CN116634876A - 包含杀镰孢菌素a、杀镰孢菌素b和杀真菌剂的混合物和组合物 - Google Patents
包含杀镰孢菌素a、杀镰孢菌素b和杀真菌剂的混合物和组合物 Download PDFInfo
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- CN116634876A CN116634876A CN202180087393.2A CN202180087393A CN116634876A CN 116634876 A CN116634876 A CN 116634876A CN 202180087393 A CN202180087393 A CN 202180087393A CN 116634876 A CN116634876 A CN 116634876A
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- fusarium
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- zoxamide
- methyl
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- 239000005857 Trifloxystrobin Substances 0.000 claims abstract description 75
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/48—Nitro-carboxylic acids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
- A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
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Abstract
本发明涉及新型混合物,包含杀镰孢菌素A和杀镰孢菌素B以及至少一种选自如下的杀真菌剂作为活性组分:醚唑、螺茂胺、氟唑菌酰胺、啶酰菌胺、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷和乙磷铝。本发明还涉及一种通过施用此类混合物防治或抑制植物病原体或防止植物病原体感染的方法。
Description
发明领域
本发明涉及新型混合物,包含杀镰孢菌素A和杀镰孢菌素B以及至少一种选自如下的杀真菌剂作为活性组分:醚唑(difenoconazole)、螺茂胺(spiroxamine)、氟唑菌酰胺(fluxapyroxad)、啶酰菌胺(boscalid)、氟茚唑菌胺(fluindapyr)、isoflucypram、inpyrfluxam、氟唑菌酰羟胺(pydiflumetofen)、二甲嘧菌胺(pyrimethanil)、氟嘧菌酯(fluoxastrobin)、四唑菌酮(metyltetraprole)、肟菌酯(trifloxystrobin)、氰霜唑(cyazofamid)、吲唑磺菌胺(amisulbrom)、苯酰菌胺(zoxamide)、清菌脲(cymoxanil)、氟啶胺(fluazinam)、霜霉灭(valifenalate)、苯噻菌胺(benthiavalicarb)、异丙菌胺(iprovalicarb)、双炔酰菌胺(mandipropamid)、烯酰吗啉(dimethomorph)、氟吡菌胺(fluopicolide)、唑嘧菌胺(ametoctradin)、氟噻唑吡乙酮(oxathiapiprolin)、苯啶菌酮(pyriofenone)、苯菌酮(metrafenone)、代森联(metiram)、代森锰锌(mancozeb)、二噻农(dithianon)、藻菌磷(fosetyl)和乙磷铝(fosetyl-Al)。本发明还涉及一种通过施用此类混合物防治或抑制植物病原体或防止植物病原体感染的方法。
发明背景
在防治影响植物或作物的植物病原性真菌的技术领域中,众所周知的是施用生物农药。这些生物农药可以或不可以与植物病原性真菌的合成化学农药组合。
已经将生物农药定义为基于微生物(细菌、真菌、病毒、线虫等)或天然产物(来自生物来源的化合物或提取物)的农药形式(U.S.Environmental Protection Agency:http://www.epa.gov/pesticides/biopesticides/)。生物农药通常通过生长和浓缩天然存在的生物体和/或其代谢物来产生,包括细菌和其他微生物、真菌、病毒、线虫、蛋白质等。它们经常被认为是病虫害综合治理(IPM)项目的重要组成部分,并且作为合成化学农药的替代品已经受到了很多实际关注。
为了防治植物病原性真菌,之前已经描述了几种包含形成孢子的细菌(如类芽孢杆菌属(Paenibacillus)数种)的微生物农药,例如参见:
