CN102458119A - 协同增效杀真菌混合物 - Google Patents
协同增效杀真菌混合物 Download PDFInfo
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- CN102458119A CN102458119A CN2010800246035A CN201080024603A CN102458119A CN 102458119 A CN102458119 A CN 102458119A CN 2010800246035 A CN2010800246035 A CN 2010800246035A CN 201080024603 A CN201080024603 A CN 201080024603A CN 102458119 A CN102458119 A CN 102458119A
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- Prior art keywords
- methyl
- pyrazol
- yls
- piperidyls
- acetyl group
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- AKTQJCBOGPBERP-UHFFFAOYSA-N triflusulfuron Chemical compound FC(F)(F)COC1=NC(N(C)C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2C)C(O)=O)=N1 AKTQJCBOGPBERP-UHFFFAOYSA-N 0.000 description 1
- IMEVJVISCHQJRM-UHFFFAOYSA-N triflusulfuron-methyl Chemical group COC(=O)C1=CC=CC(C)=C1S(=O)(=O)NC(=O)NC1=NC(OCC(F)(F)F)=NC(N(C)C)=N1 IMEVJVISCHQJRM-UHFFFAOYSA-N 0.000 description 1
- RVKCCVTVZORVGD-UHFFFAOYSA-N trinexapac-ethyl Chemical group O=C1CC(C(=O)OCC)CC(=O)C1=C(O)C1CC1 RVKCCVTVZORVGD-UHFFFAOYSA-N 0.000 description 1
- NFHRNKANAAGQOH-UHFFFAOYSA-N triphenylstannane Chemical class C1=CC=CC=C1[SnH](C=1C=CC=CC=1)C1=CC=CC=C1 NFHRNKANAAGQOH-UHFFFAOYSA-N 0.000 description 1
- 229960005486 vaccine Drugs 0.000 description 1
- JARYYMUOCXVXNK-CSLFJTBJSA-N validamycin A Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-CSLFJTBJSA-N 0.000 description 1
- DBXFMOWZRXXBRN-LWKPJOBUSA-N valifenalate Chemical compound CC(C)OC(=O)N[C@@H](C(C)C)C(=O)NC(CC(=O)OC)C1=CC=C(Cl)C=C1 DBXFMOWZRXXBRN-LWKPJOBUSA-N 0.000 description 1
- 239000005418 vegetable material Substances 0.000 description 1
- 239000004552 water soluble powder Substances 0.000 description 1
- 239000005943 zeta-Cypermethrin Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
- FJBGIXKIXPUXBY-UHFFFAOYSA-N {2-[3-(4-chlorophenyl)propyl]-2,4,4-trimethyl-1,3-oxazolidin-3-yl}(imidazol-1-yl)methanone Chemical compound C1=CN=CN1C(=O)N1C(C)(C)COC1(C)CCCC1=CC=C(Cl)C=C1 FJBGIXKIXPUXBY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- General Health & Medical Sciences (AREA)
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Abstract
本发明涉及包含式(I)化合物和一种选自如说明书所定义的A’)-C’)组的杀真菌组分II的杀真菌混合物以及包含这些混合物的组合物。
Description
本发明涉及以协同增效有效量包含如下组分作为活性组分的混合物:
1)至少一种式I化合物以及式I化合物的N-氧化物和可农用盐:
其中:
R1为1H-吡唑-1-基或苯基,其中两个上述基团未被取代或带有1或2个相同或不同的取代基Ra;
Ra为卤素、CH3、CH2CH5或CF3;
X为CH或N;
Y为O或S;
A为5员亚杂芳基,其中环成员原子除了碳原子外还包括1个硫原子和1个氮原子或1个氧原子和1个氮原子或2或3个氮原子;
Z为选自-CH2-、-CHOH-和=C=O的二价基团;
R2、R3相互独立地选自氢和CH3;
和
2)至少一种选自A′)-C′)组的杀真菌组分II:
A′)选自isopyrazam和3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(3′,4′,5′-三氟联苯-2-基)酰胺的羧酰苯胺;
B′)5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺;
C′)选自NRRL登录号为B-21661的枯草芽孢杆菌(Bacillus subtilis)菌株AQ713、NRRL登录号为B-30087的短小芽孢杆菌(Bacillus pumilus)菌株以及具有相应菌株的所有识别特性的上述芽孢杆菌属(Bacillus)菌株的突变体或变体的杀真菌菌株,
或由上述芽孢杆菌属菌株的培养得到的培养液或上清液;
或由上述芽孢杆菌属菌株产生的对植物病原性真菌呈现活性的代谢物。
此外,本发明还涉及一种使用式I化合物(本文也称为化合物I)和至少一种杀真菌组分II的混合物防治植物病原性有害真菌的方法,化合物I和杀真菌组分II在制备该类混合物中的用途以及包含这些混合物的组合物和种子。
农业实践经验已经表明在有害真菌的防治中重复和单一地施用单独的活性化合物在许多情况下导致已经对所述活性化合物产生天然或适应的耐受性的那些真菌菌株的快速选择。因此用所述活性化合物有效防治这些真菌不再可能。
为了降低耐受性真菌菌株的选择风险,目前通常将不同活性化合物的混合物用于防治有害真菌。通过组合具有不同作用机理的活性化合物,可以确保在较长时间内的成功防治。
本发明的目的是考虑到在尽可能低的施用率下有效的耐受性管理和对植物病原性有害真菌的有效防治,提供在活性化合物的施用总量降低下对有害真菌具有改进活性和尤其对某些适应症具有拓宽的活性谱的组合物(协同增效混合物)。
因此,我们发现该目的通过本文所定义的包含化合物I和至少一种杀真菌组分II的组合物实现。化合物I可以具有手性中心且可以作为纯的(R)-或(S)-异构体或作为异构体混合物存在。纯异构体及其混合物均与至少一种杀真菌组分II混合构成本发明主题。
此外,我们发现与单独用各化合物可能获得的防治相比,同时,即联合或分开施用化合物I和至少一种杀真菌组分II,或依次使用化合物I和杀真菌组分II允许更好地防治有害真菌(协同增效混合物)。
本发明组合物的化合物I和/或杀真菌组分II可以以生物学活性可能不同的不同晶型存在。
化合物I及其杀真菌活性已经描述于WO 2007/014290、WO2008/091594、WO 2008/091580、WO 2008/090181中。
杀真菌组分II、其制备及其对有害真菌的活性由下列参考文献已知:Isopyrazam为两种顺式异构体3-二氟甲基-1-甲基-N-[(1RS,4SR,9RS)-1,2,3,4-四氢-9-异丙基-1,4-亚甲基萘-5-基]吡唑-4-甲酰胺和两种反式-异构体3-二氟甲基-1-甲基-N-[(1RS,4SR,9SR)-1,2,3,4-四氢-9-异丙基-1,4-亚甲基萘-5-基]吡唑-4-甲酰胺的混合物,由WO 04/035589已知且可以以其中所述或如WO 07/068417所述方式制备。
乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺及其杀真菌活性由WO05/087773已知。
上面称为组分C′)的杀真菌的芽孢杆菌属菌株、其突变体和由所述菌株产生的对植物病原性真菌呈现活性的代谢物、其制备及其对有害真菌的作用由WO 98/50422、WO 00/29426和WO 00/58442已知,在其中也称为AQ713(QST713)和QST2808。这些菌株与在结构上与化合物I不相关的某些化学杀真菌剂的混合物已经在WO 09/037242中提及。
NRRL是美国农业研究菌种保藏中心(the Agricultural ResearchService Culture Collection)的缩写,其为在the BUDAPE ST TREATY ONTHE INTERNATIONAL RECOGNITION OF THE DEPOSIT OFMICROORGANISMS FOR THE PURPOSES OF PATENTPROCEDURE下保藏微生物菌株的国际保藏机构,地址为National Centerfor Agricultural Utilization Research,Agricultural Research Service,U.S.Department ofAgriculture,1815North Universlty Street,Peoria,Illinois61604,USA。
C′)组不仅包括枯草芽孢杆菌菌株和短小芽孢杆菌菌株的分离的纯培养物,而且包括其在全培养液(whole broth culture)中的悬浮液或作为由该菌株的全培养液得到的含代谢物的上清液或提纯的代谢物。
