CN110582484A - 三取代的甲硅烷基甲基苯氧基喹啉及其类似物 - Google Patents
三取代的甲硅烷基甲基苯氧基喹啉及其类似物 Download PDFInfo
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- CN110582484A CN110582484A CN201880029313.6A CN201880029313A CN110582484A CN 110582484 A CN110582484 A CN 110582484A CN 201880029313 A CN201880029313 A CN 201880029313A CN 110582484 A CN110582484 A CN 110582484A
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- FZXISNSWEXTPMF-UHFFFAOYSA-N terbutylazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)(C)C)=N1 FZXISNSWEXTPMF-UHFFFAOYSA-N 0.000 description 1
- 229960000351 terfenadine Drugs 0.000 description 1
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- 230000014616 translation Effects 0.000 description 1
- NKNFWVNSBIXGLL-UHFFFAOYSA-N triazamate Chemical compound CCOC(=O)CSC1=NC(C(C)(C)C)=NN1C(=O)N(C)C NKNFWVNSBIXGLL-UHFFFAOYSA-N 0.000 description 1
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- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- UGCNRZFAUBJVPT-UHFFFAOYSA-N tricyclohexyltin;hydrate Chemical compound O.C1CCCCC1[Sn](C1CCCCC1)C1CCCCC1 UGCNRZFAUBJVPT-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Quinoline Compounds (AREA)
Abstract
本公开涉及杀真菌活性化合物,更具体地,涉及三取代的甲硅烷基甲基苯氧基喹啉及其类似物、用于制备它们5的方法和中间体及其作为杀真菌活性化合物、特别是以杀真菌剂组合物的形式作为杀真菌活性化合物的用途。本公开还涉及使用这些化合物或包含其的组合物防治植物的植物病原性真菌的方法。
Description
技术领域
本公开涉及杀真菌活性化合物,更具体地,涉及三取代的甲硅烷基甲基苯氧基喹啉及其类似物、用于制备它们的方法和中间体及其作为杀真菌活性化合物、特别是以杀真菌剂组合物的形式作为杀真菌活性化合物的用途。本公开还涉及使用这些化合物或包含其的组合物防治植物的植物病原性真菌的方法。
背景技术
已知一些芳氧基喹啉表现出杀真菌活性。
在日本专利申请JP-2014/124411和国际专利申请WO 2013/002205中,某些苯氧基喹啉通常包含在下式的许多化合物的广泛公开中:
其中D和E表示5-至7-元环,X表示O、NH或N-C1-C8-烷基,B(或Y)表示C或N,并且R表示任选取代的烷氧基、任选二取代的氨基、任选取代的烷基硫烷基和任选地氧化的烷基硫烷基或硝基等。然而,JP-2014/124411和WO2013/002205既没有公开也没有暗示提供其中R表示三取代的甲硅烷基甲基的化合物。
在日本专利申请JP-2014/166991中,某些苯氧基喹啉通常包含在下式的许多化合物的广泛公开中:
其中A表示5-至7-元环,D表示5-至7-元的烃或杂环,X表示O、S、未取代或取代的碳原子或氮原子,Z和B独立地表示C或N,R表示基团CR1R2R3、C=O-R3、CR3=CRaRb、CR3=NRc、C6-C10芳基、炔基或CN。
在国际专利申请WO 2011/081174中,某些苯氧基喹啉通常包含在下式的许多化合物的广泛公开中:
其中D和E表示5-至7-元环,X表示O、NH或N-C1-C8-烷基,B(或Y)表示C或N,并且R表示任选取代的烷氧基、任选二取代的氨基、任选取代的烷基硫烷基和任选氧化的烷基硫烷基或硝基等。然而,JP-2014/124411和WO2013/002205既没有公开也没有暗示提供其中R表示三取代的甲硅烷基甲基的化合物。
在国际专利申请WO 2012/161071中,某些苯氧基喹啉通常包含在下式的许多化合物的广泛公开中:
其中D表示5-至7-元环,A1、A2、A3和A4独立地表示C或N,条件是An中至少一个为N,R表示任选取代的烷基或氰基。然而,WO 2012/161071既没有公开也没有暗示提供其中R表示三取代的甲硅烷基甲基的化合物。
然而,由于对杀真菌剂活性化合物的生态和经济要求不断增加,例如关于活性谱、毒性、选择性、施用率、残留物的形成和有利的构造,并且由于还可能存在关于抗性的问题,因此,存在开发至少在某些领域比已知化合物和组合物具有优势的新的杀真菌化合物和组合物的持续需求。
发明内容
因此,本发明提供如下所述的可用作杀真菌剂的三取代的甲硅烷基甲基苯氧基喹啉及其类似物。
活性成分
本发明提供式(I)的化合物及其盐、N-氧化物、金属络合物、类金属络合物和光学活性异构体或几何异构体
其中
·Z选自氢原子、卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C2-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基、芳基、杂环基、甲酰基、C1-C8-烷基羰基、(羟基亚氨基)C1-C8-烷基、(C1-C8-烷氧基亚氨基)C1-C8-烷基、羧基、C1-C8-烷氧基羰基、氨基甲酰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、氨基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、硫烷基、C1-C8-烷基硫烷基、C1-C8-烷基亚磺酰基、C1-C8-烷基磺酰基、C1-C6-三烷基甲硅烷基、氰基和硝基,
其中所述C1-C8-烷基、C2-C8-烯基、C2-C8-炔基和C1-C8-烷氧基可以被一个或多个Za取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基可以被一个或多个Zb取代基取代;
·n表示0、1、2、3或4;
·L表示O、S、SO、SO2、CR4R5或NR6,其中
оR4和R5独立地选自氢原子、卤素原子、羟基、C1-C8烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C1-C8-烷氧基和包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基,或它们可与它们连接的碳原子一起形成羰基;
оR6选自氢原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C3-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C3-C8-卤代炔基、C3-C7-环烷基、包含最高达9个可以相同或不同的卤素原子的C3-C7-卤代环烷基、C3-C7-环烷基-C1-C8-烷基、甲酰基、C1-C8-烷基羰基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基羰基、C1-C8-烷氧基羰基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基羰基、C1-C8-烷基磺酰基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基磺酰基、芳基-C1-C8-烷基和苯基磺酰基,其中所述C1-C8-烷基、C2-C8-烯基、C3-C8-炔基可以被一个或多个R6a取代基取代,并且其中所述C3-C7-环烷基、C3-C7-环烷基-C1-C8-烷基、芳基-C1-C8-烷基和苯基磺酰基可以被一个或多个R6b取代基取代;
·X独立地选自卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C2-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基、C1-C6-三烷基甲硅烷基、C1-C6-三烷基甲硅烷基甲基、氰基和硝基,其中所述C1-C8-烷基、C2-C8-烯基、C2-C8-炔基和C1-C8-烷氧基可以被一个或多个Xa取代基取代,并且所述C3-C7-环烷基和C4-C7-环烯基可以被一个或多个Xb取代基取代;
·W为CY1或N,其中:
-Y1选自氢原子、卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C2-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基、芳基、杂环基、甲酰基、C1-C8-烷基羰基、(羟基亚氨基)C1-C8-烷基、(C1-C8-烷氧基亚氨基)C1-C8-烷基、羧基、C1-C8-烷氧基羰基、氨基甲酰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、氨基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、硫烷基、C1-C8-烷基硫烷基、C1-C8-烷基亚磺酰基、C1-C8-烷基磺酰基、C1-C6-三烷基甲硅烷基、氰基和硝基,
其中所述C1-C8-烷基、C2-C8-烯基、C2-C8-炔基和C1-C8-烷氧基可以被一个或多个Y1a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基可以被一个或多个Y1b取代基取代;
·Y2、Y3、Y4和Y5独立地选自氢原子、卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C2-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基、芳基、杂环基、甲酰基、C1-C8-烷基羰基、(羟基亚氨基)C1-C8-烷基、(C1-C8-烷氧基亚氨基)C1-C8-烷基、羧基、C1-C8-烷氧基羰基、氨基甲酰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、氨基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、硫烷基、C1-C8-烷基硫烷基、C1-C8-烷基亚磺酰基、C1-C8-烷基磺酰基、C1-C6-三烷基甲硅烷基、氰基和硝基,其中所述C1-C8-烷基、C2-C8-烯基、C2-C8-炔基和C1-C8-烷氧基分别可以被一个或多个Y2a、Y3a、Y4a或Y5a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基分别可以被一个或多个Y2b、Y3b、Y4b或Y5b取代基取代;
·R1选自C1-C8-烷基、C2-C8-烯基、C2-C8-炔基、C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基,
其中所述C1-C8-烷基、C2-C8-烯基和C2-C8-炔基可以被一个或多个R1a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基可以被一个或多个R1b取代基取代;
·R2选自羟基、C1-C8-烷氧基、C1-C8-烷基、C2-C8-烯基、C2-C8-炔基、C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基,
其中所述C1-C8-烷氧基、C1-C8-烷基、C2-C8-烯基和C2-C8-炔基可以被一个或多个R2a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基可以被一个或多个R2b取代基取代;
·当R1和R2表示C1-C8烷基或C2-C8烯基时,它们可以与它们连接的硅原子一起形成C3-C8-硅杂环烷基环或C4-C8-硅杂环烯基环,其中所述C3-C8-硅杂环烷基环或C4-C8-硅杂环烯基环可以被一个或多个R1b取代基取代;
·R3选自氢原子、卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、C2-C8-炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、芳基、芳基-C1-C8-烷基、杂环基、杂环基-C1-C8-烷基、羟基-C1-C8-烷基、C1-C8-烷氧基-C1-C8-烷基、C1-C8-烷基羰基氧基-C1-C8-烷基、芳氧基-C1-C8-烷基、杂环氧基-C1-C8-烷基、氨基-C1-C8-烷基、C1-C8-烷基氨基-C1-C8-烷基、二-C1-C8-烷基氨基-C1-C8-烷基、芳基氨基-C1-C8-烷基、二-芳基氨基-C1-C8-烷基、杂环基氨基-C1-C8-烷基、C1-C8-烷基羰基氨基-C1-C8-烷基、C1-C8-烷氧基羰基氨基-C1-C8-烷基、C1-C8-烷基硫烷基-C1-C8-烷基、C1-C8-烷基亚磺酰基-C1-C8-烷基、C1-C8-烷基磺酰基-C1-C8-烷基和氰基-C1-C8-烷基,
其中所述C1-C8-烷基、C2-C8-烯基和C2-C8-炔基可以被一个或多个R3a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基、芳基-C1-C8-烷基、杂环基、杂环基-C1-C8-烷基、芳氧基-C1-C8-烷基和杂环氧基-C1-C8-烷基可以被一个或多个R3b取代基取代;
·当所述X与CH2-SiR1R2R3相邻时,R3和X可以与它们分别连接的硅原子和碳原子一起形成5-、6-或7-元的部分饱和的杂环,其中所述5-、6-或7-元的部分饱和的杂环可以被一个或多个R3b取代基取代;
·当R2表示C1-C8-烷氧基且R3表示C1-C8-烷氧基或C1-C8烷基时,它们可以与它们连接的硅原子一起形成5-、6-或7-元的杂环,其中所述5-、6-或7-元的杂环可以被一个或多个R2b取代基取代;
·Za、R1a、R2a、R3a、R6a、Xa、Y1a、Y2a、Y3a、Y4a和Y5a独立地选自硝基、羟基、氰基、羧基、氨基、硫烷基、五氟-λ6-硫烷基、甲酰基、氨基甲酰基、氨基甲酸酯基、C3-C7-环烷基、具有1至5个卤素原子的C3-C8-卤代环烷基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、C1-C8-烷氧基、具有1至5个卤素原子的C1-C8-卤代烷氧基、C1-C8-烷基硫烷基、具有1至5个卤素原子的C1-C8-卤代烷基硫烷基、C1-C8-烷基羰基、具有1至5个卤素原子的C1-C8-卤代烷基羰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、C1-C8-烷氧基羰基、具有1至5个卤素原子的C1-C8-卤代烷氧基羰基、C1-C8-烷基羰基氧基、具有1至5个卤素原子的C1-C8-卤代烷基羰基氧基、C1-C8-烷基羰基氨基、具有1至5个卤素原子的C1-C8-卤代烷基羰基氨基、C1-C8-烷基亚磺酰基、具有1至5个卤素原子的C1-C8-卤代烷基亚磺酰基、C1-C8-烷基磺酰基和具有1至5个卤素原子的C1-C8-卤代烷基磺酰基;
·Zb、R1b、R2b、R3b、R6b、Xb、Y1b、Y2b、Y3b、Y4b和Y5b独立地选自卤素原子、硝基、羟基、氰基、羧基、氨基、硫烷基、五氟-λ6-硫烷基、甲酰基、氨基甲酰基、氨基甲酸酯基、C1-C8-烷基、C3-C7-环烷基、具有1至5个卤素原子的C1-C8-卤代烷基、具有1至5个卤素原子的C3-C8-卤代环烷基、C2-C8-烯基、C2-C8-炔基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、C1-C8-烷氧基、具有1至5个卤素原子的C1-C8-卤代烷氧基、C1-C8-烷基硫烷基、具有1至5个卤素原子的C1-C8-卤代烷基硫烷基、C1-C8-烷基羰基、具有1至5个卤素原子的C1-C8-卤代烷基羰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、C1-C8-烷氧基羰基、具有1至5个卤素原子的C1-C8-卤代烷氧基羰基、C1-C8-烷基羰基氧基、具有1至5个卤素原子的C1-C8-卤代烷基羰基氧基、C1-C8-烷基羰基氨基、具有1至5个卤素原子的C1-C8-卤代烷基羰基氨基、C1-C8-烷基硫烷基、具有1至5个卤素原子的C1-C8-卤代烷基硫烷基、C1-C8-烷基亚磺酰基、具有1至5个卤素原子的C1-C8-卤代烷基亚磺酰基、C1-C8-烷基磺酰基和具有1至5个卤素原子的C1-C8-卤代烷基磺酰基。
如文中所用,表述“一个或多个取代基”是指取代基的数量范围为一个至基于可用的键合位点的数量计的可能取代基的最大数量,条件是满足稳定性和化学可行性的条件。
如文中所用,卤素意指氟、氯、溴或碘;甲酰基意指-CH(=O);羧基意指-C(=O)OH;羰基意指-C(=O)-;氨基甲酰基意指-C(=O)NH2;N-羟基氨基甲酰基意指-C(=O)NHOH;三氟甲磺酰基意指-SO2-CF3;SO表示亚砜基;SO2表示砜基;杂原子意指硫、氮或氧;亚甲基意指双基-CH2-;芳基通常意指苯基或萘基;除非另有说明,杂环基意指5-至7-元环、优选5-至6-元环,其可以是饱和的、部分饱和的或不饱和的,包含1至4个独立地选自N、O、S列表的杂原子。本文所用的术语“杂环基”包括杂芳基。
如文中在表述“5-至7-元环”中使用的术语“元”是指构成环的骨架原子的数量。
如文中所用,烷基、烯基和炔基以及含有这些术语的部分可以是直链或支链的。
当氨基或任何其他含有氨基基团的氨基部分被两个可以相同或不同的取代基取代时,这两个取代基可以与它们连接的氮原子一起形成杂环基、优选5-至7-元的杂环基,杂环基可以被取代或可以包含其他杂原子,例如吗啉基或哌啶基。
根据化合物中不对称中心的数量,本发明的任何化合物都可以以一种或多种光学异构体或手性异构体形式存在。因此,本发明同样涉及所有的光学异构体及其外消旋混合物或成比例的(scalemic)混合物(术语“成比例的”表示对映异构体的不同比例的混合物),以及涉及所有可能的立体异构体的所有比例的混合物。非对映异构体和/或光学异构体可根据本身本领域普通技术人员所知的方法分离。
根据化合物中双键的数量,本发明的任何化合物还可以以一种或多种几何异构体形式存在。因此,本发明同样涉及所有的几何异构体,以及所有比例的所有可能的混合物。几何异构体可根据本身本领域普通技术人员所知的一般方法分离。
根据链或环的取代基的相对位置(顺式/反式(syn/anti)或顺式/反式(cis/trans)),本发明的任何化合物都还可以以一种或多种几何异构体形式存在。因此,本发明同样涉及所有的顺式/反式(syn/anti)(或顺式/反式(cis/trans))异构体,以及所有比例的所有可能的顺式/反式(syn/anti)(或顺式/反式(cis/trans))混合物。顺式/反式(syn/anti)(或顺式/反式(cis/trans))异构体可以根据本身为本领域普通技术人员所知的一般方法分离。
当本发明的化合物可以互变异构形式存在时,本发明还包括任何互变异构形式的这种化合物,即使在没有明确提及的情况下。
式(I)的化合物在本文中称作“活性成分”。
在上述式(I)中,Z优选选自氢原子、卤素原子、羟基、C1-C6-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基、C1-C6-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷氧基和氰基,更优选Z为氢原子或C1-C6-烷基,甚至更优选Z为氢原子或甲基。
在上式(I)中,n优选为0或1。
在上式(I)中,L优选为O、N或CH2,更优选O。
在上式(I)中,X优选独立地为卤素原子、C1-C6-烷基或C1-C6-三烷基甲硅烷基甲基,更优选X独立地为氯原子、氟原子或甲基。
在上式(I)中,Y1、Y2、Y3、Y4或Y5优选独立地选自氢原子、卤素原子、C1-C6-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基、C1-C6-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷氧基和氰基,更优选Y1、Y2、Y3、Y4或Y5独立地选自氢原子、卤素原子、C1-C6-烷基和包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基,甚至更优选Y1、Y2、Y3、Y4或Y5独立地为卤素原子、氟原子、氯原子、甲基或三氟甲基。
在上式(I)中,R1优选为C1-C6-烷基、更优选甲基。
在上式(I)中,R2优选为C1-C6-烷基、更优选甲基。
在上式(I)中,R3优选选自羟基、C1-C6-烷基、C2-C6-烯基、C1-C6-烷氧基、可以被取代的芳基(例如苯基和C1-C6-烷氧基-苯基)、芳基-C1-C6-烷基、杂环基和杂环基-C1-C6-烷基,更优选R3选自羟基、C1-C6-烷基、C2-C6-烯基、C1-C6-烷氧基、芳基、芳基-C1-C6-烷基和杂环基,甚至更优选R3为羟基、甲基、乙烯基、异丙氧基、苯基、噻吩基或苄基。
在一些实施方案中,本发明化合物为式(I)的化合物,其中:
·W为CY1,其中Y1如上文所公开,优选Y1选自氢原子、卤素原子、C1-C6-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基、C1-C6-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷氧基,更优选Y1选自氢原子、卤素原子、C1-C6-烷基和包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基,甚至更优选Y1为氢原子、氟原子、氯原子、甲基或三氟甲基;
·Y2、Y3、Y4或Y5如上文所公开,优选Y2、Y3、Y4或Y5独立地选自氢原子、卤素原子、C1-C6-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基、C1-C6-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷氧基和氰基,更优选Y2、Y3、Y4或Y5独立地选自氢原子、卤素原子、C1-C6-烷基和包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基,甚至更优选Y2、Y3、Y4或Y5独立地为氢原子、氟原子、氯原子、甲基或三氟甲基;
·L如上文所公开,优选L为O、NH或CH2;
·X如上文所公开,优选X独立地为氢原子、C1-C6-烷基或C1-C6-三烷基甲硅烷基甲基,更优选X独立地为氯原子、氟原子或甲基;
·n如上文所公开,优选n为0或1;
·R1、R2和R3如文中所公开,优选R1为C1-C6-烷基,更优选甲基;优选R2为C1-C6-烷基,更优选甲基;优选R3选自羟基、C1-C6-烷基、C2-C6-烯基、C1-C6-烷氧基、可以被取代的芳基、芳基-C1-C6-烷基、杂环基和杂环基-C1-C6-烷基,更优选R3选自羟基、C1-C6-烷基、C2-C6-烯基、C1-C6-烷氧基、芳基、芳基-C1-C6-烷基和杂环基,甚至更优选R3为羟基、甲基、乙烯基、异丙氧基、苯基、噻吩基或苄基。
在一些实施方案中,本发明化合物为式(I)的化合物,其中:
·W为N;
·Y2、Y3、Y4或Y5如上文所公开,优选Y2、Y3、Y4或Y5独立地选自氢原子、卤素原子、C1-C6-烷基、包含最高达9个可以相同或不同的C1-C6-卤代烷基、C1-C6-烷氧基、包含最高达9个可以相同或不同的C1-C6-卤代烷氧基和氰基,更优选Y2、Y3、Y4或Y5独立地选自氢原子、卤素原子、C1-C6-烷基和包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基,甚至更优选Y2、Y3、Y4或Y5独立地为氢原子、氟原子、氯原子、甲基或三氟甲基;
·L如上文所公开,优选L为O、NH或CH2;
·X如上文所公开,优选X独立地为卤素原子、C1-C6-烷基或C1-C6-三烷基甲硅烷基甲基,更优选X独立地为氯原子、氟原子或甲基,
·n如上文所公开,优选n为0或1;
·R1、R2和R3如文中所公开,优选R1为C1-C6-烷基,更优选甲基;优选R2为C1-C6-烷基,更优选甲基;优选R3选自羟基、C1-C6-烷基、C2-C6-烯基、C1-C6-烷氧基、可以被取代的芳基、芳基-C1-C6-烷基、杂环基和杂环基-C1-C6-烷基,更优选R3选自羟基、C1-C6-烷基、C2-C6-烯基、C1-C6-烷氧基、芳基、芳基-C1-C6-烷基和杂环基,甚至更优选R3为羟基、甲基、乙烯基、异丙氧基、苯基、噻吩基或苄基。
上述关于本发明化合物的取代基的优选内容可以各种方式结合。因此,这些优选特征的组合提供了本发明化合物的亚类。本发明优选化合物的这种亚类的实例为:
-L的优选特征与R1、R2、R3、n、X、Y1、Y2、Y3、Y4、Y5、W和Z的一种或多种优选特征;
-R1的优选特征与L、R2、R3、n、X、Y1、Y2、Y3、Y4、Y5、W和Z的一种或多种优选特征;
-R2的优选特征与L、R1、R3、n、X、Y1、Y2、Y3、Y4、Y5、W和Z的一种或多种优选特征;
-R3的优选特征与L、R1、R2、n、X、Y1、Y2、Y3、Y4、Y5、W和Z的一种或多种优选特征;
-n的优选特征与L、R1、R2、R3、X、Y1、Y2、Y3、Y4、Y5、W和Z的一种或多种优选特征;
-X的优选特征与L、R1、R2、R3、n、Y1、Y2、Y3、Y4、Y5、W和Z的一种或多种优选特征;
-Y1的优选特征与L、R1、R2、R3、n、X、Y2、Y3、Y4、Y5、W和Z的一种或多种优选特征;
-Y2的优选特征与L、R1、R2、R3、n、X、Y1、Y3、Y4、Y5、W和Z的一种或多种优选特征;
-Y3的优选特征与L、R1、R2、R3、n、X、Y1、Y2、Y4、Y5、W和Z的一种或多种优选特征;
-Y4的优选特征与L、R1、R2、R3、n、X、Y1、Y2、Y3、Y5、W和Z的一种或多种优选特征;
-Y5的优选特征与L、R1、R2、R3、n、X、Y1、Y2、Y3、Y4、W和Z的一种或多种优选特征;
-W的优选特征与L、R1、R2、R3、n、X、Y1、Y2、Y3、Y4、Y5和Z的一种或多种优选特征;
-Z的优选特征与L、R1、R2、R3、n、p、X以及Y1、Y2、Y3、Y4、Y5和W的一种或多种优选特征。
在这些本发明化合物的取代基的优选特征的组合中,所述优选特征还可选自L、R1、R2、R3、n、X、Y1、Y2、Y3、Y4、Y5、W和Z中每一个的更加优选的特征,以形成本发明化合物的最优选的亚类。
活性成分的制备方法
本发明还涉及式(I)的化合物的制备方法。
如文中定义的式(I)的化合物可通过方法P1制备,方法P1包括使式(II)的卤代甲基芳基或其盐中的一种与式(IIIa)的二甲硅烷基衍生物反应的步骤:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义,U1表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基:
其中R1、R2和R3如文中所定义。
方法P1可根据已知方法(Organic Letters(2003),5,3483;Organic Letters(2007),9,3785;以及其中引用的参考文献)在以下物质的存在下进行:过渡金属催化剂如钯;并且如果合适,膦配体或N-杂环碳烯配体;如果合适,碱;并且如果合适,溶剂。
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义并且U1表示氯原子或溴原子的式(II)的衍生物可根据已知方法通过式(IV)的甲苯衍生物或其盐中的一种的自由基卤化反应制备:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义。
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义的式(IV)的衍生物可根据方法P4制备。
