病原性)线虫生物农药,如斯氏夜蛾线虫的情况下还可以理解为单个线虫(幼虫)的数目。
当将包含微生物农药的混合物用于作物保护中时,施用率优选为约1×106-5×1015(或更大)CFU/ha,优选约1×108-1×1013CFU/ha,甚至更优选约1×109-1×1012CFU/ha。在(昆虫病原性)线虫作为微生物农药(例如斯氏夜蛾线虫)的情况下,施用率优选为约1×105-1×1012(或更大),更优选1×108-1×1011,甚至更优选5×108-1×1010个个体(例如卵、幼虫或任何其他活体阶段形式,优选感染性幼虫阶段)/ha。
当将包含微生物农药的混合物用于种子处理时,对于植物繁殖材料的施用率优选为约1×106-1×1012(或更大)CFU/种子。优选浓度为约1×106-1×109CFU/种子。在微生物农药II的情况下,对于植物繁殖材料的施用率也优选为约1×107-1×1014(或更大)CFU/100kg种子,优选1×109至约1×1012CFU/100kg种子。
本发明还涉及包含助剂和至少一种本发明化合物或其混合物的农业化学组合物。
农业化学组合物包含杀害虫有效量的本发明化合物或其混合物。术语“杀害虫有效量”如下所定义。
本发明化合物或其混合物可以转化成农业化学组合物常用的类型,例如溶液、乳液、悬浮液、粉剂、粉末、糊、颗粒、模压品、胶囊及其混合物。组合物类型的实例是悬浮液(例如SC、OD、FS),可乳化浓缩物(例如EC),乳液(例如EW、EO、ES、ME),胶囊(例如CS、ZC),糊,锭剂,可湿性粉末或粉剂(例如WP、SP、WS、DP、DS),模压品(例如BR、TB、DT),颗粒(例如WG、SG、GR、FG、GG、MG),杀虫制品(例如LN)以及处理植物繁殖材料如种子的凝胶配制剂(例如GF)。这些和其他组合物类型在“Catalogue of pesticide formulation types andinternational coding system”,Technical Monograph,第2期,2008年5月第6版,CropLife International中有定义。
组合物如Mollet和Grubemann,Formulation technology,Wiley VCH,Weinheim,2001;或Knowles,New developments in crop protection product formulation,AgrowReports DS243,T&F Informa,London,2005所述以已知方式制备。
合适助剂的的实例是溶剂,液体载体,固体载体或填料,表面活性剂,分散剂,乳化剂,润湿剂,辅助剂,加溶剂,渗透促进剂,保护性胶体,粘附剂,增稠剂,保湿剂,驱除剂,引诱剂,进食刺激剂,相容剂,杀菌剂,防冻剂,消泡剂,着色剂,增粘剂和粘合剂。
合适的溶剂和液体载体是水和有机溶剂,如中到高沸点的矿物油馏分,例如煤油、柴油;植物或动物来源的油;脂族、环状和芳族烃类,例如甲苯、石蜡、四氢萘、烷基化萘;醇类,如乙醇、丙醇、丁醇、苄醇、环己醇;二醇类;DMSO;酮类,例如环己酮;酯类,例如乳酸酯、碳酸酯、脂肪酸酯、γ-丁内酯;脂肪酸;膦酸酯;胺类;酰胺类,例如N-甲基吡咯烷酮,脂肪酸二甲基酰胺;以及它们的混合物。
合适的固体载体或填料是矿土,例如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、粘土、白云石、硅藻土、膨润土、硫酸钙、硫酸镁、氧化镁;多糖粉末,例如纤维素、淀粉;肥料,例如硫酸铵、磷酸铵、硝酸铵、脲类;植物来源的产品,例如谷粉、树皮粉、木粉和坚果壳粉,以及它们的混合物。
合适的表面活性剂是表面活性化合物,如阴离子、阳离子、非离子和两性表面活性剂,嵌段聚合物,聚电解质,以及它们的混合物。该类表面活性剂可以用作乳化剂、分散剂、加溶剂、润湿剂、渗透促进剂、保护性胶体或辅助剂。表面活性剂的实例列于McCutcheon’s,第1卷:Emulsifiers&Detergents,McCutcheon’s Directories,Glen Rock,USA,2008(International Ed.或North American Ed.)中。
合适的阴离子表面活性剂是磺酸、硫酸、磷酸、羧酸的碱金属、碱土金属或铵盐以及它们的混合物。磺酸盐的实例是烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木素磺酸盐、脂肪酸和油的磺酸盐、乙氧基化烷基酚的磺酸盐、烷氧基化芳基酚的磺酸盐、缩合萘的磺酸盐、十二烷基-和十三烷基苯的磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例是脂肪酸和油的硫酸盐、乙氧基化烷基酚的硫酸盐、醇的硫酸盐、乙氧基化醇的硫酸盐或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸盐酯。羧酸盐的实例是烷基羧酸盐以及羧化醇或烷基酚乙氧基化物。
合适的非离子表面活性剂是烷氧基化物,N-取代的脂肪酸酰胺,胺氧化物,酯类,糖基表面活性剂,聚合物表面活性剂及其混合物。烷氧基化物的实例是诸如已经被1-50当量烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可以将氧化乙烯和/或氧化丙烯用于烷氧基化,优选氧化乙烯。N-取代的脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯类的实例是脂肪酸酯,甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨醇、乙氧基化脱水山梨醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。聚合物表面活性剂的实例是乙烯基吡咯烷酮、乙烯醇或乙酸乙烯酯的均聚物或共聚物。
合适的阳离子表面活性剂是季型表面活性剂,例如具有1或2个疏水性基团的季铵化合物,或长链伯胺的盐。合适的两性表面活性剂是烷基甜菜碱和咪唑啉类。合适的嵌段聚合物是包含聚氧乙烯和聚氧丙烯的嵌段的A-B或A-B-A类型嵌段聚合物,或包含链烷醇、聚氧乙烯和聚氧丙烯的A-B-C类型嵌段聚合物。合适的聚电解质是聚酸或聚碱。聚酸的实例是聚丙烯酸的碱金属盐或聚酸梳状聚合物。聚碱的实例是聚乙烯基胺或聚乙烯胺。
合适的辅助剂是本身具有可忽略的农药活性或者本身甚至没有农药活性且改善本发明化合物对目标物的生物学性能的化合物。实例是表面活性剂,矿物油或植物油以及其他助剂。其他实例由Knowles,Adjuvants and additives,Agrow Reports DS256,T&FInforma UK,2006,第5章列出。
合适的增稠剂是多糖(例如黄原胶、羧甲基纤维素)、无机粘土(有机改性或未改性的)、聚羧酸盐和硅酸盐。
合适的杀菌剂是拌棉醇和异噻唑啉酮衍生物如烷基异噻唑啉酮和苯并异噻唑啉酮。
合适的防冻剂是乙二醇、丙二醇、尿素和甘油。
合适的消泡剂是聚硅氧烷、长链醇和脂肪酸盐。
合适的着色剂(例如着红色、蓝色或绿色)是低水溶性颜料和水溶性染料。实例是无机着色剂(例如氧化铁、氧化钛、六氰合铁酸铁)和有机着色剂(例如茜素着色剂、偶氮着色剂和酞菁着色剂)。
合适的增粘剂或粘合剂是聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇、聚丙烯酸酯、生物蜡或合成蜡以及纤维素醚。
农业化学组合物通常包含0.01-95重量%,优选0.1-90重量%,尤其是0.5-75重量%活性物质。活性物质以90-100%,优选95-100%的纯度(根据NMR光谱)使用。
可以向活性物质或包含它们的组合物中作为预混物加入或者合适的话在紧临使用前加入(桶混合)各种类型的油、润湿剂、辅助剂、肥料或微营养素和其他农药(例如除草剂、杀虫剂、杀真菌剂、生长调节剂、安全剂、生物农药)。这些试剂可以以1:100-100:1,优选1:10-10:1的重量比与本发明组合物混合。
用户通常将本发明组合物用于前剂量装置、小背包喷雾器、喷雾罐、喷雾飞机或灌溉系统。这里将该农业化学组合物用水、缓冲剂和/或其他助剂配制至所需施用浓度,从而得到即用喷雾液或本发明农业化学组合物。每公顷农业利用区通常施用20-2000升,优选50-400升即用喷雾液。
根据一个实施方案,用户可以自己在喷雾罐中混合本发明组合物的各组分,例如成套包装的各部分或二元或三元混合物的各部分并且合适的话可以加入其他助剂。
在另一实施方案中,用户可以在喷雾罐中混合本发明组合物的各组分或部分预混的组分,例如包含本发明化合物和/或如上所定义的混合配对的组分,并且合适的话可以加入其他助剂和添加剂。
在另一实施方案中,可以联合(例如在桶混合之后)或依次使用本发明组合物的各组分或部分预混的组分,例如包含本发明化合物和/或如上所定义的混合配对的组分。
本发明化合物适合用于保护作物、植物、植物繁殖材料如种子或其中植物生长的土壤或水体以防动物害虫侵袭或侵染。因此,本发明还涉及一种植物保护方法,包括使要保护以防止动物害虫侵袭或侵染的作物、植物、植物繁殖材料如种子或其中植物生长的土壤或水体与杀害虫有效量的本发明化合物接触。
本发明化合物还适合用于防治或防除动物害虫。因此,本发明还涉及一种防治或防除动物害虫的方法,包括使动物害虫、其栖息地、繁殖地或食物供应源或作物、植物、植物繁殖材料如种子或土壤或者其中动物害虫生长或可能生长的区域、材料或环境与杀害虫有效量的本发明化合物接触。
本发明化合物通过接触和摄取二者而有效。此外,本发明化合物可以施用于任何和所有发育阶段,如卵、幼虫、蛹和成虫。
本发明化合物可以直接或者以如上所述包含它们的组合物形式施用。此外,本发明化合物可以与如上所定义的混合配对一起施用或者以如上所述包含所述混合物的组合物形式施用。所述混合物的组分可以同时,即联合或分开施用,或者依次施用,即一个紧邻一个之后并且由此在所需场所,例如植物上“就地”产生该混合物,在分开施用的情况下,顺序通常对防治措施的结果没有任何效果。
施用可以在作物、植物、植物繁殖材料如种子、土壤或区域、材料或环境被害虫侵染之前和之后均可以进行。
合适的施用方法尤其包括土壤处理、种子处理、犁沟内施用和叶面施用。土壤处理方法包括浸透土壤,滴灌(滴施于土壤上),浸渍根、块茎或球茎,或者土壤注入。种子处理技术包括拌种、种子包衣、种子撒粉、种子浸泡和种子造粒。犁沟内施用通常包括在耕种地产生犁沟、对犁沟播种、对犁沟施用杀害虫活性化合物和封闭犁沟的步骤。叶面施用是指将杀害虫活性化合物施用于植物叶面,例如通过喷雾设备施用。对于叶面施用,可能有利的是通过使用与本发明化合物组合的信息素改变害虫行为。适合特定作物和害虫的信息素对熟练技术人员是已知的且可以由信息素和信息化合物数据库,如http://www.pherobase.com公众可得。
本文所用术语“接触”包括直接接触(将化合物/组合物直接施用于动物害虫或植物上,通常施用于植物的叶面、茎或根)和间接接触(将化合物/组合物施用于动物害虫或植物的场所,即栖息地,繁殖地,其中害虫生长或可能生长的植物、种子、土壤、区域、材料或环境)二者。
术语“动物害虫”包括节肢动物、腹足动物和线虫。根据本发明优选的动物害虫是节肢动物,优选昆虫和蜘蛛,尤其是昆虫。对于作物特别相关的昆虫通常称为作物昆虫害虫。
术语“作物”是指生长和收获的作物二者。
术语“植物”包括禾谷类,例如硬粒小麦和其他小麦,黑麦,大麦,小黑麦,燕麦,稻或玉米(青饲玉米和甜玉蜀黍/甜玉米以及大田玉米);甜菜,例如糖用甜菜或饲料甜菜;水果,如仁果、核果或浆果,例如苹果、梨、李、桃、油桃、杏仁、樱桃、木瓜、草莓、悬钩子、黑莓或鹅莓;豆科植物,如菜豆、扁豆、豌豆、苜蓿或大豆;油料植物,例如油菜(油籽油菜)、白菜型油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆;葫芦科植物,例如笋瓜、南瓜、黄瓜或甜瓜;纤维植物,例如棉花、亚麻、大麻或黄麻;柑桔类水果,例如橙子、柠檬、葡萄柚或橘;蔬菜,例如茄子、菠菜、莴苣(例如卷心莴苣)、菊苣、卷心菜、芦笋、卷心菜、胡萝卜、洋葱、大蒜、韭葱、西红柿、土豆、葫芦或柿子椒;月桂类植物,例如鳄梨、肉桂或樟脑;能量和原料植物,例如玉米、大豆、油菜籽、甘蔗或油棕;烟草;坚果,例如核桃;开心果;咖啡;茶;香蕉;葡萄藤(食用葡萄和酿酒用葡萄);啤酒花;甜叶菊(也称甜菊(Stevia));天然橡胶植物或观赏和森林植物,例如花卉(例如康乃馨、矮牵牛、天竺葵/香叶天竺葵、三色堇和凤仙花),灌木,阔叶树(例如杨树)或常绿树,例如针叶树;桉树;草皮;草坪;禾草如动物饲料或观赏用途的禾草。优选的植物包括土豆、糖用甜菜、烟草、小麦、黑麦、大麦、燕麦、稻、玉米、棉花、大豆、油菜籽、豆科植物、向日葵、咖啡或甘蔗;水果;葡萄藤;观赏植物;或蔬菜,如黄瓜西红柿、菜豆或笋瓜。
术语“植物”应理解为包括野生型植物和已经通过常规育种或诱变或基因工程或其组合修饰的植物。
已经通过诱变或基因工程修饰并且具有特别商业重要性的植物包括苜蓿、油菜籽(例如油籽油菜)、菜豆、康乃馨、菊苣、棉花、茄子、桉树、亚麻、扁豆、玉米、甜瓜、木瓜、矮牵牛、李子、杨树、土豆、稻、大豆、笋瓜、糖用甜菜、甘蔗、向日葵、甜椒、烟草、西红柿和禾谷类(例如小麦),尤其是玉米、大豆、棉花、小麦和稻。在已经通过诱变或基因工程修饰的植物中,一个或多个基因已经诱变处理或整合进入植物的遗传材料中。该一个或多个诱变处理或整合的基因优选选自pat,epsps,cry1Ab,bar,cry1Fa2,cry1Ac,cry34Ab1,cry35AB1,cry3A,cryF,cry1F,mcry3a,cry2Ab2,cry3Bb1,cry1A.105,dfr,芽孢杆菌RNA酶,vip3Aa20,芽孢杆菌RNA酶抑制剂,als,bxn,bp40,asn1和ppo5。进行一个或多个基因的诱变或整合以改善植物的某些性能。也已知为性状的该类性能性能包括非生物应力耐受性、改变的生长/产量、病害耐受性、除草剂耐受性、昆虫耐受性、改性的产品质量和授粉控制。在这些性能中,特别重要的是除草剂耐受性,例如米唑啉酮耐受性、草甘膦(glyphosate)耐受性或草铵膦(glufosinate)耐受性。几种植物已经通过诱变而耐受除草剂,例如油籽油菜耐受咪唑啉酮类,例如咪草啶酸(imazamox)。或者,已经使用基因工程方法来使植物如大豆、棉花、玉米、甜菜和油籽油菜耐受除草剂,如草甘膦和草铵膦,它们中的一些可以以商标名(草甘膦)和(草铵膦)市购。此外,重要的是昆虫耐受性,尤其是鳞翅目昆虫耐受性和鞘翅目昆虫耐受性。昆虫耐受性通常通过整合cry和/或vip基因以修饰植物而实现,这些基因由苏云金芽孢杆菌(Bt)分离并编码相应Bt毒素。具有昆虫耐受性的基因修饰植物可以以包括 和的商标名市购。植物可以通过诱变或基因工程而就一种性能(单一性状)或就性能组合(叠加性状)进行修饰。叠加性状,例如除草剂耐受性和昆虫耐受性的组合越来越重要。通常而言,所有与单一或叠加性状关联的相关修饰植物以及有关诱变处理或整合的基因和相应事件的详细信息可以由一些组织的网站得到“InternationalService for the Acquisition of Agri-biotech Applications(ISAAA)”(http:// www.isaaa.org/gmapprovaldatabase)和“Center for Environmental Risk Assessment(CERA)”(http://cera-gmc.org/GMCropDatabase)。
已经惊人地发现本发明化合物的杀害虫活性可以通过修饰植物的杀虫特征提高。此外,已经发现本发明化合物适合防止昆虫耐受该杀虫特征或者适合防除已经耐受修饰植物杀虫特征的害虫。此外,本发明化合物适合防除该杀虫特征对其无效的害虫,因而可以有利地使用互补的杀虫活性。
术语“植物繁殖材料”是指植物的所有繁殖部分如种子,以及可以用于繁殖植物的无性植物材料如插条和块茎(例如土豆)。这包括种子、根、果实、块茎、球茎、地下茎、嫩枝、芽和其他植物部分。还可以包括在萌发后或出苗后由土壤移植的秧苗和幼苗。这些植物繁殖材料可以在种植或移栽之时或之前用植物保护化合物预防性处理。
术语“种子”包括所有种类的种子和植物繁殖体,包括但不限于真正的种子、种子切片(seed piece)、吸枝、球茎、鳞茎、果实、块茎、谷粒、插条、伐条(cut shoot)等,并且在优选实施方案中指真正的种子。
通常而言,“杀害虫有效量”是指对生长获得可观察到的效果所需的活性成分的量,所述效果包括坏死、死亡、阻滞、预防和去除效果,破坏效果或减少目标生物体的出现和活动的效果。对于在本发明中使用的各种化合物/组合物,杀害虫有效量可以变化。组合物的杀害虫有效量也会根据主要条件如所需杀害虫效果及持续时间、气候、目标物种、场所、施用方式等而变化。
在土壤处理、犁沟内施用或施用于害虫居住地或巢穴的情况下,活性成分量为0.0001-500g/100m2,优选0.001-20g/100m2。
为了用于例如通过叶面施用处理农作物,本发明活性成分的施用率可以为0.0001-4000g/ha,例如1-2kg/ha或1-750g/ha,理想的是1-100g/ha,更理想的是10-50g/ha,例如10-20g/ha,20-30g/ha,30-40g/ha或40-50g/ha。
本发明化合物尤其适合用于处理种子以保护种子免受虫害,尤其是免受土壤生虫害,并保护所得秧苗的根和芽以防土壤害虫和叶面昆虫。本发明因此还涉及一种保护种子以防昆虫,尤其是土壤昆虫并保护秧苗的根和芽以防昆虫,尤其是土壤和叶面昆虫的方法,所述方法包括在播种之前和/或预萌发之后用本发明化合物处理种子。优选保护秧苗的根和芽,更优选保护秧苗的芽以防刺吸式口器昆虫、嘴嚼口器害虫和线虫。