术语“全培养液”是指含有细胞和培养基的液态培养物。术语“上清液”是指当通过离心、过滤、沉降或本领域众所周知的其他方式除去在培养基中生长的细胞时留下的液态培养基。术语“代谢物”是指任何化合物、物质或发酵的副产物或具有杀真菌活性的微生物。
在上面所给变量的定义中,使用通常为所述取代基的代表的集合性术语。
术语“卤素”是指氟、氯、溴和碘。
术语“5员亚杂芳基,其中所述环成员原子除了碳原子外还包括1个硫原子和1个氮原子或1个氧原子和1个氮原子或2或3个氮原子”应理解为指具有两个连接点的芳族杂环。实例包括:1H-吡唑-3,5-二基、1H-吡唑-3,4-二基、1H-吡唑-4,5-二基、1H-吡唑-1,3-二基、1H-吡唑-1,4-二基、唑-2,4-二基、唑-2,5-二基、唑-4,5-二基、噻唑-2,4-二基、噻唑-2,5-二基、噻唑-4,5-二基、咪唑-2,4-二基、咪唑-2,5-二基、咪唑-4,5-二基、1H-[1,3,4]三唑-2,4-二基和1H-[1,2,3]三唑-4,5-二基。
化合物I的可农用盐尤其包括其阳离子和阴离子分别对化合物I的杀真菌作用没有不利影响的那些阳离子的盐或那些酸的酸加成盐。合适的阳离子因此尤其是碱金属的离子,优选钠和钾离子,碱土金属的离子,优选钙、镁和钡离子,过渡金属的离子,优选锰、铜、锌和铁离子,以及还有需要的话可以带有1-4个C1-C4烷基取代基和/或一个苯基或苄基取代基的铵离子,优选二异丙基铵、四甲基铵、四丁基铵、三甲基苄基铵,此外还有离子,锍离子,优选三(C1-C4烷基)锍,以及氧化锍离子,优选三(C1-C4烷基)氧化锍。有用酸加成盐的阴离子主要是氯离子、溴离子、氟离子、硫酸氢根、硫酸根、磷酸二氢根、磷酸氢根、磷酸根、硝酸根、碳酸氢根、碳酸根、六氟硅酸根、六氟磷酸根、苯甲酸根以及C1-C4链烷酸的阴离子,优选甲酸根、乙酸根、丙酸根和丁酸根。它们可以通过使化合物I与对应阴离子的酸,优选盐酸、氢溴酸、硫酸、磷酸或硝酸反应而形成。
在本发明混合物中,作为化合物I优选下列化合物:优选其中各取代基和各变量X、Y、Z、R1、R2、R3和A相互独立地或更优选组合地具有下列含义的那些化合物I:
一个实施方案涉及包含其中R1为1H-吡唑-1-基的化合物I的混合物,其中吡唑基带有1或2个相同或不同的取代基Ra。
另一实施方案涉及包含其中Ra选自CH3和CF3,更优选选自5-CH3和3-CF3,以及尤其是基团R1被5-CH3和3-CF3取代的化合物I的混合物。
本发明的另一实施方案涉及包含其中X为CH的化合物I的混合物。
本发明的另一实施方案涉及包含其中Y为O的化合物I的混合物。
本发明的另一实施方案涉及包含如下化合物I的混合物,其中A选自噻唑-2,4-二基、唑-2,4-二基、1H-吡唑-3,5-二基、1H-吡唑-4,5-二基和1H-[1,2,3]三唑-4,5-二基,优选A为噻唑-2,4-二基,尤其是A为其中2位的碳原子键于变量X且4位的碳原子键于基团C=Y的噻唑-2,4-二基。
另一实施方案涉及包含其中Z为二价基团-CH2-的化合物I的混合物。
另一实施方案涉及包含其中R2和R3均为氢的化合物I的混合物。
另一优选实施方案涉及如下混合物,其中化合物I选自2-[1-[(2,5-二甲基苯基)乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、2-[1-[(2,5-二氯苯基)乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-[(1R)-2,3-二氢-1H-茚-1-基]-N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑硫代甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R,4S)-1,2,3,4-四氢-4-羟基-1-萘基]-4-噻唑甲酰胺及其对映体、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-(1,2,3,4-四氢-2-甲基-1-萘基)-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R,4R)-1,2,3,4-四氢-4-羟基-1-萘基]-4-噻唑甲酰胺及其对映体、2-[1-[[5-乙基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、2-[1-[[3,5-双三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-(1,2,3,4-四氢-4-氧代-1-萘基)-4-噻唑甲酰胺、N-甲基-2-[4-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-1-哌嗪基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-(2,3-二氢-2,2-二甲基-1H-茚-1-基)-N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-4-噻唑甲酰胺、N-(2,3-二氢-2-甲基-1H-茚-1-基)-N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-4-噻唑甲酰胺、N-甲基-1-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-1H-吡唑-3-甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-2H-1,2,3-三唑-4-甲酰胺、N-甲基-1-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-1H-吡唑-4-甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R,2S)-1,2,3,4-四氢-2-甲基-1-萘基]-4-噻唑甲酰胺及其对映体、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-(1,2,3,4-四氢-2,2-二甲基-1-萘基]-4-噻唑甲酰胺、2-[1-[(3,5-二氯-1H-吡唑-1-基)乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、2-[1-[[5-氯-3-三氟甲基-1H-吡唑-1-基]乙酰基)-4-哌啶基)-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基)乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-唑甲酰胺和N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-(1,2,3,4-四氢-1-萘基)-4-噻唑甲酰胺。
特别优选的实施方案涉及其中化合物I为下式的2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(R)-1,2,3,4-四氢萘-1-基酰胺和/或其对映体的混合物:
根据一个实施方案,本发明混合物包含isopyrazam作为组分II。
根据另一实施方案,混合物包含化合物3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(3′,4′,5′-三氟联苯-2-基)酰胺作为组分II。
根据另一实施方案,混合物包含化合物5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺作为组分II。
根据另一实施方案,混合物包含NRRL登录号为B-21661的枯草芽孢杆菌菌株、具有所述菌株的所有识别特性的其突变体或由所述菌株产生的对植物病原性真菌呈现活性的代谢物作为组分II。
本发明混合物和组合物适合作为杀真菌剂。它们的特征在于对宽范围的植物病原性真菌[包括尤其源于根肿菌纲(Plasmodiophoromycetes)、Peronosporomycetes(同义词卵菌纲(Oomycetes))、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)(同义词不完全菌纲(Fungi imperfecti))的土传真菌]具有显著的效力。它们中的一些内吸有效并且可以作为叶面杀真菌剂、拌种用杀真菌剂和土壤杀真菌剂用于作物保护中。此外,它们适合防治尤其出现在木材或植物根部中的有害真菌。
本发明混合物和组合物对于在各种栽培植物如禾谷类,例如小麦、黑麦、大麦、小黑麦、燕麦或稻;甜菜,例如糖用甜菜或饲料甜菜;水果如仁果、核果或浆果,例如苹果、梨、李、桃、杏仁、樱桃、草莓、悬钩子、黑莓或鹅莓;豆科植物,例如扁豆、豌豆、苜蓿或大豆;油料植物,例如油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆;葫芦科植物,例如南瓜、黄瓜或甜瓜;纤维植物,例如棉花、亚麻、大麻或黄麻;柑桔类水果,例如橙子、柠檬、葡萄柚或橘;蔬菜,例如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、葫芦或柿子椒;月桂类植物,例如鳄梨、肉桂或樟脑;能量和原料植物,例如玉米、大豆、油菜、甘蔗或油棕;玉米;烟草;坚果;咖啡;茶;香蕉;葡萄藤(食用葡萄和酿酒用葡萄);啤酒花;草坪;天然橡胶植物或观赏和森林植物,例如花卉、灌木、阔叶树或常绿树如针叶树,以及植物繁殖材料如种子和这些植物的收获材料中防治大量植物病原性真菌特别重要。
优选将本发明混合物和组合物用于在农作物,例如土豆、糖用甜菜、烟草、小麦、黑麦、大麦、燕麦、稻、玉米、棉花、大豆、油菜、豆科植物、向日葵、咖啡或甘蔗;水果;葡萄藤;观赏植物或蔬菜如黄瓜、西红柿、菜豆或南瓜上防治大量真菌。
术语“植物繁殖材料”应理解为表示植物的所有繁殖部分如种子,以及可以用于繁殖植物的无性植物材料如插条和块茎(例如土豆)。这包括种子、根、果实、块茎、球茎、地下茎、枝、芽和其他植物部分,包括在萌发后或出苗后由土壤移植的秧苗和幼苗。这些幼苗还可以在移植之前通过经由浸渍或浇灌的完全或部分处理而保护。
优选分别将本发明化合物I和杀真菌组分II的混合物及其组合物对植物繁殖材料的处理用于在禾谷类作物如小麦、黑麦、大麦和燕麦;稻、玉米、棉花和大豆中防治大量真菌。