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义并且U1表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基的式(II)的衍生物可根据已知方法通过式(V)的羟甲基衍生物或其盐中的一种的卤化反应或磺化反应制备:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义。
式(IIIa)的二甲硅烷基衍生物是已知的或可通过已知方法制备。
其中R3表示羟基的式(I)的化合物可由其中R3表示C1-C6-烷氧基的式(I)的化合物(它们本身通过方法P1制备)根据已知方法(Organic Letters(2003),5,3483)通过酸性水解制备。
其中R3表示氟原子的式(I)的化合物可由其中R3表示C1-C6-烷氧基的式(I)的化合物(它们本身通过方法P1制备)通过已知方法(Synlett(2012),23,1064以及其中引用的参考文献)制备,或者可由其中R3表示羟基的式(I)的化合物通过已知方法(EP1908472)制备。
方法P1可以在催化剂如金属盐或络合物的存在下进行。适于该目的的金属衍生物为过渡金属催化剂如钯。适于该目的的金属盐或络合物为,例如,氯化钯、乙酸钯、四(三苯基膦)钯(0)、双(二亚苄基丙酮)钯(0)、三(二亚苄基丙酮)二钯(0)、双(三苯基膦)二氯化钯(II)、[1,1’-双(二苯基膦基)二茂铁]二氯化钯(II)、双(肉桂基)二氯二钯(II)、双(烯丙基)-二氯二钯(II)或[1,1’-双(二叔丁基膦基)二茂铁]二氯化钯(II)。
还可通过单独向反应中加入钯盐以及以下配体或盐而在反应混合物中产生钯络合物:例如,三乙基膦、三叔丁基膦、三叔丁基四氟硼酸鏻、三环己基膦、2-(二环己基膦基)联苯、2-(二叔丁基膦基)联苯、2-(二环己基膦基)-2′-(N,N-二甲基氨基)联苯、2-(叔丁基膦基)-2′-(N,N-二甲基氨基)联苯、2-二叔丁基膦基-2’,4’,6’-三异丙基联苯、2-二环己基膦基-2’,4’,6’-三异丙基联苯、2-二环己基膦基-2,6’-二甲氧基联苯、2-二环己基膦基-2’,6’-二异丙氧基联苯、三苯基膦、三-(邻甲苯基)膦、3-(二苯基膦基)苯磺酸钠、三-2-(甲氧基-苯基)膦、2,2′-双(二苯基膦基)-1,1′-联萘、1,4-双(二苯基膦基)丁烷、1,2-双(二苯基膦基)乙烷、1,4-双(二环己基膦基)丁烷、1,2-双(二环己基膦基)-乙烷、2-(二环己基膦基)-2′-(N,N-二甲基氨基)-联苯、1,1’-双(二苯基膦基)-二茂铁、(R)-(-)-1-[(S)-2-二苯基-膦基)二茂铁基]乙基二环己基膦、三-(2,4-叔丁基-苯基)亚磷酸盐、二(1-金刚烷基)-2-吗啉代基苯基膦或1,3-双(2,4,6-三甲基苯基)氯化咪唑鎓。
还可有利地从商业产品目录如Strem Chemicals的“用于有机合成的金属催化剂(Metal Catalysts for Organic Synthesis)”或Strem Chemicals的“磷配体和化合物(Phosphorous Ligands and Compounds)”中选择合适的催化剂和/或配体。
适于进行方法P1的碱可以是通常用于这种反应的无机碱和有机碱。优选使用碱土金属氢氧化物或碱金属氢氧化物,例如氢氧化钠、氢氧化钙、氢氧化钾或其他氢氧化铵衍生物;碱土金属氟化物、碱金属氟化物或氟化铵,例如氟化钾、氟化铯或四丁基氟化铵;碱土金属碳酸盐或碱金属碳酸盐,例如碳酸钠、碳酸钾、碳酸氢钾、碳酸氢钠或碳酸铯;碱金属乙酸盐或碱土金属乙酸盐,例如乙酸钠、乙酸锂、乙酸钾或乙酸钙;碱金属磷酸盐或碱土金属磷酸盐,例如磷酸三钾碱;碱金属醇盐,例如叔丁醇钾或叔丁醇钠;叔胺,例如三甲胺、三乙胺、三丁胺、N,N-二甲基苯胺、N,N-二环己基甲胺、N,N-二异丙基乙胺、N-甲基哌啶、N,N-二甲基氨基吡啶、二氮杂双环辛烷(DABCO)、二氮杂双环壬烯(DBN)或二氮杂双环十一碳烯(DBU);以及芳族碱,例如吡啶、甲基吡啶、二甲基吡啶或三甲吡啶。
适于进行方法P1的溶剂可以是常规的惰性有机溶剂。优选使用任选地卤代的脂族、脂环族或芳族烃类,例如石油醚、戊烷、己烷、庚烷、环己烷、甲基环己烷、苯、甲苯、二甲苯或十氢化萘;氯苯、二氯苯、二氯甲烷、氯仿、四氯化碳、二氯乙烷或三氯乙烷;醚类,例如二乙醚、二异丙醚、甲基叔丁基醚、甲基叔戊基醚、二噁烷、四氢呋喃、2-甲基四氢呋喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷或苯甲醚;腈类,例如乙腈、丙腈、正丁腈或异丁腈或苯甲腈;酰胺类,例如N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基甲酰苯胺、N-甲基吡咯烷酮或六甲基磷酰三胺;脲类,例如1,3-二甲基-3,4,5,6-四氢-2(1H)-嘧啶酮;酯类,例如乙酸甲酯或乙酸乙酯;亚砜类,例如二甲基亚砜;或砜类,例如环丁砜;及其混合物。
还可有利地使用共-溶剂如水或醇如甲醇、乙醇、丙醇、异丙醇或叔丁醇进行方法P1。
方法P1可以在惰性气氛如氩气或氮气气氛中进行。在进行方法P1时,每摩尔式(II)的化合物可使用1摩尔或过量的式(IIIa)的化合物和1至5摩尔的碱以及0.01至20摩尔百分比的钯络合物。也可以使用其他比例的反应组分。通过已知方法进行后处理。
如文中定义的式(I)的化合物可通过方法P2制备,该方法包括使式(VI)的化合物或其盐中的一种与式(IIIb)的硼衍生物反应的步骤:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义,U2表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基:
其中W3表示硼衍生物如硼酸、硼酸酯或三氟硼酸钾衍生物;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;且
R3表示氢原子或C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基。
应当理解,所述R1、R2和R3中的任一个都可以被取代,如式(I)的化合物的R1、R2和R3相关公开的那样。
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义并且U2表示氯原子、溴原子或碘原子的式(VI)的衍生物可根据已知方法(Patai′s Chemistry of Functional Groups-Amino,Nitroso,Nitro and Related Groups-1996)通过式(VII)的苯胺或其盐中的一种的重氮化反应制备:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义。
式(VII)的苯胺可根据已知方法(Patai′s Chemistry of Functional Groups-Amino,Nitroso,Nitro and Related Groups-1996)通过还原硝基制备。
式(IIIb)的硼衍生物是已知的或可通过已知方法制备。
方法P2可以在以下物质的存在下进行:过渡金属催化剂如钯;并且如果合适,膦配体或N-杂环碳烯配体;并且如果合适,碱;并且如果合适,溶剂。适于该目的的钯盐或络合物可以如关于方法P1所公开的那样。
适于进行方法P2的碱可以如方法P1相关公开的那样。
适于进行方法P2的溶剂可以如方法P1相关公开的那样。
还可有利地使用共-溶剂如水或醇如甲醇、乙醇、丙醇、异丙醇或叔丁醇进行本发明方法P2。
方法P2可以在惰性气氛中进行。在进行方法P2时,每摩尔式(VI)的化合物可使用1摩尔或过量的式(IIIb)的化合物和1至5摩尔的碱以及0.01至20摩尔百分比的过渡金属络合物。也可以使用其他比例的反应组分。通过已知方法进行后处理。
如文中定义的式(I)的化合物可通过方法P3制备,该方法包括使式(VI)的化合物或其盐中的一种与式(IIIc)的衍生物反应的步骤:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义,U2表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基,
其中M1表示可以被1至2个配体络合的碱金属如锂,或过渡金属如可以被1至2个配体络合的卤化镁或可以被1至2个配体络合的卤化锌;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;且
R3表示氢原子或C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基。
应当理解,所述R1、R2和R3中的任一个都可以被取代,如式(I)的化合物的R1、R2和R3相关公开的那样。
式(IIIc)的化合物是市售可得的或可根据已知方法获得:由相应的卤代衍生物通过与金属镁、金属锌或金属锂优选在无水条件下反应获得;或者优选在无水条件下使用烷基锂试剂或格氏试剂或者由烷基锂试剂或格氏试剂制备的成品络合物(manufacturedcomplex)通过卤素/金属交换反应获得;或者优选在无水条件下使用格氏试剂上的氯化锌通过金属/金属交换反应获得。
方法P3可以在以下物质的存在下进行:过渡金属催化剂如钯;并且如果合适,膦配体或N-杂环碳烯配体;并且如果合适,碱;并且如果合适,溶剂。适于该目的的钯盐或络合物可以如方法P3相关公开的那样。
适于进行方法P3的碱可以如方法P1相关公开的那样。
适于进行方法P3的溶剂可以如方法P1相关公开的那样。
方法P3可以在惰性气氛中进行。在进行方法P3时,每摩尔式(VI)的化合物可使用1摩尔或过量的式(IIIc)的化合物和1至5摩尔的碱以及0.01至20摩尔百分比的过渡金属络合物。也可以使用其他比例的反应组分。通过已知方法进行后处理。
式(I)的化合物可通过方法P4制备,该方法包括使式(VIII)的化合物或其盐中的一种与式(IX)的化合物反应的步骤,如以下反应方案所示:
方法P4
其中L表示O、S或NR6;
U3表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;且
R3表示氢原子;C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;
且n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义。
应当理解,所述R1、R2和R3中的任一个都可以被取代,如式(I)的化合物的R1、R2和R3相关公开的那样。
式(IX)的化合物是市售可得的或可通过众所周知的方法制备。
方法P4可根据已知方法(Organic Letters(2012),14,170;Organic Letters(2002),4,1623;以及其中引用的参考文献)在以下物质的存在下进行:过渡金属催化剂如钯;并且如果合适,膦配体或N-杂环碳烯配体;或者铜;并且如果合适,配体;并且如果合适,碱;并且如果合适,溶剂。
合适的钯基催化剂可以如方法P1相关公开的那样。
适于该目的的铜盐或络合物及其水合物为例如,金属铜、碘化亚铜(I)、氯化亚铜(I)、溴化亚铜(I)、氯化铜(II)、溴化铜(II)、氧化铜(II)、氧化亚铜(I)、乙酸铜(II)、乙酸亚铜(I)、噻吩-2-甲酸亚铜(I)、氰化亚铜(I)、硫酸铜(II)、双(2,2,6,6-四甲基-3,5-庚二酮)化铜、三氟甲磺酸铜(II)、六氟磷酸四(乙腈)铜(I)、四氟硼酸四(乙腈)铜(I)。
还可通过单独向反应中加入铜盐以及以下配体或盐而在反应混合物中产生铜络合物:例如乙二胺、N,N-二甲基乙二胺、N,N’-二甲基乙二胺、外消旋-反式-1,2-二氨基环己烷、外消旋-反式-N,N’-二甲基环己烷-1,2-二胺、1,1’-联萘-2,2’-二胺、N,N,N’,N’-四甲基乙二胺、脯氨酸、N,N-二甲基甘氨酸、喹啉-8-醇、吡啶、2-氨基吡啶、4-(二甲基氨基)吡啶、2,2’-联吡啶、2,6-二(2-吡啶基)吡啶、2-吡啶甲酸、2-(二甲基氨基甲基)-3-羟基吡啶、1,10-菲咯啉、3,4,7,8-四甲基-1,10-菲咯啉、2,9-二甲基-1,10-菲咯啉、4,7-二甲氧基-1,10-菲咯啉、N,N’-双[(E)-吡啶-2-基亚甲基]环己烷-1,2-二胺、N-[(E)-苯基亚甲基]、N-[(E)-苯基亚甲基]-环己胺、1,1,1-三(羟甲基)乙烷、乙二醇、2,2,6,6-四甲基庚烷-3,5-二酮、2-(2,2-二甲基丙酰基)环己酮、乙酰丙酮、二苯甲酰基甲烷、2-(2-甲基丙酰基)环己酮、联苯-2-基(二叔丁基)磷烷、亚乙基双-(二苯基膦)、N,N-二乙基水杨酰胺、2-羟基苯甲醛肟、氧代[(2,4,6-三甲基苯基)氨基]乙酸或1H-吡咯-2-甲酸。
还可有利地从商品目录如Strem Chemicals的“Metal Catalysts for OrganicSynthesis(用于有机合成的金属催化剂)”或综述(Chemical Society Reviews(2014),43,3525;Coordination Chemistry Reviews(2004),248,2337;以及其中的参考文献)中选择合适的催化剂和/或配体。
适于进行方法P4的碱可以如方法P1相关公开的那样。
适于进行方法P4的溶剂可以如方法P1相关公开的那样。
方法P4可以在惰性气氛中进行。在进行方法P4时,每摩尔式(VIII)的化合物可以使用1摩尔或过量的式(IX)的化合物和1至5摩尔的碱以及0.01至20摩尔百分比的过渡金属络合物。也可以使用其他比例的反应组分。通过已知方法进行后处理。
式(I)的化合物可通过方法P5制备,该方法包括使式(X)的化合物或其盐中的一种与式(XI)的化合物反应的步骤,如以下反应方案所示:
方法P5
其中L表示CR4R5;
R4和R5独立地表示氢原子或C1-C8烷基;
U4表示溴原子、氯原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基;
W1表示硼衍生物如硼酸、硼酸酯或三氟硼酸钾衍生物;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;
R3表示氢原子;C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;且
n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义。
应当理解,所述R1、R2和R3中的任一个都可以被取代,如式(I)的化合物的R1、R2和R3相关公开的那样。
式(XI)的化合物可通过已知方法(Journal of the American Chemical Society(1957),79,6540;Journal of Organic Chemistry(2000),(65),4913;TetrahedronLetters(2002),43,8569)制备。
方法P5可以在以下物质的存在下进行:过渡金属催化剂如钯;并且如果合适,膦配体或N-杂环碳烯配体;并且如果合适,碱;并且如果合适,溶剂。适于该目的的钯盐或络合物可以如方法P1相关公开的那样。
适于进行方法P5的碱可以如方法P1相关公开的那样。
适于进行方法P5的溶剂可以如方法P1相关公开的那样。
还可有利地根据本发明进行方法P5,使用共溶剂如水或醇,例如甲醇、乙醇、丙醇、异丙醇或叔丁醇。
方法P5可以在惰性气氛中进行。在进行方法P5时,每摩尔式(X)的化合物可使用1摩尔或过量的式(XI)的化合物和1至5摩尔的碱以及0.01至20摩尔百分比的过渡金属络合物。也可以使用其他比例的反应组分。通过已知方法进行后处理。
式(I)的化合物可通过方法P6制备,该方法包括使式(VIII)的化合物或其盐中的一种与式(XII)的化合物反应的步骤,如以下反应方案所示:
方法P6
其中L表示CR4R5;
R4和R5独立地表示氢原子、C1-C8-烷氧基或C1-C8烷基;
U3表示溴原子、氯原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基;
W2表示硼衍生物如硼酸、硼酸酯或三氟硼酸钾衍生物;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;
R3表示氢原子或C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;和
n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义。
应当理解,所述R1、R2和R3中的任一个都可以被取代,如式(I)的化合物的R1、R2和R3相关公开的那样。
式(XII)的化合物可由式(XI)的化合物通过已知方法(Tetrahedron Letters(2003),44,233和Chemistry Letters(2002),780)制备。
方法P6可以在以下物质的存在下进行:过渡金属催化剂如钯;并且如果合适,膦配体或N-杂环碳烯配体;并且如果合适,碱;并且如果合适,溶剂。适于该目的的钯盐或络合物可以如方法P1相关公开的那样。
适于进行方法P6的碱可以如方法P1相关公开的那样。
适于进行方法P6的溶剂可以如方法P1相关公开的那样。
还可有利地根据本发明进行方法P6,使用共溶剂如水或醇,例如甲醇、乙醇、丙醇、异丙醇或叔丁醇。
方法P6可以在惰性气氛中进行。在进行方法P6时,每摩尔式(VIII)的化合物可使用1摩尔或过量的式(XII)的化合物和1至5摩尔的碱以及0.01至20摩尔百分比的过渡金属络合物。也可以使用其他比例的反应组分。通过已知方法进行后处理。
方法P1、P2、P3、P4、P5和P6通常在大气压力下进行。也可在升高的压力或降低的压力下进行。
在进行方法P1、P2、P3、P4、P5和P6时,反应温度可以在相对宽的范围内变化。通常,这些方法在-78℃至200℃、优选-78℃至150℃的温度下进行。控制所述方法温度的方法是使用微波技术。
通常,反应混合物在降低的压力下浓缩。可通过已知方法如色谱法或结晶法从剩余的残余物中除去仍然可能存在的任何杂质。
后处理通过常规方法进行。通常,用水处理反应混合物,分离出有机相,并且在干燥后,将有机相在减压下浓缩。如果合适,可通过常规方法如色谱法、结晶法或蒸馏法从剩余的残余物中除去仍然可能存在的任何杂质。
式(I)的化合物可根据如上所述的一般制备方法制备。然而,应当理解,基于其常识和可获得的出版物,技术人员将能够根据希望合成的每种化合物的具体情况来调整所述方法。
用于制备活性成分的中间体
本发明还涉及用于制备式(I)的化合物的中间体。因此,本发明涉及式(IIa)的化合物及其可接受的盐:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义,U1a表示氯原子、溴原子或碘原子。
化学数据库和/或供应商的数据库中提到了以下式(IIa)的化合物,但没有任何使得能够制备和分离这些化合物的参考资料或信息:
-3-[2-氯-6-(氯甲基)苯氧基]喹啉[2115263-99-3],
-3-[2-(溴甲基)苯氧基]喹啉[1984429-33-5],
-3-[2-(溴甲基)-4-甲基苯氧基]喹啉[1965664-20-3],
-3-[2-(氯甲基)-4-甲基苯氧基]喹啉[1965657-18-4],
-3-[5-氯-2-(氯甲基)苯氧基]喹啉[1965173-09-4],
-3-[2-(溴甲基)-6-氟苯氧基]喹啉[1962784-34-4],
-3-[2-(溴甲基)-4-氟苯氧基]喹啉[1962432-94-5],
-3-[2-(氯甲基)-6-氟苯氧基]喹啉[1944013-78-8],
-3-[2-(溴甲基)-3-氟苯氧基]喹啉[1937855-08-7],
-3-[2-(溴甲基)-6-氯苯氧基]喹啉[1937132-69-8],
-3-[4-溴-2-(氯甲基)苯氧基]喹啉[1937073-70-5],
-3-[2-(氯甲基)-3-氟苯氧基]喹啉[1929477-21-3],
-3-[4-氯-2-(氯甲基)苯氧基]喹啉[1929007-47-5],
-3-[2-(溴甲基)-4-氯苯氧基]喹啉[1928589-74-5],
-3-[2-(氯甲基)苯氧基]喹啉[1927507-10-5],
-3-[5-溴-2-(溴甲基)苯氧基]喹啉[1927507-06-9],
-3-[2-(溴甲基)-3-氯苯氧基]喹啉[1927140-37-1],
-3-[2-(氯甲基)-4-氟苯氧基]喹啉[1927074-67-6],
-3-[5-溴-2-(氯甲基)苯氧基]喹啉[1926940-89-7],
-3-[3-氯-2-(氯甲基)苯氧基]喹啉[1926940-83-1],
-3-[4-溴-2-(溴甲基)苯氧基]喹啉[1925651-81-5],和
-3-[2-(溴甲基)-5-氯苯氧基]喹啉[1925623-80-8]。
根据本发明,优选的式(IIa)的化合物为:
-3-[3-氯-2-(氯甲基)苯氧基]喹啉,
-3-[2-(氯甲基)-3-氟苯氧基]喹啉,和
-3-[2-(溴甲基)苯氧基]-8-氟喹啉。
本发明还涉及式(V)的化合物及其可接受的盐:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义,
条件是式(V)的化合物不表示:
-{2-溴-6-[(8-氟喹啉-3-基)氧基]苯基}甲醇[1314009-28-3],和
-{2-氯-6-[(8-氟喹啉-3-基)氧基]苯基}甲醇[1314009-25-0]。
化学数据库和/或供应商的数据库中提到了以下式(V)的化合物,但没有任何使得能够制备和分离这些化合物的参考资料或信息:
-{2-[(3-氨基喹喔啉-2-基)氧基]苯基}甲醇[1975425-47-8],
-[5-甲基-2-(喹啉-3-基氧基)苯基]甲醇[1965687-80-2],
-[2-氯-6-(喹啉-3-基氧基)苯基]甲醇[1965406-17-0],
-[5-氯-2-(喹啉-3-基氧基)苯基]甲醇[1965406-09-0],
-[2-氟-6-(喹啉-3-基氧基)苯基]甲醇[1963098-24-9],
-[5-溴-2-(喹啉-3-基氧基)苯基]甲醇[1962859-44-4],
-{2-[(3-甲基喹喔啉-2-基)氧基]苯基}甲醇[1958608-15-5],
-[2-(喹喔啉-2-基氧基)苯基]甲醇[1940088-23-2],
-[3-氯-2-(喹啉-3-基氧基)苯基]甲醇[1936861-82-3],
-[3-氟-2-(喹啉-3-基氧基)苯基]甲醇[1929748-13-9],
-[4-氯-2-(喹啉-3-基氧基)苯基]甲醇[1928858-16-5],
-[5-氟-2-(喹啉-3-基氧基)苯基]甲醇[1927140-33-7],
-[2-(喹啉-3-基氧基)苯基]甲醇[1927074-65-4],和
-[4-溴-2-(喹啉-3-基氧基)苯基]甲醇[1926940-80-8]。
根据本发明,优选的式(V)的化合物为:
-{2-[(8-氟喹啉-3-基)氧基]苯基}甲醇,
-[2-氟-6-(喹啉-3-基氧基)苯基]甲醇,和
-[2-氯-6-(喹啉-3-基氧基)苯基]甲醇。
组合物和制剂
本发明还涉及一种组合物、特别是用于防治不想要的微生物的组合物。可将组合物施用至微生物和/或其生境。
组合物通常包含一种或多种式(I)的化合物和至少一种农业上合适的助剂,例如载体和/或表面活性剂。
载体为固体或液体,是通常为惰性的天然的或合成的、有机的或无机的物质。载体通常改善化合物对例如植物、植物部位或种子的适用性。合适的固体载体的实例包括,但不限于:铵盐,天然岩粉如高岭土、黏土、滑石、白垩、石英、绿坡缕石、蒙脱石和硅藻土,以及合成岩粉如细碎的二氧化硅、氧化铝和硅酸盐。通常用于制备颗粒剂的有用的固体载体的实例包括,但不限于:粉碎并分级的天然岩石,例如方解石、大理石、浮石、海泡石和白云石,无机和有机粉末的合成颗粒,以及有机材料如纸、锯屑、椰壳、玉米穗轴和烟草茎的颗粒。合适的液体载体的实例包括,但不限于:水、有机溶剂及其组合。合适的溶剂的实例包括极性和非极性有机化学液体,例如来自芳族和非芳族烃类(例如环己烷、链烷烃、烷基苯、二甲苯、甲苯烷基萘、氯代芳族或氯代脂族烃类如氯苯、氯乙烯或亚甲基氯);醇类和多元醇类(其也可任选地被取代、醚化和/或酯化,例如丁醇或乙二醇);酮类(例如丙酮、甲基乙基酮、甲基异丁基酮或环己酮);酯类(包括脂肪和油)和(聚)醚类;未取代的和取代的胺、酰胺(例如二甲基甲酰胺)、内酰胺(例如N-烷基吡咯烷酮)和内酯;砜和亚砜(例如二甲基亚砜)。载体也可为液化的气态增量剂,即在标准温度和标准压力下为气态的液体,例如,气溶胶喷射剂,例如卤代烃、丁烷、丙烷、氮气和二氧化碳。载体的量通常为组合物的1-99.99重量%、优选5-99.9重量%、更优选10-99.5重量%并且最优选20-99重量%。
表面活性剂可以是离子的(阳离子的或阴离子的)或非离子的表面活性剂,例如离子的或非离子的乳化剂、泡沫形成剂、分散剂、润湿剂及其任意混合物。合适的表面活性剂的实例包括,但不限于:聚丙烯酸盐;木质素磺酸盐;酚磺酸盐或萘磺酸盐;环氧乙烷和/或环氧丙烷与脂肪醇、脂肪酸或脂肪胺的缩聚物(聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚,例如烷基芳基聚乙二醇醚);取代的酚(优选烷基酚或芳基酚);磺基琥珀酸酯的盐;牛磺酸衍生物(优选烷基牛磺酸盐);聚乙氧基化的醇或酚的磷酸酯;多元醇的脂肪酯;和含有硫酸盐、磺酸盐、磷酸盐的化合物的衍生物(例如烷基磺酸盐、烷基硫酸盐、芳基磺酸盐);以及蛋白质水解产物、木质素磺酸盐废液和甲基纤维素。当式(I)的化合物和/或载体不溶于水,并且施用用水进行时,通常使用表面活性剂。其次,表面活性剂的量通常为组合物的5-40重量%。
合适的助剂的其他实例包括防水剂、干燥剂、粘合剂(胶粘剂、增粘剂、固定剂,例如羧甲基纤维素,粉末、颗粒或胶乳形式的天然聚合物和合成的聚合物,例如阿拉伯胶、聚乙烯醇和聚乙酸乙烯酯,天然的磷脂例如脑磷脂和卵磷脂以及合成磷脂、聚乙烯吡咯烷酮和甲基纤维素(tylose))、增稠剂、稳定剂(例如冷稳定剂、防腐剂、抗氧化剂、光稳定剂或其它改善化学和/或物理稳定性的试剂)、染料或颜料(例如无机颜料,例如氧化铁、氧化钛和普鲁士蓝;有机染料,例如茜素染料、偶氮染料和金属酞菁染料)、消泡剂(例如硅酮消泡剂和硬脂酸镁)、防腐剂(例如双氯酚和苄醇半缩甲醛)、二次增稠剂(纤维素衍生物、丙烯酸衍生物、黄原胶、改性粘土以及细碎的二氧化硅)、粘着剂、赤霉素和加工助剂、矿物油和植物油、香料、蜡、营养素(包括微量营养素,例如铁盐、锰盐、硼盐、铜盐、钴盐、钼盐和锌盐)、保护胶体、触变性物质、渗透剂、螯合剂和络合前体。
助剂的选择与本发明化合物的预期施用方式和/或其物理性质有关。此外,可选择助剂以赋予组合物或由其制备的使用形式特定的性质(工艺的、物理的和/或生物学的性质)。助剂的选择可允许根据具体需要定制组合物。
组合物可为任何常规形式,例如溶液剂(例如水溶液)、乳液剂、可湿性粉剂、水基悬浮剂和油基悬浮剂、粉剂、尘剂、糊剂、可溶性粉剂、可溶性颗粒剂、可传播颗粒剂、悬乳浓缩剂、用一种或多种式(I)的化合物浸渍的天然产物或合成产物、肥料以及聚合物质中的微胶囊剂。式(I)的化合物可以悬浮的、乳化的或溶解的形式存在。
可将组合物作为可即用的制剂提供给最终用户,即可通过合适的装置如喷雾装置或撒粉装置直接将所述组合物施用至植物或种子。或者,可将组合物以浓缩液的形式提供给最终用户,所述浓缩液在使用前必须进行稀释,优选用水稀释。
组合物可以常规方式制备,例如通过将式(I)的化合物与一种或多种如上文所公开的合适的助剂混合。
组合物通常包含0.01-99重量%、0.05-98重量%、优选0.1-95重量%、更优选0.5-90重量%、最优选1-80重量%的式(I)的化合物。组合物可能包含两种或更多种式(I)的化合物。在这种情况下,所述范围是指式(I)的化合物的总量。
混合物/结合物
可将式(I)的化合物和包含其的组合物与其他活性成分如杀真菌剂、杀细菌剂、杀螨剂、杀线虫剂、杀昆虫剂、除草剂、肥料、生长调节剂、安全剂或化学信息素混合。这可以允许拓宽活性谱或防止抗性发展。已知杀真菌剂、杀昆虫剂、杀螨剂、杀线虫剂和杀细菌剂的实例公开于农药手册(Pesticide Manual),第17版中。
可与式(I)的化合物混合的特别优选的杀真菌剂的实例为:
1)麦角固醇生物合成抑制剂,例如(1.001)环丙唑醇(cyproconazole)、(1.002)苯醚甲环唑(difenoconazole)、(1.003)氟环唑(epoxiconazole)、(1.004)环酰菌胺(fenhexamid)、(1.005)苯锈啶(fenpropidin)、(1.006)丁苯吗啉(fenpropimorph)、(1.007)胺苯吡菌酮(fenpyrazamine)、(1.008)氟喹唑(fluquinconazole)、(1.009)粉唑醇(flutriafol)、(1.010)抑霉唑(imazalil)、(1.011)抑霉唑硫酸盐(imazalil sulfate)、(1.012)种菌唑(ipconazole)、(1.013)叶菌唑(metconazole)、(1.014)腈菌唑(myclobutanil)、(1.015)多效唑(paclobutrazol)、(1.016)咪鲜胺(prochloraz)、(1.017)丙环唑(propiconazole)、(1.018)丙硫菌唑(prothioconazole)、(1.019)啶菌噁唑(Pyrisoxazole)、(1.020)螺环菌胺(spiroxamine)、(1.021)戊唑醇(tebuconazole)、(1.022)四氟醚唑(tetraconazole)、(1.023)三唑醇(triadimenol)、(1.024)十三吗啉(tridemorph)、(1.025)灭菌唑(triticonazole)、(1.026)(1R,2S,5S)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊醇、(1.027)(1S,2R,5R)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊醇、(1.028)(2R)-2-(1-氯环丙基)-4-[(1R)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.029)(2R)-2-(1-氯环丙基)-4-[(1S)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.030)(2R)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.031)(2S)-2-(1-氯环丙基)-4-[(1R)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.032)(2S)-2-(1-氯环丙基)-4-[(1S)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.033)(2S)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.034)(R)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.035)(S)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.036)[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.037)1-({(2R,4S)-2-[2-氯-4-(4-氯苯氧基)苯基]-4-甲基-1,3-二氧戊环-2-基}甲基)-1H-1,2,4-三唑、(1.038)1-({(2S,4S)-2-[2-氯-4-(4-氯苯氧基)苯基]-4-甲基-1,3-二氧戊环-2-基}甲基)-1H-1,2,4-三唑、(1.039)1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.040)1-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.041)1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.042)2-[(2R,4R,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.043)2-[(2R,4R,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.044)2-[(2R,4S,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.045)2-[(2R,4S,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.046)2-[(2S,4R,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.047)2-[(2S,4R,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.048)2-[(2S,4S,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.049)2-[(2S,4S,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.050)2-[1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.051)2-[2-氯-4-(2,4-二氯苯氧基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.052)2-[2-氯-4-(4-氯苯氧基)苯基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.053)2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.054)2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)戊-2-醇、(1.055)氯氟醚菌唑(Mefentrifluconazole)、(1.056)2-{[3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.057)2-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.058)2-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.059)5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊醇、(1.060)5-(烯丙基硫烷基)-1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.061)5-(烯丙基硫烷基)-1-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.062)5-(烯丙基硫烷基)-1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.063)N′-(2,5-二甲基-4-{[3-(1,1,2,2-四氟乙氧基)苯基]硫烷基}苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.064)N′-(2,5-二甲基-4-{[3-(2,2,2-三氟乙氧基)苯基]硫烷基}苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.065)N′-(2,5-二甲基-4-{[3-(2,2,3,3-四氟丙氧基)苯基]硫烷基}苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.066)N′-(2,5-二甲基-4-{[3-(五氟乙氧基)苯基]硫烷基}苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.067)N′-(2,5-二甲基-4-{3-[(1,1,2,2-四氟乙基)硫烷基]苯氧基}苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.068)N′-(2,5-二甲基-4-{3-[(2,2,2-三氟乙基)硫烷基]苯氧基}苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.069)N′-(2,5-二甲基-4-{3-[(2,2,3,3-四氟丙基)硫烷基]苯氧基}苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.070)N′-(2,5-二甲基-4-{3-[(五氟乙基)硫烷基]苯氧基}苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.071)N′-(2,5-二甲基-4-苯氧基苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.072)N′-(4-{[3-(二氟甲氧基)苯基]硫烷基}-2,5-二甲基苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.073)N′-(4-{3-[(二氟甲基)硫烷基]苯氧基}-2,5-二甲基苯基)-N-乙基-N-甲基酰亚氨基甲酰胺、(1.074)N′-[5-溴-6-(2,3-二氢-1H-茚-2-基氧基)-2-甲基吡啶-3-基]-N-乙基-N-甲基酰亚氨基甲酰胺、(1.075)N′-{4-[(4,5-二氯-1,3-噻唑-2-基)氧基]-2,5-二甲基苯基}-N-乙基-N-甲基酰亚氨基甲酰胺、(1.076)N′-{5-溴-6-[(1R)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基酰亚氨基甲酰胺、(1.077)N′-{5-溴-6-[(1S)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基酰亚氨基甲酰胺、(1.078)N′-{5-溴-6-[(顺式-4-异丙基环己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基酰亚氨基甲酰胺、(1.079)N′-{5-溴-6-[(反式-4-异丙基环己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基酰亚氨基甲酰胺、(1.080)N′-{5-溴-6-[1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基酰亚氨基甲酰胺、(1.081)Ipfentrifluconazole。
2)呼吸链复合物I或II抑制剂,例如(2.001)苯并烯氟菌唑(benzovindiflupyr)、(2.002)联苯吡菌胺(bixafen)、(2.003)啶酰菌胺(boscalid)、(2.004)萎锈灵(carboxin)、(2.005)氟吡菌酰胺(fluopyram)、(2.006)氟酰胺(flutolanil)、(2.007)氟唑菌酰胺(fluxapyroxad)、(2.008)呋吡菌胺(furametpyr)、(2.009)异丙噻菌胺(Isofetamid)、(2.010)吡唑萘菌胺(isopyrazam)(反式差向异构对映体1R,4S,9S)、(2.011)吡唑萘菌胺(反式差向异构对映体1S,4R,9R)、(2.012)吡唑萘菌胺(反式差向异构外消旋体1RS,4SR,9SR)、(2.013)吡唑萘菌胺(顺式差向异构外消旋体1RS,4SR,9RS与反式差向异构外消旋体1RS,4SR,9SR的混合物)、(2.014)吡唑萘菌胺(顺式差向异构对映体1R,4S,9R)、(2.015)吡唑萘菌胺(顺式差向异构对映体1S,4R,9S)、(2.016)吡唑萘菌胺(顺式差向异构外消旋体1RS,4SR,9RS)、(2.017)戊苯吡菌胺(penflufen)、(2.018)吡噻菌胺(penthiopyrad)、(2.019)氟唑菌酰羟胺(pydiflumetofen)、(2.020)Pyraziflumid、(2.021)氟唑环菌胺(sedaxane)、(2.022)1,3-二甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺、(2.023)1,3-二甲基-N-[(3R)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.024)1,3-二甲基-N-[(3S)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.025)1-甲基-3-(三氟甲基)-N-[2′-(三氟甲基)联苯-2-基]-1H-吡唑-4-甲酰胺、(2.026)2-氟-6-(三氟甲基)-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)苯甲酰胺、(2.027)3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺、(2.028)3-(二氟甲基)-1-甲基-N-[(3R)-1,1,3-三甲基-2,3-二氢-IH-茚-4-基]-1H-吡唑-4-甲酰胺、(2.029)3-(二氟甲基)-1-甲基-N-[(3S)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.030)Fluindapyr、(2.031)3-(二氟甲基)-N-[(3R)-7-氟-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲酰胺、(2.032)3-(二氟甲基)-N-[(3S)-7-氟-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲酰胺、(2.033)5,8-二氟-N-[2-(2-氟-4-{[4-(三氟甲基)吡啶-2-基]氧基}苯基)乙基]喹唑啉-4-胺、(2.034)N-(2-环戊基-5-氟苄基)-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.035)N-(2-叔丁基-5-甲基苄基)-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.036)N-(2-叔丁基苄基)-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.037)N-(5-氯-2-乙基苄基)-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.038)isoflucypram、(2.039)N-[(1R,4S)-9-(二氯亚甲基)-1,2,3,4-四氢-1,4-桥亚甲基萘(methanonaphthalen)-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.040)N-[(1S,4R)-9-(二氯亚甲基)-1,2,3,4-四氢-1,4-桥亚甲基萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.041)N-[1-(2,4-二氯苯基)-1-甲氧基丙-2-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.042)N-[2-氯-6-(三氟甲基)苄基]-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.043)N-[3-氯-2-氟-6-(三氟甲基)苄基]-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.044)N-[5-氯-2-(三氟甲基)苄基]-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.045)N-环丙基-3-(二氟甲基)-5-氟-1-甲基-N-[5-甲基-2-(三氟甲基)苄基]-1H-吡唑-4-甲酰胺、(2.046)N-环丙基-3-(二氟甲基)-5-氟-N-(2-氟-6-异丙基苄基)-1-甲基-1H-吡唑-4-甲酰胺、(2.047)N-环丙基-3-(二氟甲基)-5-氟-N-(2-异丙基-5-甲基苄基)-1-甲基-1H-吡唑-4-甲酰胺、(2.048)N-环丙基-3-(二氟甲基)-5-氟-N-(2-异丙基苄基)-1-甲基-1H-吡唑-4-硫代甲酰胺、(2.049)N-环丙基-3-(二氟甲基)-5-氟-N-(2-异丙基苄基)-1-甲基-1H-吡唑-4-甲酰胺、(2.050)N-环丙基-3-(二氟甲基)-5-氟-N-(5-氟-2-异丙基苄基)-1-甲基-1H-吡唑-4-甲酰胺、(2.051)N-环丙基-3-(二氟甲基)-N-(2-乙基-4,5-二甲基苄基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.052)N-环丙基-3-(二氟甲基)-N-(2-乙基-5-氟苄基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.053)N-环丙基-3-(二氟甲基)-N-(2-乙基-5-甲基苄基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.054)N-环丙基-N-(2-环丙基-5-氟苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.055)N-环丙基-N-(2-环丙基-5-甲基苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.056)N-环丙基-N-(2-环丙基苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.057)pyrapropoyne。
3)呼吸链复合物III抑制剂,例如(3.001)唑嘧菌胺(ametoctradin)、(3.002)安美速(amisulbrom)、(3.003)嘧菌酯(azoxystrobin)、(3.004)甲香菌酯(coumethoxystrobin)、(3.005)丁香菌酯(coumoxystrobin)、(3.006)氰霜唑(cyazofamid)、(3.007)醚菌胺(dimoxystrobin)、(3.008)烯肟菌酯(enoxastrobin)、(3.009)噁唑菌酮(famoxadon)、(3.010)咪唑菌酮(fenamidon)、(3.011)氟菌螨酯(flufenoxystrobin)、(3.012)氟嘧菌酯(fluoxastrobin)、(3.013)醚菌酯(kresoxim-methyl)、(3.014)苯氧菌胺(metominostrobin)、(3.015)肟醚菌胺(orysastrobin)、(3.016)啶氧菌酯(picoxystrobin)、(3.017)唑菌胺酯(pyraclostrobin)、(3.018)唑胺菌酯(pyrametostrobin)、(3.019)唑菌酯(pyraoxystrobin)、(3.020)肟菌酯(trifloxystrobin)、(3.021)(2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-氟-2-苯基乙烯基]氧基}苯基)亚乙基]氨基}氧基)甲基]苯基}-2-(甲氧基亚氨基)-N-甲基乙酰胺、(3.022)(2E,3Z)-5-{[1-(4-氯苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亚氨基)-N,3-二甲基戊-3-烯酰胺、(3.023)(2R)-2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙酰胺、(3.024)(2S)-2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙酰胺、(3.025)(3S,6S,7R,8R)-8-苄基-3-[({3-[(异丁酰氧基)甲氧基]-4-甲氧基吡啶-2-基}羰基)氨基]-6-甲基-4,9-二氧代-1,5-二氧杂环壬烷-7-基2-甲基丙酸酯、(3.026)mandestrobin、(3.027)N-(3-乙基-3,5,5-三甲基环己基)-3-甲酰氨基-2-羟基苯甲酰胺、(3.028)(2E,3Z)-5-{[1-(4-氯-2-氟苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亚氨基)-N,3-二甲基戊-3-烯酰胺、(3.029){5-[3-(2,4-二甲基苯基)-1H-吡唑-1-基]-2-甲基苄基}氨基甲酸甲酯、(3.030)metyltetraprole、(3.031)florylpicoxamid。
4)有丝分裂和细胞分裂抑制剂,例如(4.001)多菌灵(carbendazim)、(4.002)乙霉威(diethofencarb)、(4.003)噻唑菌胺(ethaboxam)、(4.004)氟吡菌胺(fluopicolid)、(4.005)戊菌隆(pencycuron)、(4.006)噻菌灵(thiabendazole)、(4.007)甲基硫菌灵(thiophanate-methyl)、(4.008)苯酰菌胺(zoxamide)、(4.009)3-氯-4-(2,6-二氟苯基)-6-甲基-5-苯基哒嗪、(4.010)3-氯-5-(4-氯苯基)-4-(2,6-二氟苯基)-6-甲基哒嗪、(4.011)3-氯-5-(6-氯吡啶-3-基)-6-甲基-4-(2,4,6-三氟苯基)哒嗪、(4.012)4-(2-溴-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.013)4-(2-溴-4-氟苯基)-N-(2-溴-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.014)4-(2-溴-4-氟苯基)-N-(2-溴苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.015)4-(2-溴-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.016)4-(2-溴-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.017)4-(2-溴-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.018)4-(2-氯-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.019)4-(2-氯-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.020)4-(2-氯-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.021)4-(2-氯-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.022)4-(4-氯苯基)-5-(2,6-二氟苯基)-3,6-二甲基哒嗪、(4.023)N-(2-溴-6-氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.024)N-(2-溴苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.025)N-(4-氯-2,6-二氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺。
5)具有多位点活性能力的化合物,例如(5.001)波尔多混合剂(bordeauxmixture)、(5.002)敌菌丹(captafol)、(5.003)克菌丹(captan)、(5.004)百菌清(chlorthalonil)、(5.005)氢氧化铜、(5.006)环烷酸铜、(5.007)氧化铜、(5.008)氯氧化铜、(5.009)硫酸铜(2+)、(5.010)二氰蒽醌(dithianon)、(5.011)多果定(dodine)、(5.012)灭菌丹(folpet)、(5.013)代森锰锌(mancozeb)、(5.014)代森锰(maneb)、(5.015)代森联(metiram)、(5.016)代森联锌(metiram zinc)、(5.017)羟基喹啉铜(oxine-copper)、(5.018)甲基代森锌(propineb)、(5.019)硫和包括多硫化钙的硫制剂、(5.020)福美双(thiram)、(5.021)代森锌(zineb)、(5.022)福美锌(ziram)、(5.023)6-乙基-5,7-二氧代-6,7-二氢-5H-吡咯并[3′,4′:5,6][1,4]二噻英并(dithiino)[2,3-c][1,2]噻唑-3-甲腈。
6)能引发宿主防御的化合物,例如(6.001)苯并噻二唑(acibenzolar-S-methyl)、(6.002)异噻菌胺(isotianil)、(6.003)烯丙苯噻唑(probenazole)、(6.004)噻酰菌胺(tiadinil)。
7)氨基酸和/或蛋白质生物合成抑制剂,例如(7.001)嘧菌环胺(cyprodinil)、(7.002)春雷霉素(kasugamycin)、(7.003)春雷霉素盐酸盐水合物(kasugamycinhydrochloride hydrate)、(7.004)氧四环素(oxytetracycline)、(7.005)嘧霉胺(pyrimethanil)、(7.006)3-(5-氟-3,3,4,4-四甲基-3,4-二氢异喹啉-1-基)喹啉。
8)ATP产生抑制剂,例如(8.001)硅噻菌胺(silthiofam)。
9)细胞壁合成抑制剂,例如(9.001)苯噻菌胺(benthiavalicarb)、(9.002)烯酰吗啉(dimethomorph)、(9.003)氟吗啉(flumorph)、(9.004)异丙菌胺(iprovalicarb)、(9.005)双炔酰菌胺(mandipropamid)、(9.006)吡吗啉(pyrimorph)、(9.007)霜霉灭(valifenalate)、(9.008)(2E)-3-(4-叔丁基苯基)-3-(2-氯吡啶-4-基)-1-(吗啉-4-基)丙-2-烯-1-酮、(9.009)(2Z)-3-(4-叔丁基苯基)-3-(2-氯吡啶-4-基)-1-(吗啉-4-基)丙-2-烯-1-酮。
10)脂质和膜合成抑制剂,例如(10.001)霜霉威(propamocarb)、(10.002)霜霉威盐酸盐(propamocarb hydrochloride)、(10.003)甲基立枯磷(tolclofos-methyl)。
11)黑色素生物合成抑制剂,例如(11.001)三环唑(tricyclazole)、(11.002)2,2,2-三氟乙基{3-甲基-1-[(4-甲基苯甲酰基)氨基]丁-2-基}氨基甲酸酯。
12)核酸合成抑制剂,例如(12.001)苯霜灵(benalaxyl)、(12.002)精苯霜灵(benalaxyl-M)(kiralaxyl)、(12.003)甲霜灵(metalaxyl)、(12.004)高效甲霜灵(metalaxyl-M)(精甲霜灵(mefenoxam))。
13)信号转导抑制剂,例如(13.001)咯菌腈(fludioxonil)、(13.002)异菌脲(iprodione)、(13.003)腐霉利(procymidone)、(13.004)丙氧喹啉(proquinazid)、(13.005)喹氧灵(quinoxyfen)、(13.006)乙烯菌核利(vinclozolin)。
14)能够起解偶联剂作用的化合物,例如(14.001)氟啶胺(fluazinam)、(14.002)消螨多(meptyldinocap)。