术语“种子处理”包括所有本领域已知的合适种子处理技术,如拌种、种子涂敷、种子撒粉、种子浸泡、种子压丸和犁沟内施用方法。优选活性化合物的种子处理施用通过在植物播种之前且在植物出苗之前对植物喷雾或撒粉而进行。
本发明还包括涂有或含有活性化合物的种子。术语“涂有和/或含有”通常是指活性成分在施用时绝大部分处于繁殖产品的表面上,但更大或更小部分的成分可能渗入繁殖产品中,这取决于施用方法。当(再)种植所述繁殖产品时,它可能吸收活性成分。
合适的种子例如为各种禾谷类、根系作物、油料作物、蔬菜、香料、观赏植物的种子,例如硬粒小麦和其他小麦、大麦、燕麦、黑麦、玉米(青饲玉米和甜玉蜀黍/甜玉米以及大田玉米)、大豆、油料作物、十字花科植物、棉花、向日葵、香蕉、稻、油籽油菜、芜菁油菜、糖用甜菜、饲料甜菜、茄子、土豆、禾草、草坪、草皮、牧草、西红柿、韭葱、南瓜/笋瓜、卷心菜、刺茎莴苣、胡椒、黄瓜、甜瓜、芸苔属(Brassica)、甜瓜、菜豆、豌豆、大蒜、洋葱、胡萝卜、块茎植物如土豆、甘蔗、烟草、葡萄、矮牵牛、天竺葵/香叶天竺葵、三色堇和凤仙花。
此外,活性化合物还可以用于处理已经通过诱变或基因工程修饰并且例如耐受除草剂或杀真菌剂或杀虫剂作用的植物的种子。该类修饰植物已经如上所详细描述。
常规种子处理配制剂例如包括可流动浓缩物FS、溶液LS、悬浮乳液(SE)、干处理用粉末DS、淤浆处理用水分散性粉末WS、水溶性粉末SS、乳液ES和EC以及凝胶配制剂GF。这些配制剂可以经稀释或不经稀释而施用于种子上。对种子的施用在播种之前进行,直接施用于种子上或在种子已经预萌发之后施用。优选施用配制剂以使得不诱发萌发。
可以在稀释2-10倍之后得到的即用配制剂中活性物质浓度优选为0.01-60重量%,更优选0.1-40重量%。
在优选实施方案中,将FS配制剂用于种子处理。FS配制剂通常可包含1-800g/l活性成分,1-200g/l表面活性剂,0-200g/l防冻剂,0-400g/l粘合剂,0-200g/l颜料和达到1升的溶剂,优选水。
用于种子处理的本发明化合物的尤其优选FS配制剂通常包含0.1-80重量%(1-800g/l)活性成分,0.1-20重量%(1-200g/l)至少一种表面活性剂,例如0.05-5重量%润湿剂和0.5-15重量%分散剂,至多20重量%,例如5-20%防冻剂,0-15重量%,例如1-15重量%颜料和/或染料,0-40重量%,例如1-40重量%粘合剂(粘结剂/粘附剂),任选至多5重量%,例如0.1-5重量%增稠剂,任选0.1-2%消泡剂和任选防腐剂如生物杀伤剂、抗氧化剂等,例如其量为0.01-1重量%,以及达到100重量%的填料/载体。
在种子处理中,本发明化合物的施用率通常为0.01g-10kg/100kg种子,优选1g-5kg/100kg种子,更优选1-1000g/100kg种子,尤其是1-200g/100kg种子,例如1-100g或5-100g/100kg种子。
因此,本发明还涉及包含如本文所定义的本发明化合物或其可农用盐的种子。本发明化合物或其可农用盐的量通常为0.1g-10kg/100kg种子,优选1g-5kg/100kg种子,尤其是1-1000g/100kg种子。对于特殊作物如莴苣,施用率可能更高。
本发明化合物还可以用于改善植物健康。因此,本发明还涉及一种通过用有效且非植物毒性量的本发明化合物处理植物、植物繁殖材料和/或其中植物生长或将要生长的场所而改善植物健康的方法。
本文所用“有效且非植物毒性量”是指以允许得到所需效果但不对被处理植物或由被处理繁殖体或被处理土壤生长的植物引起任何植物毒性症状的量使用化合物。
术语“植物”和“植物繁殖材料”如上所定义。
“植物健康”定义为由几个方面单独或相互结合决定的植物和/或其产品的状况,如产量(例如增加的生物质和/或增加的有价值成分含量),质量(例如某些成分的改善含量或组成或储存期限),植物活力(例如改善的植物生长和/或更绿的叶子(“绿化效果”),对非生物(例如干旱)和/或生物应力(例如病害)的耐受性以及生产效率(例如收获效率、加工性)。
植物健康状况的上述迹象可以相互依存或可以相互影响。各迹象在本领域中定义并且可以由熟练技术人员已知的方法确定。
本发明化合物还适合用于对抗非作物虫害。为了用于对抗所述非作物虫害,可以将本发明化合物用作诱饵组合物、凝胶、通用昆虫喷雾剂、气雾剂、超低容量施用和蚊帐(浸渍的或表面施用的)。此外,可以使用浸透和喷杆方法。
本文所用术语“非作物虫害”是指对于非作物目标特别相关的害虫,如蚂蚁、白蚁、黄蜂、蝇、蜱、蚊、蟋蟀或蟑螂。
诱饵可以是液体、固体或半固体制剂(例如凝胶)。用于组合物中的诱饵是具有足够的吸引力以刺激诸如蚂蚁、白蚁、黄蜂、蝇、蚊、蟋蟀等的昆虫或蟑螂食用它的产品。吸引力可以通过使用进食刺激剂或性信息素控制。食物刺激剂例如并不穷举地选自动物和/或植物蛋白质(肉-、鱼-或血液膳食,昆虫部分、蛋黄)、动物和/或植物来源的脂肪和油或单-、低聚-或聚有机糖类,尤其是蔗糖、乳糖、果糖、右旋糖、葡萄糖、淀粉、果胶或甚至糖蜜或蜂蜜。水果、作物、植物、动物、昆虫的新鲜或腐败部分或其特定部分也可以用作进食刺激剂。已知性信息素更具昆虫特异性。特殊信息素描述于文献(例如http://www.pherobase.com)中并且对本领域熟练技术人员是已知的。
为了用于诱饵组合物中,活性成分的典型含量为0.001-15重量%,理想的是0.001-5重量%活性化合物。
本发明化合物的配制剂如气雾剂(例如在喷雾罐中)、油喷雾剂或泵喷雾剂高度适于非专业使用者来防治害虫如蝇、跳蚤、蜱、蚊或蟑螂。气雾剂配方优选由如下组分构成:活性化合物,溶剂,此外还有助剂,如乳化剂、芳香油,合适的话还有稳定剂以及需要的话推进剂。
油喷雾配制剂与气雾剂配方的不同在于没有使用推进剂。
对于在喷雾组合物中的使用,活性成分含量为0.001-80重量%,优选0.01-50重量%,最优选0.01-15重量%。
本发明化合物及其相应的组合物还可以用于蚊香片和熏蒸片,发烟盒、蒸发器板或长效蒸发器以及扑蛾纸、扑蛾垫或其他与热无关的蒸发器体系中。
用本发明化合物及其相应组合物控制由昆虫传递的传染性疾病(例如疟疾、登革热和黄热病,淋巴丝虫病以及利什曼病)的方法也包括处理棚屋和房子的表面、空气喷雾和浸渍窗帘、帐篷、衣物、蚊帐、采采蝇网等。施用于纤维、织物、编织物、无纺织物、网状材料或箔以及篷布上的杀虫组合物优选包含包括杀虫剂、任选的驱除剂和至少一种粘合剂的混合物。
本发明化合物及其组合物可以用于保护木质材料如树木、护栏、枕木、框架、艺术作品等,以及建筑物,还有建筑材料、家具、皮革、纤维、乙烯基制品、电线和电缆等以防蚂蚁和/或白蚁,并防止蚂蚁和白蚁损害作物或人类(例如当害虫侵入房子和公共设施时)。
材料保护中的常规施用率例如为0.001-2000g或0.01-1000g活性化合物/m2被处理材料,理想的是0.1-50g活性化合物/m2被处理材料。
用于浸渍材料的杀虫组合物通常含有0.001-95重量%,优选0.1-45重量%,更优选1-25重量%至少一种驱除剂和/或杀虫剂。
本发明化合物尤其适合有效防除动物害虫如节肢动物、腹足动物和线虫,包括但不限于:
鳞翅目(Lepidoptera)昆虫,例如小蜡螟(Achroia grisella),长翅卷蛾属(Acleris spp.),如A.fimbriana,西黑头长翅卷蛾(A.gloverana),黑头长翅卷蛾(A.variana);Acrolepiopsis assectella,桑剑纹夜蛾(Acronicta major),褐带卷蛾属(Adoxophyes spp.),如拟小黄卷叶蛾(A.cyrtosema),苹果小卷叶蛾(A.orana);烦夜蛾(Aedia leucomelas),地夜蛾属(Agrotis spp.),如警纹地老虎(A.exclamationis)、燕青地老虎(A.fucosa)、小地老虎(A.ipsilon)、A.orthogoma、黄地老虎(A.segetum)、A.subterranea;棉叶波纹夜蛾(Alabama argillacea),螺旋粉虱(Aleurodicusdisperses),波林尺蛾(Alsophila pometaria),葡萄天蛾(Ampelophaga rubiginosa),Amyelois transitella,Anacampsis sarcitella,Anagasta kuehniella,桃条麦蛾(Anarsia lineatella),栎黄条大蚕蛾(Anisota senatoria),柞蚕(Antheraea pernyi),干煞夜蛾属(Anticarsia(=Thermesia)spp.),如黎豆夜蛾(A.gemmatalis);Apamea spp.,Aproaerema modicella,黄卷蛾属(Archips spp.),如果树黄卷蛾(A.argyrospila),杏黄卷蛾(A.fuscocupreanus),玫瑰黄卷蛾(A.rosana),A.xyloseanus;苹果银蛾(Argyresthiaconjugella),条小卷蛾属(Argyroploce spp.),带卷蛾属(Argyrotaenia spp.),如短叶松带卷蛾(A.velutinana);Athetis mindara,Austroasca viridigrisea,丫纹夜蛾(Autographa gamma),黑点丫纹夜蛾(Autographa nigrisigna),甘蓝夜蛾(Barathrabrassicae),Bedellia spp.,Bonagota salubricola,籼弄蝶(Borbo cinnara),棉叶穿孔潜蛾(Bucculatrix thurberiella),松尺蠖(Bupalus piniarius),Busseola spp.,卷叶蛾属(Cacoecia spp.),如枞卷叶蛾(C.murinana)、黄尾卷叶蛾(C.podana);穿孔螟(Cactoblastis cactorum),粉斑螟蛾(Cadra cautella),Calingo braziliensis,Caloptilis theivora,Capua reticulana,Carposina spp.,如桃蛀果蛾(C.niponensis),桃小食心虫(C.sasakii);茎蜂属(Cephus spp.),麦茎大跳甲(Chaetocnema aridula),冬尺蛾(Cheimatobia brumata),禾草螟属(Chilo spp.),如C.indicus)、二化螟(C.suppressalis)、C.partellus;Choreutis pariana,色卷蛾属(Choristoneura spp.),如柳色卷蛾(C.conflictana),云杉色卷蛾(C.fumiferana),苹果大卷叶蛾(C.longicellana),欧洲云杉卷叶蛾(C.murinana),西部云杉色卷蛾(C.occidentalis),C.rosaceana;夜蛾属(Chrysodeixis(=Pseudoplusia)spp.),南方银纹夜蛾如(C.eriosoma),大豆尺蠖(C.includens);粘虫(Cirphis unipuncta),葡萄果蠹蛾(Clysiaambiguella),Cnaphalocerus spp.,稻纵卷叶野螟(Cnaphalocrocis medinalis),云卷蛾属(Cnephasia spp.),向日葵螟(Cochylis hospes),鞘蛾属(Coleophora spp.),Coliaseurytheme,茶枝尖细蛾属(Conopomorpha spp.),Conotrachelus spp.,Copitarsia spp.,米螟(Corcyra cephalonica),玉米根结网毛虫(Crambus caliginosellus),早熟禾草螟(Crambus teterrellus),Crocidosema(=Epinotia)aporema,Cydalima(=Diaphania)perspectalis,小卷蛾属(Cydia(=Carpocapsa)spp.),如苹果小卷蛾(C.pomonella),坚果卷叶蛾(C.latiferreana);Dalaca noctuides,核桃配片舟蛾(Datana integerrima),Dasychira pinicola,松毛虫属(Dendrolimus spp.),如欧洲松毛虫(D.pini)、赤松毛虫(D.spectabilis),落叶松毛虫(D.sibiricus);葡萄小卷叶野螟(Desmia funeralis),Diaphania spp.,如黄瓜绢野螟(D.nitidalis),甜瓜绢野螟(D.hyalinata);西南玉米杆草螟(Diatraea grandiosella),小蔗螟(Diatraea saccharalis),Diphthera festiva,金刚钻属(Earias spp.),如埃及钻夜蛾(E.insulana),翠纹金刚钻(E.vittella);Ecdytolophaaurantianu,Egira(=Xylomyges)curialis,南美玉米苗斑螟(Elasmopalpuslignosellus),甘蔗钻心虫(Eldana saccharina),葡萄小食心虫(Endopiza viteana),榆秋黄尺蛾(Ennomos subsignaria),墨西哥水稻螟(Eoreuma loftini),粉斑螟属(Ephestiaspp.),如干果粉斑螟(E.cautella)、烟草粉斑螟(E.elutella)、地中海粉斑螟(E.kuehniella);夜小卷蛾(Epinotia aporema),苹果褐卷蛾(Epiphyas postvittana),菩提松尺蛾(Erannis tiliaria),蕉弄蝶(Erionota thrax),螟蛾属(Etiella spp.),Euliaspp.,女贞细卷蛾(Eupoecilia ambiguella),黄毒蛾(Euproctis chrysorrhoea),切夜蛾属(Euxoa spp.),Evetria bouliana,Faronta albilinea,夜蛾属(Feltia spp.),如粒肤地虎(F.Subterranean);蜡螟(Galleria mellonella),Gracillaria spp.,食心虫属(Grapholita spp.),如李小食心虫(G.funebrana)、梨小食心虫(G.molesta),苹果小食心虫(G.inopinata);Halysidota spp.,黑拟蛉蛾(Harrisina americana),Hedylepta spp.,棉铃虫属(Helicoverpa spp.),如棉铃虫(H.armigera(=Heliothis armigera))、美洲棉铃虫(H.zea(=Heliothis zea));实夜蛾属(Heliothis spp.),如烟实夜蛾(H.assulta))、H.subflexa、烟芽夜蛾(H.virescens);Hellula spp.,如菜心野螟(H.undalis)、菜螟(H.rogatalis);Helocoverpa gelotopoeon,Hemileuca oliviae,Herpetogrammalicarsisalis,Hibernia defoliaria,褐织蛾(Hofmannophila pseudospretella),向日葵同斑螟(Homoeosoma electellum),茶长卷蛾(Homona magnanima),Hypena scabra,美国白蛾(Hyphantria cunea),樱桃巢蛾(Hyponomeuta padella),苹果巢蛾(Hyponomeutamalinellus),柿蒂虫(Kakivoria flavofasciata),番茄虫蛾(Keiferialycopersicella),铁杉尺蠖蛾(Lambdina fiscellaria fiscellaria),西方铁杉尺蠖蛾(Lambdina fiscellaria lugubrosa),豆卷叶螟(Lamprosema indicata),蠹食心虫(Laspeyresia molesta),大豆食心虫(Leguminivora glycinivorella),Lerodea eufala,Leucinodes orbonalis,雪毒蛾(Leucoma salicis),潜叶蛾属(Leucoptera spp.),如咖啡潜叶蛾(L.coffeella)、旋纹潜蛾(L.scitella);Leuminivora lycinivorella,苹果斑幕潜叶蛾(Lithocolletis blancardella),绿果冬夜蛾(Lithophane antennata),Llattiaocto(=Amyna axis),葡萄浆果小卷蛾(Lobesia botrana),Lophocampa spp.,豆白隆切根虫(Loxagrotis albicosta),Loxostege spp.,如甜菜网螟(L.sticticalis),L.cereralis;毒蛾属(Lymantria spp.),如舞毒蛾(L.dispar)、模毒蛾(L.monacha);桃潜蛾(Lyonetia clerkella),Lyonetia prunifoliella,天幕毛虫属(Malacosoma spp.),如苹天幕毛虫(M.americanum)、草原天幕毛虫(M.californicum)、森林天幕毛虫(M.constrictum)、黄褐天幕毛虫(M.neustria);甘蓝夜蛾属(Mamestra spp.),如甘蓝夜蛾(M.brassicae)、蓓带夜蛾(M.configurata);Mamstra brassicae,Manduca spp.,如番茄天蛾(M.quinquemaculata)、烟草天蛾(M.sexta);刷须野螟属(Marasmia spp),Marmaraspp.,豆野螟(Maruca testulalis),Megalopyge