术语“栽培植物”应理解为包括已经通过育种、诱变或基因工程修饰的植物,包括但不限于上市销售或开发的农业生物技术产品(参见http://www.bio.org/speeches/pubs/er/agri_products.asp)。基因修饰植物是其基因材料通过使用在自然条件下不易通过杂交、突变或自然重组得到的重组DNA技术修饰的植物。通常将一个或多个基因整合到基因修饰植物的遗传材料中以改善植物的某些性能。这类基因修饰还包括但不限于蛋白质、寡肽或多肽的靶向翻译后修饰,例如通过糖基化或聚合物加成如异戊二烯化、乙酰化或法呢基化结构部分或PEG结构部分。
本发明混合物和组合物特别适合防治下列植物病害:
蔬菜、油菜(例如芸苔生链格孢(A.brassicola)或芸苔链格孢(A.brassicae))、糖用甜菜(A.tenuis)、水果、稻、大豆、土豆(例如早疫链格孢(A.solani)或链格孢(A.alternata))、西红柿(例如早疫链格孢或链格孢)和小麦上的链格孢属(Alternaria)(链格孢叶斑病);平脐蠕孢属(Bipolaris)和内脐蠕孢属(Drechslera)(有性型:旋孢腔菌属(Cochliobolus)),例如玉米上的小斑病(玉蜀黍平脐蠕孢(D.maydis))或大斑病(玉米生离蠕孢(B.zeicola)),例如禾谷类上的斑枯病(麦根腐平脐蠕孢(B.sorokiniana))以及例如稻和草坪上的稻平脐蠕孢(B.oryzae));禾谷类(例如小麦或大麦)上的小麦白粉菌(Blumeria(旧名:Erysiphe)graminis)(白粉病);水果和浆果(例如草莓)、蔬菜(例如莴苣、胡萝卜、根芹菜和卷心菜)、油菜、花卉、葡萄藤、森林植物和小麦上的灰葡萄孢(Botrytis cinerea)(有性型:灰葡萄孢霉(Botryotinia fuckeliana):灰霉病);玉米、禾谷类如大麦(例如大麦网斑内脐蠕孢(D.teres),网斑病)和小麦(例如D.tritici-repentis:褐斑病)、稻和草坪上的内脐蠕孢属(同义词长蠕孢属(Helminthosporium),有性型:核腔菌属(Pyrenophora));葡萄藤上的埃斯卡(Esca)(葡萄藤枯萎病,干枯病);糖用甜菜(甜菜白粉菌(E.betae))、蔬菜(例如豌豆白粉菌(E.pisi))如葫芦(例如二孢白粉菌(E.cichoracearum))、卷心菜、油菜(例如E.cruciferarum)上的白粉菌属(Erysiphe)(白粉病);各种植物上的镰孢霉属(Fusarium)(有性型:赤霉属(Gibberella))(枯萎病,根腐病或茎腐病),例如禾谷类(例如小麦或大麦)上的禾本科镰孢(F.graminearum)或大刀镰孢(F.culmorum)(根腐病、痂病或银尖病),西红柿上的尖镰孢(F.oxysporum),大豆上的茄镰孢(F.solani)和玉米上的轮枝镰孢(F.verticillioides);禾谷类(例如小麦或大麦)和玉米上的禾顶囊壳(Gaeumannomyces graminis)(全蚀病);禾谷类(例如玉蜀黍赤霉(G.zeae))和稻(例如藤仓赤霉(G.fujikuroi):恶苗病)上的赤霉属;葡萄藤上的葡萄黑腐病菌(Guignardia bidwellii)(黑腐病);禾谷类(例如小麦或大麦)上的雪霉叶枯菌(Microdochium(同义词Fusarium)nivale(雪霉病);丛梗孢属(Monilinia),例如核果和其他蔷薇科植物上的核果链核盘菌(M.laxa)、桃褐腐菌(M.fructicola)和M.fructigena(花腐病和枝腐病,褐腐病);禾谷类、香蕉、浆果和花生上的球腔菌属(Mycosphaerella),例如小麦上的禾生球腔菌(M.graminicola)(无性型:小麦壳针孢(Septoria tritici),壳针孢叶斑病)或香蕉上的斐济球腔菌(M.fijiensis)(Sigatoka黑斑病);卷心菜(例如芸苔霜霉(P.brassicae))、油菜(例如寄生霜霉(P.parasitica))、洋葱(例如大葱霜霉(P.destructor))、烟草(烟草霜霉(P.tabacina))和大豆(例如大豆霜霉病菌(P.manshurica))上的霜霉属(Peronospora)(霜霉病);大豆上的豆薯层锈菌(Phakopsora pachyrhizi)和山马蟥层锈菌(P.meibomiae)(大豆锈病);各种植物如柿子椒和葫芦(例如辣椒疫霉(P.capsici))、大豆(例如大豆疫霉(P.megasperma),同义词P.sojae)、土豆和西红柿(例如致病疫霉(P.infestans):晚疫病)上的疫霉属(Phytophthora)(枯萎病,根腐病,叶腐病,茎腐病和果树腐烂病);霜霉属(Plasmopara),例如葡萄藤上的葡萄生单轴霉(P.viticola)(葡萄藤霜霉病);各种植物上的柄锈菌属(Puccinia)(锈病),例如禾谷类如小麦、大麦或黑麦上的小麦柄锈菌(P.triticina)(小麦褐锈病或叶锈病),条形柄锈病(P.striiformis)(条锈病或黄锈病),大麦柄锈病(P.hordei)(大麦黄矮叶锈病),禾柄锈菌(P.graminis)(茎锈病或黑锈病)或小麦叶锈菌(P.recondita)(褐锈病或叶锈病),以及芦笋上的柄锈菌属(例如天门冬属柄锈病(P.asparagi));小麦上的小麦黄斑叶枯病菌(Pyrenophora(无性型:Drechslera)tritici-repentis)(黄斑病)或大麦上的大麦网斑内脐蠕孢(P.teres)(网斑病);梨孢属(Pyricularia),例如稻上的稻瘟病菌(P.oryzae)(有性型:Magnaporthe grisea,稻瘟病)以及草坪和禾谷类上的稻梨孢菌(P.grisea);草坪、稻、玉米、小麦、棉花、油菜、向日葵、大豆、糖用甜菜、蔬菜和各种其他植物(例如终极腐霉菌(P.ultimum)或瓜果腐霉(P.aphanidermatum))上的腐霉属(Pythium)(立枯病);棉花、稻、土豆、草坪、玉米、油菜、土豆、糖用甜菜、蔬菜和各种其他植物上的丝核菌属(Rhizoctonia),例如大豆上的立枯丝核菌(R.solani)(根腐病和茎腐病),稻上的R.solani(纹枯病)或小麦或大麦上的禾谷丝核菌(R.Cerealis)(小麦纹枯病);大麦、黑麦和小黑麦上的黑麦喙孢(Rhynchosporium secalis)(叶斑病);各种植物上的壳针孢属(Septoria),例如大豆上的大豆壳针孢(S.glycines)(褐斑病),小麦上的小麦壳针孢(S.tritici)(壳针孢叶斑病)和禾谷类上的颖枯壳多孢(S.(同义词Stagonospora)nodorum)(壳多孢斑枯病);葡萄藤上的葡萄钩丝壳(Uncinula(同义词Erysiphe)necator)(白粉病,无性型:Oidium tuckeri);禾谷类上的壳多孢属(Stagonospora),例如小麦上的颖枯壳多孢(S.nodorum)(壳多孢斑枯病,有性态:颖枯球腔菌(Leptosphaeria[同义词Phaeosphaeria]nodorum));苹果(例如苹果黑星病(V.inaequalis))和梨上的黑星菌属(Venturia)(黑星病)。
混合物及其组合物还分别适合防治有害真菌以保护储藏的产品或收获品以及保护材料。术语“保护材料”应理解为表示保护工业和非活体材料,如粘合剂、胶、木材、纸张和纸板、纺织品、皮革、漆分散体、塑料、冷却润滑剂(colling lubricant)、纤维或织物以防有害微生物如真菌和细菌侵染和破坏。
混合物及其组合物可以分别用于改善植物健康。本发明还涉及一种通过分别用有效量的化合物I及其组合物处理植物、其繁殖材料和/或其中植物生长或将要生长的场所而改善植物健康的方法。
术语“植物健康”应理解为表示植物和/或其产品由各种迹象如产量(例如增加的生物量和/或增加的有价值成分含量)、植物活力(例如改善的植物生长和/或更绿的叶子(“绿化效应”))、质量(例如某些成分的增加含量或组成)和对非生命和/或生命应力的耐受性单独或相互组合确定的状况。对植物健康状况所提到的迹象可以相互依赖或可以相互影响。
化合物I和/或杀真菌组分II可以以生物学活性可能不同的不同晶型存在。它们同样为本发明主题。
混合物直接或以组合物形式通过用杀真菌有效量的活性物质处理真菌或需要防止真菌侵袭的植物、植物繁殖材料如种子、土壤、表面、材料或空间而使用。施用可以在植物、植物繁殖材料如种子、土壤、表面、材料或空间被真菌侵染之前和之后进行。
本发明还涉及包含溶剂或固体载体以及至少一种化合物I的农业化学组合物及其在防治有害真菌中的用途。
化合物I和杀真菌组分、其N-氧化物及其盐可以转化成农业化学组合物常用的类型,例如溶液、乳液、悬浮液、粉剂、粉末、糊和颗粒。组合物的类型取决于特定的意欲目的;在每种情况下应确保本发明化合物精细和均匀分布。
组合物类型的实例是悬浮液(SC、OD、FS),可乳化浓缩物(EC),乳液(EW、EO、ES),糊,锭剂,可湿性粉末或粉剂(WP、SP、SS、WS、DP、DS)或可以是水溶性的或可湿性的颗粒(GR、FG、GG、MG),以及处理植物繁殖材料如种子的凝胶配制剂(GF)。
组合物类型(例如SC、OD、FS、EC、WG、SG、WP、SP、SS、WS、GF)通常以稀释形式使用。组合物类型如DP、DS、GR、FG、GG和MG通常不经稀释使用。
组合物以已知方式制备(参见US 3,060,084,EP-A 707445(对于液体浓缩物),Browning:“Agglomeration”,Chemical Engineering,1967年12月4日,147-48,Perry’s Chemical Engineer’s Handbook,第4版,McGraw-Hill,New York,1963,第8-57及后续页,WO 91/13546,US4,172,714,US 4,144,050,US 3,920,442,US 5,180,587,US 5,232,701,US5,208,030,GB 2,095,558,US 3,299,566,Klingman:Weed Control as aScience(John Wiley&Sons,New York,1961),Hance等:Weed ControlHandbook(第8版,Blackwell Scientific,Oxford,1989)以及Mollet,H.和Grubemann,A.:Formulation Technology(Wiley VCH Verlag,Weinheim,2001)。
农业化学组合物还可以包含常用于农业化学组合物的助剂。所用助剂分别取决于特定施用形式和活性物质。