15)其他化合物,例如(15.001)脱落酸(Abscisic acid)、(15.002)苯噻硫氰(benthiazole)、(15.003)bethoxazin、(15.004)卡巴西霉素(capsimycin)、(15.005)香芹酮(carvone)、(15.006)灭螨猛(chinomethionat)、(15.007)硫杂灵(cuffraneb)、(15.008)环氟菌胺(cyflufenamid)、(15.009)霜脲氰(cymoxanil)、(15.010)环丙磺酰胺(cyprosulfamide)、(15.011)flutianil、(15.012)三乙膦酸铝(fosetyl-aluminium)、(15.013)三乙膦酸钙(fosetyl-calcium)、(15.014)三乙膦酸钠(fosetyl-sodium)、(15.015)异硫氰酸甲酯(methyl isothiocyanate)、(15.016)苯菌酮(metrafenon)、(15.017)米多霉素(mildiomycin)、(15.018)纳他霉素(natamycin)、(15.019)福美镍(nickel dimethyldithiocarbamate)、(15.020)酞菌酯(nitrothal-isopropyl)、(15.021)oxamocarb、(15.022)氟噻唑吡乙酮(oxathiapiprolin)、(15.023)奥施康定(oxyfenthiin)、(15.024)五氯苯酚及其盐、(15.025)亚磷酸及其盐、(15.026)霜霉威乙膦酸盐(propamocarb-fosetylate)、(15.027)pyriofenone(氯酚酮(chlazafenone))、(15.028)异丁乙氧喹啉(tebufloquin)、(15.029)叶枯酞(tecloftalam)、(15.030)甲磺菌胺(tolnifanide)、(15.031)1-(4-{4-[(5R)-5-(2,6-二氟苯基)-4,5-二氢-1,2-噁唑-3-基]-1,3-噻唑-2-基}哌啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(15.032)1-(4-{4-[(5S)-5-(2,6-二氟苯基)-4,5-二氢-1,2-噁唑-3-基]-1,3-噻唑-2-基}哌啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(15.033)2-(6-苄基吡啶-2-基)喹唑啉、(15.034)dipymetitrone、(15.035)2-[3,5-双(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-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.036)2-[3,5-双(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-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.037)2-[3,5-双(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-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.038)2-[6-(3-氟-4-甲氧基苯基)-5-甲基吡啶-2-基]喹唑啉、(15.039)2-{(5R)-3-[2-(1-{[3,5-双(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-噁唑-5-基}-3-氯苯基甲磺酸酯、(15.040)2-{(5S)-3-[2-(1-{[3,5-双(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-噁唑-5-基}-3-氯苯基甲磺酸酯、(15.041)Ipflufenoquin、(15.042)2-{2-氟-6-[(8-氟-2-甲基喹啉-3-基)氧基]苯基}丙-2-醇、(15.043)2-{3-[2-(1-{[3,5-双(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-噁唑-5-基}-3-氯苯基甲磺酸酯、(15.044)2-{3-[2-(1-{[3,5-双(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-噁唑-5-基}苯基甲磺酸酯、(15.045)2-苯基苯酚及其盐、(15.046)3-(4,4,5-三氟-3,3-二甲基-3,4-二氢异喹啉-1-基)喹啉、(15.047)quinofumelin、(15.048)4-氨基-5-氟嘧啶-2-醇(互变异构形式:4-氨基-5-氟嘧啶-2(1H)-酮)、(15.049)4-氧代-4-[(2-苯乙基)氨基]丁酸、(15.050)5-氨基-1,3,4-噻二唑-2-硫醇、(15.051)5-氯-N′-苯基-N′-(丙-2-炔-1-基)噻吩-2-磺酰肼、(15.052)5-氟-2-[(4-氟苄基)氧基]嘧啶-4-胺、(15.053)5-氟-2-[(4-甲基苄基)氧基]嘧啶-4-胺、(15.054)9-氟-2,2-二甲基-5-(喹啉-3-基)-2,3-二氢-1,4-苯并氧杂吖庚因(benzoxazepine)、(15.055)丁-3-炔-1-基{6-[({[(Z)-(1-甲基-1H-四唑-5-基)(苯基)亚甲基]氨基}氧基)甲基]吡啶-2-基}氨基甲酸酯、(15.056)(2Z)-3-氨基-2-氰基-3-苯基丙烯酸乙酯、(15.057)吩嗪-1-甲酸、(15.058)3,4,5-三羟基苯甲酸丙酯、(15.059)喹啉-8-醇、(15.060)喹啉-8-醇硫酸酯(2∶1)、(15.061){6-[({[(1-甲基-1H-四唑-5-基)(苯基)亚甲基]氨基}氧基)甲基]吡啶-2-基}氨基甲酸叔丁酯、(15.062)5-氟-4-亚氨基-3-甲基-1-[(4-甲基苯基)磺酰基]-3,4-二氢嘧啶-2(1H)-酮、(15.063)aminopyrifen。
这里如上所述的所有指定的(1)至(15)类混配物都可以游离化合物的形式和/或——如果其官能团有此能力的话——其农业上可接受的盐的形式存在。
式(I)的化合物和包含其的组合物也可与一种或多种生物防治剂结合。
可与式(I)的化合物和包含其的组合物结合的生物防治剂的实例为:
(A)选自以下的抗菌剂:
(A1)细菌,例如(A1.1)枯草芽孢杆菌(Bacillus subtilis)、特别是菌株QST713/AQ713(可作为SERENADE OPTI或SERENADE ASO从Bayer CropScience LP,US获得,NRRL登记号B21661并记载于US专利号6060051中);(A1.2)解淀粉芽孢杆菌(Bacillusamyloliquefaciens)、特别是菌株D747(可作为Double NickelTM从Certis,US获得,登记号FERM BP-8234并公开于US专利号7094592中);(A1.3)短小芽孢杆菌(Bacillus pumilus)、特别是菌株BU F-33(NRRL登记号50185);(A1.4)解淀粉枯草芽孢杆菌变种(Bacillussubtilis var.amyloliquefaciens)菌株FZB24(可作为从Novozymes.US获得);(A1.5)类芽孢杆菌属(Paenibacillus sp.)菌株,登记号NRRL B-50972或登记号NRRL B-67129,并记载于国际专利公开号WO 2016/154297中;和
(A2)真菌,例如(A2.1)出芽短梗霉(Aureobasidium pullulans),特别是菌株DSM14940的芽生孢子;(A2.2)出芽短梗霉,菌株DSM14941的芽生孢子;(A2.3)出芽短梗霉,特别是菌株DSM14940和DSM14941的芽生孢子的混合物;
(B)选自以下的杀真菌剂:
(B1)细菌,例如(B1.1)枯草芽孢杆菌、特别是菌株QST713/AQ713(可作为SERENADEOPTI或SERENADE ASO从Bayer CropScience LP,US获得,NRRL登记号B21661并记载US专利号6060051中);(B1.2)短小芽孢杆菌、特别是菌株QST2808(可作为从BayerCropScience LP,US获得,登记号NRRL B-30087并记载于US专利号6245551中);(B1.3)短小芽孢杆菌、特别是菌株GB34(可作为Yield从Bayer AG,DE获得);(B1.4)短小芽孢杆菌、特别是菌株BU F-33(NRRL登记号50185);(B1.5)解淀粉芽孢杆菌、特别是菌株D747(可作为Double Nickel TM从Certis,US获得,登记号FERM BP-8234并公开于US专利号7094592中);(B1.6)枯草芽孢杆菌Y1336(可作为WP从Bion-Tech,台湾获得,在台湾注册为生物杀真菌剂,注册号4764、5454、5096和5277);(B1.7)解淀粉芽孢杆菌菌株MBI 600(可作为SUBTILEX从BASF SE获得);(B1.8)枯草芽孢杆菌菌株GB03(可作为从Bayer AG,DE获得);(B1.9)解淀粉枯草芽孢杆菌变种菌株FZB24(可作为杀真菌剂或ECO(EPA注册号70127-5)从Novozymes BiologicalsInc.,Salem,Virginia或Syngenta Crop Protection,LLC,Greensboro,North Carolina获得);(B1.10)蕈状芽胞杆菌(Bacillus mycoides),分离株J(可作为BmJ TGAI或WG从CertisUSA获得);(B1.11)地衣芽孢杆菌(Bacillus licheniformis)、特别是菌株SB3086(可作为EcoGuard TM Biofungicide和Green Releaf从Novozymes获得);(B1.12)类芽孢杆菌属菌株,登记号NRRL B-50972或登记号NRRL B-67129,并记载于国际专利公开号WO 2016/154297中。
在一些实施方案中,生物防治剂为产生泛革素(fengycin)型化合物或制磷脂菌素(plipastatin)型化合物、伊枯草素(iturin)型化合物和/或表面活性素(surfactin)型化合物的枯草芽孢杆菌菌株或解淀粉芽孢杆菌菌株。关于背景,参见以下综述文章:Ongena,M.等人,“Bacillus Lipopeptides:Versatile Weapons for Plant DiseaseBiocontrol,”Trends in Microbiology,第16卷,第3期,2008年3月,第115-125页。能够产生脂肽的芽孢杆菌菌株包括枯草芽孢杆菌QST713(可作为SERENADE OPTI或SERENADE ASO从Bayer CropScience LP,US获得,NRRL登记号B21661并记载于US专利号6060051中)、解淀粉芽孢杆菌菌株D747(可作为Double NickelTM从Certis,US获得,登记号FERM BP-8234并公开于US专利号7094592中);枯草芽孢杆菌MBI600(可作为从BeckerUnderwood,US EPA获得,登记号71840-8);枯草芽孢杆菌Y1336(可作为WP从Bion-Tech,台湾获得,在台湾注册为生物杀真菌剂,注册号4764、5454、5096和5277);解淀粉芽孢杆菌、特别是菌株FZB42(可作为从ABiTEP,DE获得);和解淀粉枯草芽孢杆菌变种FZB24(可作为杀真菌剂或ECO(EPA注册号70127-5)从Novozymes Biologicals Inc.,Salem,Virginia或Syngenta CropProtection,LLC,Greensboro,North Carolina获得);和
(B2)真菌,例如:(B2.1)盾壳霉(Coniothyrium minitans)、特别是菌株CON/M/91-8(登记号DSM-9660;例如购自Bayer的);(B2.2)核果梅奇酵母(Metschnikowia fructicola)、特别是菌株NRRL Y-30752(例如);(B2.3)小球壳孢(Microsphaeropsis ochracea)(例如购自Prophyta的);(B2.5)木霉属(Trichoderma spp.),包括深绿木霉(Trichoderma atroviride),记载于国际申请号PCT/IT2008/000196中的菌株SC1;(B2.6)哈茨木霉(Trichoderma harzianum rifai)菌株KRL-AG2(也称作菌株T-22,/ATCC 208479,例如购自BioWorks,US的PLANTSHIELD T-22G、和TurfShield);(B2.14)粉红粘帚霉(Gliocladium roseum),购自W.F.Stoneman Company LLC的菌株321U;(B2.35)黄色蠕形霉(Talaromyces flavus),菌株V117b;(B2.36)棘孢木霉(Trichoderma asperellum),购自Isagro的菌株ICC 012;(B2.37)棘孢木霉,菌株SKT-1(例如购自Kumiai Chemical Industry的);(B2.38)深绿木霉,菌株CNCM I-1237(例如购自Agrauxine,FR的WP);(B2.39)深绿木霉,菌株号V08/002387;(B2.40)深绿木霉,菌株NMI号V08/002388;(B2.41)深绿木霉,菌株NMI号V08/002389;(B2.42)深绿木霉,菌株NMI号V08/002390;(B2.43)深绿木霉,菌株LC52(例如Agrimm Technologies Limited的Tenet);(B2.44)深绿木霉,菌株ATCC 20476(IMI 206040);(B2.45)深绿木霉,菌株T11(IMI352941/CECT20498);(B2.46)钩状木霉(Trichoderma harmatum);(B2.47)哈茨木霉;(B2.48)哈茨木霉T39(例如购自Makhteshim,US的);(B2.49)哈茨木霉、特别是菌株KD(例如购自Biological ControlProducts,SA(被Becker Underwood收购)的Trichoplus);(B2.50)哈茨木霉,菌株ITEM908(例如购自Koppert的Trianum-P);(B2.51)哈茨木霉,菌株TH35(例如Mycontrol的Root-Pro);(B2.52)绿木霉(Trichoderma virens)(也称作绿粘帚霉(Gliocladium virens))、特别是菌株GL-21(例如Certis,US的SoilGard 12G);(B2.53)绿色木霉(Trichodermaviride),菌株TV1(例如Koppert的Trianum-P);(B2.54)白粉寄生孢(Ampelomycesquisqualis)、特别是菌株AQ 10(例如IntrachemBio Italia的AQ);(B2.56)出芽短梗霉、特别是菌株DSM14940的芽生孢子;(B2.57)出芽短梗霉、特别是菌株DSM14941的芽生孢子;(B2.58)出芽短梗霉、特别是菌株DSM14940和DSM 14941的芽生孢子的混合物(例如bio-ferm,CH的);(B2.64)芽枝状枝孢(Cladosporium cladosporioides),菌株H39(Stichting Dienst Landbouwkundig Onderzoek);(B2.69)链孢粘帚菌(Gliocladiumcatenulatum)(同义词:Clonostachys rosea f.catenulate)菌株J1446(例如AgBio Inc.的以及例如Kemira Agro Oy的);(B2.70)蜡蚧轮枝菌(Lecanicillium lecanii)(先前称为蜡蚧轮枝孢(Verticillium lecanii)),菌株KV01的分生孢子(例如Koppert/Arysta的);(B2.71)蠕形青霉(Penicilliumvermiculatum);(B2.72)异常毕赤酵母(Pichia anomala),菌株WRL-076(NRRL Y-30842);(B2.75)深绿木霉,菌株SKT-1(FERM P-16510);(B2.76)深绿木霉,菌株SKT-2(FERM P-16511);(B2.77)深绿木霉,菌株SKT-3(FERM P-17021);(B2.78)盖姆斯木霉(Trichodermagamsii)(原绿色木霉(T.viride)),菌株ICC080(IMI CC 392151 CABI,例如AGROBIOSOL DEMEXICO,S.A.DE C.V.的BioDerma);(B2.79)哈茨木霉,菌株DB 103(例如Dagutat Biolab的T-Gro 7456);(B2.80)多孢木霉(Trichoderma polysporum),菌株IMI 206039(例如BINABBio-Innovation AB,Sweden的Binab TF WP);(B2.81)子座木霉(Trichodermastromaticum)(例如Ceplac,Brazil的Tricovab);(B2.83)奥德曼细基格孢(Ulocladiumoudemansii)、特别是菌株HRU3(例如Botry-Zen Ltd,NZ的Botry-);(B2.84)黑白轮枝孢(Verticillium albo-atrum)(原大丽轮枝菌(V.dahliae)),菌株WCS850(CBS 276.92;例如Tree Care Innovations的Dutch Trig);(B2.86)厚垣轮枝孢菌(Verticilliumchlamydosporium);(B2.87)棘孢木霉菌株ICC 012和盖姆斯木霉菌株ICC 080的混合物(称作例如BIO-TAMTM的产品,购自Bayer CropScience LP,US)。
可与式(I)的化合物和包含其的组合物结合的生物防治剂的其他实例为:
选自以下的细菌:蜡样芽胞杆菌(Bacillus cereus)、特别是蜡样芽胞杆菌菌株CNCM I-1562和坚强芽孢杆菌(Bacillus firmus)菌株I-1582(登记号CNCM I-1582);枯草芽孢杆菌菌株OST 30002(登记号NRRL B-50421);苏云金芽孢杆菌(Bacillusthuringiensis),特别是苏云金芽孢杆菌以色列亚种(B.thuringiensis subspeciesisraelensis)(血清型H-14),菌株AM65-52(登记号ATCC 1276);苏云金芽孢杆菌鲇泽亚种(B.thuringiensis subsp.aizawai),特别是菌株ABTS-1857(SD-1372);苏云金芽孢杆菌库尔斯塔克亚种(B.thuringiensis subsp.kurstaki)菌株HD-1;苏云金芽孢杆菌拟步行甲亚种菌株NB 176(SD-5428);穿刺芽孢杆菌(Pasteuria penetrans);巴斯德氏芽菌属(Pasteuria spp.)(肾形线虫(Rotylenchulus reniformis nematode))-PR3(登记号ATCCSD-5834);细黄链霉菌(Streptomycesmicroflavus)菌株AQ6121(=QRD 31.013,NRRL B-50550);和鲜黄链霉菌(Streptomyces galbus)菌株AQ 6047(登记号NRRL 30232);
选自以下的真菌和酵母:球孢白僵菌(Beauveria bassiana),特别是菌株ATCC74040;蜡蚧菌属(Lecanicillium spp.),特别是菌株HRO LEC 12;绿僵菌(Metarhiziumanisopliae),特别是菌株F52(DSM3884或ATCC 90448);玫烟色拟青霉(Paecilomycesfumosoroseus)(现用名:玫烟色棒束孢(Isaria fumosorosea)),特别是菌株IFPC 200613,或菌株Apopka 97(登记号ATCC 20874);和淡紫色拟青霉(Paecilomyces lilacinus),特别是淡紫色拟青霉菌株251(AGAL 89/030550);
选自以下的病毒:棉褐带卷蛾(Adoxophyes orana)(夏季水果卷叶蛾(summerfruit tortrix))颗粒体病毒(GV)、苹果蠹蛾(Cydia pomonella)(codling moth)颗粒体病毒(GV)、棉铃虫(Helicoverpa armigera)(cotton bollworm)核多角体病毒(NPV)、甜菜夜蛾(Spodoptera exigua)(beet armyworm)mNPV、草地贪夜蛾(Spodoptera frugiperda)(fall armyworm)mNPV和海灰翅夜蛾(Spodoptera littoralis)(非洲棉叶虫(Africancotton leafworm))NPV。
作为“接种体”添加到植物或植物部位或植物器官并凭借其特定性能促进植物生长和植物健康的细菌和真菌。实例为:土壤杆菌属(Agrobacterium spp.),茎瘤固氮根瘤菌(Azorhizobium caulinodans),固氮螺菌属(Azospirillum spp.),固氮菌属(Azotobacterspp.),慢生根瘤菌属(Bradyrhizobium spp.),伯克霍尔德菌属(Burkholderia spp.),特别是洋葱伯克霍尔德菌(Burkholderia cepacia)(先前称为洋葱假单胞菌(Pseudomonascepacia)),巨孢囊霉属(Gigaspora spp.)或Gigaspora monosporum,球囊霉属(Glomusspp.),蜡蘑属(Laccaria spp.),布氏乳杆菌(Lactobacillus buchneri),类球囊霉属(Paraglomus spp.),Pisolithus tinctorus,假单胞菌属(Pseudomonas spp.),根瘤菌属(Rhizobium spp.),特别是三叶草根瘤菌(Rhizobium trifolii),须腹菌属(Rhizopogonspp.),硬皮马勃属(Scleroderma spp.),乳牛肝菌属(Suillus spp.)和链霉菌属(Streptomyces spp.)。
可用作生物防治剂的植物提取物和由微生物形成的包括蛋白质和次生代谢物的产物,例如大蒜(Allium sativum)、苦艾(Artemisia absinthium)、印楝素(azadirachtin)、Biokeeper WP、Cassia nigricans、苦皮藤(Celastrus angulatus)、Chenopodium anthelminticum、几丁质、Armour-Zen、欧洲鳞毛蕨(Dryopteris filix-mas)、问荆(Equisetum arvense)、Fortune Aza、Fungastop、Heads Up(藜麦皂苷提取物(Chenopodium quinoa saponin extract))、除虫菊(Pyrethrum)/除虫菊酯(Pyrethrins)、苏里南苦木(Quassia amara)、栎(Quercus)、皂树(Quillaja)、Regalia、″RequiemTM杀昆虫剂″、鱼藤酮(rotenone)、鱼尼丁(ryania)/兰尼碱(ryanodine)、聚合草(Symphytumofficinale)、菊蒿(Tanacetum vulgare)、百里酚(thymol)、Triact 70、TriCon、Tropaeulum majus、大荨麻(Urtica dioica)、藜芦碱(Veratrin)、白槲寄生(Viscumalbum)、十字花科(Brassicaceae)提取物(特别是油菜粉或芥茉粉)。
可分别与式(I)的化合物和包含其的组合物混合的杀昆虫剂、杀螨剂和杀线虫剂的实例为:
(1)乙酰胆碱酯酶(AChE)抑制剂,例如氨基甲酸酯类,例如棉铃威(alanycarb)、涕灭威(aldicarb)、噁虫威(bendiocarb)、丙硫克百威(benfuracarb)、丁酮威(butocarboxim)、丁酮砜威(butoxycarboxim)、甲萘威(carbaryl)、克百威(carbofuran)、丁硫克百威(carbosulfan)、乙硫苯威(ethiofencarb)、仲丁威(fenobucarb)、伐虫脒(formetanate)、呋线威(furathiocarb)、异丙威(isoprocarb)、甲硫威(methiocarb)、灭多威(methomyl)、速灭威(metolcarb)、杀线威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、久效威(thiofanox)、唑蚜威(triazamate)、混杀威(trimethacarb)、灭除威(XMC)和灭杀威(xylylcarb);或有机磷酸酯类,例如乙酰甲胺磷(acephate)、甲基吡啶磷(azamethiphos)、乙基谷硫磷(azinphos-ethyl)、甲基谷硫磷(azinphos-methyl)、硫线磷(cadusafos)、氯氧磷(chlorethoxyfos)、毒虫畏(chlorfenvinphos)、氯甲硫磷(chlormephos)、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)、苯硫磷(EPN)、乙硫磷(ethion)、灭线磷(ethoprophos)、伐灭磷(famphur)、苯线磷(fenamiphos)、杀螟硫磷(fenitrothion)、倍硫磷(fenthion)、噻唑膦(fosthiazate)、庚烯磷(heptenophos)、imicyafos、异柳磷(isofenphos)、O-(甲氧基氨基硫代磷酰基)水杨酸异丙酯(isopropyl O-(methoxyaminothiophosphoryl)salicylate)、异噁唑磷(isoxathion)、马拉松(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)、亚砜磷(oxydemeton-methyl)、甲基对硫磷(parathion-methyl)、稻丰散(phenthoate)、甲拌磷(phorate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、辛硫磷(phoxim)、甲基嘧啶磷(pirimiphos-methyl)、丙溴磷(profenofos)、胺丙畏(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)、特丁硫磷(terbufos)、杀虫畏(tetrachlorvinphos)、甲基乙拌磷(thiometon)、三唑磷(triazophos)、敌百虫(triclorfon)和蚜灭磷(vamidothion)。
(2)GABA门控氯化物通道阻断剂,例如环戊二烯有机氯类,例如氯丹(chlordane)和硫丹(endosulfan),或苯基吡唑类(phenylpyrazoles(fiproles)),例如乙虫腈(ethiprole)和氟虫腈(fipronil)。
(3)钠通道调节剂,例如拟除虫菊酯类(pyrethroids),例如氟丙菊酯(acrinathrin)、丙烯菊酯(allethrin)、d-顺式-反式丙烯菊酯、d-反式丙烯菊酯、联苯菊酯(bifenthrin)、生物丙烯菊酯(bioallethrin)、生物丙烯菊酯s-环戊烯基同分异构体、生物苄呋菊酯(bioresmethrin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、β-氟氯氰菊酯、三氟氯氰菊酯(cyhalothrin)、λ-三氟氯氰菊酯、γ-三氟氯氰菊酯、氯氰菊酯(cypermethrin)、α-氯氰菊酯、β-氯氰菊酯、θ-氯氰菊酯、ζ-氯氰菊酯、苯醚氰菊酯[(1R)-反式同分异构体](cyphenothrin[(1R)-trans isomer])、溴氰菊酯(deltamethrin)、右旋烯炔菊酯[(EZ)-(1R)同分异构体](empenthrin[(EZ)-(1R)isomer])、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、氰戊菊酯(fenvalerate)、氟氰戊菊酯(flucythrinate)、氟氯苯菊酯(flumethrin)、τ-氟胺氰菊酯(tau-fluvalinate)、苄螨醚(halfenprox)、炔咪菊酯(imiprothrin)、噻嗯菊酯(kadethrin)、momfluorothrin、氯菊酯(permethrin)、苯醚菊酯[(1R)-反式同分异构体](phenothrin[(1R)-trans isomer])、右旋炔丙菊酯(prallethrin)、除虫菊素(除虫菊)(pyrethrins(pyrethrum))、苄呋菊酯(resmethrin)、氟硅菊酯(silafluofen)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、胺菊酯[(1R)同分异构体](tetramethrin[(1R)isomer)])、四溴菊酯(tralomethrin)和四氟苯菊酯(transfluthrin)或滴滴涕(DDT)或甲氧滴滴涕(methoxychlor)。
(4)烟碱能乙酰胆碱受体(nAChR)竞争调节剂,例如新烟碱类(neonicotinoids),例如啶虫脒(acetamiprid)、噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、烯啶虫胺(nitenpyram)、噻虫啉(thiacloprid)和噻虫嗪(thiamethoxam),或烟碱(nicotine),或氟啶虫胺腈(sulfoxaflor),或氟吡呋喃酮(flupyradifurone)。
(5)烟碱能乙酰胆碱受体(nAChR)变构调节剂,例如多杀菌素类(spinosyns),例如乙基多杀菌素(spinetoram)和多杀菌素(spinosad)。
(6)谷氨酸酯门控氯化物通道(GluCl)变构调节剂,例如阿维菌素类(avermectins)/米尔倍霉素类(milbemycins),例如阿维菌素(abamectin)、甲氨基阿维菌素苯甲酸盐(emamectin benzoate)、雷皮菌素(lepimectin)和弥拜菌素(milbemectin)。