lanata,Melanchra picta,暮眼蝶(Melanitis leda),Mocis spp.,如M.lapites,稻毛胫夜蛾(M.repanda);Mocis latipes,Monochroa fragariae,粘虫(Mythimna separata),Nemapogon cloacella,Neoleucinodeselegantalis,伪尺蛾属(Nepytia spp.),Nymphula spp.,Oiketicus spp.,豆啮叶野螟(Omiodes indicata),甘薯茎螟(Omphisa anastomosalis),冬尺蠖蛾(Operophterabrumata),黄杉合毒蛾(Orgyia pseudotsugata),Oria spp.,Orthaga thyrisalis,秆野螟属(Ostrinia spp.),如欧洲玉米螟(O.nubilalis);稻负泥虫(Oulema oryzae),苹尺蛾(Paleacrita vernata),小眼夜蛾(Panolis flammea),稻弄蝶属(Parnara spp.),普通蛀茎夜蛾(Papaipema nebris),大凤蝶(Papilio cresphontes),脐橙螟蛾(Paramyeloistransitella),葡萄透翅蛾(Paranthrene regalis),无棕榈蝶蛾(Paysandisia archon),螟蛉属(Pectinophora spp.),如彩色螟蛉(P.gossypiella);疆夜蛾(Peridroma saucia),潜叶蛾属(Perileucoptera spp.),如咖啡潜叶蛾(P.coffeella);圆掌舟蛾(Phalerabucephala),Phryganidia californica,烟尺蛾属(Phthorimaea spp.),如马铃薯麦蛾(P.operculella);柑桔潜叶蛾(Phyllocnistis citrella),潜叶蛾属(Phyllonorycterspp.),如斑幕潜叶蛾(P.blancardella),山楂潜叶蛾(P.crataegella),P.issikii,金纹细蛾(P.ringoniella);菜粉蝶属(Pieris spp.),如欧洲粉蝶(P.brassicae)、菜粉蝶(P.rapae)、绿脉菜粉蝶(P.napi);Pilocrocis tripunctata,苜蓿绿夜蛾(Plathypenascabra),Platynota spp.,如P.flavedana,P.idaeusalis,P.stultana;荷兰石竹小卷蛾(Platyptilia carduidactyla),豆灰蝶(Plebejus argus),印度谷螟(Plodiainterpunctella),Plusia spp,菜蛾(Plutella maculipennis),小菜蛾(Plutellaxylostella),Pontia protodica,Prays spp.,斜纹夜蛾属(Prodenia spp.),二点委夜蛾(Proxenus lepigone),粘虫属(Pseudaletia spp.),如P.sequax,一星粘虫(P.unipuncta);玉米螟(Pyrausta nubilalis),Rachiplusia nu,Richia albicosta,Rhizobius ventralis,Rhyacionia frustrana,Sabulodes aegrotata,Schizuraconcinna,Schoenobius spp.,Schreckensteinia festaliella,白禾螟属(Scirpophagaspp.),如三化螟(S.incertulas),S.innotata;Scotia segetum,大螟属(Sesamia spp.),如水稻大螟(S.inferens),葡萄修虎蛾(Seudyra subflava),麦蛾(Sitotrogacerealella),葡萄卷叶蛾(Sparganothis pilleriana),Spilonota lechriaspis,苹果小卷蛾(S.ocellana),灰翅夜蛾属(Spodoptera(=Lamphygma)spp.),如S.eridania,甜菜夜蛾(S.exigua),草地夜蛾(S.frugiperda)、S.latisfascia,海灰翅夜蛾(S.littoralis)、斜纹夜蛾(S.litura)、黄条粘虫(S.omithogalli);Stigmella spp.,Stomopteryxsubsecivella,Strymon bazochii,棉卷叶野螟(Sylepta derogata),Synanthedon spp.,如小桃翅蛾(S.exitiosa),Tecia solanivora,Telehin licus,Thaumatopoeapityocampa,Thaumatotibia(=Cryptophlebia)leucotreta,松异舟蛾(Thaumetopoeapityocampa),Thecla spp.,Theresimima ampelophaga,Thyrinteina spp,Tildeniainconspicuella,Tinea spp.,如T.cloacella,袋谷蛾(T.pellionella);幕谷蛾(Tineolabisselliella),Tortrix spp.,如栎绿卷蛾(T.viridana);毛颤蛾(Trichophagatapetzella),粉夜蛾属(Trichoplusia spp.),如粉纹夜蛾(T.ni);Tuta(=Scrobipalpula)absoluta,(Udea spp.,如温室结网野螟(U.rubigalis);Virachola spp.,苹果巢蛾(Yponomeuta padella)和Zeiraphera canadensis;
鞘翅目(Coleoptera)昆虫,例如Acalymma vittatum,菜豆象(Acanthoscehdesobtectus),喙丽金龟属(Adoretus spp.),杨树萤叶甲(Agelastica alni),Agrilus spp.,如A.anxius、A.Planipennis、梨窄吉丁(A.sinuatus);叩甲属(Agriotes spp.),如细胸叩头虫(A.fuscicollis)、条叩头虫(A.lineatus)、暗色叩头虫(A.obscurus);Alphitobiusdiaperinus,Amphimallus solstitialis,Anisandrus dispar,奥国塞丽金龟(Anisopliaaustriaca),家具窃蠹(Anobium punctatum),铜绿异丽金龟(Anomala corpulenta),红铜丽金龟(Anomala rufocuprea),星天牛属(Anoplophora spp.),如光肩星天牛(A.glabripennis);花象甲属(Anthonomus spp.),如胡椒跳甲(A.eugenii)、棉铃象甲(A.grandis)、苹花象(A.pomorum);圆皮蠹属(Anthrenus spp.),Aphthona euphoridae,梨象属(Apion spp.),阿鳃金龟属(Apogonia spp.),Athous haemorrhoidalis,隐翅甲属(Atomaria spp.),如甜菜隐食甲(A.linearis);毛皮蠹属(Attagenus spp.),黄守瓜(Aulacophora femoralis),纵坑切梢小蠹(Blastophagus piniperda),Blitophagaundata,Bruchidius obtectus,豆象属(Bruchus spp.),如欧洲兵豆象(B.lentis)、豌豆象(B.pisorum)、蚕豆象(B.rufimanus);苹卷象(Byctiscus betulae),Callidiellumrufipenne,Callopistria floridensis,绿豆象(Callosobruchus chinensis),Camerariaohridella,甜菜大龟甲(Cassida nebulosa),豆叶甲(Cerotoma trifurcata),金花金龟(Cetonia aurata),龟象属(Ceuthorhynchus spp.),如白菜籽龟象(C.assimilis)、芫菁龟象(C.napi);甜菜胫跳甲(Chaetocnema tibialis),Cleonus mendicus,宽胸叩头虫属(Conoderus spp.),如烟草金针虫(C.vespertinus);Conotrachelus nenuphar,根颈象属(Cosmopolites spp.),新西兰草地蛴螬(Costelytra zealandica),石刁柏负泥虫(Crioceris asparagi),正锈赤扁谷盗(Cryptolestes ferrugineus),杨干隐喙象(Cryptorhynchus lapathi),Ctenicera spp.,如C.destructor;象虫属(Curculio spp.),Cylindrocopturus spp.,Cyclocephala spp.,玉米铁甲虫(Dactylispa balyi),蛀茎虫(Dectes texanus),皮蠹属(Dermestes spp.),叶甲属(Diabrotica spp.),如对星瓢虫(D.undecimpunctata),南美叶甲(D.speciosa),长角叶甲(D.longicornis),D.semipunctata,玉米根萤叶甲(D.virgifera);柑椐象鼻虫(Diaprepes abbreviates),姓野螟属(Dichocrocis spp.),稻铁甲虫(Dicladispa armigera),阿根廷兜虫(Diloboderusabderus),Diocalandra frumenti(Diocalandra stigmaticollis),Enaphalodesrufulus,食植瓢虫属(Epilachna spp.),如墨西哥豆瓢虫(E.varivestis)、马铃薯瓢虫(E.vigintioctomaculata);毛跳甲属(Epitrix spp.),如烟草跳甲(E.hirtipennis)、E.similaris;Eutheola humilis,棉灰蒙象变种(Eutinobothrus brasiliensis),烟草钻孔虫(Faustinus cubae),Gibbium psylloides,Gnathocerus cornutus,菜螟(Hellulaundalis),非洲独角仙(Heteronychus arator),Hylamorpha elegans,欧洲松树皮象(Hylobius abietis),家天牛(Hylotrupes bajulus),Hypera spp.,如埃及苜蓿叶象(H.brunneipennis)、紫苜蓿叶象(H.postica);绿鳞象甲(Hypomeces squamosus),果小蠹属(Hypothenemus spp.),云杉八齿小蠹(Ips typographus),Lachnosternaconsanguinea,烟草甲(Lasioderma serricorne),Latheticus oryzae,Lathridius spp.,Lema spp.,如烟草负泥虫(L.bilineata),黑角负泥虫(L.melanopus);马铃薯叶甲属(Leptinotarsa spp.),如马铃薯叶甲(L.decemlineata);Leptispa pygmaea,甜菜叩甲(Limonius californicus),稻水象甲(Lissorhoptrus oryzophilus),筒喙象属(Lixusspp.),Luperodes spp.,粉蠹属(Lyctus spp.),如褐粉蠹(L.bruneus);Liogenys fuscus,大趾属(Macrodactylus spp.),如M.subspinosus;玛绢金龟(Maladera matrida),Megaplatypus mutates,Megascelis spp.,Melanotus communis,菜花露尾甲属(Meligethes spp.),如油菜露尾甲(M.aeneus);Melolontha spp.,如大栗鳃金龟(M.hippocastani)、五月鳃金龟(M.melolontha);西印度蔗螟(Metamasius hemipterus),Microtheca spp.,Migdolus spp.,如M.fryanus,墨天牛属(Monochamus spp.),如松墨天牛(M.alternatus);Naupactus xanthographus,黄蛛甲(Niptus hololeucus),Oberiabrevis,Oemona hirta,椰蛀犀金龟(Oryctes rhinoceros),锯谷盗(Oryzaephilussurinamensis),Oryzaphagus oryzae,黑葡萄耳象(Otiorrhynchus sulcatus),草莓根象甲(Otiorrhynchus ovatus),黑葡萄耳象(Otiorrhynchus sulcatus),Oulema melanopus,水稻负泥虫(Oulema oryzae),小青花金龟(Oxycetonia jucunda),Phaedon spp.,如小猿叶虫(P.brassicae)、辣根猿叶甲(P.cochleariae);Phoracantha recurva,梨树叶象(Phyllobius pyri),庭园发丽金龟(Phyllopertha horticola),食叶鳃金龟属(Phyllophaga spp.),如P.helleri;条跳甲属(Phyllotreta spp.),如P.chrysocephala、大豆淡足跳甲(P.nemorum)、黄曲条菜跳甲(P.striolata)、黄狭条跳甲(P.vittula);庭园发丽金龟(Phyllopertha horticola),日本金龟子(Popillia japonica),小象甲属(Premnotrypes spp.),Psacothea hilaris,油菜蓝跳甲(Psylliodes chrysocephala),大谷蠹(Prostephanus truncates),Psylliodes spp.,蛛甲属(Ptinus spp.),Pulgasaltona,谷蠹(Rhizopertha dominica),红棕属(Rhynchophorus spp.,如R.billineatus,红棕象甲(R.ferrugineus),棕榈象甲(R.palmarum),R.phoenicis,R.vulneratus;Saperdacandida,Scolytus schevyrewi,Scyphophorus acupunctatus,豌豆叶象(Sitonalineatus),谷象属(Sitophilus spp.),谷象(S.granaria),米象(S.oryzae),玉米象(S.zeamais);尖隐喙象属(Sphenophorus spp.),如S.levis;Stegobium paniceum,茎干象属(Sternechus spp.),如S.subsignatus;Strophomorphus ctenotus,Symphyletes spp.,Tanymecus spp.,黄粉虫(Tenebrio molitor),Tenebrioides mauretanicus;拟谷盗属(Tribolium spp.),如赤拟谷盗(T.castaneum);斑皮蠹属(Trogoderma spp.)、籽象属(Tychius spp.)、脊虎天牛属(Xylotrechus spp.),如X.pyrrhoderus;以及距步甲属(Zabrus spp.),如Z.Tenebrioides);