合适助剂的实例是溶剂,固体载体,分散剂或乳化剂(例如其他加溶剂、保护性胶体、表面活性剂和粘附剂),有机和无机增稠剂、杀菌剂、防冻剂、消泡剂,合适的话还有着色剂和增粘剂或粘合剂(例如用于种子处理配制剂)。
粉末、撒播材料和粉剂可以通过将化合物I和合适的话其他活性物质与至少一种固体载体混合或同时研磨而制备。
颗粒如涂覆颗粒、浸渍颗粒和均质颗粒可以通过将活性物质与固体载体粘附而制备。
农业化学组合物通常包含0.01-95重量%,优选0.1-90重量%,最优选0.5-90重量%的活性物质。活性物质以90-100%,优选95-100%的纯度(根据NMR光谱)使用。
为了处理植物繁殖材料,尤其是种子,通常使用水溶性浓缩物(LS),流动性浓缩物(FS),干处理用粉末(DS),淤浆处理用水分散性粉末(WS),水溶性粉末(SS),乳液(ES),可乳化浓缩物(EC)和凝胶(GF)。这些组合物可以经稀释或不经稀释而施用于植物繁殖材料,尤其是种子上。所述组合物在稀释2-10倍后在即用制剂中给出0.01-60重量%,优选0.1-40重量%的活性物质浓度。
在优选实施方案中,将悬浮液类型(FS)的组合物用于种子处理。FS组合物通常可以包含1-800g/l活性物质,1-200g/l表面活性剂,0-200g/l防冻剂,0-400g/l粘合剂,0-200g/l颜料以及至多1L溶剂,优选水。
含水施用形式可通过加入水由乳液浓缩物、糊或可湿性粉末(可喷雾粉末、油分散体)制备。为制备乳液、糊或油分散体,可借助润湿剂、增粘剂、分散剂或乳化剂将该物质直接或溶于油或溶剂中后在水中均化。或者可以制备由活性物质、润湿剂、增粘剂、分散剂或乳化剂以及合适的话溶剂或油组成的浓缩物且该类浓缩物适于用水稀释。
即用制剂中的活性物质浓度可以在较宽范围内变化。它们通常为0.0001-10重量%,优选0.001-1重量%的活性物质。
活性物质也可成功用于超低容量法(ULV),其中可以施用包含超过95重量%活性物质的组合物,或甚至施用不含添加剂的活性物质。
当用于植物保护中时,活性物质的施用量取决于所需效果的种类为0.001-2kg/ha,优选0.005-2kg/ha,更优选0.05-0.9kg/ha,尤其是0.1-0.75kg/ha。
在植物繁殖材料如种子例如通过撒粉、包衣或浸透种子的处理中,通常要求活性物质的量为1-10,000g/100kg,优选1-1000g/100kg,更优选1-100g/100kg,最优选5-100g/100kg植物繁殖材料(优选种子)。
当用于保护材料或储存产品中时,活性物质的施用量取决于施用区域的种类和所需效果。在材料保护中常用的施用量例如为0.001g-2kg,优选0.005g-1kg活性物质/立方米被处理材料。
可以向活性物质或包含它们的组合物中加入各种类型的油、润湿剂、辅助剂、除草剂、杀菌剂、其他杀真菌剂和/或杀虫剂,合适的话在紧临使用前加入(桶混合)。这些试剂可以以1∶100-100∶1,优选1∶10-10∶1的重量比与本发明组合物混合。
呈杀真菌剂使用形式的本发明组合物还可以与其他活性物质(例如除草剂、杀虫剂、生长调节剂、杀真菌剂或肥料)一起作为预混物存在或合适的话在紧临施用前混合(桶混合)。
根据本发明,将化合物I与杀真菌组分II一起施用应理解为表示在作用位置(即要防治的有害真菌或其栖息地如侵染的植物,植物繁殖材料,尤其是种子,表面、材料或土壤以及要防止真菌侵袭的植物,植物繁殖材料,尤其是种子,土壤,表面,材料或空间)以有效量同时存在化合物I和至少一种杀真菌组分II。这可以通过以同时,即联合(例如以桶混物)或分开施用化合物I和杀真菌组分II或依次施用化合物I和杀真菌组分II而实现,其中选择各次施用之间的时间间隔以确保首先施用的活性物质在施用其他活性物质时仍以足够量存在于作用位置。施用顺序对本发明的操作不太重要。
在本发明混合物及其组合物,即包含一种化合物I和一种杀真菌组分II的本发明组合物中,化合物I与组分II的重量比通常取决于所用活性物质的性能;该重量比通常为1∶100-100∶1,常常为1∶50-50∶1,优选1∶20-20∶1,更优选1∶10-10∶1,尤其是1∶3-3∶1。
在三元混合物即包含一种化合物I(组分1)以及一种杀真菌组分II(组分2)和另一种活性物质(组分3),例如选自A)-F)组的活性物质的本发明组合物中,组分1与组分2的重量比取决于所用活性物质的性能,通常为1∶100-100∶1,常常为1∶50-50∶1,优选1∶20-20∶1,更优选1∶10-10∶1,尤其是1∶3-3∶1;并且组分1与组分3的重量比通常为1∶100-100∶1,常常为1∶50-50∶1,优选1∶20-20∶1,更优选1∶10-10∶1,尤其是1∶3-3∶1。
在混合物和组合物中,有利地选择化合物I/杀真菌组分II的比例以产生协同增效效果。
术语“协同增效效果”应理解为尤其指由Colby公式定义的效果(Colby,S.R.,“计算除草剂组合的协同增效和拮抗响应”,Weeds,15,第20-22页,1967)。
术语“协同增效效果”还应理解为指通过使用Tammes方法定义的效果(Tammes,P.M.L.,“Isoboles,a graphic representation of synergismin pesticides”,Netherl.J.Plant Pathol.70,1964)。
各组分可以单独使用或者已经部分或完全相互混合而制备本发明的组合物。还可以将它们作为结合组合物如多组分成套包装来包装和进一步使用。
在本发明的一个实施方案中,成套包装可以包含一种或多种(包括所有)可以用于制备本发明农业化学组合物的组分。例如这些成套包装可以包含一种或多种杀真菌剂组分和/或助剂组分和/或杀虫剂组分和/或生长调节剂组分和/或除草剂。一种或多种组分可以组合在一起或预配制。在其中两种以上组分提供在成套包装中的那些实施方案中,各组分可以组合一起并直接包装在单独容器如罐、瓶、桶、袋、囊或箱中。在其他实施方案中,成套包装的两种或更多种组分可以分开包装,即不预配制。成套包装可以直接包含一个或多个分开的容器如罐、桶、瓶、袋、囊或箱,其中各容器包含农业化学组合物的单独组分。在两种形式中,成套包装的某一组分可以与其他组分分开或一起或者作为本发明结合组合物的一种组分用于制备本发明组合物。
当将二元混合物或包含它们的组合物以杀真菌剂使用形式与其他杀真菌剂混合时,在许多情况下拓宽了杀真菌活性谱或防止了杀真菌剂耐受性的产生。此外,在许多情况下得到协同增效作用。
本发明化合物可以与其一起使用的下列活性物质用来说明可能的组合,但不限制它们:
A)嗜球果伞素类:
腈嘧菌酯(azoxystrobin)、甲香菌酯(coumethoxystrobin)、丁香菌酯(coumoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enestroburin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、唑胺菌酯(pyrametostrobin)、唑菌酯(pyraoxystrobin)、pyribencarb、肟菌酯(trifloxystrobin)、2-[2-((2,5-二甲基苯氧基甲基)苯基)-3-甲氧基丙烯酸甲酯和2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧甲基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺;
B)羧酰胺类:
-羧酰苯胺类:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、麦锈灵(benodanil)、bixafen、啶酰菌胺(boscalid)、萎锈灵(carboxin)、呋菌胺(fenfuram)、环酰菌胺(fenhexamid)、氟酰胺(flutolanil)、fluxapyroxad、呋吡唑灵(furametpyr)、isopyrazam、异噻菌胺(isotianil)、kiralaxyl、丙氧灭绣胺(mepronil)、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)(mefenoxam)、甲呋酰胺(ofurace)、霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、戊苯吡菌胺(penflufen)、吡噻菌胺(penthiopyrad)、sedaxane、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil)、2-氨基-4-甲基噻唑-5-甲酰苯胺、N-(4′-三氟甲硫基联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺和N-(2-(1,3,3-三甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺;
-羧酸吗啉化物:烯酰吗啉(dimethomorph)、氟吗啉(flumorph)、丁吡吗啉(pyrimorph);
-苯甲酰胺类:氟联苯菌(flumetover)、氟吡菌胺(fluopicolide)、氟吡菌酰胺(fluopyram)、苯酰菌胺(zoxamide);
-其他羧酰胺类:氯环丙酰胺(carpropamid)、双氯氰菌胺(dicyclomet)、双炔酰菌胺(mandiproamid)、土霉素(oxytetracyclin)、硅噻菌胺(silthiofam)和N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺;
C)唑类:
-三唑类:戊环唑(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(diniconazole)、烯唑醇M(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、oxpoconazole、多效唑(paclobutrazole)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、三唑酮(triadimefon)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、烯效唑(uniconazole);
-咪唑类:氰霜唑(cyazofamid)、烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizol);
-苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
-其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)和2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔氧基乙酰胺;
D)杂环化合物
-嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、二氟林(diflumetorim)、异嘧菌醇(fenarimol)、嘧菌腙(ferimzone)、嘧菌胺(mepanipyrim)、氯草定(nitrapyrin)、氟苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
-哌嗪类:嗪氨灵(triforine);
-吗啉类:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorph-acetate)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);
-哌啶类:苯锈啶(fenpropidin);
-二羧酰亚胺类:氟菌安(fluoroimid)、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
-非芳族5员杂环:唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、flutianil、异噻菌酮(octhilinone)、噻菌灵(probenazole)、5-氨基-2-异丙基-3-氧代-4-邻甲苯基-2,3-二氢吡唑-1-硫代甲酸S-烯丙基酯;
-其他:噻二唑素(acibenzolar-S-methyl)、ametoctradin、吲唑磺菌胺(amisulbrom)、敌菌灵(anilazin)、灭瘟素(blasticidin-S)、敌菌丹(captafol)、克菌丹(captan)、灭螨蜢(chinomethionat)、棉隆(dazomet)、咪菌威(debacarb)、哒菌清(diclomezine)、野燕枯(difenzoquat)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)、氰菌胺(fenoxanil)、灭菌丹(folpet)、恶喹酸(oxolinic acid)、粉病灵(piperalin)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、唑菌嗪(triazoxide)、三环唑(tricyclazole)、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑和5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶;
E)氨基甲酸盐类
-硫代-和二硫代氨基甲酸盐:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、磺菌威(methasulphocarb)、代森联(metiram)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);
-氨基甲酸盐:苯噻菌胺(benthiavalicarb)、乙霉威(diethofencarb)、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、霜霉威盐酸盐(propamocarbhydrochlorid)、valifenalate和N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
F)其他活性物质
-胍类:胍、多果定(dodine)、多果定游离碱、双胍盐(guazatine)、双胍辛胺(guazatine-acetate)、双胍辛醋酸盐(iminoctadine)、双胍辛胺三乙酸盐(iminoctadine-triacetate)、双八胍盐(iminoctadine-tris(albesilate));-抗生素类:春雷素(kasugamycin)、水合春雷素(kasugamycinhydrochloride-hydrate)、链霉素(streptomycin)、多氧霉素(polyoxine)、井冈霉素(validamycin A);
-硝基苯基衍生物:乐杀螨(binapacryl)、氯硝胺(dicloran)、敌螨通(dinobuton)、敌螨普(dinocap)、异丙消(nitrothal-isopropyl)、四氯硝基苯(tecnazen);
-有机金属化合物:三苯锡基盐,例如薯瘟锡(fentin-acetate)、三苯锡氯(fentin chloride)或毒菌锡(fentin hydroxide);
-含硫杂环化合物:二噻农(dithianon)、稻瘟灵(isoprothiolane);
-有机磷化合物:克瘟散(edifenphos)、藻菌磷(fosetyl)、乙磷铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、亚磷酸及其盐、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl);
-有机氯化合物:百菌清(chlorothalonil)、抑菌灵(dichlofluanid)、双氯酚(dichlorophen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯酚(pentachlorphenole)及其盐、四氯苯酞(phthalide)、五氯硝基苯(quintozene)、甲基托布津(thiophanate-methyl)、对甲抑菌灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺;
-无机活性物质:波尔多液(Bordeaux混合物)、醋酸铜、氢氧化铜、王铜(copper oxychloride)、碱式硫酸铜、硫;
-抗真菌生物控制剂、植物生物活化剂:白粉寄生孢(Ampelomycesquisqualis)(例如来自德国Intrachem Bio GmbH&Co.KG的AQ),黄曲霉(Aspergillus flavus)(例如来自瑞士Syngenta的),出芽短梗霉(Aureobasidium pullulans)(例如来自德国bio-ferm GmbH的),短小芽孢杆菌(例如NRRL登录号为B-30087,来自美国AgraQuest Inc.的和Plus),枯草芽孢杆菌(例如NRRL号为B-21661的分离物,来自美国AgraQuest Inc.的 MAX和ASO),解淀粉枯草芽孢杆菌变种(Bacillus subtilis var.amyloliquefaciens)FZB24(例如来自美国Novozyme Biologicals,Inc.的),橄榄假丝酵母(Candida oleophila)I-82(例如来自美国Ecogen Inc.的),假丝酵母(Candida saitoana)(例如来自美国Micro Flo Company(BASF SE)和Arysta的(与溶菌酶的混合物)和),壳聚糖(例如来自新西兰BotriZen Ltd.的ARMOUR-ZEN),粉红粘帚霉(Clonostachys rosea f.catenulate),也称为链孢粘帚霉(Gliocladiumcatenulatum)(例如来自芬兰Verdera的分离物J1446:),盾壳霉(Coniothyrium minitans)(例如来自德国Prophyta的),栗疫菌(Cryphonectria parasitica)(例如来自法国CNICM的Endothia parasitica),浅白隐球酵母(Cryptococcus albidus)(例如来自南非Ancho r Bio-Technologies的YIE LD),尖孢镰刀菌(Fusarium oxysporum)(例如来自意大利S.I.A.P.A.的来自法国Natural Plant Protection的),Metschnikowiafructicola(例如来自以色列Agrogreen的),双胞镰孢(Microdochium dimerum)(例如来自法国Agrauxine的),大伏革菌(Phlebiopsis gigantean)(例如来自芬兰Verdera的),Pseudozyma flocculosa(例如来自加拿大Plant Products Co.Ltd.的),寡雄腐霉(Pythium oligandrum)DV74(例如来自捷克共和国Remeslo SSRO,Biopreparaty的),Reynoutriasachlinensis(例如来自美国Marrone BioInnovations的),黄蓝状菌(Talaromyces flavus)V117b(例如来自德国Prophyta的),棘孢木霉(Trichoderma asperellum)SKT-1(例如来自日本Kumiai Chemical Industry Co.,Ltd.的),深绿木霉(T.atroviride)LC52(例如来自新西兰Agrimm Technologies Ltd的),哈茨木霉(T.harzianum)T-22(例如来自美国FirmaBioWorks Inc.的),哈茨木霉TH 35(例如来自以色列Mycontrol Ltd.的ROOT),哈茨木霉T-39(例如来自以色列Mycontrol Ltd.和以色列Makhteshim Ltd.的和TRICHODERMA),哈茨木霉和绿色木霉(T.viride)(例如来自新西兰Agrimm Technologies Ltd的TRICHOPEL),哈茨木霉ICC012和绿色木霉ICC080(例如来自意大利Isagro Ricerca的WP),多孢木霉(T.polysporum)和哈茨木霉(例如来自瑞典BINABBio-Innovation AB的),康氏木霉(T.stromaticum)(例如来自巴西C.E.P.L.A.C.的),绿木霉(T.virens)GL-21(例如来自美国Certis LLC的),绿色木霉(例如来自印度EcosenseLabs.(India)Pvt.Ltd.的例如来自印度T.Stanes&Co.Ltd.的F),绿色木霉TV1(例如来自意大利Agribiotec srl的绿色木霉TV1),奥德曼细基格孢(Ulocladium oudemansii)HRU3(例如来自新西兰Botry-Zen Ltd的);