(7)保幼激素模拟物,例如保幼激素类似物,例如烯虫乙酯(hydroprene)、烯虫炔酯(kinoprene)和烯虫酯(methoprene),或苯氧威(fenoxycarb)或吡丙醚(pyriproxyfen)。
(8)其他非特异性(多位点)抑制剂,例如烷基卤化物类,例如甲基溴和其他烷基卤化物;或氯化苦(chloropicrine)或硫酰氟(sulphuryl fluoride)或硼砂(borax)或吐酒石(tartar emetic)或异氰酸甲酯产生剂,例如diazomet和威百亩(metam)。
(9)弦音器官(chordotonal organ)调节剂,例如吡蚜酮(pymetrozine)或氟啶虫酰胺(flonicamid)。
(10)螨生长抑制剂,例如四螨嗪(clofentezine)、噻螨酮(hexythiazox)和氟螨嗪(diflovidazin),或乙螨唑(etoxazole)。
(11)昆虫中肠膜微生物干扰剂,例如苏云金芽孢杆菌以色列亚种、球形芽孢杆菌(Bacillus sphaericus)、苏云金芽孢杆菌鲇泽亚种、苏云金芽孢杆菌库尔斯塔克亚种、苏云金芽孢杆菌拟步行甲亚种和B.t.植物蛋白:Cry1Ab、Cry1Ac、Cry1Fa、Cry1A.105、Cry2Ab、Vip3A、mCry3A、Cry3Ab、Cry3Bb、Cry34Ab1/35Ab1。
(12)线粒体ATP合酶抑制剂,例如ATP干扰剂,例如丁醚脲(diafenthiuron),或有机锡化合物类,例如三唑锡(azocyclotin)、三环锡(cyhexatin)和苯丁锡(fenbutatinoxide),或炔螨特(propargite),或四氯杀螨砜(tetradifon)。
(13)通过间隔质子梯度作用的氧化磷酸化解偶联剂,例如溴虫腈(chlorfenapyr)、二硝甲酚(DNOC)和氟虫胺(sulfluramid)。
(14)烟碱能乙酰胆碱受体通道阻断剂,例如杀虫磺(bensultap)、杀螟丹盐酸盐(cartap hydrochloride)、杀虫环(thiocyclam)和杀虫双(thiosultap-sodium)。
(15)0型几丁质生物合成抑制剂,例如双三氟虫脲(bistrifluron)、定虫隆(chlorfluazuron)、二氟脲(diflubenzuron)、氟环脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、虱螨脲(lufenuron)、氟酰脲(novaluron)、多氟脲(noviflumuron)、氟苯脲(teflubenzuron)和杀铃脲(triflumuron)。
(16)1型几丁质生物合成抑制剂,例如噻嗪酮(buprofezin)。
(17)蜕皮干扰剂(特别是对于双翅目(Diptera),即双翅类昆虫(dipterans)),例如灭蝇胺(cyromazine)。
(18)蜕皮激素受体激动剂,例如环虫酰肼(chromafenozide)、氯虫酰肼(halofenozide)、甲氧虫酰肼(methoxyfenozide)和虫酰肼(tebufenozide)。
(19)章鱼胺受体激动剂,例如双甲脒(amitraz)。
(20)线粒体复合物III电子传递抑制剂,例如氟蚁腙(hydramethylnon)或灭螨醌(acequinocyl)或嘧螨酯(fluacrypyrim)。
(21)线粒体复合物I电子传递抑制剂,例如METI杀螨剂类,例如喹螨醚(fenazaquin)、唑螨酯(fenpyroximate)、嘧螨醚(pyrimidifen)、哒螨灵(pyridaben)、吡螨胺(tebufenpyrad)和唑虫酰胺(tolfenpyrad),或鱼藤酮(rotenone)(鱼藤属(Derris))。
(22)电压依赖型钠通道阻断剂,例如茚虫威(indoxacarb)或氰氟虫腙(metaflumizone)。
(23)乙酰基辅酶A(CoA)羧化酶抑制剂,例如特窗酸和特特拉姆酸(tetramicacid)衍生物,例如螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)和螺虫乙酯(spirotetramat)。
(24)线粒体复合物IV电子传递抑制剂,例如膦类化合物,例如磷化铝、磷化钙、膦和磷化锌,或氰化物类,例如氰化钙、氰化钾和氰化钠。
(25)线粒体复合物II电子传递抑制剂,例如β-酮腈衍生物类(beta-keto nitrilederivatives),例如腈吡螨酯(cyenopyrafen)和丁氟螨酯(cyflumetofen)和羧酰苯胺类(carboxanilide),例如pyflubumide。
(28)兰尼碱(ryanodine)受体调节剂,例如二酰胺类,例如氯虫苯甲酰胺(chlorantraniliprole)、氰虫酰胺(cyantraniliprole)和氟虫双酰胺(flubendiamide),
(29)其他活性成分,例如啶喃环丙虫酯(Afidopyropen)、阿福拉纳(Afoxolaner)、印楝素(Azadirachtin)、Benclothiaz、苯螨特(Benzoximate)、联苯肼酯(Bifenazate)、溴虫氟苯双酰胺(Broflanilide)、溴螨酯(Bromopropylate)、灭螨猛(Chinomethionat)、氯丙炔菊酯(Chloroprallethrin)、冰晶石(Cryolite)、环溴虫酰胺(Cyclaniliprole)、环氧虫啶(Cycloxaprid)、氯氟氰虫酰胺(Cyhalodiamide)、Dicloromezotiaz、三氯杀螨醇(Dicofol)、ε-甲氧苄氟菊酯(epsilon-Metofluthrin)、epsilon-Momfluthrin、Flometoquin、Fluazaindolizine、联氟砜(Fluensulfone)、嘧虫胺(Flufenerim)、氟菌螨酯(Flufenoxystrobin)、丁虫腈(Flufiprole)、Fluhexafon、氟吡菌酰胺(Fluopyram)、氟雷拉纳(Fluralaner)、Fluxametamide、呋喃虫酰肼(Fufenozide)、戊吡虫胍(Guadipyr)、Heptafluthrin、氯噻啉(Imidaclothiz)、异菌脲(Iprodione)、κ-联苯菊酯(kappa-Bifenthrin)、κ-七氟菊酯(kappa-Tefluthrin)、Lotilaner、氯氟醚菊酯(Meperfluthrin)、哌虫啶(Paichongding)、啶虫丙醚(Pyridalyl)、Pyrifluquinazon、嘧螨胺(Pyriminostrobin)、Spirobudiclofen、四氟醚菊酯(Tetramethylfluthrin)、氟氰虫酰胺(Tetraniliprole)、四氯虫酰胺(Tetrachlorantraniliprole)、Tigolaner、Tioxazafen、硫氟肟醚(Thiofluoximate)、三氟苯嘧啶(Triflumezopyrim)和碘甲烷(iodomethane);此外,基于坚强芽孢杆菌的制剂(I-1582,BioNeem,Votivo),以及以下化合物: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(由WO2006/043635获知)(CAS 885026-50-6)、{1′-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]-5-氟螺[吲哚-3,4′-哌啶]-1(2H)-基}(2-氯吡啶-4-基)甲酮(由WO2003/106457获知)(CAS 637360-23-7)、2-氯-N-[2-{1-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]哌啶-4-基}-4-(三氟甲基)苯基]异烟酰胺(由WO2006/003494获知)(CAS 872999-66-1)、3-(4-氯-2,6-二甲基苯基)-4-羟基-8-甲氧基-1,8-二氮杂螺[4.5]癸-3-烯-2-酮(由WO 2010052161获知)(CAS 1225292-17-0)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-2-氧代-1,8-二氮杂螺[4.5]癸-3-烯-4-基乙基碳酸酯(由EP 2647626获知)(CAS-1440516-42-6)、4-(丁-2-炔-1-基氧基)-6-(3,5-二甲基哌啶-1-基)-5-氟嘧啶(由WO2004/099160获知)(CAS 792914-58-0)、PF1364(由JP2010/018586获知)(CAS 1204776-60-2)、N-[(2E)-1-[(6-氯吡啶-3-基)甲基]吡啶-2(1H)-亚基]-2,2,2-三氟乙酰胺(由WO2012/029672获知)(CAS 1363400-41-2)、(3E)-3-[1-[(6-氯-3-吡啶基)甲基]-2-吡啶亚基]-1,1,1-三氟丙-2-酮(由WO2013/144213获知)(CAS1461743-15-6)、N-[3-(苄基氨基甲酰基)-4-氯苯基]-1-甲基-3-(五氟乙基)-4-(三氟甲基)-1H-吡唑-5-甲酰胺(由WO2010/051926获知)(CAS 1226889-14-0)、5-溴-4-氯-N-[4-氯-2-甲基-6-(甲基氨基甲酰基)苯基]-2-(3-氯-2-吡啶基)吡唑-3-甲酰胺(由CN103232431获知)(CAS 1449220-44-3)、4-[5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(顺式-1-氧代-3-硫杂环丁烷基)苯甲酰胺、4-[5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(反式-1-氧代-3-硫杂环丁烷基)苯甲酰胺和4-[(5S)-5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(顺式-1-氧代-3-硫杂环丁烷基)苯甲酰胺(由WO 2013/050317 A1获知)(CAS 1332628-83-7)、N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚磺酰基]丙酰胺、(+)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚磺酰基]丙酰胺和(-)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚磺酰基]丙酰胺(由WO 2013/162715 A2、WO 2013/162716 A2、US 2014/0213448A1获知)(CAS1477923-37-7)、5-[[(2E)-3-氯-2-丙烯-1-基]氨基]-1-[2,6-二氯-4-(三氟甲基)苯基]-4-[(三氟甲基)亚磺酰基]-1H-吡唑-3-甲腈(由CN 101337937 A获知)(CAS 1105672-77-2)、3-溴-N-[4-氯-2-甲基-6-[(甲基氨基)硫代甲基]苯基]-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(Liudaibenjiaxuanan,由CN 103109816 A获知)(CAS 1232543-85-9)、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(由WO 2012/034403A1获知)(CAS 1268277-22-0)、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(由WO2011/085575 A1获知)(CAS 1233882-22-8)、4-[3-[2,6-二氯-4-[(3,3-二氯-2-丙烯-1-基)氧基]苯氧基]丙氧基]-2-甲氧基-6-(三氟甲基)嘧啶(由CN 101337940 A获知)(CAS1108184-52-6)、(2E)-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]肼甲酰胺和2(Z)-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]肼甲酰胺(由CN 101715774A获知)(CAS 1232543-85-9)、环丙烷甲酸3-(2,2-二氯乙烯基)-2,2-二甲基-4-(1H-苯并咪唑-2-基)苯酯(由CN 103524422 A获知)(CAS 1542271-46-4)、(4aS)-7-氯-2,5-二氢-2-[[(甲氧基羰基)[4-[(三氟甲基)硫基]苯基]氨基]羰基]-茚并[1,2-e][1,3,4]噁二嗪-4a(3H)-甲酸甲酯(由CN102391261A获知)(CAS 1370358-69-2)、6-脱氧-3-O-乙基-2,4-二-O-甲基-,1-[N-[4-[1-[4-(1,1,2,2,2-五氟乙氧基)苯基]-1H-1,2,4-三唑-3-基]苯基]氨基甲酸酯]-α-L-吡喃甘露糖(由US2014/0275503 A1获知)(CAS 1181213-14-8)、8-(2-环丙基甲氧基-4-三氟甲基苯氧基)-3-(6-三氟甲基哒嗪-3-基)-3-氮杂二环[3.2.1]辛烷(CAS 1253850-56-4)、(8-反式)-8-(2-环丙基甲氧基-4-三氟甲基苯氧基)-3-(6-三氟甲基哒嗪-3-基)-3-氮杂二环[3.2.1]辛烷(CAS933798-27-7)、(8-顺式)-8-(2-环丙基甲氧基-4-三氟甲基苯氧基)-3-(6-三氟甲基哒嗪-3-基)-3-氮杂二环[3.2.1]辛烷(由WO 2007040280 A1、WO 2007040282 A1获知)(CAS934001-66-8)、N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)硫基]-丙酰胺(由WO 2015/058021 A1、WO 2015/058028 A1获知)(CAS 1477919-27-9)和N-[4-(氨基硫代甲基)-2-甲基-6-[(甲基氨基)羰基]苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(由CN 103265527 A获知)(CAS 1452877-50-7)、5-(1,3-二氧杂环己-2-基)-4-[[4-(三氟甲基)苯基]甲氧基]嘧啶(由WO 2013/115391 A1获知)(CAS 1449021-97-9)、3-(4-氯-2,6-二甲基苯基)-4-羟基-8-甲氧基-1-甲基-1,8-二氮杂螺[4.5]癸-3-烯-2-酮(由WO 2010/066780 A1、WO 2011/151146 A1获知)(CAS 1229023-34-0)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-1,8-二氮杂螺[4.5]癸烷-2,4-二酮(由WO 2014/187846 A1获知)(CAS 1638765-58-8)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-2-氧代-1,8-二氮杂螺[4.5]癸-3-烯-4-基碳酸乙酯(由WO 2010/066780 A1、WO 2011151146 A1获知)(CAS1229023-00-0)、N-[1-[(6-氯-3-吡啶基)甲基]-2(1H)-吡啶亚基]-2,2,2-三氟乙酰胺(由DE 3639877 A1、WO 2012029672 A1获知)(CAS 1363400-41-2)、[N(E)]-N-[1-[(6-氯-3-吡啶基)甲基]-2(1H)-吡啶亚基]-2,2,2-三氟乙酰胺(由WO 2016005276 A1获知)(CAS1689566-03-7)、[N(Z)]-N-[1-[(6-氯-3-吡啶基)甲基]-2(1H)-吡啶亚基]-2,2,2-三氟乙酰胺(CAS 1702305-40-5)、3-内型-3-[2-丙氧基-4-(三氟甲基)苯氧基]-9-[[5-(三氟甲基)-2-吡啶基]氧基]-9-氮杂双环[3.3.1]壬烷(由WO 2011/105506 A1、WO 2016/133011A1获知)(CAS 1332838-17-1)。
可与式(I)的化合物和包含其的组合物混合的安全剂的实例为,例如,解草嗪(benoxacor)、解毒喹(cloquintocet(-mexyl))、解草胺腈(cyometrinil)、环丙磺酰胺(cyprosulfamide)、二氯丙烯胺(dichlormid)、解草唑(fenchlorazole(-ethyl))、解草啶(fenclorim)、解草胺(flurazole)、氟草肟(fluxofenim)、解草噁唑(furilazole)、双苯噁唑酸(isoxadifen(-ethyl))、吡唑解草酯(mefenpyr(-diethyl))、萘二甲酸酐(naphthalicanhydride)、解草腈(oxabetrinil)、2-甲氧基-N-({4-[(甲基氨基甲酰基)氨基]苯基}磺酰基)苯甲酰胺(CAS 129531-12-0)、4-(二氯乙酰基)-1-氧杂-4-氮杂螺[4.5]癸烷(CAS71526-07-3)、2,2,5-三甲基-3-(二氯乙酰基)-1,3-噁唑烷(CAS 52836-31-4)。
可与式(I)的化合物和包含其的组合物混合的除草剂的实例为:
乙草胺(acetochlor)、三氟羧草醚(acifluorfen、acifluorfen-sodium)、苯草醚(aclonifen)、甲草胺(alachlor)、二丙烯草胺(allidochlor)、枯杀达(alloxydim、alloxydim-sodium)、莠灭净(ametryn)、氨唑草酮(amicarbazone)、先甲草胺(amidochlor)、酰嘧磺隆(amidosulfuron)、4-氨基-3-氯-6-(4-氯-2-氟-3-甲基苯基)-5-氟吡啶-2-甲酸、氯丙嘧啶酸(aminocyclopyrachlor)、aminocyclopyrachlor-potassium、aminocyclopyrachlor-methyl、氯氨吡啶酸(aminopyralid)、杀草强(amitrole)、氨基磺酸铵(ammoniumsulfamate)、莎稗磷(anilofos)、磺草灵(asulam)、莠去津(atrazine)、唑啶草酮(azafenidin)、四唑嘧磺隆(azimsulfuron)、氟丁酰草胺(beflubutamid)、草除灵(benazolin、benazolin-ethyl)、乙丁氟灵(benfluralin)、呋草黄(benfuresate)、苄嘧磺隆(bensulfuron、bensulfuron-methyl)、地散磷(bensulide)、灭草松(bentazone)、双环磺草酮(benzobicyclon)、吡草酮(benzofenap)、氟吡草酮(bicyclopyron)、甲羧除草醚(bifenox)、双丙氨膦(bilanafos、bilanafos-sodium)、双草醚(bispyribac、bispyribac-sodium)、除草定(bromacil)、溴丁酰草胺(bromobutide)、溴酚污(bromofenoxim)、溴苯腈(bromoxynil)、丁酰溴苯腈(bromoxynil-butyrate)、溴苯腈钾(bromoxynil-potassium)、庚酰溴苯腈(bromoxynil-heptanoate)和辛酰溴苯腈(bromoxynil-octanoate)、羟草酮(busoxinone)、丁草胺(butachlor)、氟丙嘧草酯(butafenacil)、抑草磷(butamifos)、丁烯草胺(butenachlor)、仲丁灵(butralin)、丁苯草酮(butroxydim)、丁草敌(butylate)、唑草胺(cafenstrole)、双酰草胺(carbetamide)、氟唑草酮(carfentrazone、carfentrazone-ethyl)、草灭畏(chloramben)、氯溴隆(chlorbromuron)、伐草克(chlorfenac、chlorfenac-sodium)、燕麦酯(chlorfenprop)、甲基氯芴素(chlorflurenol、chlorflurenol-methyl)、氯草敏(chloridazon)、氯嘧磺隆(chlorimuron、chlorimuron-ethyl)、chlorophthalim、绿麦隆(chlorotoluron)、氯酞酸甲酯(chlorthal-dimethyl)、氯磺隆(chlorsulfuron)、吲哚酮草酯(cinidon、cinidon-ethyl)、环庚草醚(cinmethylin)、醚磺隆(cinosulfuron)、氯酰草膦(clacyfos)、烯草酮(clethodim)、炔草酸(clodinafop)、炔草酯(clodinafop-propargyl)、异噁草松(clomazone)、氯甲酰草胺(clomeprop)、二氯吡啶酸(clopyralid)、氯酯磺草胺(cloransulam、cloransulam-methyl)、苄草隆(cumyluron)、氨基氰(cyanamide)、氰草津(cyanazine)、环草敌(cycloate)、cyclopyrimorate、环丙嘧磺隆(cyclosulfamuron)、噻草酮(cycloxydim)、氰氟草酯(cyhalofop、cyhalofop-butyl)、环草津(cyprazine)、2,4-D、2,4-D-丁氧基乙酯(2,4-D-butotyl)、2,4-D-丁酯(2,4-D-butyl)、2,4-D-二甲基铵(2,4-D-dimethylammonium)、2,4-D-二乙醇胺(2,4-D-diolamin)、2,4-D-乙酯(2,4-D-ethyl)、2-乙基己酯(2-ethylhexyl)、2,4-D-异丁酯、2,4-D-异辛酯、2,4-D-异丙基铵、2,4-D-钾、2,4-D-三异丙醇铵和2,4-D-三乙醇胺、2,4-DB、2,4-DB-丁酯、2,4-DB-二甲基铵、2,4-DB-异辛酯、2,4-DB-钾和2,4-DB-钠、杀草隆(daimuron(dymron))、茅草枯(dalapon)、棉隆(dazomet)、正癸醇、甜菜安(desmedipham)、detosyl-pyrazolate(DTP)、麦草畏(dicamba)、敌草腈(dichlobenil)、2-(2,4-二氯苄基)-4,4-二甲基-1,2-噁唑烷-3-酮、2-(2,5-二氯苄基)-4,4-二甲基-1,2-噁唑烷-3-酮、2,4-滴丙酸(dichlorprop)、精2,4-滴丙酸(dichlorprop-P)、禾草灵(diclofop、diclofop-methyl)、diciofop-P-methyl、双氯磺草胺(diclosulam)、野燕枯(difenzoquat)、吡氟酰草胺(diflufenican)、二氟吡隆(diflufenzopyr、diflufenzopyr-sodium)、噁唑隆(dimefuron)、哌草丹(dimepiperate)、二甲草胺(dimethachlor)、异戊乙净(dimethametryn)、二甲吩草胺(dimethenamid)、精二甲吩草胺(dimethenamid-P)、dimetrasulfuron、氨氟灵(dinitramine)、特乐酚(dinoterb)、双苯酰草胺(diphenamid)、敌草快(diquat)、diquat-dibromid、氟硫草定(dithiopyr)、敌草隆(diuron)、DNOC、茵多酸(endothal)、EPTC、戊草丹(esprocarb)、乙丁烯氟灵(ethalfluralin)、胺苯磺隆(ethametsulfuron、ethametsulfuron-methyl)、乙嗪草酮(ethiozin)、乙氧呋草黄(ethofumesate)、氟乳醚(ethoxyfen、ethoxyfen-ethyl)、乙氧嘧磺隆(ethoxysulfuron)、乙氧苯草胺(etobenzanid)、F-9600、F-5231(即N-{2-氯-4-氟-5-[4-(3-氟丙基)-5-氧代-4,5-二氢-1H-四唑-1-基]苯基}乙基磺酰胺)、F-7967(即3-[7-氯-5-氟-2-(三氟甲基)-1H-苯并咪唑-4-基]-1-甲基-6-(三氟甲基)嘧啶-2,4(1H,3H)-二酮)、噁唑禾草灵(fenoxaprop)、精噁唑禾草灵(fenoxaprop-P)、噁唑禾草灵(fenoxaprop-ethyl)、精噁唑禾草灵(fenoxaprop-P-ethyl)、fenoxasulfone、fenquinotrione、四唑酰草胺(fentrazamide)、麦草伏(flamprop)、高效麦草氟异丙酯(flamprop-M-isopropyl)、高效麦草氟甲酯(flamprop-M-methyl)、啶嘧磺隆(flazasulfuron)、双氟磺草胺(florasulam)、吡氟禾草灵(fluazifop)、精吡氟禾草灵(fluazifop-P)、吡氟禾草灵丁酯(fluazifop-butyl)、精吡氟禾草灵丁酯(fluazifop-P-butyl)、氟酮磺隆(flucarbazone、flucarbazone-sodium)、氟吡磺隆(flucetosulfuron)、氯乙氟灵(fluchloralin)、氟噻草胺(flufenacet)、氟哒嗪草酯(flufenpyr、flufenpyr-ethyl)、唑嘧磺草胺(flumetsulam)、氟烯草酸(flumiclorac、flumiclorac-pentyl)、丙炔氟草胺(flumioxazin)、氟草隆(fluometuron)、9-羟基笏甲酸(fiurenol)、芴丁酯(flurenol-butyl)、flurenol-dimethylammonium和芴醇甲酯(flurenol-methyl)、乙羧氟草醚(fluoroglycofen、fluoroglycofen-ethyl)、四氟丙酸(flupropanate)、氟啶嘧磺隆(flupyrsulfuron、flupyrsulfuron-methyl-sodium)、氟啶草酮(fluridone)、氟咯草酮(flurochloridone)、氯氟吡氧乙酸(fluroxypyr、fluroxypyr-meptyl)、呋草酮(flurtamone)、嗪草酸(fluthiacet)、嗪草酸甲酯(fluthiacet-methyl)、氟磺胺草醚(fomesafen)、氟磺胺草醚钠(fomesafen-sodium)、甲酰氨磺隆(foramsulfuron)、杀木膦(fosamine)、草铵膦(glufosinate)、草铵膦-铵、精草铵膦-钠(glufosinate-P-sodium)、精草铵膦-铵、精草铵膦-钠、草甘膦、草甘膦-铵、草甘膦-异丙基铵、草甘膦-二铵、草甘膦-二甲基铵、草甘膦-钾、草甘膦-钠和草硫膦(glyphosate-trimesium)、H-9201(即O-(2,4-二甲基-6-硝基苯基)O-乙基异丙基硫代磷酰胺酯(O-(2,4-dimethyl-6-nitrophenyl)O-ethylisopropylphosphoramidothioate)、氟氯吡啶酯(halauxifen、halauxifen-methyl)、氟硝磺酰胺(halosafen)、氯吡嘧磺隆(halosulfuron、halosulfuron-methyl)、氟吡禾灵(haloxyfop)、精氟吡禾灵(haloxyfop-P)、氟吡禾灵乙氧基乙酯、精氟吡禾灵乙氧基乙酯、氟吡禾灵甲酯、精氟吡禾灵甲酯、环嗪酮(hexazinone)、HW-02(即(2,4-二氯苯氧基)乙酸1-(二甲氧基磷酰基)乙酯)、咪草酸(imazamethabenz、imazamethabenz-methyl)、甲氧咪草烟(imazamox)、甲氧咪草烟-铵、甲咪唑烟酸(imazapic)、甲咪唑烟酸-铵、咪唑烟酸(imazapyr)、咪唑烟酸-异丙铵、咪唑喹啉酸(imazaquin)、咪唑喹啉-铵、咪唑乙烟酸(imazethapyr)、咪唑乙烟酸亚铵(imazethapyr-immonium)、唑吡嘧磺隆(imazosulfuron)、茚草酮(indanofan)、三嗪茚草胺(indaziflam)、碘甲磺隆(iodosulfuron)、甲基碘磺隆钠盐(iodosulfuron-methyl-sodium)、碘苯腈(ioxynil)、辛酰碘苯腈(ioxynil-octanoate)、碘苯腈-钾和碘苯腈-钠、ipfencarbazone、异丙隆(isoproturon)、异噁隆(isouron)、异噁酰草胺(isoxaben)、异噁唑草酮(isoxaflutole)、特胺灵(karbutilate)、KUH-043(即3-({[5-(二氟甲基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-基]甲基}磺酰基)-5,5-二甲基-4,5-二氢-1,2-噁唑)、ketospiradox、乳氟禾草灵(lactofen)、环草定(lenacil)、利谷隆(linuron)、MCPA、MCPA-丁氧基乙酯(MCPA-butotyl)、MCPA-二甲基铵、MCPA-2-乙基己酯、MCPA-异丙基铵、MCPA-钾和MCPA-钠、MCPB、MCPB-甲酯、MCPB-乙酯和MCPB-钠、2-甲-4-氯丙酸(mecoprop)、2-甲-4-氯丙酸钠和2-甲-4-氯丙酸丁氧基乙酯、精2-甲-4-氯丙酸(mecoprop-P)、精2-甲-4-氯丙酸丁氧基乙酯、精2-甲-4-氯丙酸-二甲基铵、精2-甲-4-氯丙酸-二乙基己酯和精2-甲-4-氯丙酸-钾、苯噻酰草胺(mefenacet)、氟磺酰草胺(mefluidide)、甲基二磺隆(mesosulfurone、mesosulfuron-methyl)、甲基磺草酮(mesotrione)、甲基苯噻隆(methabenzthiazuron)、威百亩(metam)、噁唑酰草胺(metamifop)、苯嗪草酮(metamitron)、吡唑草胺(metazachlor)、嗪吡嘧磺隆(metazosulfuron)、甲基苯噻隆(methabenzthiazuron)、甲硫嘧磺隆(methiopyrsulfuron)、methiozolin、异硫氰酸甲酯(methyl