双翅目(Diptera)昆虫,例如Aedes spp.,如伊蚊属(Aedes spp.),如埃及伊蚊(A.aegypti)、白纹伊蚊(A.albopictus)、剌扰伊蚊(A.vexans);墨西哥果蝇(Anastrephaludens);按蚊属(Anopheles spp.),如白足按蚊(A.albimanus)、灾难按蚊(A.crucians)、费氏按蚊(A.freeborni)、冈比亚按蚊(A.gambiae)、白踝按蚊(A.leucosphyrus)、五斑按蚊(A.maculipennis)、微小按蚊(A.minimus)、四斑按蚊(A.quadrimaculatus)、中华按蚊(A.sinensis);Bactrocera invadens,花园毛蚊(Bibio hortulanus),绿头蝇(Calliphoraerythrocephala),红头丽蝇(Calliphora vicina),地中海实蝇(Ceratitis capitata),金蝇属(Chrysomyia spp.),如蛆症金蝇(C.bezziana),C.hominivorax、腐败金蝇(C.macellaria);Chrysops atlanticus,鹿蝇(Chrysops discalis),静斑虻(Chrysopssilacea),锥蝇属(Cochliomyia spp.),如螺旋蝇(C.hominivorax);瘿蚊属(Contariniaspp.),如高粱瘿蚊(C.sorghicola);嗜人瘤蝇蛆(Cordylobia anthropophaga),库蚊属(Culex spp.),如斑蚊(C.nigripalpus),尖音库蚊(C.pipiens),致倦库蚊(C.quinquefasciatus),媒斑蚊(C.tarsalis),三带喙库蚊(C.tritaeniorhynchus);狂怒库蠓(Culicoides furens),无饰脉毛蚊(Culiseta inornata),黑尾脉毛蚊(Culisetamelanura),黄蝇属(Cuterebra spp.),瓜蝇(Dacus cucurbitae),油橄榄实蝇(Dacusoleae),油菜叶瘿蚊(Dasineura brassicae),Dasineura oxycoccana,地种蝇属(Deliaspp.),如葱蝇(D.antique),麦地种蝇(D.coarctata),灰地种蝇(D.platura),甘蓝地种蝇(D.radicum);人肤皮蝇(Dermatobia hominis),果蝇属(Drosophila spp.),如斑翅果蝇(D.suzukii),厕蝇属(Fannia spp.),如小毛厕蝇(F.canicularis);胃蝇属(Gastraphilusspp.),如马蝇(G.intestinalis);Geomyza tipunctata,Glossina spp.,如G.fuscipes、刺舌蝇(G.morsitans)、须舌蝇(G.palpalis)、胶舌蝇(G.tachinoides),扰血蝇(Haematobiairritans),Haplodiplosis equestris,潜蝇属(Hippelates spp.),黑蝇属(Hylemyiaspp.),如花生田灰地种蝇(H.platura);皮蝇属(Hypoderma spp.),如纹皮蝇(H.lineata);Hyppobosca spp.,水稻菲岛毛眼水蝇(Hydrellia philippina),Leptoconops torrens,Liriomyza spp.,如美洲斑潜蝇(L.sativae)、美国潜叶蝇(L.trifolii);Lucilia spp.,如L.caprina、铜绿蝇(L.cuprina)、丝光绿蝇(L.sericata);Lycoria pectoralis,Mansoniatitillanus,Mayetiola spp.,如麦瘿蚊(M.destructor);Musca spp.,如秋家蝇(M.autumnalis)、家蝇(M.domestica);厩腐蝇(Muscina stabulans);Oestrus spp.,如羊狂蝇(O.ovis);Opomyza florum,Oscinella spp.,如瑞典麦秆蝇(O.frit);稻瘿蚊(Orseolia oryzae),天仙子泉蝇(Pegomya hysocyami),银足白蛉(Phlebotomusargentipes),草种蝇属(Phorbia spp.),如葱蝇(P.antiqua)、萝卜蝇(P.brassicae)、麦地种蝇(P.coarctata);Phytomyza gymnostoma,Prosimulium mixtum,胡萝卜茎蝇(Psilarosae,哥伦比亚鳞蚊(Psorophora columbiae),Psorophora discolor,Rhagoletis spp.,如樱桃实蝇(R.cerasi)、R.cingulate、R.indifferens、R.mendax、苹果实蝇(R.pomonella);Rivellia quadrifasciata,麻蝇属(Sarcophaga spp.),如赤尾麻蝇(S.haemorrhoidalis);带蚋(Simulium vittatum),Sitodiplosis mosellana,螫蝇属(Stomoxys spp.),如厩螫蝇(S.calcitrans);虻属(Tabanus spp.),如北美黑虻(T.atratus)、牛虻(T.bovinus)、红色原虻(T.lineola)、二毛虫(T.similis);Tanniaspp.,Thecodiplosis japonensis,Tipula oleracea,欧洲大蚊(Tipula paludosa)和污蝇属(Wohlfahrtia spp.);
缨翅目(Thysanoptera)昆虫,例如稻蓟马(Baliothrips biformis),兰花蓟马(Dichromothrips corbetti),Dichromothrips ssp.,Echinothrips americanus,Enneothrips flavens,花蓟马属(Frankliniella spp.),如烟褐蓟马(F.fusca)、苜蓿花蓟马(F.occidentalis)、东方花蓟马(F.tritici);阳蓟马属(Heliothrips spp.),温室蓟马(Hercinothrips femoralis),卡蓟马属(Kakothrips spp.),Microcephalothripsabdominalis,Neohydatothrips samayunkur,Pezothrips kellyanus,腹突皱针蓟马(Rhipiphorothrips cruentatus),硬蓟马属(Scirtothrips spp.),如桔硬蓟马(S.citri),S.dorsalis,S.perseae;Stenchaetothrips spp,Taeniothrips cardamoni,Taeniothrips inconsequens;蓟马属(Thrips spp.),如T.imagines、T.hawaiiensis、稻蓟马(T.oryzae)、棕榈蓟马(T.palmi)、T.parvispinus、烟蓟马(T.tabaci);
半翅目(Hemiptera)昆虫,例如合欢木虱(Acizzia jamatonica),Acrosternumspp.,如拟绿蝽(A.hilare);无网长管蚜属(Acyrthosipon spp.),如A.onobrychis、豌豆蚜(A.pisum);落叶松球蚜(Adelges laricis),Adelges tsugae,Adelphocoris spp.,如A.rapidus,A.superbus;沫蜂属(Aeneolamia spp.),隆脉木虱属(Agonoscena spp.),茄无网蚜(Aulacorthum solani),Aleurocanthus woglumi,白粉虱属(Aleurodes spp.),Aleurodicus disperses,甘蔗穴粉虱(Aleurolobus barodensis),丝绒粉虱属(Aleurothrixus spp.),杧果叶蝉属(Amrasca spp.),南瓜缘蝽(Anasa tristis),拟丽蝽属(Antestiopsis spp.),Anuraphis cardui,肾圆盾蚧属(Aonidiella spp.),梨瘤蚜(Aphanostigma piri),Aphidula nasturtii,蚜属(Aphis spp.),如A.craccivora,甜菜蚜(A.fabae)、草莓根蚜(A.forbesi)、棉蚜(A.gossypii)、北美茶藨子蚜(A.grossulariae)、A.maidiradicis,苹果蚜(A.pomi)、接骨木蚜(A.sambuci)、希奈德蚜(A.schneideri)、卷叶蚜(A.spiraecola);葡萄阿小叶蝉(Arboridia apicalis),轮背猎蝽(Arilus critatus),小圆盾蚧属(Aspidiella spp.),圆盾蚧属(Aspidiotus spp.),Atanus spp.,Aulacaspisyasumatsui,茄无网蚜(Aulacorthum solani),Bactericera cockerelli(Paratriozacockerelli),粉虱属(Bemisia spp.),如银叶粉虱(B.argentifolii)、烟粉虱(B.tabaci(Aleurodes tabaci));土长蝽属(Blissus spp.),如玉米长蝽(B.leucopterus);Brachycaudus spp.,如飞廉短尾蚜(B.cardui),李短尾蚜(B.helichrysi),桃短尾蚜(B.persicae),B.prunicola;微管蚜属(Brachycolus spp.),Brachycorynella asparagi,甘蓝蚜(Brevicoryne brassicae),Cacopsylla spp.,如C.fulguralis、C.pyricola(梨木虱(Psylla piri));小褐稻虱(Calligypona marginata),俊盲蝽属(Calocoris spp.),斑腿微刺盲蝽(Campylomma livida),Capitophorus horni,Carneocephala fulgida,异背长蝽属(Cavelerius spp.),Ceraplastes spp.,Ceratovacuna lanigera,Ceroplastesceriferus,Cerosipha gossypii,Chaetosiphon fragaefolii,Chionaspis tegalensis,Chlorita onukii,Chromaphis juglandicola,Chrysomphalus ficus,Cicadulina mbila,Cimex spp.,如热带臭虫(C.hemipterus)、温带臭虫(C.lectularius);Coccomytilushalli,软蚧属(Coccus spp.),如C.hesperidum、C.pseudomagnoliarum;Corythuchaarcuata,Creontiades dilutus,茶藨子隐瘤蚜(Cryptomyzus ribis),Chrysomphalusaonidum,茶藨隐瘤蚜(Cryptomyzus ribis),Ctenarytaina spatulata,黑斑烟盲蝽(Cyrtopeltis notatus),Dalbulus spp.,胡椒缘蝽(Dasynus piperis),粉虱(Dialeurades spp.),如D.citrifolii;Dalbulus maidis,木虱属(Diaphorina spp.),如D.citri;白背盾蚧属(Diaspis spp.),如D.bromeliae;Dichelops furcatus,厚氏长棒网蝽(Diconocoris hewetti),Doralis spp.,高加索冷杉椎球蚜(Dreyfusianordmannianae),云杉椎球蚜(Dreyfusia piceae),履绵蚧属(Drosicha spp.);西圆尾蚜属(Dysaphis spp.),如车前圆尾蚜(D.plantaginea)、梨西圆尾蚜(D.pyri)、居根西圆尾蚜(D.radicola);Dysaulacorthum pseudosolani;棉红蝽属(Dysdercus spp.),如棉红蝽(D.cingulatus)、D.intermedius;灰粉蚧属(Dysmicoccus spp.),Edessa spp.,Geocorisspp.,小绿叶蝉属(Empoasca spp.),如蚕豆微叶蝉(D.fabae)、索拉纳小绿叶蝶(D.solana);Epidiaspis leperii,绵蚜属(Eriosoma spp.),如E.lanigerum,E.pyricola;斑叶蝉属(Erythroneura spp.);扁盾蝽属(Eurygaster spp.),如麦扁盾蝽(E.integriceps);钝鼻叶蝉(Euscelis bilobatus),美洲蝽属(Euschistus spp.),如大豆褐椿(E.heros)、烟草蝽(E.impictiventris)、褐臭蝽(E.servus);Fiorinia theae,咖啡地粉蚧(Geococcus coffeae),Glycaspis brimblecombei;茶翅蝽属(Halyomorpha spp.),如茶翅蝽(H.halys);角盲椿(Heliopeltis spp.),玻璃叶蝉(Homalodisca vitripennis(=H.coagulata)),Horcias nobilellus,李大尾蚜(Hyalopterus pruni),茶藨苦菜超瘤蚜(Hyperomyzus lactucae),吹绵蚧属(Icerya spp.),如I.purchase;片角叶蝉属(Idiocerus spp.),扁喙叶蝉属(Idioscopus spp.),灰飞虱(Laodelphax striatellus),蜡蚧属(Lecanium spp.),Lecanoideus floccissimus,蛎盾蚧属(Lepidosaphes spp.),如L.ulmi;稻缘蝽属(Leptocorisa spp.),棉红铃喙缘蝽(Leptoglossus phyllopus),萝卜蚜(Lipaphis erysimi),草盲蝽属(Lygus spp.),如草盲蝽(L.hesperus)、美洲牧草盲蝽(L.lineolaris)、牧草盲蝽(L.pratensis);Maconellicoccus hirsutus,Marchalinahellenica,蔗黑长蝽(Macropes excavatus),长管蚜属(Macrosiphum spp.),如蔷薇长管蚜(M.rosae)、麦长管蚜(M.avenae)、大戟长管蚜(M.euphorbiae);Macrostelesquadrilineatus,Mahanarva fimbriolata,筛豆龟蝽(Megacopta cribraria),巢莱修尾蚜(Megoura viciae),Melanaphis pyrarius,高粱蚜(Melanaphis sacchari);Melanocallis(=Tinocallis)caryaefoliae,Metcafiella spp.,麦无网蚜(Metopolophium dirhodum),黑缘平翅斑蚜(Monellia costalis),Monelliopsis pecanis;Myzocallis coryli,Murgantia spp.,瘤蚜属(Myzus spp.),如冬葱蚜(M.ascalonicus)、李瘤蚜(M.cerasi)、M.nicotianae、桃蚜(M.persicae)、黄药子瘤蚜(M.varians);黑茶藨子衲长管蚜(Nasonovia ribis-nigri),Neotoxoptera formosana,Neomegalotomus spp,黑尾叶蝉属(Nephotettix spp.),如马来亚黑尾叶蝉(N.malayanus)、二条黑尾叶蝉(N.nigropictus)、细小黑尾叶蝉(N.parvus)、二点黑尾叶蝉(N.virescens);绿蝽属(Nezara spp.),如稻绿蝽(N.viridula);褐飞虱(Nilaparvata lugens),Nysius huttoni,稻蝽属(Oebalus spp.),如O.pugnax;Oncometopia spp.,Orthezia praelonga,Oxycaraenus hyalinipennis,杨梅粉虱(Parabemisia myricae),片盾蚧属(Parlatoria spp.),Parthenolecanium spp.,如P.corni、P.persicae;瘿绵蚜属(Pemphigus spp.),如囊柄瘿绵蚜(P.bursarius)、P.populivenae;玉米蜡蝉(Peregrinus maidis)、蔗飞虱(Perkinsiella saccharicida)、绵粉蚧属(Phenacoccus spp.),如P.aceris,P.gossypii;杨平翅绵蚜(Phloeomyzuspasserinii),忽布疣蚜(Phorodon humuli),葡萄根瘤蚜属(Phylloxera spp.),如P.devastatrix;甜菜拟网蝽(Piesma quadrata),壁蝽属(Piezodorus spp.),如P.guildinii;苏铁褐点并盾蚧(Pinnaspis aspidistrae),臀纹粉蚧属(Planococcusspp.),如P.citri、P.ficus;Prosapia bicincta,梨形原绵蚧(Protopulvinariapyriformis),棉伪斑腿盲蝽(Psallus seriatus),Pseudacysta persea,桑盾蚧(Pseudaulacaspis pentagona),粉蚧属(Pseudococcus spp.),如康氏粉蚧(P.comstocki);木虱属(Psylla spp.),如苹木虱(P.mali);金小蜂属(Pteromalus spp.),(Pulvinaria amygdali,Pyrilla spp.,笠圆盾蚧属(Quadraspidiotus spp.),如Q.perniciosus;Quesada gigas,平刺粉蚧属(Rastrococcus spp.),Reduvius senilis,Rhizoecus americanus,红猎蝽属(Rhodnius spp.),冬葱瘤蛾蚜(Rhopalomyzusascalonicus);缢管蚜属(Rhopalosiphum spp.),如萝卜蚜(R.pseudobrassicas)、苹草缢管蚜(R.insertum)、玉米蚜(R.maidis)、禾谷缢管蚜(R.padi);Sagatodes spp.,可可褐盲蝽(Sahlbergella singularis),黑盔蚧属(Saissetia spp.),Sappaphis mala,Sappaphismali,,Scaptocoris spp.,葡萄带叶蝉(Scaphoides titanus),麦二叉蚜(Schizaphisgraminum),Schizoneura lanuginosa,稻黑蝽属(Scotinophora spp.),刺盾蚧(Selenaspidus articulatus),禾谷网蚜(Sitobion avenae),长唇基飞虱属(Sogataspp.),白背飞虱(Sogatella furcifera),Solubea insularis,Spissistilus festinus(=Stictocephala festina),梨冠网蝽(Stephanitis nashi),Stephanitis pyrioides,Stephanitis takeyai,Tenalaphara malayensis,Tetraleurodes perseae,Therioaphismaculate,Thyanta spp.,如T.accerra、T.perditor;Tibraca spp.,广胸沫蝉属(Tomaspisspp.),声蚜属(Toxoptera spp.),如桔二叉蚜(T.aurantii);白粉虱属(Trialeurodesspp.),如T.abutilonea、T.ricini、白粉虱(T.vaporariorum);锥猎蝽属(Triatoma spp.),个木虱属(Trioza spp.),小叶蝉属(Typhlocyba spp.),尖盾蚧属(Unaspis spp.),如U.Citri、矢尖蚧(U.yanonensis);以及葡萄根瘤蚜(Viteus vitifolii);