-其他:联苯、拌棉醇(bronopol)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、二苯胺、苯菌酮(metrafenone)、pyriofenone、米多霉素(mildiomycin)、喹啉铜(oxine-copper)、调环酸钙(prohexadione-calcium)、螺茂胺(spiroxamine)、tebufloquin、对甲抑菌灵、N-(环丙基甲氧亚氨基-(6-二氟甲氧基-2,3-二氟苯基)甲基)-2-苯基乙酰胺、N′-(4-(4-氯-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(4-(4-氟-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(2-甲基-5-三氟甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、N′-(5-二氟甲基-2-甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(1,2,3,4-四氢萘-1-基)酰胺、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(R)-1,2,3,4-四氢萘-1-基酰胺、甲氧基乙酸6-叔丁基-8-氟-2,3-二甲基喹啉-4-基酯和N-甲基-2-{1-[(5-甲基-3-三氟甲基-1H-吡唑-1-基)乙酰基]哌啶-4-基}-N-[(1R)-1,2,3,4-四氢萘-1-基]-4-噻唑甲酰胺;
G)生长调节剂
脱落酸(abscisic acid)、先甲草胺(amidochlor)、嘧啶醇(ancymidol)、苄胺基嘌呤(6-benzylaminopurine)、油菜素内酯(brassinolide)、地乐胺(butralin)、矮壮素阳离子(chlormequat)(矮壮素(chlormequat chloride))、氯化胆碱(choline chloride)、环丙酸酰胺(cyclanilide)、丁酰肼(daminozide)、敌草克(dikegulac)、噻节因(dimethipin)、2,6-二甲基吡啶(2,6-dimethylpuridine)、乙烯利(ethephon)、抑芽敏(flumetralin)、呋嘧醇(flurprimidol)、达草氟(fluthiacet)、调吡脲(forchlorfenuron)、九二O(gibberellic acid)、抗倒胺(inabenfide)、吲哚-3-乙酸、抑芽丹(maleichydrazide)、氟草磺(mefluidide)、助壮素阳离子(mepiquat)(助壮素(mepiquat chloride))、萘乙酸、N-6-苄基腺嘌呤、多效唑、调环酸(prohexadione)(调环酸钙)、茉莉酸丙酯(prohydrojasmon)、赛二唑素(thidiazuron)、抑芽唑(triapenthenol)、脱叶磷(tributylphosphorotrithioate)、2,3,5-三碘苯甲酸、抗倒酯(trinexapac-ethyl)和烯效唑;
H)除草剂
-乙酰胺类:乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、异丙甲草胺(metolachlor)、吡草胺(metazachlor)、草萘胺(napropamide)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、扑草胺(propachlor)、噻醚草胺(thenylchlor);-氨基酸衍生物:双丙氨酰膦(bilanafos)、草甘膦(glyphosate)、草铵膦(glufosinate)、草硫膦(sulfosate);
-芳氧基苯氧基丙酸酯类:炔草酯(clodinafop)、氰氟草酯(cyhalofop-butyl)、唑禾草灵(fenoxaprop)、吡氟禾草灵(fluazifop)、吡氟氯禾灵(haloxyfop)、恶唑酰草胺(metamifop)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、喹禾灵(四氢糠基酯)(quizalofop-p-tefuryl);
-联吡啶类:敌草快阳离子(diquat)、对草快阳离子(paraquat);
-(硫代)氨基甲酸酯类:黄草灵(asulam)、苏达灭(butylate)、长杀草(carbetamide)、异苯敌草(desmedipham)、哌草丹(dimepiperate)、扑草灭(eptam)(EPTC)、禾草畏(esprocarb)、草达灭(molinate)、坪草丹(orbencarb)、苯敌草(phenmedipham)、苄草丹(prosulfocarb)、稗草畏(pyributicarb)、杀草丹(thiobencarb)、野麦畏(triallate);
-环己二酮类:丁氧环酮(butroxydim)、烯草酮(clethodim)、噻草酮(cycloxydim)、环苯草酮(profoxydim)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim);
-二硝基苯胺类:氟草胺(benfluralin)、丁氟消草(ethalfluralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、氟乐灵(trifluralin);
-二苯基醚类:氟锁草醚(acifluorfen)、苯草醚(aclonifen)、治草醚(bifenox)、氯甲草(diclofop)、氯氟草醚(ethoxyfen)、氟黄胺草醚(fomesafen)、乳氟禾草灵(lactofen)、乙氧氟草醚(oxyfluorfen);
-羟基苄腈类:溴苯腈(bromoxynil)、敌草腈(dichlobenil)、碘苯腈(ioxynil);
-咪唑啉酮类:咪草酯(imazamethabenz)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr);
-苯氧基乙酸类:稗草胺(clomeprop)、2,4-二氯苯氧基乙酸(2,4-D)、2,4-DB、2,4-滴丙酸(dichlorprop)、MCPA、2甲4氯乙硫酯(MCPA-thioethyl)、MCPB、2甲4氯丙酸(mecoprop);
-吡嗪类:杀草敏(chloridazon)、氟哒嗪草酯(flufenpyr-ethyl)、达草氟、达草灭(norflurazon)、达草止(pyridate);
-吡啶类:氨草啶(aminopyralid)、二氯皮考啉酸(clopyralid)、吡氟草胺(diflufenican)、氟硫草定(dithiopyr)、氟草同(fluridone)、氟草烟(fluroxypyr)、毒莠定(picloram)、氟吡酰草胺(picolinafen)、噻氟啶草(thiazopyr);
-磺酰脲类:磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟啶黄隆(flupyrsulfuron)、酰胺磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、甲基碘磺隆(iodosulfuron)、甲磺胺磺隆(mesosulfuron)、metazosulfuron、甲黄隆(metsulfuron-methyl)、烟嘧黄隆(nicosulfuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、三氟甲磺隆(tritosulfuron)、1-((2-氯-6-丙基咪唑并[1,2-b]哒嗪-3-基)磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲;
-三嗪类:莠灭净(ametryn)、莠去津(atrazine)、草净津(cyanazine)、戊草津(dimethametryn)、乙嗪草酮(ethiozin)、六嗪同(hexazinone)、苯嗪草(metamitron)、赛克津(metribuzin)、扑草净(prometryn)、西玛津(simazine)、特丁津(terbuthylazine)、去草净(terbutryn)、苯氧丙胺津(triaziflam);
-脲类:绿麦隆(chlorotoluron)、香草隆(daimuron)、敌草隆(diuron)、伏草隆(fluometuron)、异丙隆(isoproturon)、利谷隆(linuron)、噻唑隆(methabenzthiazuron)、丁唑隆(tebuthiuron);
-其他乙酰乳酸合成酶抑制剂:双草醚钠盐(bispyribac-sodium)、氯酯磺草胺(cloransulam-methyl)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟酮磺隆(flucarbazone)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、嘧苯胺磺隆(ortho-sulfamuron)、五氟磺草胺(penoxsulam)、丙氧基卡巴腙(propoxycarbazone)、丙酯草醚(pyribambenz-propyl)、嘧苯草肟(pyribenzoxim)、环酯草醚(pyriftalid)、肟啶草(pyriminobac-methyl)、pyrimisulfan、嘧硫苯甲酸(pyrithiobac)、pyroxasulfone、甲氧磺草胺(pyroxsulam);