isothiocyanate)、溴谷隆(metobromuron)、异丙甲草胺(metolachlor)、精异丙甲草胺(S-metolachlor)、磺草唑胺(metosulam)、甲氧隆(metoxuron)、嗪草酮(metribuzin)、甲磺隆(metsulfuron、metsulfuron-methyl)、禾草敌(molinat)、绿谷隆(monolinuron)、单嘧磺隆(monosulfuron)、单嘧磺酯(monosulfuron-ester)、MT-5950(即N-(3-氯-4-异丙基苯基)-2-甲基戊酰胺)、NGGC-011、敌草胺(napropamide)、NC-310(即[5-(苄氧基)-1-甲基-1H-吡唑-4-基](2,4-二氯苯基)甲酮)、草不隆(neburon)、烟嘧磺隆(nicosulfuron)、壬酸(pelargonic acid)、氟草敏(norflurazon)、油酸(脂肪酸)、坪草丹(orbencarb)、嘧苯胺磺隆(orthosulfamuron)、氨磺乐灵(oryzalin)、丙炔噁草酮(oxadiargyl)、噁草酮(oxadiazon)、环氧嘧磺隆(oxasulfuron)、噁嗪草酮(oxaziclomefon)、乙氧氟草醚(oxyfluorfen)、百草枯(paraquat、paraquat dichloride)、克草猛(pebulate)、二甲戊灵(pendimethalin)、penoxsulam、五氯苯酚(pentachlorophenol)、环戊噁草酮(pentoxazone)、烯草胺(pethoxamid)、石油油料(petroleum oils)、甜菜宁(phenmedipham)、氨氯吡啶酸(picloram)、氟吡酰草胺(picolinafen)、唑啉草酯(pinoxaden)、哌草磷(piperophos)、丙草胺(pretilachlor)、氟嘧磺隆(primisulfuron、primisulfuron-methyl)、氨氟乐灵(prodiamine)、环苯草酮(profoxydim)、扑灭通(prometon)、扑草净(prometryn)、毒草胺(propachlor)、敌稗(propanil)、噁草酸(propaquizafop)、扑灭津(propazine)、苯胺灵(propham)、异丙草胺(propisochlor)、丙苯磺隆(propoxycarbazone、propoxycarbazone-sodium)、propyrisulfuron、炔苯酰草胺(propyzamide)、苄草丹(prosulfocarb)、氟磺隆(prosulfuron)、双唑草腈(pyraclonil)、吡草醚(pyraflufen、pyraflufen-ethyl)、磺酰草吡唑(pyrasulfotole)、吡唑特(pyrazolynate(pyrazolate))、吡嘧磺隆(pyrazosulfuron、pyrazosulfuron-ethyl)、苄草唑(pyrazoxyfen)、pyribambenz、异丙酯草醚(pyribambenz-isopropyl)、丙酯草醚(pyribambenz-propyl)、嘧啶肟草醚(pyribenzoxim)、稗草丹(pyributicarb)、pyridafol、哒草特(pyridate)、环酯草醚(pyriftalide)、嘧草醚(pyriminobac、pyriminobac-methyl)、pyrimisulfan、嘧草硫醚(pyrithiobac、pyrithiobac-sodium)、pyroxasulfone、甲氧磺草胺(pyroxsulam)、二氯喹啉酸(quinclorac)、氯甲喹啉酸(quinmerac)、灭藻醌(quinoclamine)、喹禾灵(quizalofop)、喹禾灵乙酯(quizalofop-ethyl)、精喹禾灵(quizalofop-P)、精喹禾灵乙酯(quizalofop-P-ethyl)、喹禾糠酯(quizalofop-P-tefuryl)、砜嘧磺隆(rimsulfuron)、苯嘧磺草胺(saflufenacil)、烯禾啶(sethoxydim)、环草隆(siduron)、西玛津(simazine)、西草净(simetryn)、SL-261、磺草酮(sulcotrion)、甲磺草胺(sulfentrazone)、甲嘧磺隆(sulfometuron、sulfometuron-methyl)、磺酰磺隆(sulfosulfuron)、SYN-523、SYP-249(即1-乙氧基-3-甲基-1-氧代丁-3-烯-2-基5-[2-氯-4-(三氟甲基)苯氧基]-2-硝基苯甲酸酯)、SYP-300(即1-[7-氟-3-氧代-4-(丙-2-炔-1-基)-3,4-二氢-2H-1,4-苯并噁嗪-6-基]-3-丙基-2-硫代咪唑烷-4,5-二酮)、2,3,6-TBA、TCA(三氯乙酸)、三氟乙酸钠、丁噻隆(tebuthiuron)、呋喃磺草酮(tefuryltrione)、环磺酮(tembotrione)、吡喃草酮(tepraloxydim)、特草定(terbacil)、特草灵(terbucarb)、特丁通(terbumeton)、特丁津(terbuthylazine)、特丁净(terbutryn)、噻吩草胺(thenylchlor)、噻唑烟酸(thiazopyr)、噻酮磺隆(thiencarbazone、thiencarbazone-methyl)、噻吩磺隆(thifensulfuron、thifensulfuron-methyl)、禾草丹(thiobencarb)、tiafenacil、tolpyralate、苯吡唑草酮(topramezone)、三甲苯草酮(tralkoxydim)、triafamone、野燕畏(tri-allate)、醚苯磺隆(triasulfuron)、三嗪氟草胺(triaziflam)、苯磺隆(tribenuron、tribenuron-methyl)、三氯吡氧乙酸(triclopyr)、草达津(trietazine)、三氟啶磺隆(trifloxysulfuron、trifloxysulfuron-sodium)、trifludimoxazin、氟乐灵(trifluralin)、氟胺磺隆(triflusulfuron、triflusulfuron-methyl)、三氟甲磺隆(tritosulfuron)、硫酸脲、灭草敌(vernolate)、XDE-848、ZJ-0862(即3,4-二氯-N-{2-[(4,6-二甲氧基嘧啶-2-基)氧基]苄基}苯胺),以及以下化合物:
植物生长调节剂的实例为:
活化酯(Acibenzolar)、苯并噻二唑(acibenzolar-S-methyl)、5-氨基乙酰丙酸(5-aminolevulinic acid)、嘧啶醇(ancymidol)、6-苄基氨基嘌呤、芸苔素内酯(Brassinolid)、儿茶素(catechine)、矮壮素(chlormequat chloride)、调果酸(cloprop)、环丙酰胺酸(cyclanilide)、3-(环丙-1-烯基)丙酸、丁酰肼(daminozide)、棉隆、正癸醇、调呋酸(dikegulac)、敌草克钠(dikegulac-sodium)、茵多酸(endothal)、菌多酸-二钾(endothal-dipotassium)、茵多酸-二钠(endothal-disodium)和茵多酸-单(N,N-二甲基烷基铵)、乙烯利(ethephon)、氟节胺(flumetralin)、9-羟基笏甲酸、芴丁酯、呋嘧醇(flurprimidol)、氯吡脲(forchlorfenuron)、赤霉酸(gibberellic acid)、抗倒胺(inabenfide)、吲哚-3-乙酸(IAA)、4-吲哚-3-基丁酸、稻瘟灵(isoprothiolane)、烯丙苯噻唑(probenazole)、茉莉酸(jasmonic acid)、马来酰肼、助壮素(mepiquat chloride)、1-甲基环丙烯、茉莉酸甲酯、2-(1-萘基)乙酰胺、1-萘乙酸、2-萘氧基乙酸、硝基酚盐混合物(nitrophenoxide mixture)、多效唑(paclobutrazol)、N-(2-苯乙基)-β-丙氨酸、N-苯基邻苯二甲酸、调环酸(prohexadione)、调环酸-钙(prohexadione-calcium)、茉莉酮(prohydrojasmone)、水杨酸、独角金内酯(strigolactone)、四氧硝基苯(tecnazene)、噻苯隆(thidiazuron)、三十烷醇(triacontanol)、抗倒酯(trinexapac、trinexapac-ethyl)、tsitodef、烯效唑(uniconazole)、精烯效唑(uniconazole-P)。
方法和用途
式(I)的化合物和包含其的组合物具有有效的杀微生物活性和/或植物防御调节潜力。可将它们用于防治不想要的微生物,例如不想要的真菌和细菌。它们在作物保护(它们防治引起植物病害的微生物)中或对于保护材料(例如,工业材料、木材、贮存物)是特别有用的,如下文更详细地说明的那样。更具体地,式(I)的化合物和包含其的组合物可被用于保护种子、发芽的种子、出土的幼苗、植物、植物部位、果实、收获的产物和/或植物生长的土壤免受不想要的微生物的侵袭。
如文中使用的防治或防治(control or controlling)包括不想要的微生物的保护性处理、治疗性处理和根除性处理。不想要的微生物可以是致病细菌、致病病毒、致病卵菌或致病真菌,更具体地是植物病原性细菌、植物病原性病毒、植物病原性卵菌或植物病原性真菌。如下文中所详述的,这些植物病原性微生物是广谱的植物病害的病原体。
更具体地,可将式(I)的化合物和包含其的组合物用作杀真菌剂。为本发明的目的,术语“杀真菌剂”是指可在作物保护中用于防治不想要的真菌和/或用于防治卵菌纲(Oomycetes)的化合物或组合物,所述真菌如根肿菌纲(Plasmodiophoromycetes)、壶菌纲(Chytridiomycetes)、接合菌纲(Zygomycetes)、子囊菌纲(Ascomycetes)、担子菌纲(Basidiomycetes)和半知菌纲(Deuteromycetes)。
还可将式(I)的化合物和包含其的组合物用作抗菌剂。特别地,它们可在作物保护中使用,例如用于防治不想要的细菌,例如假单胞菌科(Pseudomonadaceae)、根瘤菌科(Rhizobiaceae)、黄单胞菌科(Xanthomonadaceae)、肠杆菌科(Enterobacteriaceae)、棒状杆菌科(Corynebacteriaceae)和链霉菌科(Streptomycetaceae)。
式(I)的化合物和包含其的组合物也可在作物保护中用作抗病毒剂。例如,式(I)的化合物和包含其的组合物可以对以下植物病毒的病害具有功效:例如烟草花叶病毒(TMV)、烟草脆裂病毒、烟草矮化病毒(TStuV)、烟草曲叶病毒(VLCV)、烟草脉带花叶病毒(TVBMV)、烟草坏死矮缩病毒(TNDV)、烟草线条病毒(TSV)、马铃薯X病毒(PVX)、马铃薯Y病毒、马铃薯S病毒、马铃薯M病毒和马铃薯A病毒、马铃薯奥古巴花叶病毒(PAMV)、马铃薯帚顶病毒(PMTV)、马铃薯卷叶病毒(PLRV)、苜蓿花叶病毒(AMV)、黄瓜花叶病毒(CMV)、黄瓜绿斑驳花叶病毒(CGMMV)、黄瓜黄化病病毒(CuYV)、西瓜花叶病毒(WMV)、番茄斑萎病毒(TSWV)、番茄环斑病毒(TomRSV)、甘蔗花叶病毒(SCMV)、水稻矮缩病毒、水稻条叶枯病毒、水稻黑条矮缩病毒、草莓斑驳病毒(SMoV)、草莓镶脉病毒(SVBV)、草莓轻型黄边病毒(SMYEV)、草莓皱缩病毒(SCrV)、蚕豆萎蔫病毒(BBWV)和甜瓜坏死斑点病毒(MNSV)。
本发明还涉及一种防治不想要的微生物、特别是不想要的植物病原性微生物如不想要的真菌、卵菌和细菌的方法,包括将一种或多种式(I)的化合物或包含其的组合物施用至微生物和/或其生境(植物、植物部位、种子、果实或植物生长的土壤)的步骤。
通常,当式(I)的化合物和包含其的组合物在用于防治植物病原性真菌和/或植物病原性卵菌的治疗性方法或保护性方法中使用时,将其有效且植物-相容的量施用至植物、植物部位、果实、种子或施用至植物生长的土壤或基质。可用于培育植物的合适的基质包括基于无机物的基质,例如矿物棉,特别是岩棉、珍珠岩、沙或砂砾;有机基质,例如泥煤、松树皮或锯屑;以及基于石油的基质如聚合物泡沫或塑料珠。有效且植物-相容的量意指足以防治或破坏农田上存在的或易于出现的真菌,并且不会引起所述作物的任何明显的植物毒性症状的量。根据待防治的真菌、作物的类型、作物生长阶段、气候条件和式(I)的各化合物和包含其的组合物,这样的量可在宽范围内变化。该量可通过本领域技术人员能力范围内的系统性田间试验确定。
植物和植物部位
可将式(I)的化合物和包含其的组合物施用于任何植物或植物部位。
植物意指所有的植物和植物种群,例如需要和不需要的野生植物或作物植物(包括天然存在的作物植物)。作物植物可为可通过常规育种和优化方法或通过生物技术和基因工程方法或这些方法的组合而获得的植物,包括遗传修饰植物(GMO或转基因植物)以及可受植物育种者权保护和不受植物育种者权保护的植物栽培种。
遗传修饰植物(GMO或转基因植物)是异源基因已被稳定地整合到基因组中的植物。表述“异源基因”主要意指在植物体外提供或组装的基因,并且当其被引入至细胞核、叶绿体或线粒体的基因组中时,该基因通过表达目的蛋白或多肽或通过下调或使其他存在于植物中的基因沉默(利用例如反义技术、共抑制技术、RNA干扰-RNAi-技术或microRNA-miRMA-技术)而赋予转化的植物新的或改进的农学特性或其他特性。位于基因组中的异源基因也称为转基因。由其在植物基因组中的特定位置限定的转基因被称为转化株系或转基因株系。
植物栽培种理解为意指具有新特性(“性状”)且已通过常规育种、诱变或重组DNA技术获得的植物。它们可为栽培种、变种、生物型或基因型。
植物部位理解为意指植物的所有地上和地下部位和器官,例如芽、叶、针叶、茎、干、花、子实体、果实、种子、根、球茎和根状茎。植物部位也包括采收材料和无性繁殖和有性繁殖材料,例如插条、块茎、根状茎、分檗(slips)和种子。
可根据本发明的方法处理的植物包括以下植物:棉花、亚麻、葡萄树、果树、蔬菜,如蔷薇科属(Rosaceae sp.)(例如仁果,例如苹果和梨,以及核果,例如杏、樱桃、扁桃和桃,和软果,例如草莓)、茶藨子科属(Ribesioidae sp.)、胡桃科属(Juglandaceae sp.)、桦木科属(Betulaceae sp.)、漆树科属(Anacardiaceae sp.)、壳斗科属(Fagaceae sp.)、桑科属(Moraceae sp.)、木犀科属(Oleaceae sp.)、猕猴桃科属(Actinidaceae sp.)、樟科属(Lauraceae sp.)、芭蕉科属(Musaceae sp.)(例如香蕉树和绿化树(plantations))、茜草科属(Rubiaceae sp.)(例如咖啡)、山茶科属(Theaceae sp.)、梧桐科属(Sterculiceaesp.)、芸香科属(Rutaceae sp.)(例如柠檬、橙子和葡萄柚)、茄科属(Solanaceae sp.)(例如西红柿)、百合科属(Liliaceae sp.)、菊科属(Asteraceae sp.)(例如莴苣)、伞形科属(Umbelliferae sp.)、十字花科属(Cruciferae sp.)、藜科属(Chenopodiaceae sp.)、葫芦科属(Cucurbitaceae sp.)(例如黄瓜)、葱科属(Alliaceae sp.)(例如韭菜、洋葱)、蝶形花科属(Papilionaceae sp.)(例如豌豆);主要的作物植物,例如禾本科属(Gramineae sp.)(例如玉米、草皮草(turf),谷类如小麦、黑麦、水稻、大麦、燕麦、粟和黑小麦)、菊科属(Asteraceae sp.)(例如向日葵)、十字花科属(Brassicaceae sp.)(例如白球甘蓝、红球甘蓝、椰菜、花椰菜、抱子甘蓝、小白菜、球茎甘蓝、萝卜和油菜、芥菜、辣根和水芹)、豆科属(Fabacae sp.)(例如豆、花生)、蝶形花科属(Papilionaceae sp.)(例如大豆)、茄科属(Solanaceae sp.)(例如马铃薯)、藜科属(Chenopodiaceae sp.)(例如糖用甜菜、饲用甜菜、叶甜菜(swiss chard)、甜菜根);用于园艺和森林区域的有用植物和观赏植物;以及这些植物各自的遗传修饰品种。
可通过上述公开方法处理的植物和植物栽培种包括对一种或多种生物胁迫具有耐受性的植物和植物栽培种,即,所述植物对动物和微生物害虫(例如对线虫、昆虫、螨、植物病原性真菌、细菌、病毒和/或类病毒)表现出更好的抵抗力。
可通过上述公开方法处理的植物和植物栽培种包括对一种或多种非生物胁迫具有抗性的那些植物。非生物胁迫条件可包括例如干旱、低温暴露、热暴露、渗透胁迫、水涝、提高的土壤含盐度、增强的矿物暴露、臭氧暴露、强光暴露、有限的氮营养素利用度、有限的磷营养素利用度、避荫。
可通过上述公开方法处理的植物和植物栽培种包括那些以提高的产量特性为特征的植物。所述植物中提高的产量可以是以下因素的结果:例如,改良的植物生理机能、生长和发育,例如水利用效率、保水效率、改善的氮利用、增强的碳同化作用、改善的光合作用、提高的发芽率和加速成熟。此外,产量还受改进的植物构造的影响(在胁迫和非胁迫条件下),包括但不限于:提早开花、对杂交种子生产的开花控制、秧苗活力、植株大小、节间数和节间距、根系生长、种子大小、果实大小、荚果大小、荚果数或穗数、每个荚果或穗的种子数量、种子质量、增强的种子饱满度、减少的种子分散、减少的荚果开裂以及抗倒伏。其他的产量特征包括种子组成,如碳水化合物含量和组成,例如棉或淀粉、蛋白质含量、油含量和组成、营养价值、抗营养化合物的降低、改善的加工性和更好的贮存稳定性。
可通过上述公开方法处理的植物和植物栽培种包括为已经表现出杂种优势或杂种活力的特性的杂种植物的植物和植物栽培种,所述特性通常会导致更高的产量、活力、健康度和对生物和非生物胁迫的抗性。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括为除草剂-耐受性植物的植物和植物栽培种,即,对一种或多种给定的除草剂具有耐受性的植物。这类植物可以通过遗传转化或通过选择含有赋予所述除草剂耐受性的突变的植物获得。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括为昆虫-抗性的转基因植物的植物和植物栽培种,即,对某些目标昆虫的攻击具有抗性的植物。这类植物可通过遗传转化或通过选择含有赋予所述昆虫抗性的突变的植物获得。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括为抗病转基因植物的植物和植物栽培种,即,对某些目标昆虫的攻击具有抗性的植物。这类植物可通过遗传转化或通过选择含有赋予所述昆虫抗性的突变的植物获得。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括对非生物胁迫具有耐受性的植物和植物栽培种。这类植物可通过遗传转化或通过选择含有赋予所述胁迫耐受性的突变的植物获得。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括显示出改变的采收产物的数量、质量和/或贮存稳定性和/或改变的采收产物的具体成分的性质的植物和植物栽培种。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括具有改变的纤维特性的植物和植物栽培种,例如棉花植物。这类植物可通过遗传转化或通过选择含有赋予所述改变的纤维特性的突变的植物获得。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括具有改变的油分布特性的植物和植物栽培种,例如油菜或相关的芸苔属(Brassica)植物。这类植物可通过遗传转化或通过选择含有赋予所述改变的油分布特性的突变的植物获得。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括具有改变的落粒(seed shattering)特性的植物和植物栽培种,例如油菜或相关的芸苔属植株。这类植物可通过遗传转化或通过选择含有赋予所述改变的落粒特性的突变的植物获得,并且这类植物包括具有延迟或降低的落粒特性的植物,例如油菜植物。
可通过上述公开方法处理的植物和植物栽培种(通过植物生物技术方法如基因工程获得)包括具有改变的翻译后蛋白修饰模式的植物和植物栽培种,例如烟草植物。
病原体
可根据本发明处理的真菌病害的病原体的非限制实例包括:
由白粉病病原体引起的病害,例如白粉菌(Blumeria)属种,例如小麦白粉菌(Blumeria graminis);叉丝单囊壳(Podosphaera)属种,例如白叉丝单囊壳(Podosphaeraleucotricha);单囊壳(Sphaerotheca)属种,例如凤仙花单囊壳(Sphaerothecafuliginea);钩丝壳(Uncinula)属种,例如葡萄钩丝壳(Uncinula necator);
由锈病病原体引起的病害,例如胶锈菌(Gymnosporangium)属种,例如褐色胶锈菌(Gymnosporangium sabinae);驼孢锈(Hemileia)属种,例如咖啡驼孢锈菌(Hemileiavastatrix);层锈菌(Phakopsora)属种,例如豆薯层锈菌(Phakopsora pachyrhizi)或山马蝗层锈菌(Phakopsora meibomiae);柄锈菌(Puccinia)属种,例如隐匿柄锈菌(Pucciniarecondita)、禾柄锈菌(Puccinia graminis)或条形柄锈菌(Puccinia striiformis);单胞锈菌(Uromyces)属种,例如疣顶单胞锈菌(Uromyces appendiculatus);
由卵菌纲(Oomycetes)病原体引起的病害,例如,白锈菌(Albugo)属种,例如菜白锈菌(Albugo candida);盘霜霉(Bremia)属种,例如莴苣盘霜霉(Bremia lactucae);霜霉(Peronospora)属种,例如豌豆霜霉(Peronospora pisi)或十字花科霜霉(P.brassicae);疫霉(Phytophthora)属种,例如致病疫霉(Phytophthora infestans);轴霜霉(Plasmopara)属种,例如葡萄轴霜霉(Plasmopara viticola);假霜霉(Pseudoperonospora)属种,例如草假霜霉(Pseudoperonospora humuli)或古巴假霜霉(Pseudoperonospora cubensis);腐霉(Pythium)属种,例如终极腐霉(Pythium ultimum);
由以下病原体引起的叶斑枯病(leaf blotch)和叶萎蔫病(leaf wilt)病害:例如,链格孢(Alternaria)属种,例如早疫病链格孢(Alternaria solani);尾孢(Cercospora)属种,例如菾菜生尾孢(Cercospora beticola);枝孢(Cladiosporium)属种,例如黄瓜枝孢(Cladiosporium cucumerinum);旋孢腔菌(Cochliobolus)属种,例如禾旋孢腔菌(Cochliobolus sativus)(分生孢子形式:内脐蠕孢属(Drechslera),同义词:长蠕孢菌(Helminthosporium))或宫部旋孢腔菌(Cochliobolus miyabeanus);炭疽菌(Colletotrichum)属种,例如菜豆炭疽菌(Colletotrichumlindemuthanium);棒孢菌(Corynespora)属种,例如山扁豆生棒孢(Corynespora cassiicola);锈斑病菌(Cycloconium)属种,例如孔雀斑病(Cycloconium oleaginum);间座壳(Diaporthe)属种,例如柑桔间座壳(Diaporthe citri);痂囊腔菌(Elsinoe)属种,例如柑桔痂囊腔菌(Elsinoe fawcettii);盘长孢(Gloeosporium)属种,例如悦色盘长孢(Gloeosporiumlaeticolor);小丛壳(Glomerella)属种,例如围小丛壳(Glomerella cingulata);球座菌(Guignardia)属种,例如葡萄球座菌(Guignardia bidwelli);小球腔菌(Leptosphaeria)属种,例如斑污小球腔菌(Leptosphaeria maculans);大毁壳(Magnaporthe)属种,例如灰色大毁壳(Magnaporthe grisea);微座孢属(Microdochium),例如雪霉微座孢(Microdochium nivale);球腔菌(Mycosphaerella)属种,例如禾生球腔菌(Mycosphaerella graminicola)、落花生球腔菌(Mycosphaerella arachidicola)或斐济球腔菌(Mycosphaerella fijiensis);暗球腔菌(Phaeosphaeria)属种,例如颖枯暗球腔菌(Phaeosphaeria nodorum);核腔菌(Pyrenophora)属种,例如圆核腔菌(Pyrenophorateres)或偃麦草核腔菌(Pyrenophora tritici repentis);柱隔孢(Ramularia)属种,例如辛加柱隔孢(Ramularia collo-cygni)或白斑柱隔孢(Ramularia areola);喙孢(Rhynchosporium)属种,例如黑麦喙孢(Rhynchosporium secalis);壳针孢(Septoria)属种,例如芹菜小壳针孢(Septoria apii)或西红柿壳针孢(Septorialycopersici);壳多胞菌(Stagonospora)属种,例如颖枯壳多孢(Stagonospora nodorum);核瑚菌(Typhula)属种,例如肉孢核瑚菌(Typhula incarnata);黑星菌(Venturia)属种,例如苹果黑星病菌(Venturia inaequalis);
由以下病原体引起的根和茎的病害:例如,伏革菌(Corticium)属种,例如禾伏革菌(Corticium graminearum);镰孢(Fusarium)属种,例如尖镰孢(Fusarium oxysporum);顶囊壳(Gaeumannomyces)属种,例如禾顶囊壳(Gaeumannomyces graminis);根肿菌属(Plasmodiophora),例如根肿病菌(Plasmodiophora brassicae);丝核菌(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);帚枝杆孢(Sarocladium)属种,例如稻帚枝杆孢(Sarocladium oryzae);小核菌(Sclerotium)属种,例如稻腐小核菌(Sclerotiumoryzae);塔普斯(Tapesia)属种,例如塔普斯梭状芽孢杆菌(Tapesia acuformis);根串珠霉(Thielaviopsis)属种,例如烟草根串珠霉(Thielaviopsis basicola);