膜翅目(Hymenoptera)昆虫,例如Acanthomyops interjectus,新疆菜叶蜂(Athalia rosae),Atta spp.,如A.capiguara、切叶蚁(A.cephalotes)、切叶蚁(A.cephalotes)、A.laevigata、A.robusta、A.sexdens、A.texana,熊蜂属(Bombus spp.),Brachymyrmex spp.,Camponotus spp.,如佛罗里达弓背蚁(C.floridanus)、C.pennsylvanicus、C.modoc;Cardiocondyla nuda,Chalibion sp,举腹蚁属(Crematogaster spp.),天鹅绒蚂蚁(Dasymutilla occidentalis),松叶蜂属(Diprionspp.),姬胡蜂(Dolichovespula maculata),Dorymyrmex spp.,Dryocosmus kuriphilus,Formica spp.,实蜂属(Hoplocampa spp.),如H.minuta、苹叶蜂(H.testudinea);Iridomyrmex humilis,毛蚁属(Lasius spp.),如黑毛蚁(L.niger),阿根廷蚁(Linepithema humile),Liometopum spp.,Leptocybe invasa,Monomorium spp.,如小黄家蚁(M.pharaonis),Monomorium,Nylandria fulva,Pachycondyla chinensis,Paratrechina longicornis,Paravespula spp.,如P.germanica、P.pennsylvanica、P.vulgaris;Pheidole spp.,如褐大头蚁(P.megacephala);Pogonomyrmex spp.,如红蚂蚁(P.barbatus)、收割机蚂蚁(P.californicus),胡蜂(Polistes rubiginosa),Prenolepisimpairs,Pseudomyrmex gracilis,Schelipron spp.,Sirex cyaneus,Solenopsis spp.,如热带火蚁(S.geminata)、红火蚁(S.invicta)、S.molesta、黑火蚁(S.richteri)、南方火蚁(S.xyloni);Sphecius speciosus,Sphex spp.,Tapinoma spp.,如T.melanocephalum、T.sessile;Tetramorium spp.,如T.caespitum、T.bicarinatum,大胡蜂属(Vespa spp.),如黄边胡蜂(V.crabro);Vespula spp.,如大黄蜂(V.squamosa);Wasmanniaauropunctata,Xylocopa sp;
直翅目(Orthoptera)昆虫,例如居屋艾蟋(Acheta domestica),意大利蝗(Calliptamus italicus),澳洲草栖蝗(Chortoicetes terminifera),Ceuthophilusspp.,Diastrammena asynamora,摩洛哥戟纹蝗(Dociostaurus maroccanus),Gryllotalpaspp.,如非洲蝼蛄(G.africana)、蝼蛄(G.gryllotalpa);Gryllus spp.,非洲蔗蝗(Hieroglyphus daganensis),印度黄檀蝗(Kraussaria angulifera),Locusta spp.,如飞蝗(L.migratoria)、褐色拟飞蝗(L.pardalina;Melanoplus spp.,如双纹黑蝗(M.bivittatus)、红足黑蝗(M.femurrubrum)、墨西哥黑蝗(M.mexicanus)、迁飞黑蝗(M.sanguinipes)、石栖黑蝗(M.spretus);条纹红蝗(Nomadacris septemfasciata),塞纳加尔小车蝗(Oedaleus senegalensis),Scapteriscus spp.,Schistocerca spp.,如美洲沙漠蝗(S.americana),沙漠蝗(S.gregaria),Stemopelmatus spp.,庭疾灶螽(Tachycinesasynamorus)和Zonozerus variegatus;
蜘蛛纲(Arachnida)害虫,例如蜱螨目(Acari),如软蜱科(Argasidae)、硬蜱科(Ixodidae)和疥螨科(Sarcoptidae),如花蜱属(Amblyomma spp.)(例如长星形壁虱(A.americanum)、热带花蜱(A.variegatum)、斑点钝眼蜱(A.maculatum)),锐缘蜱属(Argasspp.),如波斯锐缘蜱(A.persicu),牛蜱属(Boophilus spp.),如牛壁虱(B.annulatus)、消色牛蜱(B.decoloratus)、微小牛蜱(B.microplus),Dermacentor spp.,如森林革蜱(D.silvarum)、安氏革蜱(D.andersoni)、美洲大革蜱(D.variabilis),璃眼蜱属(Hyalommaspp.),如长喙璃眼蜱(H.truncatum),硬蜱属(Ixodes spp.),如蓖子硬蜱(I.ricinus)、浅红硬蜱(I.rubicundus)、黑脚硬蜱(I.scapularis)、全环硬蜱(I.holocyclus)、太平洋硬蜱(I.pacificus),Rhipicephalus sanguineus,钝缘蜱属(Ornithodorus spp.),如毛白钝缘蜱(O.moubata、赫氏钝缘蜱(O.hermsi)、回归热蜱(O.turicata),柏氏禽刺螨(Ornithonyssus bacoti),刺耳扁虱(Otobius megnini),鸡皮刺螨(Dermanyssusgallinae),痒螨属(Psoroptes spp.),如绵羊疥病(P.ovis),扇头蜱属(Rhipicephalusspp.),如血红扇头蜱(R.sanguineus)、具尾扇头蜱(R.appendiculatus)、外翻扇头蜱(R.evertsi),根螨属(Rhizoglyphus spp.),疥螨属(Sarcoptes spp.),如人疥螨(S.scabiei);以及瘿螨科(Eriophyidae),包括Aceria spp.,如A.sheldoni、A.anthocoptes,Acallitus spp.,刺皮节蜱属(Aculops spp.),如A.lycopersici、桔锈螨(A.pelekassi);刺瘿螨属(Aculus spp.),如苹果刺锈螨(A.schlechtendali);Colomerusvitis,枣叶锈螨(Epitrimerus pyri),桔皱叶刺瘿螨(Phyllocoptruta oleivora;Eriophytes ribis和瘿螨属(Eriophyes spp.),如柑橘瘿螨(Eriophyes sheldoni);跗绒螨科(Tarsonemidae),包括半跗线螨属(Hemitarsonemus spp.),Phytonemus pallidus和侧多食跗线螨(Polyphagotarsonemus latus),狭跗线螨属(Stenotarsonemus spp.),Steneotarsonemus spinki;细须螨科(Tenuipalpidae),包括短须螨属(Brevipalpusspp.),如紫红短须螨(B.phoenicis);叶螨科(Tetranychidae),包括始叶螨属(Eotetranychus spp.),真叶螨属(Eutetranychus spp.),小爪螨属(Oligonychus spp.),Petrobia latens,Tetranychus spp.,如朱砂叶螨(T.cinnabarinus)、T.evansi、神泽叶螨(T.kanzawai)、太平洋叶螨(T.pacificus)、T.phaseulus、棉叶螨(T.telarius)和二点叶螨(T.urticae);苜蓿苔螨(Bryobia praetiosa);全爪螨属(Panonychus spp.),如苹果叶螨(P.ulmi)、橘全爪螨(P.citri);Metatetranychus spp.和小爪螨属(Oligonychus spp.),如草地小爪螨(O.pratensis))、O.perseae,Vasates lycopersici;Raoiella indica,果螨科(Carpoglyphidae),包括Carpoglyphus spp.;Penthaleidae spp.,如Halotydeusdestructor;蠕形螨科(Demodicidae)数种,如Demodex spp.;Trombicidea,包括Trombicula spp.;巨刺螨科(Macronyssidae),包括Ornothonyssus spp.;蒲螨科(Pyemotidae),包括Pyemotes tritici;Tyrophagus putrescentiae;螨科(Acaridae),包括Acarus siro;蜘蛛目(Araneida),例如毒蜘蛛(Latrodectus mactans),Tegenariaagrestis,Chiracanthium sp,Lycosa sp,Achaearanea tepidariorum和褐丝蛛(Loxosceles reclusa);
线虫动物门(Phylum Nematoda)害虫,例如植物寄生性线虫,如根结线虫,根结线虫属(Meloidogyne),如北方根结线虫(M.hapla)、南方根结线虫(M.incognita)、爪哇根结线虫(M.javanica);胞囊线虫,球胞囊线虫属(Globodera),如马铃薯金线虫(G.rostochiensis);胞囊线虫属(Heterodera),如禾谷胞囊线虫(H.avenae)、大豆胞囊线虫(H.glycines)、甜菜胞囊线虫(H.schachtii)、三叶草胞囊线虫(H.trifolii);种子肿瘿线虫,粒线虫属(Anguina);茎叶线虫,滑刃线虫属(Aphelenchoides),如水稻干尖线虫(A.besseyi);刺线虫,针刺线虫属(Belonolaimus),如杂草刺线虫(B.longicaudatus);松线虫,伞滑刃线虫属(Bursaphelenchus),如松材线虫(B.lignicolus)、松材线虫(B.xylophilus);环形线虫,环纹线虫属(Criconema),小环线虫属(Criconemella),如C.xenoplax和C.ornata,以及轮线虫属(Criconemoides),如Criconemoides informis,中环线虫属(Mesocriconema);球茎线虫,茎线虫属(Ditylenchus),如腐烂茎线虫(D.destructor)、甘薯茎线虫(D.dipsaci);锥线虫,锥线虫属(Dolichodorus);螺旋形线虫,多带螺旋(Heliocotylenchus multicinctus);鞘线虫和鞘形线虫,鞘线虫属(Hemicycliophora)和Hemicriconemoides属;Hirshmanniella属;冠线虫,纽带线虫(Hoplolaimus)属;假根结线虫,真珠线虫属(Nacobbus);针线虫,长针线虫属(Longidorus)如伸展长针线虫(L.elongatus);根腐线虫,短体线虫属(Pratylenchus),如最短尾短体线虫(P.brachyurus)、疏忽短体线虫(P.neglectus)、穿刺短体线虫(P.penetrans)、P.curvitatus、古迪短体线虫(P.goodeyi);穿孔线虫,穿孔线虫属(Radopholus),如香蕉穿孔线虫(R.similis);Rhadopholus spp.;Rhodopholus spp.;肾形线虫,肾状线虫属(Rotylenchulus spp.),如盘旋线虫(R.robustus)、肾形肾脏线虫(R.reniformis);盾线虫(Scutellonema)属;残根线虫,毛刺线虫属(Trichodorus spp.,如T.obtusus、原始毛刺线虫(T.primitivus);类毛刺属(Paratrichodorus),如P.minor;阻长线虫,矮化线虫属(Tylenchorhynchus),如克莱顿矮化线虫(T.claytoni)、不定矮化线虫(T.dubius);柑桔线虫,小垫刃线虫(Tylenchulus)属,如柑桔半穿刺线虫(T.semipenetrans);剑线虫,剑线虫属(Xiphinema);以及其他植物寄生性线虫种属;
等翅目(Isoptera)昆虫,例如黄颈木白蚁(Calotermes flavicollis),Coptotermes spp.,如台湾乳白蚁(C.formosanus)、C.gestroi、C.acinaciformis;Cornitermes cumulans,Cryptotermes spp.,如C.brevis、C.cavifrons;Globitermessulfureus,Heterotermes spp.,如金黄异白蚁(H.aureus)、长头异白蚁(H.longiceps)、甘蔗白蚁(H.tenuis);Leucotermes flavipes,土白蚁属(Odontotermes spp.),Incisitermes spp.,如I.minor、I.Snyder;Marginitermes hubbardi,Mastotermes spp.,如M.darwiniensis,Neocapritermes spp.,如N.opacus,N.parvus;Neotermes spp.,Procornitermes spp.,Zootermopsis spp.,如Z.angusticollis、Z.nevadensis,散白蚁属(Reticulitermes spp.),如R.hesperus、R.tibialis、黄胸散白蚁(R.speratus)、黄肢散白蚁(R.flavipes)、R.grassei、欧洲散白蚁(R.lucifugus)、R.santonensis、美小黑散白蚁(R.virginicus);Termes natalensis;
蜚蠊目(Blattaria)昆虫,例如Blatta spp.,如东方蜚蠊(B.orientalis)、B.lateralis;Blattella spp.,如B.asahinae、德国小蠊(B.germanica);马德拉蜚蠊(Leucophaea maderae),Panchlora nivea,Periplaneta spp.,如美洲大蠊(P.americana)、澳洲蜚蠊(P.australasiae)、棕色蜚蠊(P.brunnea)、黑胸大蠊(P.fuligginosa)、日本大蠊(P.japonica);Supella longipalpa,Parcoblattapennsylvanica,Eurycotis floridana,Pycnoscelus surinamensis,蚤目(Siphonoptera)昆虫,例如Cediopsylla simples,角叶蚤属(Ceratophyllus spp.),Ctenocephalidesspp.,如(猫跳蚤(C.felis)、狗跳蚤(C.canis),印鼠客蚤(Xenopsylla cheopis),致痒蚤(Pulex irritans),Trichodectes canis,穿皮潜蚤(Tunga penetrans)和具带病蚤(Nosopsyllus fasciatus);
缨尾目(Thysanura)昆虫,例如西洋衣鱼(Lepisma saccharina)、Ctenolepismaurbana和斑衣鱼(Thermobia domestica);
唇足纲(Chilopoda)害虫,例如地蜈蚣属(Geophilus spp.)、蚰蜒属(Scutigeraspp.),如Scutigera coleoptrata;
倍足纲(Diplopoda)害虫,例如Blaniulus guttulatus、Julus spp.、Narceusspp.;
综合纲(Symphyla)害虫,例如Scutigerella immaculata,