-其他:胺唑草酮(amicarbazone)、三唑胺(aminotriazole)、莎稗磷(anilofos)、氟丁酰草胺(beflubutamid)、草除灵(benazolin)、bencarbazone、benfluresate、吡草酮(benzofenap)、噻草平(bentazone)、苯并双环酮(benzobicyclon)、bicyclopyrone、除草定(bromacil)、溴丁酰草胺(bromobutide)、氟丙嘧草酯(butafenacil)、草胺磷(butamifos)、胺草唑(cafenstrole)、氟酮唑草(carfentrazone)、吲哚酮草酯(cinidon-ethyl)、敌草索(chlorthal)、环庚草醚(cinmethylin)、异恶草酮(clomazone)、苄草隆(cumyluron)、cyprosulfamide、麦草畏(dicamba)、苯敌快(difenzoquat)、二氟吡隆(diflufenzopyr)、稗内脐蠕孢菌(Drechslera monoceras)、敌草腈(endothal)、乙呋草黄(ethofumesate)、乙苯酰草(etobenzanid)、fenoxasulfone、四唑酰草胺(fentrazamide)、氟烯草酸(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、胺草唑(flupoxam)、氟咯草酮(fluorochloridone)、呋草酮(flurtamone)、茚草酮(indanofan)、异恶草胺(isoxaben)、异氟草(isoxaflutole)、环草定(lenacil)、敌稗(propanil)、拿草特(propyzamide)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、硝草酮(mesotrione)、甲胂酸(methyl arsonic acid)、抑草生(naptalam)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon)、氯嗪草(oxaziclomefone)、戊唑草(pentoxazone)、唑啉草酯(pinoxaden)、双唑草腈(pyraclonil)、吡草醚(pyraflufen-ethyl)、pyrasulfotole、苄草唑(pyrazoxyfen)、吡唑特(pyrazolynate)、灭藻醌(quinoclamine)、嘧啶肟草醚(saflufenacil)、磺草酮(sulcotrione)、磺胺草唑(sulfentrazone)、特草定(terbacil)、tefuryltrione、tembotrione、thiencarbazone、topramezone、(3-[2-氯-4-氟-5-(3-甲基-2,6-二氧代-4-三氟甲基-3,6-二氢-2H-嘧啶-1-基)苯氧基]吡啶-2-基氧基)乙酸乙酯、6-氨基-5-氯-2-环丙基嘧啶-4-甲酸甲酯、6-氯-3-(2-环丙基-6-甲基苯氧基)哒嗪-4-醇、4-氨基-3-氯-6-(4-氯苯基)-5-氟吡啶-2-甲酸、4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-甲酸甲酯和4-氨基-3-氯-6-(4-氯-3-二甲基氨基-2-氟苯基)吡啶-2-甲酸甲酯;
I)杀虫剂:
-有机(硫代)磷酸酯:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorvos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基对硫磷(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxydemeton-methyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、田乐磷(sulprophos)、杀虫威(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
-氨基甲酸酯类:棉铃威(alanycarb)、涕灭威(aldicarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、唑蚜威(triazamate);
-合成除虫菊酯类:丙烯除虫菊(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊(pyrethrin)I和II、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、丙氟菊酯(profluthrin)、四氟甲醚菊酯(dimefluthrin);
-昆虫生长调节剂:a)几丁质合成抑制剂:苯甲酰脲类:定虫隆(chlorfluazuron)、灭蝇胺(cyramazin)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);噻嗪酮(buprofezin)、茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、四螨嗪(clofentazine);b)蜕皮激素拮抗剂:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)保幼激素类似物:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威;d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat);
-烟碱受体激动剂/拮抗剂化合物:噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)、1-(2-氯噻唑-5-基甲基)-2-硝酰亚氨基(nitrimino)-3,5-二甲基-[1,3,5]三嗪烷(triazinane);
-GABA拮抗剂化合物:硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、5-氨基-1-(2,6-二氯-4-甲基苯基)-4-亚磺酰氨酰基(sulfinamoyl)-1H-吡唑-3-硫代甲酰胺;
-大环内酯杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)、乙基多杀菌素(spinetoram);
-线粒体电子传输抑制剂(METI)I杀螨剂:喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、嘧虫胺(flufenerim);
-METI II和III化合物:灭螨醌(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
-分离剂:氟唑虫清(chlorfenapyr);
-氧化磷酸化抑制剂:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)、克螨特(propargite);
-昆虫蜕皮(moulting)抑制剂化合物:灭蝇胺(cryomazine);
-混合功能氧化酶抑制剂:增效醚(piperonyl butoxide);
-其他:benclothiaz、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)、拒嗪酮(pymetrozine)、硫、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、氯虫酰胺(chlorantraniliprole)、cyazypyr(HGW86)、cyenopyrafen、吡氟硫磷(flupyrazofos)、丁氟螨酯(cyflumetofen)、amidoflumet、imicyafos、双三氟虫脲(bistrifluron)和pyrifluquinazon。
称为组分2的活性物质、其制备及其对有害真菌的活性是已知的(参见http://www.alanwood.net/pesticides/);这些物质可市购。由IUPAC命名描述的化合物、其制备及其杀真菌活性同样是已知的(参见Can.J.Plant Sci.48(6),587-94,1968;EP-A 141 317;EP-A 152 031;EP-A 226 917;EP-A 243 970;EP-A 256 503;EP-A 428 941;EP-A 532 022;EP-A 1028 125;EP-A 1 035 122;EP-A 1 201 648;EP-A 1 122 244,JP2002316902;DE 19650197;DE 10021412;DE 102005009458;US3,296,272;US 3,325,503;WO 98/46608;WO 99/14187;WO 99/24413;WO 99/27783;WO 00/29404;WO 00/46148;WO 00/65913;WO01/54501;WO 01/56358;WO 02/22583;WO 02/40431;WO 03/10149;WO 03/11853;WO 03/14103;WO 03/16286;WO 03/53145;WO03/61388;WO 03/66609;WO 03/74491;WO 04/49804;WO 04/83193;WO 05/120234;WO 05/123689;WO 05/123690;WO 05/63721;WO05/87772;WO 05/87773;WO 06/15866;WO 06/87325;WO 06/87343;WO 07/82098;WO 07/90624)。
混合物及其组合物的杀真菌作用可以由下述试验证实。
制备储备溶液:将溶剂/乳化剂体积比为99/1的丙酮和/或二甲亚砜与基于乙氧基化烷基酚的润湿剂/乳化剂Wettol的混合物加入25mg化合物中得到总共10ml。然后加水至总体积为100ml。
将该储备溶液用所述溶剂/乳化剂/水混合物稀释至给定浓度。
将肉眼测定的侵染叶面积百分数转化成以未处理对照的%表示的效力。
效力(E)使用Abbot公式按如下计算:
E=(1-α/β)·100
α对应于被处理植物的真菌侵染百分数,和
β对应于未处理(对照)植物的真菌侵染百分数
效力为0表示被处理植物的侵染程度对应于未处理对照植物的侵染程度;效力为100表示被处理植物未被侵染。
活性化合物组合的预期效力使用Colby公式确定(Colby,S.R.“计算除草剂组合的协同增效和拮抗响应”,Weeds,15,第20-22页,1967)并与观察到的效力相比较。
Colby公式:E=x+y-x·y/100
E为以浓度a和b使用活性化合物A和B的混合物时的预期效力,以相对于未处理对照的百分数表示
x为以浓度a使用活性化合物A时的效力,以相对于未处理对照的百分数表示
y为以浓度b使用活性化合物B时的效力,以相对于未处理对照的百分数表示。
温室试验
实施例1:对由葡萄生单轴霉(Plasmopara viticola)引起的葡萄藤霜霉病的杀真菌防治