由以下病原体引起的肉穗花序和散穗花序病害(包括玉米穗轴):例如,链格孢属种,例如链格孢属(Alternaria spp.);曲霉(Aspergillus)属种,例如黄曲霉(Aspergillusflavus);枝孢(Cladosporium)属种,例如芽枝状枝孢(Cladosporium cladosporioides);麦角菌(Claviceps)属种,例如麦角菌(Claviceps purpurea);镰孢(Fusarium)属种,例如黄色镰孢(Fusarium culmorum);赤霉(Gibberella)属种,例如玉蜀黍赤霉(Gibberellazeae);小画线壳(Monographella)属种,例如雪腐小画线壳(Monographella nivalis);壳多孢(Stagnospora)属种,例如颖枯壳多孢(Stagnospora nodorum);
由黑粉菌引起的病害:例如,轴黑粉菌(Sphacelotheca)属种,例如丝孢堆黑粉菌(Sphacelotheca reiliana);腥黑粉菌(Tilletia)属种,例如小麦网腥黑粉菌(Tilletiacaries)或小麦矮腥黑粉菌(Tilletia controversa);条黑粉菌(Urocystis)属种,例如隐条黑粉菌(Urocystis occulta);黑粉菌(Ustilago)属种,例如裸黑粉菌(Ustilago nuda);
由以下病原体引起的果实腐烂:例如,曲霉属种,例如黄曲霉;葡萄孢(Botrytis)属种,例如灰葡萄孢(Botrytis cinerea);链核盘菌(Monilinia)属种,例如核果链核盘菌(Monilinia laxa);青霉(Penicillium)属种,例如扩展青霉(Penicillium expansum)或产紫青霉(Penicillium purpurogenum);根霉菌属(Rhizopus),例如匍枝根霉(Rhizopusstolonifer);核盘菌(Sclerotinia)属种,例如核盘菌(Sclerotinia sclerotiorum);轮枝菌(Verticilium)属种,例如黑白轮枝菌(Verticilium alboatrum);
由以下病原体引起的种传的和土传的腐烂和萎蔫病害,以及幼苗的病害:例如,链格孢属种,例如芸薹链格孢(Alternaria brassicicola);丝囊霉(Aphanomyces)属种,例如根腐丝囊霉(Aphanomyces euteiches);壳二孢(Ascochyta)属种,例如兵豆壳二孢(Ascochyta lentis);曲霉属种,例如黄曲霉;枝孢属种,例如草本枝孢(Cladosporiumherbarum);旋孢腔菌属种,例如禾旋孢腔菌(分生孢子形式:内脐蠕孢属,离蠕孢属(Bipolaris),同义词:长蠕孢菌);炭疽菌属种,例如毛核炭疽菌(Colletotrichumcoccodes);镰孢属种,例如黄色镰孢;赤霉属种,例如玉蜀黍赤霉;壳球孢(Macrophomina)属种,例如菜豆壳球孢(Macrophomina phaseolina);微座孢属,例如雪霉微座孢;小画线壳属种,例如雪腐小画线壳;青霉属种,例如扩展青霉;茎点霉(Phoma)属种,例如黑胫茎点霉(Phoma lingam);拟茎点霉(Phomopsis)属种,例如大豆拟茎点霉(Phomopsis sojae);疫霉属种,例如恶疫霉(Phytophthora cactorum);核腔菌属种,例如麦类核腔菌(Pyrenophoragraminea);梨孢(Pyricularia)属种,例如稻梨孢(Pyricularia oryzae);腐霉属种,例如终极腐霉;丝核菌属种,例如立枯丝核菌;根霉菌属种,例如稻根霉菌(Rhizopus oryzae);小核菌属种,例如齐整小核菌(Sclerotium rolfsii);壳针孢属种,例如颖枯壳针孢(Septoria nodorum);核瑚菌属种,例如肉孢核瑚菌;轮枝孢菌(Verticillium)属种,例如大丽花轮枝孢(Verticillium dahliae);
由以下病原体引起的癌性病害、菌瘿和扫帚病(witches’broom):例如,丛赤壳(Nectria)属种,例如仁果干癌丛赤壳菌(Nectria galligena);
由以下病原体引起的萎缩病害:例如,轮枝孢菌属种,例如(Verticilliumlongisporum);镰孢属种,例如尖镰孢;
由以下病原体引起的叶、花和果实的变形:例如,外担菌(Exobasidium)属种,例如坏损外担菌(Exobasidium vexans);外囊菌(Taphrina)属种,例如桃外囊菌(Taphrinadeformans);
由以下病原体引起的木本植物退行性病害:例如,依科(Esca)属种,例如根霉格孢菌(Phaeomoniella chlamydospora)、鸡腿蘑丝孢(Phaeoacremonium aleophilum)或地中海孢孔菌(Fomitiporia mediterranea);灵芝(Ganoderma)属种,例如狭长孢灵芝(Ganoderma boninense);
由以下病原体引起的植物块茎的病害:例如,丝核菌属种,例如立枯丝核菌;长蠕孢菌属种,例如茄病长蠕孢(Helminthosporium solani);
由以下细菌性病原体引起的病害:例如,黄单胞菌(Xanthomonas)属种,例如野油菜黄单胞菌白叶枯变种(Xanthomonas campestris pv.oryzae);假单胞菌(Pseudomonas)属种,例如丁香假单胞菌黄瓜角斑病致病变种(Pseudomonas syringae pv.lachrymans);欧文氏菌(Erwinia)属种,例如噬淀粉欧文氏菌(Erwinia amylovora);韧皮杆菌(Liberibacter)属种,例如亚洲韧皮杆菌(Liberibacter asiaticus);木杆菌属(Xyella)属种,例如苛养木杆菌(Xylella fastidiosa);罗尔斯通氏菌(Ralstonia)属种,例如青枯雷尔氏菌(Ralstonia solanacearum);Dickeya属种,例如Dickeya solani;棒形杆菌(Clavibacter)属种,例如密执安棒形杆菌(Clavibacter michiganensis);链霉菌属种,例如疮痂病链霉菌(Streptomyces scabies)。
大豆病害:
由以下病原体引起的叶、茎、荚和种子的真菌病害:例如,轮纹叶斑病(Alternarialeaf spot)(Alternaria spec.atrans tenuissima)、炭疽病(Anthracnose)(Colletotrichum gloeosporoides dematium var.truncatum)、褐斑病(brown spot)(大豆壳针孢(Septoria glycines))、尾孢菌叶斑病和叶枯病(cercospora leaf spot andblight)(菊池尾孢(Cercospora kikuchii))、笄霉叶枯病(choanephora leaf blight)(漏斗笄霉(Choanephora infundibulifera trispora(同义词)))、疏毛核菌霉属叶斑病(dactuliophora leaf spot)(Dactuliophora glycines)、大豆霜霉病(downy mildew)(东北霜霉(Peronospora manshurica))、内脐蠕孢枯萎病(drechslera blight)(Drechsleraglycini)、蛙眼叶斑病(frogeye leaf spot)(大豆尾孢(Cercospora sojina))、小光壳叶斑病(leptosphaerulina leaf spot)(三叶草小光壳(Leptosphaerulina trifolii))、叶点霉属叶斑病(phyllostica leaf spot)(大豆生叶点霉(Phyllosticta sojaecola))、荚和茎枯萎病(大豆拟茎点霉)、白粉病(扩散叉丝壳(Microsphaera diffusa))、棘壳孢叶斑病(Pyrenochaeta glycines)、气生丝核菌(rhizoctonia aerial)、叶枯病和网枯病(foliage and web blight)(立枯丝核菌)、锈病(豆薯层锈菌、山马蝗层锈菌)、黑星病(scab)(大豆痂圆孢(Sphaceloma glycines))、匍柄霉叶枯病(匍柄霉(Stemphyliumbotryosum))、猝死综合病症(sudden death syndrome)(大豆猝死综合症病菌(Fusariumvirguliforme))、靶斑病(target spot)(山扁豆生棒孢(Corynespora cassiicola))。
由以下病原体引起的根部和茎部的真菌病害:例如,黑色根腐病(野百合丽赤壳菌(Calonectria crotalariae))、炭腐病(菜豆生壳球孢(Macrophomina phaseolina))、镰孢枯萎病或萎蔫、根腐以及荚和根颈腐烂病(尖镰孢、直喙镰孢(Fusarium orthoceras)、半裸镰孢(Fusarium semitectum)、木贼镰孢(Fusarium equiseti))、mycoleptodiscus根腐病(Mycoleptodiscus terrestris)、新赤壳属病(neocosmospora)(侵营新赤壳(Neocosmospora vasinfecta))、荚和茎枯萎病(pod and stem blight)(菜豆间座壳(Diaporthe phaseolorum))、茎腐败(大豆北方茎溃疡病菌(Diaporthe phaseolorumvar.caulivora))、疫霉腐病(大雄疫霉(Phytophthora megasperma)、褐茎腐病(大豆茎褐腐病菌(Phialophora gregata))、腐霉病(pythium rot)(瓜果腐霉(Pythiumaphanidermatum)、畸雌腐霉(Pythium irregulare)、德巴利腐霉(Pythium debaryanum)、群结腐霉(Pythium myriotylum)、终极腐霉)、丝核菌根腐病、茎腐(stem decay)和立枯病(立枯丝核菌)、核盘菌茎腐病(sclerotinia stem decay)(核盘菌)、核盘菌白绢病(sclerotinia southern blight)(Sclerotinia rolfsii)、根串珠霉根腐病(thielaviopsis root rot)(烟草根串珠霉)。
霉菌毒素
此外,式(I)的化合物和包含其的组合物可以降低采收材料和由其制得的食物和饲料中的霉菌毒素含量。霉菌毒素特别包括但不排除以下物质:脱氧萎镰菌醇(deoxynivalenol)(DON)、瓜萎镰菌醇(nivalenol)、15-Ac-DON、3-Ac-DON、T2-毒素和HT2-毒素、伏马菌素(fumonisins)、玉米赤霉烯酮(zearalenon)、念珠菌毒素(moniliformin)、镰菌素(fusarin)、蛇形菌素(diaceotoxyscirpenol)(DAS)、白僵菌素(beauvericin)、恩镰孢菌素(enniatin)、层出镰孢菌素(fusaroproliferin)、fusarenol、赭曲霉毒素(ochratoxins)、棒曲霉素(patulin)、麦角生物碱(ergot alkaloids)和黄曲霉毒素(aflatoxins),这些物质可例如由以下真菌产生:镰刀菌属种(Fusarium spec.),例如锐顶镰刀菌(F.acuminatum)、亚洲镰孢菌(F.asiaticum)、燕麦镰刀菌(F.avenaceum)、克地镰刀菌(F.crookwellense)、黄色镰孢菌(F.culmorum)、禾谷镰刀菌(F.graminearum)(玉蜀黍赤霉)、水贼镰刀菌(F.equiseti)、水稻恶苗病菌(F.fujikoroi)、香蕉镰刀菌(F.musarum)、尖孢镰刀菌(F.oxysporum)、再育镰刀菌(F.proliferatum)、梨孢镰刀菌(F.poae)、小麦冠腐病菌(F.pseudograminearum)、接骨木镰刀菌(F.sambucinum)、藤草镰刀菌(F.scirpi)、半裸镰刀菌(F.semitectum)、茄病镰刀菌(F.solani)、拟枝孢镰刀菌(F.sporotrichoides)、F.langsethiae、胶孢镰刀菌(F.subglutinans)、三线镰孢菌(F.tricinctum)、串珠镰刀菌(F.verticillioides)等;以及由曲霉属真菌属种(Aspergillus spec.)产生,例如黄曲霉(A.flavus)、寄生曲霉(A.parasiticus)、特异曲霉(A.nomius)、棕曲霉(A.ochraceus)、棒曲霉(A.clavatus)、土曲霉(A.terreus)、杂色曲霉(A.versicolor);青霉菌属种(Penicillium spec.),例如纯绿青霉(P.verrucosum)、鲜绿青霉(P.viridicatum)、桔青霉(P.citrinum)、梨青霉(P.expansum)、棒形青霉(P.claviforme)、娄地青霉(P.roqueforti);麦角菌属种,例如紫麦角菌(C.purpurea)、纺锤麦角菌(C.fusiformis)、雀稗麦角菌(C.paspali)、非洲麦角菌(C.africana);葡萄穗霉属种(Stachybotrys spec.)及其他。
材料保护
式(I)的化合物和包含其的组合物也可用于保护材料、尤其是用于保护工业材料抵抗植物病原性真菌的侵袭和破坏。
此外,式(I)的化合物和包含其的组合物可单独或与其他活性成分结合用作防污组合物。
在本发明上下文中,工业材料理解为意指为了工业应用而制备的无生命材料。例如,保护免于微生物的改变或破坏的工业材料可以是胶粘剂、胶水、纸、壁纸和木板/硬纸板、纺织品、地毯、皮革、木材、纤维和薄纱、油漆和塑料制品、冷却润滑剂和其他可以被微生物污染或破坏的材料。可被微生物的增殖损害的生产设备的零件和建筑物,例如冷却水回路、冷却和加热系统以及通风和空调设备,也可以包括在待保护材料的范围内。在本发明范围内的工业材料优选包括胶粘剂、胶料(sizes)、纸和卡片、皮革、木材、油漆、冷却润滑剂和传热流体,更优选木材。
式(I)的化合物和包含其的组合物可防止不良效果,例如腐烂、腐坏、变色、褪色或发霉。
在处理木材的情况下,式(I)的化合物和包含其的组合物也可以用于抵抗易于在木材表面或内部生长的真菌病害。
木材意指所有类型的木材品种,以及该木材的所有类型的意图用于建筑的加工品(working),例如实木、高密度木材、胶合板(laminated wood)和夹板(plywood)。此外,式(I)的化合物和包含其的组合物可用于保护与盐水或苦咸水接触的物体,尤其是船体(hulls)、筛(screens)、网(nets)、建筑物、系泊设备和信号系统,以免受污染。
式(I)的化合物和包含其的组合物也可用于保护贮存物。贮存物理解为意指植物或动物来源的天然物质或其天然来源的加工产品,并且其需要长期保护。植物来源的贮存物,例如植物或植物部位,例如茎、叶、块茎、种子、果实、谷粒,可以在新鲜采收时或在通过(预)干燥、润湿、粉碎、研磨、压榨或烘烤加工后进行保护。贮存物还包括木材,为未加工的,例如建筑木材、电线杆和栅栏,或以成品形式,例如家具。动物来源的贮存物为例如兽皮、皮革、毛皮和毛发。式(I)的化合物和包含其的组合物可以预防多种不良效果,例如腐烂、腐坏、变色、褪色或发霉。
能够降解或改变工业材料的微生物包括,例如细菌、真菌、酵母菌、藻类和粘质生物体。式(I)的化合物和包含其的组合物优选抗真菌,尤其是霉菌、木材变色菌(wood-discoloring fungi)和腐木菌(wood-destroying fungi)(子囊菌、担子菌、半知菌和接合菌),以及抗粘质生物体和藻类。实例包括以下属的微生物:链格孢属,例如细链格孢(Alternaria tenuis);曲霉属,例如黑曲霉(Aspergillus niger);毛壳菌属(Chaetomium),例如球毛壳(Chaetomium globosum);粉孢革菌属(Coniophora),例如粉孢革菌(Coniophora puetana);香燕菌属(Lentinus),例如虎皮香燕菌(Lentinustigrinus);青霉菌属,例如灰绿青霉(Penicillium glaucum);多孔菌属(Polyporus),例如变色多孔菌(Polyporus versicolor);短梗霉属(Aureobasidium),例如出芽短梗霉(Aureobasidium pullulans);核茎点属(Sclerophoma),例如Sclerophoma pityophila;木霉属(Trichoderma),例如绿色木霉(Trichoderma viride);线嘴壳属(Ophiostoma spp.)、长喙壳属(Ceratocystis spp.)、霉属(Humicola spp.)、彼得壳属(Petriella spp.)、毛束霉属(Trichurus spp.)、革盖菌属(Coriolus spp.)、粘褶菌属(Gloeophyllum spp.)、侧耳属(Pleurotus spp.)、卧孔菌属(Poria spp.)、干朽菌属(Serpula spp.)和干酪菌属(Tyromyces spp.)、枝孢菌属、拟青霉属(Paecilomyces spp.)、毛霉属(Mucor spp.)、埃希氏菌属(Escherichia),例如大肠杆菌(Escherichia coli);假单胞菌属(Pseudomonas),例如绿脓假单胞菌(Pseudomonas aeruginosa);葡萄球菌属(Staphylococcus),例如金黄色酿脓葡萄球菌(Staphylococcus aureus)、假丝酵母属(Candida spp.)和酵母属(Saccharomyces spp.),例如酿酒酵母(Saccharomyces cerevisae)。
种子处理
式(I)的化合物和包含其的组合物还可用于保护种子免受不想要的微生物,例如植物病原性微生物,例如植物病原性真菌或植物病原性卵菌的侵袭。本文中使用的术语种 子包括休眠的种子、经催芽的种子、已发芽的种子和具有长出的根和叶的种子。
因此,本发明还涉及一种用于保护种子免受不想要的微生物侵袭的方法,该方法包括使用式(I)的化合物或包含其的组合物处理种子的步骤。
使用式(I)的化合物或包含其的组合物处理种子不仅保护种子,还保护发芽植物、幼苗和经处理的种子出苗后的植物,使其免受植物病原性微生物的侵袭。因此,本发明还涉及一种用于保护种子、发芽植物和幼苗的方法。
可在播种前、播种时或其后不久进行种子处理。
当在播种前进行种子处理时(例如,所谓的拌种应用),可如下进行种子处理:可将种子置于具有所需量的式(I)的化合物或包含其的组合物的混合器中,混合种子和式(I)的化合物或包含其的组合物,直至实现在种子上的均匀分布。如果合适,然后可以干燥种子。
本发明还涉及使用式(I)的化合物或包含其的组合物处理的种子。
优选地,在其足够稳定使得在处理期间不发生损害的状态下处理种子。通常,可在采收和播种后不久之间的任意时间处理种子。通常使用已从植物中分离出来并且已经除去穗轴、外壳、茎、表皮、绒毛或果肉的种子。例如,可使用已经采收、清洁并且干燥至含水量小于15重量%的种子。或者,也可使用例如干燥后用水处理然后再干燥的种子,或刚引发后的种子,或以催芽条件储存的种子或预发芽的种子,或在育苗盘、育苗带或育苗纸上播种的种子。
施用至种子的式(I)的化合物或包含其的组合物的量通常为,使得种子的发芽不受损害,或所得植物不受损害。特别是在式(I)的化合物在某些施用率下会表现出植物毒性效应的情况下,必须确保这一点。当确定施用至种子的式(I)的化合物的量时,还应当考虑转基因植物的固有表现型,以使用最小量的化合物实现最佳的种子和发芽植物保护。
式(I)的化合物可以其自身形式直接施用至种子,即,不使用任何其他组分,并且不经稀释。还可将包含一种或多种式(I)的化合物的组合物施用至种子。
式(I)的化合物和包含其的组合物适于保护任意植物品种的种子。优选的种子为谷类(例如小麦、大麦、黑麦、粟、黑小麦和燕麦)、油菜、玉米、棉花、大豆、稻、马铃薯、向日葵、菜豆、咖啡、豌豆、甜菜(例如糖用甜菜和饲用甜菜)、花生、蔬菜(例如西红柿、黄瓜、洋葱和莴苣)、草坪植物和观赏植物的种子。更优选小麦、大豆、油菜、玉米和稻的种子。
式(I)的化合物和包含其的组合物可用于处理转基因种子,特别是能够表达抗害虫、抗除草损害或抗非生物胁迫的多肽或蛋白从而增加保护作用的植物的种子。能够表达抗害虫、抗除草损害或抗非生物胁迫的多肽或蛋白的植物的种子可含有至少一种异源基因,该异源基因允许表达所述多肽或蛋白。转基因种子中的这些异源基因可源于例如以下微生物菌属:芽孢杆菌属(Bacillus)、根瘤菌属(Rhizobium)、假单胞菌属(Pseudomonas)、沙雷氏菌属(Serratia)、木霉菌属、棒形杆菌属(Clavibacter)、球囊霉属(Glomus)或粘帚霉属(Gliocladium)。这些异源基因优选来源于芽孢杆菌属(Bacillus sp.),在这种情况下,基因产物可以有效抵抗欧洲玉米螟和/或西方玉米根虫。特别优选地,所述异源基因来源于苏云金芽孢杆菌(Bacillus thuringiensis)。
应用
式(I)的化合物可以其本身的形式应用,或例如以可即用的溶液剂、乳液剂、水基悬浮剂或油基悬浮剂、粉剂、可湿性粉剂、糊剂、可溶性粉剂、尘剂、可溶性颗粒剂、可传播颗粒剂、悬乳浓缩剂、经式(I)的化合物浸渍的天然产物、经式(I)的化合物浸渍的合成物质、肥料或聚合物质中的微胶囊剂的形式应用。
以常规方式完成施用,例如通过灌溉、喷洒、雾化、撒播、粉化、发泡、涂抹等。也可通过超低容量法、通过滴灌系统或灌溉施用来施用式(I)的化合物,将其施用于垄沟内或将其注入到土壤茎(soil stem)或植物躯干(trunk)中。还可通过植物创伤包扎物(woundseal)、敷料(paint)或其他创伤敷料(wound dressing)来施用式(I)的化合物。
施用至植物、植物部位、果实、种子或土壤的式(I)的化合物的有效且植物相容的量取决于多种因素,例如使用的化合物/组合物、处理对象(植物、植物部位、果实、种子或土壤)、处理类型(粉化、喷洒、拌种)、处理目的(治疗性的和保护性的)、微生物的类型、微生物的发育阶段、微生物的敏感性、作物生长阶段和环境条件。
当使用式(I)的化合物作为杀真菌剂时,施用率可根据施用的种类而在相对宽的范围内变化。对于植物部位如叶的处理,施用率范围可以为0.1-10000g/ha、优选10-1000g/ha、更优选50-300g/ha(在通过灌溉或滴灌施用的情况下,甚至可降低施用率,尤其是当使用惰性物质如岩棉或珍珠岩时)。对于种子的处理,施用率范围可以为0.1-200g/100kg种子、优选1-150g/100kg种子、更优选2.5-25g/100kg种子、甚至更优选2.5-12.5g/100kg种子。对于土壤的处理,施用率范围可以为0.1-10000g/ha、优选1-5000g/ha。
这些施用率仅仅是示例,并且不意图限制本发明的范围。
可根据以下实施例进一步理解本教导的各个方面,所述实施例不应被解释为以任何方式限制本教导的范围。
实施例
表1以非限制性方式说明了本发明式(I)的化合物的实施例:
下文表1中提及的式(I)的化合物根据下文结合具体实施例详述的程序和文中所公开方法的一般描述制备。
在表1中,除非另有说明,M+H(ApcI+)意指通过正大气压化学电离在质谱中观察到的分子离子峰加上1a.m.u.(原子质量单位)。
在表1中,使用下文所述方法根据EEC Directive 79/831 Annex V.A8通过反相色谱柱(C 18)上的HPLC(高效液相色谱)测定logP值:
温度:40℃;流动相:0.1%的甲酸水溶液和乙腈;线性梯度为10%乙腈至95%乙腈;
使用具有已知logP值的直链的烷-2-酮(包括3至16个碳原子)进行校准(使用两种连续的烷酮之间的线性内插法通过保留时间测定logP值)。使用200nm至400nm的UV-光谱和色谱信号的峰值测定λ最大值。
在表1中,(X)n残基与苯环的连接点基于苯环的上述编号。
表2以非限制性方式说明了本发明式(IIa)的化合物及其可接受的盐:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义,U1a表示氯原子、溴原子或碘原子。
在表2中,M+H(ApcI+)和logP如表1所定义。
在表2中,(X)n残基与苯环的连接点基于苯环的上述编号。
表2:
表3以非限制性方式说明了本发明式(V)的化合物及其可接受的盐:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如文中所定义。
在表3中,M+H(ApcI+)和logP如表1所定义。
在表3中,(X)n残基与苯环的连接点基于苯环的上述编号。
表3:
表4提供了表1中所选定数量的化合物的NMR数据(1H)。
以1H-NMR峰列表的形式说明所选实施例的1H-NMR数据。对于每个信号峰,列出了以ppm计的λ值和括号中的信号强度。
尖峰信号的强度与NMR谱的打印实施例中的以cm计的信号高度相关并且显示了信号强度的真实关系。从宽信号中,可以显示几个峰或信号的中间部分以及它们与谱图中的最强信号相比的相对强度。
1H-NMR峰列表与常规的1H-NMR打印件相似,因此通常包含在常规的NMR说明中列出的所有峰。此外,与常规的1H-NMR打印件一样,它们可以显示溶剂的信号、同样是本发明目的的目标化合物的立体异构体的信号和/或杂质峰的信号。为显示在溶剂和/或水的δ-范围内的化合物信号,在1H-NMR峰列表中示出了常见的溶剂峰,例如DMSO于d6-DMSO中的峰和水的峰,并且平均来看通常具有高的强度。
目标化合物的立体异构体的峰和/或杂质的峰通常具有比目标化合物(例如纯度>90%)的峰平均更低的强度。这样的立体异构体和/或杂质可以是特定的制备方法所特有的。因此,它们的峰可以通过“副产物指纹(side-products-fingerprints)”帮助识别对制备方法的再现性。
使用已知方法(MestreC、ACD模拟,以及使用经验估算的预期值)计算目标化合物的峰的专业人员可视需要任选地使用额外的强度过滤器来分离目标化合物的峰。这种分离与常规的1H-NMR说明中的挑选相关峰类似。
可在研究公开数据库(the Research Disclosure Database)第564025号的出版物“专利申请中的NMR峰列表数据的引用(Citation of NMR Peaklist Data withinPatent Applications)”中找到峰列表的NMR-数据说明的其他详细信息。
表4:NMR峰列表
制备实施例
制备实施例1:2-甲基-3-{2-[(三甲基甲硅烷基)甲基]苯氧基}喹啉(化合物I.05)的制备
在氩气密封的干燥的RadleysTM瓶中,将150mg(0.47mmol)的3-(2-溴苯氧基)-2-甲基喹啉和153mg(0.71mmol)的三甲基[(4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷-2-基)-甲基]硅烷的混合物在3mL的四氢呋喃中的溶液与0.5mL的溶有36mg(0.048mmol)的1,1’-双(二苯基-膦基)二茂铁氯化钯(II)和466mg(1.43mmol)的碳酸铯的水溶液一起在80℃下加热60小时。将冷却的反应混合物在硅藻土饼上过滤。硅藻土饼用四氢呋喃洗涤,并将有机相在真空下浓缩,得到249mg的残余物。通过硅胶柱色谱法(梯度正庚烷/乙酸乙酯)纯化该残余物,得到33mg(20%)的2-甲基-3-{2-[(三甲基甲硅烷基)甲基]苯氧基}喹啉。LogP=5.05。质量(M+H)=322。
制备实施例2:3-(2-{[二甲基(2-噻吩基)甲硅烷基]甲基}苯氧基)-8-氟喹啉(化合物I.46)的制备
步骤1:3-[2-(溴甲基)苯氧基]-8-氟喹啉的制备
向841mg(3.32mmol)的8-氟-3-(2-甲基苯氧基)喹啉在40mL的四氯化碳的溶液中加入484mg(1.66mmol)的1,3-二溴-5,5-二甲基乙内酰脲和57mg(0.166mmol)的过氧化二苯甲酰(dibenzoylperoxyde)。将反应混合物在回流下加热8小时,同时用荧光灯[G23电灯泡-11W-900流明]照射。将冷却的混合物倾倒在硫代硫酸钠的水溶液上,并用二氯甲烷萃取。将有机相在硫酸镁上干燥,并在真空下浓缩,得到1.26g的油状橙色残余物。通过硅胶柱色谱法(正庚烷/乙酸乙酯97/3)纯化该残余物,得到694mg(62%)的被约10%的3-[2-(二溴甲基)苯氧基]-8-氟喹啉污染的3-[2-(溴甲基)苯氧基]-8-氟喹啉。LogP=3.65。质量(M+H)=322。
步骤2:3-(2-{[二甲基(2-噻吩基)甲硅烷基]甲基}苯氧基)-8-氟喹啉的制备
在氩气下在干燥的RadleysTM瓶中,将100mg(0.30mmol)的3-[2-(溴甲基)苯氧基]-8-氟喹啉、174mg(0.60mm0l)的1,1,2,2-四甲基-1,2-二(2-噻吩基)二硅烷、1.8mg(0.006mmol)的联苯-2-基(二-叔丁基)膦[Johnphos]、2.6mg(0.015mmol)的氯化钯(II)和0.15mL(0.90mmol)的N,N-二异丙基乙胺的混合物在5mL的无水N-甲基吡咯烷酮中的溶液在70℃下加热3小时。将冷却的反应混合物用饱和的LiCl水溶液洗涤,并用乙酸乙酯萃取。将有机萃取物在硫酸镁上干燥。将有机相在真空下浓缩,得到326mg的黑色油状残余物。通过制备型HPLC(梯度乙腈/水+0.1%HCO2H)纯化,得到43mg(36%)的3-(2-{[二甲基(2-噻吩基)甲硅烷基]甲基}苯氧基)-8-氟喹啉。LogP=5.60。质量(M+H)=394。