革翅目(Dermaptera)昆虫,例如欧洲球螋(Forficula auricularia),
弹尾目(Collembola)昆虫,例如棘跳虫属(Onychiurus ssp.),如武装棘跳虫(Onychiurus armatus),
等足目(Isopoda)害虫,例如鼠妇(Armadillidium vulgare)、栉水虱(Oniscusasellus)、球鼠妇(Porcellio scaber);
毛虱目(Phthiraptera)昆虫,例如畜虱属(Damalinia spp.);人虱属(Pediculusspp.),如人头虱(Pediculus humanus capitis)、人体虱(Pediculus humanus corporis),Pediculus humanus humanus;阴虱(Pthirus pubis);血虱属(Haematopinus spp.),如牛血虱(Haematopinus eurysternus)、猪血虱(Haematopinus suis);颚虱属(Linognathusspp.),如犊颚虱(Linognathus vituli);牛虱(Bovicola bovis)、鸡虱(Menopongallinae)、大鸡虱(Menacanthus stramineus)和水牛盲虱(Solenopotes capillatus),嚼虱属(Trichodectes spp.);
可以由式(I)化合物防治的其他害虫品种的实例包括软体动物门(PhylumMollusca),双壳纲(Bivalvia),例如饰贝属(Dreissena spp.);腹足纲(Gastropoda),例如阿勇蛞蝓属(Arion spp.)、双脐螺属(Biomphalaria spp.)、小泡螺属(Bulinus spp.)、Deroceras spp.、土蜗属(Galba spp.)、椎实螺属(Lymnaeas pp.)、钉螺属(Oncomelaniaspp.),福寿螺(Pomacea canaliclata),琥珀螺属(Succinea spp.);蠕虫纲(helminths),例如十二指肠钩口线虫(Ancylostoma duodenale)、斯里兰卡钩口线虫(Ancylostomaceylanicum)、巴西钩口线虫(Acylostoma braziliensis)、钩口线虫属(Ancylostomaspp.)、似引蛔线虫(Ascaris lubricoides)、蛔虫属(Ascaris spp.)、马来布鲁线虫(Brugia malayi)、帝汶布鲁线虫(Brugia timori)、仰口线虫属(Bunostomum spp.)、夏伯特线虫属(Chabertia spp.)、枝睾吸虫属(Clonorchis spp.)、古柏线虫属(Cooperiaspp.)、双腔吸虫属(Dicrocoelium spp.)、丝状网尾线虫(Dictyocaulus filaria)、阔叶裂头绦虫(Diphyllobothrium latum)、麦地那龙线虫(Dracunculus medinensis)、细粒棘球绦虫(Echinococcus granulosus)、多房棘球绦虫(Echinococcus multilocularis)、蠕形住肠蛲虫(Enterobius vermicularis)、片吸虫属(Faciola spp.)、血矛线虫属(Haemonchus spp.)如捻转血矛线虫(Haemonchus contortus);异刺线虫属(Heterakisspp.)、矮小啮壳绦虫(Hymenolepis nana)、猪圆线虫属(Hyostrongulus spp.)、罗阿罗阿线虫(Loa Loa)、细颈线虫属(Nematodirus spp.)、结节线虫属(Oesophagostomum spp.)、后睾吸虫属(Opisthorchis spp.)、旋盘尾丝虫(Onchocerca volvulus)、奥斯脱线虫属(Ostertagia spp.)、并殖吸虫属(Paragonimus spp.)、血吸虫属(Schistosomen spp.)、富氏类圆线虫(Strongyloides fuelleborni)、粪类圆线虫(Strongyloides stercoralis)、粪圆线虫属(Stronyloides spp.)、牛带绦虫(Taenia saginata)、猪带绦虫(Taeniasolium)、旋毛形线虫(Trichinella spiralis)、本地毛形线虫(Trichinella nativa)、株布氏旋毛虫(Trichinella britovi)、南方旋毛虫(Trichinella nelsoni)、伪方定毛形线虫(Trichinella pseudopsiralis)、毛圆线虫属(Trichostrongulus spp.)、毛首鞭形线虫(Trichuris trichuria)、班氏吴策线虫(Wuchereria bancrofti)。
本发明化合物适合用于处理或保护动物以防寄生虫侵染或感染。因此,本发明还涉及本发明化合物在在制造用于处理或保护动物以防寄生虫侵染或感染的药物中的用途。此外,本发明涉及一种处理或保护动物以防寄生虫侵染和感染的方法,包括对动物口服、局部或胃肠外给予或施用杀寄生虫有效量的本发明化合物。
本发明还涉及本发明还涉及本发明化合物在处理或保护动物以防寄生虫侵染和感染中的非治疗用途。此外,本发明涉及一种处理或保护动物以防寄生虫侵染和感染的非治疗方法,包括对场所施用杀寄生虫有效量的本发明化合物。
本发明化合物进一步适合用于在动物中和动物上防除或防治寄生虫。此外,本发明涉及一种在动物中和动物上防除或防治寄生虫的方法,包括使寄生虫与杀寄生虫有效量的本发明化合物接触。
本发明还涉及本发明化合物在防治或防除寄生虫中的非治疗用途。此外,本发明涉及一种防除或防治寄生虫的非治疗方法,包括对场所施用杀寄生虫有效量的本发明化合物。
本发明化合物可以通过接触(经由土壤、玻璃、墙壁、蚊帐、地毯、毛毯或动物部分)和摄取(例如诱饵)二者而有效。此外,本发明化合物可以施用于任何和所有发育阶段。
本发明化合物可以直接或者以包含本发明化合物的组合物形式施用。
本发明化合物还可以与对病原性寄生虫起作用的混合配对一起施用,例如与合成球虫病化合物,聚醚抗生素,如氨丙啉、氯苯胍、托三嗪、莫能菌素、盐霉素、马度米星、拉沙里菌素、甲基盐霉素或生度米星,或与如上所定义的其他混合配对一起施用,或者以包含所述混合物的组合物形式施用。
本发明化合物和包含它们的组合物可以口服、胃肠外或局部,例如经皮施用。本发明化合物可以内吸或者非内吸地有效。
施用可以预防性、治疗性或非治疗性地进行。此外,施用可以预防性地对预期出现寄生虫的地方进行。
本文所用术语“接触”包括直接接触(将化合物/组合物直接施用于寄生虫上,包括直接施用于动物上或者排除直接施用于动物上,例如对后者而言施用于其场所)和间接接触(将化合物/组合物施用于寄生虫的场所)二者。通过寄生虫的场所接触寄生虫为本发明化合物的非治疗用途的实例。
术语“场所”是指栖息地,食物供应源,繁殖地,其中寄生虫在动物之外生长或可能生长的区域、材料或环境。
本文所用术语“寄生虫”包括体内和体外寄生虫。在本发明的一些实施方案中,可能优选体内寄生虫。在其他实施方案中,可能优选体外寄生虫。在温血动物和鱼类中的侵染包括但不限于虱、咬虱、蜱、羊鼻蝇蛆、羊蜱蝇、螯蝇、家蝇、蝇、myiasitic蝇幼虫、恙螨、蚋、蚊和蚤。
本发明化合物尤其可以用于分别防治下列目和属的寄生虫:
蚤(蚤目),例如猫蚤(Ctenocephalides felis)、狗蚤(Ctenocephalides canis)、印鼠客蚤(Xenopsylla cheopis)、致痒蚤(Pulex irritans)、穿皮潜蚤(Tunga penetrans)和具带病蚤(Nosopsyllus fasciatus),
蟑螂(蜚蠊目-Blattodea),例如德国小蠊(Blattella germanica)、Blattellaasahinae、美洲蟑螂(Periplaneta americana)、日本大蠊(Periplaneta japonica)、棕色蜚蠊(Periplaneta brunnea)、Periplaneta fuligginosa、澳洲蜚蠊(Periplanetaaustralasiae)和东方蜚蠊(Blatta orientalis),
蝇、蚊(双翅目),例如埃及伊蚊(Aedes aegypti)、白纹伊蚊(Aedes albopictus)、剌扰伊蚊(Aedes vexans)、墨西哥果蝇(Anastrepha ludens)、五斑按蚊(Anophelesmaculipennis)、Anopheles crucians、白足按蚊(Anopheles albimanus)、疟蚊(Anophelesgambiae)、Anopheles freeborni、海南岛白踝按蚊(Anopheles leucosphyrus)、云南微小按蚊(Anopheles minimus)、四斑按蚊(Anopheles quadrimaculatus)、红头丽蝇(Calliphora vicina)、蛆症金蝇(Chrysomya bezziana)、Chrysomya hominivorax、Chrysomya macellaria、鹿蝇(Chrysops discalis)、Chrysops silacea、Chrysopsatlanticus、螺旋蝇(Cochliomyia hominivorax)、嗜人瘤蝇蛆(Cordylobiaanthropophaga)、狂怒库蠓(Culicoides furens)、尖音库蚊(Culex pipiens)、斑蚊(Culexnigripalpus)、致倦库蚊(Culex quinquefasciatus)、媒斑蚊(Culex tarsalis)、Culisetainornata、Culiseta melanura、人肤皮蝇(Dermatobia hominis)、小毛厕蝇(Fanniacanicularis)、马蝇(Gasterophilus intestinalis)、刺舌蝇(Glossina morsitans)、须舌蝇(Glossina palpalis)、Glossina fuscipes、胶舌蝇(Glossina tachinoides)、Haematobia irritans、Haplodiplosis equestris、潜蝇属(Hippelates)、纹皮蝇(Hypoderma lineata)、Leptoconops torrens、Lucilia caprina、铜绿蝇(Luciliacuprina)、丝光绿蝇(Lucilia sericata)、Lycoria pectoralis、沼蚊属(Mansonia)、家蝇(Musca domestica)、厩腐蝇(Muscina stabulans)、羊狂蝇(Oestrus ovis)、银足白蛉(Phlebotomus argentipes)、Psorophora columbiae、Psorophora discolor、Prosimuliummixtum、赤尾肉蝇(Sarcophaga haemorrhoidalis)、肉蝇属(Sarcophaga)、带蚋(Simuliumvittatum)、厩螫蝇(Stomoxys calcitrans)、牛虻(Tabanus bovinus)、Tabanus atratus、红色原虻(Tabanus lineola)和Tabanus similis;
虱(毛虱目),例如人头虱(Pediculus humanus capitis)、人体虱(Pediculushumanus corporis)、阴虱(Pthirus pubis)、牛血虱(Haematopinus eurysternus)、猪血虱(Haematopinus suis)、牛颚虱(Linognathus vituli)、Bovicola bovis、鸡虱(Menopongallinae)、Menacanthus stramineus和Solenopotes capillatus,
壁虱和寄生螨(寄螨目(Parasitiformes)):壁虱(蜱亚目(Ixodida)),例如黑脚硬蜱(Ixodes scapularis)、全环硬蜱(Ixodes holocyclus)、太平洋硬蜱(Ixodespacificus)、棕色犬壁虱(Rhiphicephalus sanguineus)、安氏革螨(Dermacentorandersoni)、美洲大革螨(Dermacentor variabilis)、长星形壁虱(Amblyommaamericanum)、Ambryomma maculatum、Ornithodorus hermsi、Ornithodorus turicata以及寄生螨(甲螨亚目(Mesostigmata)),例如柏氏禽刺螨(Ornithonyssus bacoti)和鸡皮刺螨(Dermanyssus gallinae);
辐螨亚目(Actinedida)(前气门亚目(Prostigmata))和粉螨亚目(Acaridida)(无气门目(Astigmata)),例如Acarapis spp.、Cheyletiella spp.、Ornithocheyletia spp.、鼠螨属(Myobia)、Psorergates spp.、蠕形螨属(Demodex)、恙螨属(Trombicula)、Listrophorus spp.、粉螨属(Acarus)、食酪螨属(Tyrophagus)、嗜木螨属(Caloglyphus)、Hypodectes spp.、Pterolichus spp.、痒螨属(Psoroptes)、疥螨属(Chorioptes)、耳痒螨属(Otodectes)、Sarcoptes spp.、背肛螨属(Notoedres)、膝螨属(Knemidocoptes)、Cytodites spp.和Laminosioptes spp.;
臭虫(Heteropterida):温带臭虫(Cimex lectularius)、热带臭虫(Cimexhemipterus)、Reduvius senilis、锥蝽属(Triatoma)、锥蝽属(Rhodnius)、Panstrongylusssp.和Arilus critatus,
虱目(Anoplurida),例如Haematopinus spp.、Linognathus spp.、Pediculusspp.、Phtirus spp.和Solenopotes spp.;
食毛目(Mallophagida)(Arnblycerina和Ischnocerina亚目),例如Trimenoponspp.、Menopon spp.、Trinoton spp.、Bovicola spp.、Werneckiella spp.、Lepikentronspp.、Trichodectes spp.和Felicola spp.;
蛔虫(线虫纲(Nematoda)):
金针虫和Trichinosis(毛管目(Trichosyringida)),例如毛形科(Trichinellidae)(毛形属(Trichinella))、毛首科(Trichuridae)、Trichuris spp.、毛细线虫属(Capillaria);
杆形目(Rhabditida),例如小杆线虫属(Rhabditis)、Strongyloides spp.、Helicephalobus spp.;
圆线虫目(Strongylida),例如Strongylus spp.、Ancylostoma spp.、美洲钩虫(Necator americanus)、Bunostomum spp.(钩虫)、毛圆线虫属(Trichostrongylus)、捻转血矛线虫(Haemonchus contortus)、Ostertagia spp.、Cooperia spp.、细颈线虫属(Nematodirus)、Dictyocaulus spp.、Cyathostoma spp.、结节线虫属(Oesophagostomum)、猪肾虫(Stephanurus dentatus)、Ollulanus spp.、夏伯特线虫属(Chabertia)、猪肾虫、气管比翼线虫(Syngamus trachea)、Ancylostoma spp.、钩虫属(Uncinaria)、球首线虫属(Globocephalus)、Necator spp.、后圆线虫属(Metastrongylus)、毛样缪勒线虫(Muellerius capillaris)、Protostrongylus spp.、管圆线虫属(Angiostrongylus)、Parelaphostrongylus spp.、Aleurostrongylus abstrusus和肾膨结线虫(Dioctophymarenale);
肠线虫(蛔目(Ascaridida)),例如似蚓蛔线虫(Ascaris lumbricoides)、猪蛔虫(Ascaris suum)、鸡蛔虫(Ascaridia galli)、马副蛔虫(Parascaris equorum)、蛲虫(Enterobius vermicularis)(蛲虫)、犬弓首蛔虫(Toxocara canis)、犬蛔虫(Toxascarisleonine)、Skrjabinema spp.和马尖尾线虫(Oxyuris equi);
Camallanida,例如Dracunculus medinensis(麦地那龙线虫);
旋尾目(Spirurida),例如Thelazia spp.、丝虫属(Wuchereria)、Brugia spp.、Onchocerca spp.、Dirofilari spp.、Dipetalonema spp.、Setaria spp.、Elaeophoraspp.、狼尾旋线虫(Spirocerca lupi)和丽线虫属(Habronema);