使葡萄藤插条在盆中生长到4-5叶阶段。将这些植物用含有浓度如下表所述的活性成分或其混合物的含水悬浮液喷雾至滴流。使植物风干。第二天通过在叶子下侧喷雾葡萄生单轴霉的含水孢子悬浮液用该悬浮液对它们接种。然后将试验植株立即转移到22-24℃和相对湿度接近100%的潮湿室中保持24小时。在20-25℃和约50-80%相对湿度下在温室中栽培5天。为了刺激病害症状的爆发,再次将植株转移到潮湿室中保持24小时。然后以患病叶面积百分数肉眼评价下侧叶表面上的真菌侵袭程度。
微试验
在二甲亚砜中将活性化合物单独配制成浓度为10000ppm的储备溶液。
实施例2:对晚疫病病原体致病疫霉(Phytophthora infestans)的活性
将储备溶液根据配比混合,用移液管移至微滴定板(MTP)中并用水稀释至所述浓度。然后加入含豌豆汁基含水营养培养基的致病疫霉孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天之后在405nm下使用吸收光度计测量MTP。将测量的参数与不含活性化合物的对照方案的生长(100%)以及不含真菌和活性化合物的空白值比较以确定病原体在相应活性化合物中的相对生长百分数。将这些百分数转化成效力。
实施例3:在微滴定板测试中对稻瘟病菌(Pyricularia oryzae)的活性
将储备溶液根据配比混合,用移液管移至微滴定板(MTP)中并用水稀释至所述浓度。然后加入稻瘟病菌在生物麦芽水溶液中的孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天之后在405nm下使用吸收光度计测量MTP。
将测量的参数与不含活性化合物的对照方案的生长(100%)以及不含真菌和活性化合物的空白值比较以确定病原体在相应活性化合物中的相对生长百分数。将这些百分数转化成效力。
Claims (15)
1.一种混合物,其以协同增效有效量包含如下组分作为活性化合物:
1)至少一种式I化合物以及式I化合物的N-氧化物和可农用盐:
其中:
R1为1H-吡唑-1-基或苯基,其中两个上述基团未被取代或带有1或2个相同或不同的取代基Ra;
Ra为卤素、CH3、CH2CH5或CF3;
X为CH或N;
Y为O或S;
A为5员亚杂芳基,其中环成员原子除了碳原子外还包括1个硫原子和1个氮原子或1个氧原子和1个氮原子或2或3个氮原子;
Z为选自-CH2-、-CHOH-和=C=O的二价基团;
R2、R3相互独立地选自氢和CH3;
和
2)至少一种选自A′)-C′)组的杀真菌组分II:
A′)选自isopyrazam和3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(3′,4′,5′-三氟联苯-2-基)酰胺的羧酰苯胺;
B′)5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺;
C′)选自NRRL登录号为B-21661的枯草芽孢杆菌(Bacillus subtilis)菌株AQ713、NRRL登录号为B-30087的短小芽孢杆菌(Bacillus pumilus)菌株以及具有相应菌株的所有识别特性的上述芽孢杆菌属(Bacillus)菌株的突变体或变体的杀真菌菌株,
或由上述芽孢杆菌属菌株的培养得到的培养液或上清液;
或由上述芽孢杆菌属菌株产生的对植物病原性真菌呈现活性的代谢物。
2.根据权利要求1的混合物,包含至少一种其中X为CH的化合物I。
3.根据权利要求1或2的混合物,包含至少一种其中R1为1H-吡唑-1-基的化合物I,其中吡唑基带有1或2个相同或不同的取代基Ra。
4.根据权利要求1-3中任一项的混合物,包含至少一种其中A为噻唑-2,4-二基的化合物I,其中2位的碳原子与变量X键合且4位的碳原子与基团C=Y键合。
5.根据权利要求1-4中任一项的混合物,包含至少一种其中Z为二价基团-CH2-并且其中R2和R3均为氢的化合物I。
6.根据权利要求1的混合物,其中化合物I选自2-[1-[(2,5-二甲基苯基)乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、2-[1-[(2,5-二氯苯基)乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-[(1R)-2,3-二氢-1H-茚-1-基]-N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑硫代甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R,4S)-1,2,3,4-四氢-4-羟基-1-萘基]-4-噻唑甲酰胺及其对映体、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-(1,2,3,4-四氢-2-甲基-1-萘基)-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R,4R)-1,2,3,4-四氢-4-羟基-1-萘基]-4-噻唑甲酰胺及其对映体、2-[1-[[5-乙基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、2-[1-[[3,5-双三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-(1,2,3,4-四氢-4-氧代-1-萘基)-4-噻唑甲酰胺、N-甲基-2-[4-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-1-哌嗪基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-(2,3-二氢-2,2-二甲基-1H-茚-1-基)-N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-4-噻唑甲酰胺、N-(2,3-二氢-2-甲基-1H-茚-1-基)-N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-4-噻唑甲酰胺、N-甲基-1-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-1H-吡唑-3-甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-2H-1,2,3-三唑-4-甲酰胺、N-甲基-1-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-1H-吡唑-4-甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-[(1R,2S)-1,2,3,4-四氢-2-甲基-1-萘基]-4-噻唑甲酰胺及其对映体、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-(1,2,3,4-四氢-2,2-二甲基-1-萘基]-4-噻唑甲酰胺、2-[1-[(3,5-二氯-1H-吡唑-1-基)乙酰基]-4-哌啶基]-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、2-[1-[[5-氯-3-三氟甲基-1H-吡唑-1-基]乙酰基)-4-哌啶基)-N-甲基-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-噻唑甲酰胺、N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基)乙酰基]-4-哌啶基]-N-[(1R)-1,2,3,4-四氢-1-萘基]-4-唑甲酰胺和N-甲基-2-[1-[[5-甲基-3-三氟甲基-1H-吡唑-1-基]乙酰基]-4-哌啶基]-N-(1,2,3,4-四氢-1-萘基)-4-噻唑甲酰胺。
7.根据权利要求6的混合物,其中化合物I为2-{1-[2-(5-甲基-3-三氟甲基-吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(R)-1,2,3,4-四氢萘-1-基酰胺和/或其对映体。
8.根据权利要求1-7中任一项的混合物,包含化合物3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(3′,4′,5′-三氟联苯-2-基)酰胺作为组分II。
9.根据权利要求1-7中任一项的混合物,包含化合物5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺作为组分II。
10.根据权利要求1-7中任一项的混合物,包含NRRL登录号为B-21661的枯草芽孢杆菌菌株、具有所述菌株的所有识别特性的其突变体或由所述菌株产生的对植物病原性真菌呈现活性的代谢物作为组分II。
11.根据权利要求1-10中任一项的混合物,以100∶1-1∶100的重量比包含化合物I和组分II。
12.一种农业化学组合物,包含溶剂或固体载体和根据权利要求1-11中任一项的混合物。
13.根据权利要求12的组合物,包含至少一种其他活性物质。
14.一种防治植物病原性有害真菌的方法,所述方法包括用有效量的如权利要求1-11中任一项所定义的至少一种化合物I和杀真菌组分II或如权利要求12或13所定义的组合物处理真菌或要防止真菌侵袭的材料、植物、土壤或种子。
15.植物繁殖材料,以0.1-10,000g活性化合物/100kg植物繁殖材料的量包含根据权利要求1-11中任一项的混合物。
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Cited By (4)
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CN107711889A (zh) * | 2012-05-30 | 2018-02-23 | 拜耳作物科学股份公司 | 包含生物防治剂和杀虫剂的组合物 |
CN108669088A (zh) * | 2012-05-30 | 2018-10-19 | 拜耳作物科学股份公司 | 包含生物防治剂和选自细胞壁合成抑制剂的杀真菌剂的组合物 |
CN103451117A (zh) * | 2012-06-04 | 2013-12-18 | 华中农业大学 | 一种防治土壤环境病原菌的芽胞杆菌制剂及制备方法和应用 |
CN103451117B (zh) * | 2012-06-04 | 2015-03-04 | 华中农业大学 | 一种防治土壤环境病原菌的芽胞杆菌制剂及制备方法和应用 |
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