制备实施例3:[2-氯-6-(喹啉-3-基氧基)苄基](二甲基)硅醇(化合物I.25)的制备
在氩气下在干燥的RadleysTM瓶中,将128mg(0.42mmol)的3-[3-氯-2-(氯甲基)苯氧基]喹啉、179mg(0.84mmol)的1,2-二乙氧基-1,1,2,2-四甲基二硅烷、13mg(0.042mmol)的联苯-2-基(二-叔丁基)膦、3.7mg(0.021mmol)的氯化钯(II)和0.21mL(1.26mmol)的N,N-二异丙基乙胺的混合物在5mL的无水N-甲基吡咯烷酮中的溶液在80℃下加热8小时。将冷却的反应混合物用饱和的LiCl水溶液洗涤,并用乙酸乙酯萃取。将有机萃取物在硫酸镁上干燥。将有机相在真空下浓缩,得到330mg的棕橙色(brown orange)残余物。通过制备型HPLC(梯度乙腈/水+0.1%HCO2H)纯化,得到75mg(49%)的[2-氯-6-(喹啉-3-基氧基)苄基](二甲基)硅醇。LogP=3.48。质量(M+H)=344。
制备实施例4:8-氟-2-甲基-3-{2-[(三甲基甲硅烷基)甲基]苯氧基}喹啉(化合物I.17)的制备
在-78℃下,向0.6mL(0.72mmol)的1.2M的三甲基甲硅烷基氯化镁的四氢呋喃溶液中加入0.9mL(0.63mmol)的0.7M的氯化锌的四氢呋喃溶液。将溶液在-78℃下搅拌1小时。另外加入100mg(0.3mmol)的3-(2-溴苯氧基)-8-氟-2-甲基-喹啉、13.7mg(0.015mmol)的三(二亚苄基丙酮)二钯和8.7mg(0.03mmol)的三叔丁基四氟硼酸鏻,并将混合物缓慢升回至室温,然后在100℃下加热1小时。将冷却的反应混合物在硅藻土饼上过滤,并在真空下浓缩。将残余物用水稀释,用乙酸乙酯萃取,并在硫酸镁上干燥。将有机相在真空下浓缩,得到150mg的棕色油。通过硅胶柱色谱法(正庚烷/乙酸乙酯90/10)纯化该残余物,得到80mg(78%)的8-氟-2-甲基-3-{2-[(三甲基甲硅烷基)甲基]苯氧基}喹啉。LogP=5.85。质量(M+H)=340。
生物学数据
实施例A:对稻梨孢的体外细胞试验
溶剂:二甲基亚砜
培养基:14.6g无水D-葡萄糖(VWR),
7.1g真菌学蛋白胨(Oxoid),
1.4g颗粒状酵母提取物(Merck),QSP 1升
接种体:孢子悬浮液
将试验化合物溶于二甲基亚砜中,并使用该溶液制备所需浓度范围的溶液。试验中使用的二甲基亚砜的最终浓度≤1%。
制备稻梨孢的孢子悬浮液并稀释至所需的孢子密度。
评估化合物在液体培养试验中抑制孢子萌发和菌丝生长的能力。将化合物以所需浓度加入到具有孢子的培养基中。温育5天后,通过菌丝生长的光谱测量来测定化合物的真菌-毒性。通过比较含有杀真菌剂的孔中的吸光度值与没有杀真菌剂的对照孔中的吸光度来确定对真菌生长的抑制。
在该试验中,本发明的以下化合物在20ppm的活性成分浓度下显示出70-79%的功效:I.43、I.51、I.55、I.58、I.61、I.63、I.64
在该试验中,本发明的以下化合物在20ppm的活性成分浓度下显示出80-89%的功效:I.08、I.15、I.26、I.33、I.35、I.38、I.45、I.48、I.60、I.65
在该试验中,本发明的以下化合物在20ppm的活性成分浓度下显示出90-100%的功效:I.01、I.02、I.03、I.04、I.05、I.06、I.07、I.09、I.10、I.11、I.12、I.13、I.14、I.16、I.18、I.19、I.20、I.23、I.28、I.29、I.30、I.31、I.32、I.34、I.37、I.39、I.40、I.42、I.44、I.46、I.50、I.52、I.54、I.59
实施例B:对菜豆炭疽菌的体外细胞试验
溶剂:二甲基亚砜
培养基:14.6g无水D-葡萄糖(VWR),
7.1g真菌学蛋白胨(Oxoid),
1.4g颗粒状酵母提取物(Merck),QSP 1升
接种体:孢子悬浮液
将试验化合物溶于二甲基亚砜中,并使用该溶液制备所需浓度范围的溶液。试验中使用的二甲基亚砜的最终浓度≤1%。
制备菜豆炭疽菌的孢子悬浮液并稀释至所需的孢子密度。
评估化合物在液体培养试验中抑制孢子萌发和菌丝生长的能力。将化合物以所需浓度加入到具有孢子的培养基中。温育5天后,通过菌丝生长的光谱测量来测定化合物的真菌-毒性。通过比较含有杀真菌剂的孔中的吸光度值与没有杀真菌剂的对照孔中的吸光度来确定对真菌生长的抑制。
在该试验中,本发明的以下化合物在20ppm的活性成分浓度下显示出70-79%的功效:I.35、I.39、I.43、I.54、I.62
在该试验中,本发明的以下化合物在20ppm的活性成分浓度下显示出80-89%的功效:I.08、I.12、I.16、I.24、I.26、I.29、I.37、I.41、I.45、I.48、I.57、I.65
在该试验中,本发明的以下化合物在20ppm的活性成分浓度下显示出90-100%的功效:I.01、I.02、I.03、I.04、I.05、I.06、I.07、I.09、I.10、I.11、I.13、I.14、I.15、I.18、I.19、I.20、I.22、I.23、I.25、I.27、I.30、I.32、I.33、I.34、I.40、I.44、I.46、I.47、I.56、I.59、I.60、I.61、I.63、I.64
实施例C:对灰葡萄孢(灰霉)的体内预防性试验
溶剂:5体积% 的二甲基亚砜
10体积% 的丙酮
乳化剂:1μL的80/mg的活性成分
使活性成分可溶并在二甲基亚砜/丙酮//80的混合物中均质化,然后在水中稀释至所需浓度。
通过喷洒如上所述制备的活性成分处理小黄瓜的幼苗。对照植物仅用丙酮/二甲基亚砜/80的水溶液处理。
在24小时后,通过用灰葡萄孢孢子的水悬浮液喷洒叶面来侵染植物。将被侵染的小黄瓜植物在17℃和90%的相对湿度下温育4至5天。
接种4至5天后对试验进行评估。0%意指相当于对照植物的功效的功效,而100%的功效意指没有观察到病害。
在该试验中,本发明的以下化合物在500ppm的活性成分浓度下显示出70-79%的功效:I.01、I.40
在该试验中,本发明的以下化合物在500ppm的活性成分浓度下显示出80-89%的功效:I.32、I.63
在该试验中,本发明的以下化合物在500ppm的活性成分浓度下显示出90-100%的功效:I.02、I.05、I.07、I.10、I.11、I.12、I.13、I.14、I.17、I.18、I.20、I.22、I.24、I.25、I.26、I.27、I.31、I.33、I.34、I.44、I.46、I.47、I.56、I.60、I.61
实施例D:对菜豆炭疽菌(大豆叶斑病)的体内预防性试验
溶剂:5体积% 的二甲基亚砜
10体积% 的丙酮
乳化剂:1μL的80/mg的活性成分
使活性成分可溶并在二甲基亚砜/丙酮//80的混合物中均质化,然后在水中稀释至所需浓度。
通过喷洒如上所述制备的活性成分处理大豆幼苗。对照植物仅用丙酮/二甲基亚砜/80的水溶液处理。
在24小时后,通过用菜豆炭疽菌孢子的含水悬浮液喷洒叶面来侵染植物。将被侵染的大豆植物在20℃和100%的相对湿度下温育24小时,然后在20℃和90%的相对湿度下温育6天。
接种7天后对试验进行评估。0%意指相当于对照植物的功效的功效,而100%的功效意指没有观察到病害。
在该试验中,本发明的以下化合物在500ppm的活性成分浓度下显示出70-79%的功效:I.32、I.33、I.56、I.64
在该试验中,本发明的以下化合物在500ppm的活性成分浓度下显示出80-89%的功效:I.11、I.22、I.31、I.38、I.40
在该试验中,本发明的以下化合物在500ppm的活性成分浓度下显示出90-100%的功效:I.05、I.06、I.10、I.13、I.14、I.17、I.19、I.20、I.25、I.27、I.44、I.46、I.47、I.51、I.61
实施例E:对苹果黑星病菌(苹果)的体内预防性试验
溶剂:24.5重量份的丙酮
24.5重量份的二甲基乙酰胺
乳化剂:1重量份的烷基芳基聚乙二醇醚
为制备合适的活性成分制剂,将1重量份的活性成分与所述量的溶剂和乳化剂混合,并用水将浓液稀释至所需浓度。
为测试预防活性,用活性成分制剂以指定的施用率喷洒幼苗。在喷洒涂层干燥后,给植物接种苹果黑星病的病原体(苹果黑星菌)的水性孢子悬浮液,然后将植物在约20℃和100%的相对大气湿度的培养箱中保持1天。
然后将植物置于约21℃和约90%的相对大气湿度的温室中。
接种10天后对试验进行评估。0%意指相当于未处理的对照组的功效的功效,而100%的功效意指没有观察到病害。
在该试验中,本发明的以下化合物在250ppm的活性成分浓度下显示出90-100%的功效:I.31
实施例F:对圆核腔菌(大麦)的体内预防性试验
溶剂:49重量份的N,N-二甲基乙酰胺
乳化剂:1重量份的烷基芳基聚乙二醇醚
为制备合适的活性成分制剂,将1重量份的活性成分与所述量的溶剂和乳化剂混合,并用水将浓液稀释至所需浓度。
为测试预防活性,用活性成分制剂以指定的施用率喷洒幼苗。在喷洒涂层干燥后,给植物接种圆核腔菌的孢子悬浮液,然后将植物在约20℃和100%的相对大气湿度的培养箱中保持48小时。
然后将植物置于约20℃的温度和约80%的相对大气湿度的温室中。
接种8天后对试验进行评估。0%意指相当于未处理的对照组的功效的功效,而100%的功效意指没有观察到病害。
在该试验中,本发明的以下化合物在500ppm的活性成分浓度下显示出70-79%的功效:I.13、I.18。
Claims (15)
1.式(I)的化合物及其盐、N-氧化物、金属络合物、类金属络合物和光学活性异构体或几何异构体
其中
·Z选自氢原子、卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C2-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基、芳基、杂环基、甲酰基、C1-C8-烷基羰基、(羟基亚氨基)C1-C8-烷基、(C1-C8-烷氧基亚氨基)C1-C8-烷基、羧基、C1-C8-烷氧基羰基、氨基甲酰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、氨基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、硫烷基、C1-C8-烷基硫烷基、C1-C8-烷基亚磺酰基、C1-C8-烷基磺酰基、C1-C6-三烷基甲硅烷基、氰基和硝基,
其中所述C1-C8-烷基、C2-C8-烯基、C2-C8-炔基和C1-C8-烷氧基可以被一个或多个Za取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基可以被一个或多个Zb取代基取代;
·n表示0、1、2、3或4;
·L表示O、S、SO、SO2、CR4R5或NR6,其中
οR4和R5独立地选自氢原子、卤素原子、羟基、C1-C8烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C1-C8-烷氧基和包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基,或它们可与它们连接的碳原子一起形成羰基;
οR6选自氢原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C3-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C3-C8-卤代炔基、C3-C7-环烷基、包含最高达9个可以相同或不同的卤素原子的C3-C7-卤代环烷基、C3-C7-环烷基-C1-C8-烷基、甲酰基、C1-C8-烷基羰基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基羰基、C1-C8-烷氧基羰基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基羰基、C1-C8-烷基磺酰基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基磺酰基、芳基-C1-C8-烷基和苯基磺酰基,其中所述C1-C8-烷基、C2-C8-烯基、C3-C8-炔基可以被一个或多个R6a取代基取代,并且其中所述C3-C7-环烷基、C3-C7-环烷基-C1-C8-烷基、芳基-C1-C8-烷基和苯基磺酰基可以被一个或多个R6b取代基取代;X独立地选自卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C2-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基、C1-C6-三烷基甲硅烷基、C1-C6-三烷基甲硅烷基甲基、氰基和硝基,其中所述C1-C8-烷基、C2-C8-烯基、C2-C8-炔基和C1-C8-烷氧基可以被一个或多个Xa取代基取代,并且所述C3-C7-环烷基和C4-C7-环烯基可以被一个或多个Xb取代基取代;
·W为CY1或N,其中:
-Y1选自氢原子、卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C2-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基、芳基、杂环基、甲酰基、C1-C8-烷基羰基、(羟基亚氨基)C1-C8-烷基、(C1-C8-烷氧基亚氨基)C1-C8-烷基、羧基、C1-C8-烷氧基羰基、氨基甲酰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、氨基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、硫烷基、C1-C8-烷基硫烷基、C1-C8-烷基亚磺酰基、C1-C8-烷基磺酰基、C1-C6-三烷基甲硅烷基、氰基和硝基,
其中所述C1-C8-烷基、C2-C8-烯基、C2-C8-炔基和C1-C8-烷氧基可以被一个或多个Y1a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基可以被一个或多个Y1b取代基取代;
·Y2、Y3、Y4和Y5独立地选自氢原子、卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代烯基、C2-C8-炔基、包含最高达9个可以相同或不同的卤素原子的C2-C8-卤代炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷氧基、芳基、杂环基、甲酰基、C1-C8-烷基羰基、(羟基亚氨基)C1-C8-烷基、(C1-C8-烷氧基亚氨基)C1-C8-烷基、羧基、C1-C8-烷氧基羰基、氨基甲酰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、氨基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、硫烷基、C1-C8-烷基硫烷基、C1-C8-烷基亚磺酰基、C1-C8-烷基磺酰基、C1-C6-三烷基甲硅烷基、氰基和硝基,其中所述C1-C8-烷基、C2-C8-烯基、C2-C8-炔基和C1-C8-烷氧基分别可以被一个或多个Y2a、Y3a、Y4a或Y5a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基分别可以被一个或多个Y2b、Y3b、Y4b或Y5b取代基取代;
·R1选自C1-C8-烷基、C2-C8-烯基、C2-C8-炔基、C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基,
其中所述C1-C8-烷基、C2-C8-烯基和C2-C8-炔基可以被一个或多个R1a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基可以被一个或多个R1b取代基取代;
·R2选自羟基、C1-C8-烷氧基、C1-C8-烷基、C2-C8-烯基、C2-C8-炔基、C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基,其中所述C1-C8-烷氧基、C1-C8-烷基、C2-C8-烯基和C2-C8-炔基可以被一个或多个R2a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基和杂环基可以被一个或多个R2b取代基取代;
·当R1和R2表示C1-C8烷基或C2-C8烯基时,它们可以与它们连接的硅原子一起形成C3-C8-硅杂环烷基环或C4-C8-硅杂环烯基环,其中所述C3-C8-硅杂环烷基环或C4-C8-硅杂环烯基环可以被一个或多个R1b取代基取代;
·R3选自氢原子、卤素原子、C1-C8-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基、C2-C8-烯基、C2-C8-炔基、C3-C7-环烷基、C4-C7-环烯基、羟基、C1-C8-烷氧基、芳基、芳基-C1-C8-烷基、杂环基、杂环基-C1-C8-烷基、羟基-C1-C8-烷基、C1-C8-烷氧基-C1-C8-烷基、C1-C8-烷基羰基氧基-C1-C8-烷基、芳氧基-C1-C8-烷基、杂环氧基-C1-C8-烷基、氨基-C1-C8-烷基、C1-C8-烷基氨基-C1-C8-烷基、二-C1-C8-烷基氨基-C1-C8-烷基、芳基氨基-C1-C8-烷基、二-芳基氨基-C1-C8-烷基、杂环基氨基-C1-C8-烷基、C1-C8-烷基羰基氨基-C1-C8-烷基、C1-C8-烷氧基羰基氨基-C1-C8-烷基、C1-C8-烷基硫烷基-C1-C8-烷基、C1-C8-烷基亚磺酰基-C1-C8-烷基、C1-C8-烷基磺酰基-C1-C8-烷基和氰基-C1-C8-烷基,
其中所述C1-C8-烷基、C2-C8-烯基和C2-C8-炔基可以被一个或多个R3a取代基取代,并且其中所述C3-C7-环烷基、C4-C7-环烯基、芳基、芳基-C1-C8-烷基、杂环基、杂环基-C1-C8-烷基、芳氧基-C1-C8-烷基和杂环氧基-C1-C8-烷基可以被一个或多个R3b取代基取代;
·当所述X与CH2-SiR1R2R3相邻时,R3和X可以与它们分别连接的硅原子和碳原子一起形成5-、6-或7-元的部分饱和的杂环,其中所述5-、6-或7-元的部分饱和的杂环可以被一个或多个R3b取代基取代;
·当R2表示C1-C8-烷氧基且R3表示C1-C8-烷氧基或C1-C8烷基时,它们可以与它们连接的硅原子一起形成5-、6-或7-元的杂环,其中所述5-、6-或7-元的杂环可以被一个或多个R2b取代基取代;
·Za、R1a、R2a、R3a、R6a、Xa、Y1a、Y2a、Y3a、Y4a和Y5a独立地选自硝基、羟基、氰基、羧基、氨基、硫烷基、五氟-λ6-硫烷基、甲酰基、氨基甲酰基、氨基甲酸酯基、C3-C7-环烷基、具有1至5个卤素原子的C3-C8-卤代环烷基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、C1-C8-烷氧基、具有1至5个卤素原子的C1-C8-卤代烷氧基、C1-C8-烷基硫烷基、具有1至5个卤素原子的C1-C8-卤代烷基硫烷基、C1-C8-烷基羰基、具有1至5个卤素原子的C1-C8-卤代烷基羰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、C1-C8-烷氧基羰基、具有1至5个卤素原子的C1-C8-卤代烷氧基羰基、C1-C8-烷基羰基氧基、具有1至5个卤素原子的C1-C8-卤代烷基羰基氧基、C1-C8-烷基羰基氨基、具有1至5个卤素原子的C1-C8-卤代烷基羰基氨基、C1-C8-烷基亚磺酰基、具有1至5个卤素原子的C1-C8-卤代烷基亚磺酰基、C1-C8-烷基磺酰基和具有1至5个卤素原子的C1-C8-卤代烷基磺酰基;
·Zb、R1b、R2b、R3b、R6b、Xb、Y1b、Y2b、Y3b、Y4b和Y5b独立地选自卤素原子、硝基、羟基、氰基、羧基、氨基、硫烷基、五氟-λ6-硫烷基、甲酰基、氨基甲酰基、氨基甲酸酯基、C1-C8-烷基、C3-C7-环烷基、具有1至5个卤素原子的C1-C8-卤代烷基、具有1至5个卤素原子的C3-C8-卤代环烷基、C2-C8-烯基、C2-C8-炔基、C1-C8-烷基氨基、二-C1-C8-烷基氨基、C1-C8-烷氧基、具有1至5个卤素原子的C1-C8-卤代烷氧基、C1-C8-烷基硫烷基、具有1至5个卤素原子的C1-C8-卤代烷基硫烷基、C1-C8-烷基羰基、具有1至5个卤素原子的C1-C8-卤代烷基羰基、C1-C8-烷基氨基甲酰基、二-C1-C8-烷基氨基甲酰基、C1-C8-烷氧基羰基、具有1至5个卤素原子的C1-C8-卤代烷氧基羰基、C1-C8-烷基羰基氧基、具有1至5个卤素原子的C1-C8-卤代烷基羰基氧基、C1-C8-烷基羰基氨基、具有1至5个卤素原子的C1-C8-卤代烷基羰基氨基、C1-C8-烷基硫烷基、具有1至5个卤素原子的C1-C8-卤代烷基硫烷基、C1-C8-烷基亚磺酰基、具有1至5个卤素原子的C1-C8-卤代烷基亚磺酰基、C1-C8-烷基磺酰基和具有1至5个卤素原子的C1-C8-卤代烷基磺酰基。
2.根据权利要求1所述的式(I)的化合物,其中Z选自氢原子、卤素原子、羟基、C1-C6-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基、C1-C6-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷氧基和氰基。
3.根据权利要求1或2所述的式(I)的化合物,其中L为O、N或CH2。
4.根据前述权利要求中任一项所述的式(I)的化合物,其中X独立地为卤素原子、C1-C6-烷基或C1-C6-三烷基甲硅烷基甲基。
5.根据前述权利要求中任一项所述的式(I)的化合物,其中Y1、Y2、Y3、Y4或Y5独立地选自氢原子、卤素原子、C1-C6-烷基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷基、C1-C6-烷氧基、包含最高达9个可以相同或不同的卤素原子的C1-C6-卤代烷氧基和氰基。
6.根据前述权利要求中任一项所述的式(I)的化合物,其中R1和/或R2为C1-C6-烷基。
7.根据前述权利要求中任一项所述的式(I)的化合物,其中R3选自羟基、C1-C6-烷基、C2-C6-烯基、C1-C6-烷氧基、可以被一个或多个R3b取代的芳基、芳基-C1-C6-烷基、杂环基和杂环基-C1-C6-烷基。
8.根据前述权利要求中任一项所述的式(I)的化合物,其中W为CY1,Y1如权利要求1或5中所述。
9.根据权利要求1至7中任一项所述的式(I)的化合物,其中W为N。
10.组合物,其包含一种或多种根据权利要求1至9中任一项所述的式(I)的化合物和至少一种农业上合适的助剂。
11.防治不想要的植物病原性微生物的方法,包括将一种或多种根据权利要求1至9中任一项所述的式(I)的化合物或根据权利要求10的组合物施用至微生物和/或其生境的步骤。
12.制备根据权利要求1至9中任一项所述的式(I)的化合物的步骤,包括使式(II)的卤代甲基芳基或其盐中的一种与式(IIIa)的二甲硅烷基衍生物反应的步骤:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如权利要求1中所述,U1表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基,
其中R1、R2和R3如权利要求1中所述。
13.制备根据权利要求1至9中任一项所述的式(I)的化合物的方法,包括以下步骤:
(a)使式(VI)的化合物或其盐中的一种与式(IIIb)的硼衍生物反应:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如权利要求1中所述,U2表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基,
其中W3表示硼衍生物;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;且
R3表示氢原子或C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;或
(b)使式(VI)的化合物或其盐中的一种与式(IIIc)的衍生物反应:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如权利要求1中所述,U2表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基,
其中M1表示碱金属或过渡金属;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;和
R3表示氢原子或C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;或
(c)使式(VIII)的化合物或其盐中的一种与式(IX)的化合物反应:
其中L表示O、S或NR6;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;
R3表示氢原子或C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;且
U3表示氯原子、溴原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基;或
(d)使式(VIII)的化合物或其盐中的一种与式(IX)的化合物反应:
其中L表示O、S或NR6;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;和
R3表示氢原子或C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;或
(e)使式(X)的化合物或其盐中的一种与式(XI)的化合物反应:
其中L表示CR4R5;
R4和R5独立地表示氢原子或C1-C8烷基;
U4表示溴原子、氯原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基;
W1表示硼衍生物;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;和
R3表示氢原子;C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;或
(f)使式(VIII)的化合物或其盐中的一种与式(XII)的化合物反应:
其中L表示CR4R5;
R1和R2独立地表示C1-C8-烷基、C2-C8-烯基、C3-C7-环烷基、芳基或杂环基;
R3表示氢原子或C1-C8-烷基;包含最高达9个可以相同或不同的卤素原子的C1-C8-卤代烷基;C2-C8-烯基;C2-C8-炔基;C3-C7-环烷基;C4-C7-环烯基;芳基;芳基-C1-C8-烷基;C1-C8-烷氧基;杂环基;杂环基-C1-C8-烷基;羟基-C1-C8-烷基;C1-C8-烷氧基-C1-C8-烷基;C1-C8-烷基羰基氧基-C1-C8-烷基;芳氧基-C1-C8-烷基;杂环氧基-C1-C8-烷基;氨基-C1-C8-烷基;C1-C8-烷基氨基-C1-C8-烷基;二-C1-C8-烷基氨基-C1-C8-烷基;芳基氨基-C1-C8-烷基;二-芳基氨基-C1-C8-烷基;杂环基氨基-C1-C8-烷基;C1-C8-烷基羰基氨基-C1-C8-烷基;C1-C8-烷氧基羰基氨基-C1-C8-烷基;C1-C8-烷基硫烷基-C1-C8-烷基;C1-C8-烷基亚磺酰基-C1-C8-烷基;C1-C8-烷基磺酰基-C1-C8-烷基或氰基-C1-C8-烷基;
R4和R5独立地表示氢原子、C1-C8-烷氧基或C1-C8烷基;
U3表示溴原子、氯原子、碘原子、甲磺酰基、甲苯磺酰基或三氟甲磺酰基;且
W2表示硼衍生物。
14.式(IIa)的化合物及其可接受的盐:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如权利要求1中所述,U1a表示氯原子、溴原子或碘原子。
15.式(V)的化合物及其可接受的盐:
其中L、n、X、Y1、Y2、Y3、Y4、Y5、W和Z如权利要求1中所述,
条件是式(V)的化合物不表示:
-{2-溴-6-[(8-氟喹啉-3-基)氧基]苯基}甲醇[1314009-28-3],和
-{2-氯-6-[(8-氟喹啉-3-基)氧基]苯基}甲醇[1314009-25-0]。
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