棘头虫(棘头动物门(Acanthocephala)),例如Acanthocephalus spp.、猪巨吻棘头虫(Macracanthorhynchus hirudinaceus)和棘头虫属(Oncicola);
扁虫类(Planarians)(扁形动物门(Plathelminthes)):
肝吸虫(Flukes)(吸虫纲(Trematoda)),例如肝片形吸虫属(Faciola)、Fascioloides magna、并殖吸虫属(Paragonimus)、双腔吸虫属(Dicrocoelium)、布氏姜片吸虫(Fasciolopsis buski)、华枝睾吸虫(Clonorchis sinensis)、血吸虫属(Schistosoma)、毛毕吸虫属(Trichobilharzia)、有翼翼形吸虫(Alaria alata)、并殖吸虫属和Nanocyetes spp;
Cercomeromorpha,尤其是Cestoda(绦虫),例如裂头绦虫属(Diphyllobothrium)、Tenia spp.、棘球绦虫属(Echinococcus)、犬复孔绦虫(Dipylidium caninum)、Multicepsspp.、膜壳绦虫属(Hymenolepis)、中殖孔绦虫属(Mesocestoides)、Vampirolepis spp.、Moniezia spp.、Anoplocephala spp.、Sirometra spp.、Anoplocephala spp.和Hymenolepis spp.。
本文所用术语“动物”包括温血动物(包括人类)和鱼类。优选哺乳动物,如牛、绵羊、猪、骆驼、鹿、马、小猪、家禽、兔、山羊、狗和猫,水牛、驴、黇鹿和驯鹿,以及还有产皮动物如貂、丝鼠和浣熊,禽类如母鸡、鹅、火鸡和鸭以及鱼类如淡水鱼和咸水鱼如鲑鱼、鲤鱼和鳗鱼。特别优选家养动物,如狗或猫。
通常而言,“杀寄生虫有效量”是指对生长获得可观察到的效果所需的活性成分的量,所述效果包括坏死、死亡、阻滞、预防和去除效果,破坏效果或减少目标生物体的出现和活动的效果。对于用于本发明的各种化合物/组合物,杀寄生虫有效量可以变化。组合物的杀寄生虫有效量也会根据主要条件如所需杀寄生虫效果及持续时间、目标物种、施用方式等而变化。
通常有利的是以0.5-100mg/kg/天,优选1-50mg/kg/天的总量施用本发明化合物。
为了对温血动物口服给药,可以将式I化合物配制成动物饲料、动物饲料预混物、动物饲料浓缩物、丸剂、溶液、糊、悬浮液、浸液、凝胶、片剂、大丸剂和胶囊。此外,式I化合物可以在其饮用水中给药于动物。对于口服给药,所选择的剂型应为动物提供0.01-100mg/kg动物体重/天,优选0.5-100mg/kg动物体重/天的式I化合物。
或者,式I化合物可以肠胃外给药于动物,例如通过腔内、肌内、静脉内或皮下注射。式I化合物可以分散或溶于对于皮下注射而言生理上可接受的载体中。或者,式I化合物可配制成皮下给药用植入物。此外,式I化合物可以透皮给药于动物。对于肠胃外给药,所选剂型应为动物提供0.01-100mg/kg动物体重/天的式I化合物。
式I化合物还可以浸液、粉剂、粉末、套环、挂牌(medallions)、喷雾剂、香波、滴施(spot-on)和喷淋(pour-on)配制剂形式以及以软膏或水包油或油包水乳液局部给药于动物。对于局部施用,浸液和喷雾剂通常含有0.5-5,000ppm,优选1-3,000ppm式I化合物。此外,式I化合物可以配制成动物,特别是四足动物如牛和绵羊用耳贴。
合适的制剂是:
-溶液,如口服溶液、稀释后口服给药用浓缩物、用于皮肤上或用于体腔内的溶液、喷淋配制剂、凝胶;
-口服或皮肤给药乳液和悬浮液;半固体制剂;
-其中将活性化合物在软膏基质中或在水包油或油包水乳液基质中加工的配制剂;
-固体制剂如粉末、预混物或浓缩物、颗粒、丸剂、片剂、大丸剂、胶囊;气雾剂和吸入剂,以及含有活性化合物的成型制品。
适合注射的组合物通过将活性成分溶于合适的溶剂中并任选加入其他助剂如酸、碱、缓冲盐、防腐剂和加溶剂而制备。适合注射液的助剂在本领域中是已知的。过滤这些溶液并无菌填充。
口服溶液直接给药。浓缩物在预先稀释至使用浓度之后口服给药。口服溶液和浓缩物根据上面对注射液所述的现有技术制备,并不必需无菌程序。
用于皮肤上的溶液滴施、涂施、擦施、洒施或喷施。
用于皮肤上的溶液根据现有技术以及上面对注射液所述制备,并不必需无菌程序。
将凝胶施加或涂敷在皮肤上或引入体腔中。凝胶通过用足以得到具有软膏状稠度的透明材料的增稠剂处理如在注射液情况下所述制备的溶液而制备。合适的增稠剂在本领域中是已知的。
将喷淋配制剂倒在或喷雾在限定的皮肤区域,活性化合物渗透进皮肤并内吸起作用。
喷淋配制剂通过将活性化合物在合适的皮肤相容性溶剂或溶剂混合物中溶解、悬浮或乳化而制备。合适的话加入其他助剂如着色剂、生物吸收促进物质、抗氧化剂、光稳定剂、粘合剂。合适的助剂在本领域中是已知的。
乳液可以口服、经皮给药或作为注射液给药。
乳液呈油包水型或水包油型。
它们通过将活性化合物溶于疏水性或亲水性相中并借助合适的乳化剂以及合适的话其他助剂如着色剂、吸收促进物质、防腐剂、抗氧化剂、光稳定剂、粘度提高物质用另一相的溶剂均化而制备。合适的疏水相(油)、合适的亲水相、合适的乳化剂和合适的其他乳液用助剂在本领域中是已知的。
悬浮液可以口服或局部/经皮给药。它们通过将活性化合物悬浮于悬浮剂中而制备,合适的话加入其他助剂如润湿剂、着色剂、生物吸收促进物质、防腐剂、抗氧化剂、光稳定剂。合适的悬浮剂和合适的其他悬浮液用助剂—包括润湿剂—在本领域中是已知的。
半固体制剂可以口服或局部/经皮给药。它们与上述悬浮液和乳液的不同仅在于它们具有更高粘度。
为了生产固体制剂,将活性化合物与合适的赋形剂混合,合适的话加入助剂,并且制成所需剂型。适合该目的的助剂在本领域中是已知的。
可以用于本发明的组合物通常可以包含约0.001-95%本发明化合物。
即用制剂以10重量ppm-80重量%,优选0.1-65重量%,更优选1-50重量%,最优选5-40重量%的浓度含有对寄生虫,优选体外寄生虫起作用的化合物。
在使用前稀释的制剂以0.5-90重量%,优选1-50重量%的浓度含有对体外寄生虫起作用的化合物。
此外,制剂以10重量ppm-2重量%,优选0.05-0.9重量%,非常特别优选0.005-0.25重量%的浓度包含对抗体内寄生虫的式I化合物。
局部施用可以用含有化合物的成型制品如套环、挂牌、耳贴、在身体部分上固定用的绑带以及粘合条和箔进行。
通常有利的是施用在三周内以10-300mg/kg,优选20-200mg/kg,最优选25-160mg/kg被处理动物体重的总量释放本发明化合物的固体配制剂。
实施例
A.制备实施例
适当改变原料,使用如方案1和下列合成实施例所述程序得到其他化合物I。以此方式得到的化合物与物理数据一起列于下表中。
下面所示产物通过熔点测定、NMR光谱法或经由HPLC-MS或HPLC光谱法的质量([m/z])或保留时间(RT;[min.])表征。
HPLC-MS=联用的高效液相色谱法-质谱法;
HPLC方法1:Phenomenex Kinetex 1.7μm XB-C18 100A;50×2.1mm;移动相;A:水+0.1%三氟乙酸(TFA);B:乙腈+0.1%TFA;梯度:在1.50分钟内5-100%B;100%B 0.20min;流速:在60℃下在1.50分钟内0.8-1.0ml/min。MS:四极电喷射离子化,80V(正模式)。
方案1:化合物I-9的合成
实施例1:制备5-甲基-1-(1-甲基-2-甲基磺酰氧基乙基)吡唑-4-甲酸乙酯(B)
向1-(2-羟基-1-甲基乙基)-5-甲基吡唑-4-甲酸乙酯A(16g,纯度92%,69.2mmol)在150mL二氯甲烷中的搅拌溶液中滴加甲磺酰氯(24g,208mmol)。将该混合物冷却至-40℃并滴加在50mL二氯甲烷中的三乙胺(21g,208mmol)。继续搅拌并将该混合物逐渐温热至0℃。滴加100mL水并分离各层。将有机相用水(100mL)洗涤,在硫酸钠上干燥并在减压下除去溶剂,得到甲磺酸酯B(25g,纯度80%),其不经进一步提纯使用。
实施例2:制备5-甲基-1-[1-甲基-2-[1-甲基亚丙基氨基]氧基乙基]吡唑-4-甲酸乙酯(C)
向2-丁酮肟(3.92g,45mmol)在70mL乙腈中的溶液中加入碳酸铯(14.7g,45mmol)并将该混合物在室温下搅拌20分钟。然后滴加甲磺酸酯B(5.4g,15mmol)在20mL乙腈中的溶液并继续搅拌48小时。将反应混合物过滤并减压除去溶剂。通过反相快速层析(H2O/MeOH,100:0→0:100)提纯而得到1.18g肟C(28%,4.2mmol)。HPLC-MS:RT 1.118min,m/z[MH]+282.2
实施例3:制备5-甲基-1-[1-甲基-2-[1-甲基亚丙基氨基]氧基乙基]吡唑-4-甲酸(D)
向吡唑甲酸乙酯C(715mg,2.54mmol)在25mL乙醇中的溶液中加入在5mL水中的LiOH(183mg,7.64mmol)并将反应混合物在室温下搅拌过夜。加入额外的LiOH(150mg,6.26mmol)并将该混合物在50℃下搅拌8小时。减压除去溶剂并用水稀释残余物。将该混合物用乙酸乙酯洗涤(3×20mL),通过加入2N HCl水溶液酸化至pH 1并过滤沉淀的酸D。额外地,将该溶液用乙酸乙酯萃取(2×20mL),将合并的有机层在硫酸钠上干燥,过滤并减压除去溶剂。合并的羧酸D(572mg,2.26mmol,89%)在不经进一步提纯下使用。1H-NMR(MeOD,500MHz):δ=1.04(t,3H),1.46(d,3H),1.68(s,3H),2.15(q,2H),2.50(s,3H),4.16-4.28(m,2H),4.71-4.81(m,1H),7.87(s,1H)ppm。
实施例4:制备N-乙基-5-甲基-1-[1-甲基-2-[1-甲基亚丙基氨基]氧基乙基]-N-哒嗪-4-基吡唑-4-甲酰胺(I-9)
向258mg(1.0mmol)5-甲基-1-[1-甲基-2-[1-甲基亚丙基氨基]氧基乙基]吡唑-4-甲酸在10mL DMF中的溶液中加入乙氨基哒嗪(370mg,3.0mmol)、HATU[O-(7-氮杂苯并三唑-1-基)-N,N,N′,N′-四甲基脲六氟磷酸盐](1.52g,4.0mmol)和三乙胺(606mg,6.0mmol)。将所得混合物在室温下搅拌过夜并减压除去溶剂。通过快速层析(环己烷/EtOAc/MeOH,100:0:0→0:100:0→0:0:100)提纯得到190mg标题化合物I-9(53%)。HPLC-MS:RT0.872min,m/z[MH]+358.9。
以相同方式得到其中RP1、RP2和RP3在每种情况下为H的下列式I化合物,即落入通式I*下的化合物。
(A)在化合物I-4至I-9的情况下:单一异构体,E或Z未测定
(B) 在每种情况下标记与式I*的吡唑环的N原子的连接
B.生物学实施例
本发明式I化合物的活性可以由下面所述生物学试验证实和评价。
若无其他说明,试验溶液按如下制备:
将活性化合物以所需浓度溶于1:1(体积比)蒸馏水:丙酮混合物中。在使用当天通常以ppm浓度(重量/体积)制备试验溶液。
B.1豇豆蚜(Aphis craccivora)
在记录害虫种群之后喷雾被约100-150只各阶段的蚜虫盘踞的盆栽豇豆植株。24、72和120小时后记录种群降低。
在该试验中,与未处理对照相比,化合物I-1、I-2、I-3、I-4、I-5、I-6、I-7、I-8和I-9分别在500ppm下显示出至少75%的死亡率。
B.2棉蚜(Aphis gossypii,混合生命阶段)
在环己酮中将活性化合物配制成在1.3ml管中供应的10,000ppm溶液。将这些管插入装备有雾化喷嘴的自动静电喷雾器中并将它们作为储备溶液使用,在1:1(体积比)水:丙酮中由该储备溶液产生更低稀释度。非离子表面活性剂以0.01%(体积)的量包括在该溶液中。
在处理之前通过将来自主蚜虫群体的重度侵染叶子置于各子叶的顶部而将子叶阶段的棉花植株用蚜虫侵染。使蚜虫经过整夜转移而实现80-100只蚜虫/植株的侵染并移走宿主叶子。然后通过装备有雾化喷嘴的自动静电植株喷雾器喷雾侵染的植株。在喷雾器通风橱中干燥各植株,从喷雾器中取出,然后在生长室中在荧光光照下于25℃和20-40%相对湿度下维持24小时光照期。5天后相对于未处理对照植株上的死亡率测定被处理植株上的蚜虫死亡率。
在该试验中,与未处理对照相比,化合物I-3、I-4、I-5、I-6、I-7、I-8和I-9分别在300ppm下显示出至少75%的死亡率。
B.3银叶粉虱(Bemisia argentifolii,成虫)
在环己酮中将活性化合物配制成在1.3ml管中供应的10,000ppm溶液。将这些管插入装备有雾化喷嘴的自动静电喷雾器中并作为储备溶液使用,在1:1(体积比)水:丙酮中由该储备溶液产生更低稀释度。非离子表面活性剂以0.01%(体积)的量包括在该溶液中。
通过装备有雾化喷嘴的自动静电植株喷雾器喷雾子叶阶段的棉花植株(每盆一株)。在喷雾器通风橱中干燥各植株,然后从喷雾器中取出。将各盆置于塑料杯中并引入约10-12只粉虱成虫(约3-5天龄)。使用抽吸装置和连接于防护移液管头的0.6cm无毒管(R-3603)收集昆虫。然后将含有收集的昆虫的该管头轻轻地插入含有处理植株的土壤中,使昆虫爬出该管头而到达叶面上取食。将杯子用可反复使用的筛盖(150微米网眼的聚酯筛网PeCap,来自Tetko,Inc.)覆盖。将试验植株在生长室中于25℃和20-40%相对湿度下保持3天,避免直接暴露于荧光(24小时光照期)以防止在杯内截热。在处理3天后评价与未处理对照植株相比较的死亡率。
在该试验中,与未处理对照相比,化合物I-2、I-3、I-4、I-5、I-6、I-7、I-8和I-9分别在300ppm下显示出至少75%的死亡率。
B.4巢菜修尾蚜(Megoura viciae)
活性化合物在3:1(体积比)水:DMSO中以不同浓度的配制化合物配制。
将菜豆叶片放入填充有0.8%琼脂和2.5ppm OPUSTM的微滴定板中。将叶片用2.5μl试验溶液喷雾并将5-8只蚜虫成虫放入微滴定板中,然后在荧光下将后者密闭并保持在23±1℃和50±5%相对湿度下6天。基于有活力的繁殖蚜虫评价死亡率。然后肉眼评价蚜虫死亡率和繁殖力。
在该试验中,与未处理对照相比,化合物I-1、I-2、I-3、I-4、I-5、I-6、I-7和I-9分别在2500ppm下显示出至少75%的死亡率。
B.5绿桃蚜(Myzus persicae)
在环己酮中将活性化合物配制成在1.3ml管中供应的10,000ppm溶液。将这些管插入装备有雾化喷嘴的自动静电喷雾器中并将它们作为储备溶液使用,在1:1(体积比)水:丙酮中由该储备溶液产生更低稀释度。非离子表面活性剂以0.01%(体积)的量包括在该溶液中。
在处理之前通过将来自主群体的重度侵染叶子置于处理植株的顶部而将第一真叶阶段的柿子椒植株侵染。使蚜虫经过整夜转移而实现30-50只蚜虫/植株的侵染并移走宿主叶子。然后通过装备有雾化喷嘴的自动静电植株喷雾器喷雾侵染的植株。在喷雾器通风橱中干燥各植株,取出,然后在生长室中在荧光光照下于25℃和20-40%的相对湿度下维持24小时光照期。5天后相对于未处理对照植株上的死亡率测定被处理植株上的蚜虫死亡率。
在该试验中,与未处理对照相比,化合物I-2、I-3、I-4、I-5、I-6、I-7、I-8和I-9分别在300ppm下显示出至少75%的死亡率。
B.6墨西哥棉铃象(Anthonomus grandis)
在3:1(体积比)水:DMSO中配制化合物。
为了评价对墨西哥棉铃象(Anthonomus grandis)的防治,测试单元由含有昆虫膳食和20-30只墨西哥棉铃象卵的24孔微滴定板构成。使用定制微雾化器将不同浓度的配制化合物以20μl喷雾于昆虫膳食上,重复两次。在施用之后,将微滴定板在23±1℃和50±5%相对湿度下温育5天。然后肉眼评价卵和幼虫死亡率。
在该试验中,与未处理对照相比,化合物I-2和I-6分别在2500ppm下显示出至少75%的死亡率。
B.7兰花蓟马(Dichromothrips corbetti)
在1:1(体积比)水:丙酮中配制活性化合物。以0.1体积%的量加入表面活性剂(Alkamuls EL 620)。在喷雾之前将Vanda兰花花瓣清洁、洗涤并风干。将花瓣浸入测试溶液中3秒钟,风干,放入可密封的塑料中并用20只成虫接种。将被处理花瓣在28-29℃和50-60%相对湿度下保持于保持室内。72小时后记录死亡百分数。
在该试验中,与未处理对照相比,化合物I-4和I-6分别在500ppm下显示出至少75%的死亡率。
B.8菜蛾(Plutella xylostella)
在1:1(体积比)水:丙酮和0.1体积%Alkamuls EL 620表面活性剂中配制活性化合物。将卷心菜叶的6cm叶片浸入试验溶液中3秒钟并在衬有潮湿滤纸的陪替氏板中风干。将叶片用10只三龄幼虫接种并在25-27℃和50-60%湿度下保持3天。处理72小时后评价死亡率。
在该试验中,与未处理对照相比,化合物I-4和I-6分别在500ppm下显示出至少75%的死亡率。
Claims (15)
1.式I的吡唑化合物及其盐、立体异构体、互变异构体和N-氧化物:
其中
V为O、S或NR1a,其中R1a选自H、C1-C10烷基、C1-C4卤代烷基、C3-C10环烷基、C3-C10环烷基甲基、C3-C10卤代环烷基、C2-C10链烯基、C2-C10卤代链烯基、C2-C10炔基、C1-C10烷氧基-C1-C4烷基、ORa、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的相同或不同取代基,或者
其中R1a和R4与R4所键合的碳原子和R1a所键合的氮原子以及所述碳原子和所述氮原子之间的氮原子一起形成含有2个氮原子作为杂原子且可以进一步含有1或2相互独立地选自NRB、O和S的杂原子的4-8员杂环,其中S可以被氧化,和/或其中该杂环可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代;
D为C1-C8亚烷基、C3-C8亚环烷基、C3-C8亚杂环烷基、C2-C8亚链烯基、C3-C8亚环烯基、C3-C8亚杂环烯基或C2-C8亚炔基,其中D可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代;
U为N或CRU;
T为S、O或NR1b,其中R1b选自H、C1-C10烷基、C1-C4卤代烷基、C3-C10环烷基、C3-C10环烷基甲基、C3-C10卤代环烷基、C2-C10链烯基、C2-C10卤代链烯基、C2-C10炔基、C1-C10烷氧基-C1-C4烷基、ORa、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的相同或不同取代基;
RP1、RP2、RP3和RU相互独立地选自H、卤素、C1-C4烷基、C1-C3卤代烷基、C1-C4烷氧基、C1-C3卤代烷氧基、C1-C4烷硫基、C1-C3卤代烷硫基、C1-C4烷基亚磺酰基、C1-C3卤代烷基亚磺酰基、C1-C4烷基磺酰基、C1-C3卤代烷基磺酰基、C3-C6环烷基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基或C1-C4烷氧基-C1-C4烷基;
R1为H、CN、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C4烷氧基-C1-C4烷基、C2-C10链烯基、C2-C10卤代链烯基、C2-C10炔基、C3-C10卤代炔基、C1-C5亚烷基-CN、ORa、C1-C5亚烷基-ORa、C(Y)Rb、C1-C5亚烷基-C(Y)Rb、C(Y)ORc、C1-C5亚烷基-C(Y)ORc、S(O)2Rd、NReRf、C1-C5亚烷基-NReRf、C(Y)NRgRh、C1-C5亚烷基-C(Y)NRgRh、S(O)nNReRf、C(Y)NRiNReRf、C1-C5亚烷基-S(O)2Rd、C1-C5亚烷基-S(O)nNReRf、C1-C5亚烷基-C(Y)NRiNReRf、苯基、杂环基、杂芳基、苯基-C1-C5烷基、C3-C10环烷基-C1-C5烷基、杂环基-C1-C5烷基和杂芳基-C1-C5烷基,其中后提到的7个基团的环可以未被取代或者可以带有1、2、3、4或5个选自基团Ry和Rx的相同或不同取代基;
R2和R3相互独立地选自H、卤素、CN、NO2、C1-C10烷基、C2-C10链烯基和C2-C10炔基,其中后提到的3个基团可以未被取代、可以部分或完全被卤代或者可以带有1、2或3个相同或不同的取代基Rx,或者其中R2和R3进一步选自ORa、SRa、C(Y)Rb、C(Y)ORc、S(O)Rd、S(O)2Rd、NReRf、C(Y)NRgRh、杂环基、杂芳基、C3-C10环烷基、C5-C10环烯基和苯基,其中后提到的5个基团可以未被取代或者可以带有1、2、3、4或5个选自基团Ry和Rx的相同或不同取代基,并且其中
R4为H、C1-C6烷基、C1-C6烷基-X、C3-C6环烷基或C3-C6环烷基-X,其中X选自O、S或NRB,其中C1-C6烷基或C3-C6环烷基可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代;以及
R5为C1-C6烷基、C1-C6烷基-X、C3-C6环烷基或C3-C6环烷基-X,其中X选自O、S或NRB,其中C1-C6烷基或C3-C6环烷基可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代,或者其中
R4和R5与它们所键合的碳原子一起形成可以含有1、2或3个相互独立地选自NRB、O和S的杂原子的3-8员饱和或不饱和碳环或杂环,其中S可以被氧化和/或该碳环或杂环可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代;
并且其中RA为卤素、NO2、CN、C1-C6烷基、C1-C6烷氧基、C1-C6卤代烷基、C1-C6卤代烷氧基、C3-C6环烷基、C3-C6环烷氧基、C3-C6卤代环烷基、C3-C6卤代环烷氧基、C2-C4链烯基、C2-C4炔基、S(O)nRD、=O、=S、=NRC、=NORC和=NSRC;或者其中
键合于相同碳原子或者相邻碳原子的两个RA与它们所键合的碳原子一起形成可以含有1或2个相互独立地选自NRB、O和S的杂原子的3-6员饱和或不饱和碳环或杂环,其中S可以被氧化;
并且其中RB为H、C1-C2烷基、C1-C2卤代烷基、C1-C2烷基羰基、C1-C2卤代烷基羰基或C1-C2烷氧羰基;
RC为H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6卤代环烷基;
RD为H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6卤代环烷基、C1-C4烷氧基或C1-C4卤代烷氧基;
n为0、1或2;
Y为O或S;
Ra、Rb、Rc相互独立地选自H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基甲基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
Rd选自C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基甲基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;并且其中
Re和Rf相互独立地选自H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基甲基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、C1-C4烷基羰基、C1-C4卤代烷基羰基、C1-C4烷基磺酰基、C1-C4卤代烷基磺酰基、杂环基、杂环基-C1-C4烷基、杂环基羰基、杂环基磺酰基、苯基、苯基羰基、苯基磺酰基、杂芳基、杂芳基羰基、杂芳基磺酰基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的12个基团中的环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
或者
Re和Rf与它们所键合的氮原子一起形成可以带有选自O、S和N的另一杂原子作为环成员原子的5或6员饱和或不饱和杂环并且其中该杂环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
并且其中Rg和Rh相互独立地选自H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、杂环基、杂环基-C1-C4烷基、苯基、杂芳基、苯基-C1-C4烷基和杂芳基-C1-C4烷基,其中后提到的6个基团中的环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
Ri选自H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基、C3-C6环烷基甲基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基、C1-C4烷氧基-C1-C4烷基、苯基和苯基-C1-C4烷基,其中后提到的2个基团中的苯基环可以未被取代或者可以带有1、2、3、4或5个相互独立地选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C4卤代烷氧基的取代基;
Rx为CN、NO2、C1-C4烷氧基、C1-C4卤代烷氧基、S(O)nRd、S(O)nNReRf、C1-C10烷基羰基、C1-C4卤代烷基羰基、C1-C4烷氧羰基、C1-C4卤代烷氧羰基、C3-C6环烷基、5-7员杂环基、5或6员杂芳基、苯基、C3-C6环烷氧基、3-6员杂环氧基和苯氧基,其中后提到的7个基团可以未被取代或者可以带有1、2、3、4或5个相同或不同的基团Ry;以及
Ry选自卤素、CN、NO2、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、S(O)nRd、S(O)nNReRf、C1-C4烷基羰基、C1-C4卤代烷基羰基、C1-C4烷氧羰基、C1-C4卤代烷氧羰基、C3-C6环烷基、C3-C6卤代环烷基、C2-C4链烯基、C2-C4卤代链烯基、C2-C4炔基和C1-C4烷氧基-C1-C4烷基。
2.根据权利要求1的式I化合物,其中V为O或S,优选V为O。
3.根据权利要求1或2的式I化合物,其中D为C1-C8亚烷基、C3-C8亚环烷基或C3-C8亚杂环烷基,优选C1-C8亚烷基,其中D可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代。
4.根据权利要求3的式I化合物,其中D为支化C2-C8亚烷基,优选α-支化C2-C8亚烷基,其中支化C2-C8亚烷基可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代。
5.根据权利要求3或4的式I化合物,其中D为CH(CH3)CH2,其中优选CH2基团键合于V且CH(CH3)基团键合于吡唑结构部分的氮原子,从而得到V-CH2CH(CH3)-N的联缀。
6.根据前述权利要求中任一项的式I化合物,其中R4为H、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6环烷基甲基,并且R5为C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6环烷基甲基,其中在每种情况下C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或C3-C6环烷基甲基可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代,或者其中R4和R5与它们所键合的碳原子一起形成可以含有1或2个相互独立地选自NRB、O和S的杂原子的非芳族5-6员碳环或杂环,其中S可以被氧化,和/或其中该碳环或杂环可以未被取代或者可以部分或完全被相互独立地选自RA的取代基取代。
7.根据前述权利要求中任一项的式I化合物,其中U为N或CH,优选U为N,以及T为O且RP1、RP2和RP3为H。
8.根据前述权利要求中任一项的式I化合物,其中R1为H、C1-C2烷基或C1-C2烷氧基-C1-C2烷基,优选R1为C1-C2烷基,以及其中R2和R3相互独立地选自H、卤素、CN、C1-C4烷基、C1-C4卤代烷基、C3-C4环烷基、C3-C4卤代环烷基、ORa和SRa,其中Ra为C1-C4烷基、C1-C4卤代烷基、C3-C4环烷基或C3-C4卤代环烷基,其中优选R2为C1-C2烷基、C1-C2卤代烷基、C3环烷基或C3卤代环烷基,更优选CH3或卤代甲基,以及其中优选R3为H。
9.根据前述权利要求中任一项的式I化合物,其中RA为卤素、CN、C1-C2烷基、C1-C2卤代烷基、C1-C2烷氧基、C1-C2卤代烷氧基、C3-C4环烷基、C3-C4卤代环烷基、C3-C4环烷氧基或C3-C4卤代环烷氧基,或者其中两个RA键合于相同碳原子并且与它们所键合的碳原子一起形成环丙烷。
10.一种组合物,包含至少一种根据权利要求1-9中任一项的化合物和至少一种惰性液体和/或固体载体。
11.一种防治动物害虫的农业组合物,包含至少一种如权利要求1-9中任一项所定义的化合物和至少一种惰性液体和/或固体可接受载体以及需要的话至少一种表面活性剂。
12.一种防治或防除无脊椎动物害虫的方法,该方法包括使所述害虫或其食物供应源、栖息地或繁殖地与杀害虫有效量的至少一种如权利要求1-9中任一项所定义的化合物接触。
13.一种保护生长的植物以防无脊椎动物害虫侵袭或侵染的方法,该方法包括使植物或者其中植物生长的土壤或水体与杀害虫有效量的至少一种如权利要求1-9中任一项所定义的化合物接触。
14.种子,以0.1g-10kg/100kg种子的量包含如权利要求1-9中任一项所定义的化合物或其对映体、非对映体或盐。
15.如权利要求1-9中任一项所定义的化合物在保护生长的植物以防无脊椎动物害虫侵袭或侵染中的用途。
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RU2516290C2 (ru) * | 2007-08-27 | 2014-05-20 | Басф Се | Пиразольные соединения и их использование в способе борьбы с беспозвоночными вредителями, в способе защиты материала размножения растений, в способе лечения или защиты животных от инвазии или инфицирования, в материале размножения растений и сельскохозяйственные композиции, содержащие пиразольные соединения |
JP2012503623A (ja) | 2008-09-24 | 2012-02-09 | ビーエーエスエフ ソシエタス・ヨーロピア | 無脊椎動物系害虫防除用ピラゾール化合物 |
EA020661B1 (ru) * | 2008-09-24 | 2014-12-30 | Басф Се | Пиразольные соединения для борьбы с беспозвоночными вредителями |
EP2236505A1 (de) | 2009-04-03 | 2010-10-06 | Bayer CropScience AG | Acylierte Aminopyridine und - pyridazine als Insektizide |
JP5937199B2 (ja) * | 2011-04-21 | 2016-06-22 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 新規殺有害生物ピラゾール化合物 |
WO2013156318A1 (en) | 2012-04-16 | 2013-10-24 | Basf Se | Substituted pesticidal pyrazole compounds |
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2015
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- 2015-01-30 US US15/114,974 patent/US9955692B2/en active Active
- 2015-01-30 CN CN201580006598.8A patent/CN105939999A/zh active Pending
- 2015-01-30 CR CR20160397A patent/CR20160397A/es unknown
- 2015-01-30 AU AU2015212838A patent/AU2015212838A1/en not_active Abandoned
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- 2015-01-30 JP JP2016549280A patent/JP2017510550A/ja active Pending
- 2015-01-30 MX MX2016009945A patent/MX2016009945A/es unknown
- 2015-01-30 CA CA2935662A patent/CA2935662A1/en not_active Abandoned
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US20160345581A1 (en) | 2016-12-01 |
CA2935662A1 (en) | 2015-08-06 |
BR112016015345B1 (pt) | 2021-09-28 |
EP3099676A1 (en) | 2016-12-07 |
US9955692B2 (en) | 2018-05-01 |
ES2707751T3 (es) | 2019-04-04 |
MX2016009945A (es) | 2016-10-31 |
BR112016015345A8 (pt) | 2020-06-09 |
KR20160113719A (ko) | 2016-09-30 |
AU2015212838A1 (en) | 2016-08-18 |
CR20160397A (es) | 2016-10-27 |
EP3099676B1 (en) | 2018-10-24 |
IL246422A0 (en) | 2016-08-31 |
WO2015114106A1 (en) | 2015-08-06 |
BR112016015345A2 (pt) | 2017-08-08 |
JP2017510550A (ja) | 2017-04-13 |
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