WO 1999/059412公开了多粘类芽孢杆菌(Paenibacillus polymyxa)菌株PKB1(具有ATCC登记号202127),其具有对抗几种植物病原性真菌的活性。
WO 2011/069227公开了多粘类芽孢杆菌菌株JB05-01-1(具有ATCC登记号PTA-10436),其具有对抗病原性细菌(主要是经食物传播的人病原性细菌)的高度抑制作用。
称作AC-1的另一多粘类芽孢杆菌菌株由“Biocontrol activity ofPaenibacillus polymyxa AC-1against Pseudomonas syringae and its interactionwith Arabidopsis thaliana”2016Microbiological Research 185DOI:10.1016/j.micres.2016.01.004和Green Biotech Co.,Ltd.45-70Yadang-ri,Gyoha-Eup PajuKyungki-Do,Korea(South)413-830的产品Topseed已知。
另一假定称作HY96-2的多粘类芽孢杆菌菌株由Biocontrol Science andTechnology 24(4),426-435(2014)已知并且将按照名称KangDiLeiDe由Shanghai ZeyuanMarine Biotechnology Co.,Ltd销售。
WO2016/154297公开了类芽孢杆菌属数种菌株的突变体,包括菌株NRRL B-50972和NRRL B-67129以及与杀镰孢菌素具有结构相似性的脂肽,称为Paeniserine和Paeniprolixin。
WO2019/221988公开了类芽孢杆菌属数种的突变体,包括菌株NRRL B-67304、NRRLB-67306和NRRL B-67615。
WO2020/181053公开了类芽孢杆菌属数种菌株NRRL B-50374、NRRL B-67721、NRRLB-67723和NRRL B-67724。
WO2019/155253公开了多粘类芽孢杆菌菌株VMC10/96。
WO2018/195603公开了类芽孢杆菌属数种10.6D和类芽孢杆菌属数种9.4E。
类芽孢杆菌属菌株、它们的一些代谢物和合成化学农药的组合也已有公开,例如参见:
WO2017/137351公开了三种不同的类芽孢杆菌属菌株,这些菌株的重要代谢物以及这些菌株和代谢物与合成化学农药的协同增效组合。
如本文中使用的术语类芽孢杆菌属菌株与术语类芽孢杆菌属数种菌株相同并且意指类芽孢杆菌属的细菌菌株形式。类芽孢杆菌属包括类芽孢杆菌属数种的全部种类。
已知类芽孢杆菌属产生许多抗生素代谢物,它们是脂肽,例如多粘菌素、八肽菌素、多肽菌素、pelgipeptin和杀镰孢菌素。杀镰孢菌素是从类芽孢杆菌属数种分离的来自环状脂缩酚酸肽(lipodepsipeptide)类别的一组抗生素,其经常共有以下结构特征:由6个氨基酸残基组成的大环,其中三个氨基酸残基是L-Thr、D-allo-Thr和D-Ala,以及通过酰胺键连接N-末端L-Thr残基的15-胍基-3-羟基十五烷酸尾部(ChemMedChem 7,871-882,2012;J.Microbiol.Meth.85,175-182,2011,其中表1)。这些化合物通过N-末端L-Thr羟基和C-末端D-Ala羰基之间的内酯桥环化。缩酚酸肽(depsipeptide)环内氨基酸残基的位置通常从上述L-Thr(其自身也携带GHPD链)开始编号并且结束于C-末端D-Ala。从类芽孢杆菌属分离的杀镰孢菌素的非限制性实例称为LI-F03、LI-F04、LI-F05、LI-F07和LI-F08(J.Antibiotics 40(11),1506-1514,1987;Heterocycles 53(7),1533-1549,2000;Peptides 32,1917-1923,2011)以及杀镰孢菌素A(也称为LI-F04a)、杀镰孢菌素B(也称为LI-F04b)、杀镰孢菌素C(也称为LI-F03a)和杀镰孢菌素D(也称为LI-F03b)(J.Antibiotics49(2),129-135,1996;J.Antibiotics 50(3),220-228,1997)。杀镰孢菌素的氨基酸链不是通过核糖体产生的,而是通过非核糖体肽合成酶产生的。已知的杀镰孢菌素的结构式显示于表1中(Biotechnol Lett.34,1327-1334,2012;其中的图1)。称为LI-F03a、LI-F03b直至LI-F08a和LI-F08b的化合物和如本文所述式I和I.1的杀镰孢菌素因其在杀镰孢菌素家族内的结构(例如参见表1)在本文中也称为杀镰孢菌素LI-F03a、LI-F03b直至LI-F08a和LI-F08b。
在分离的杀镰孢菌素抗生素中,杀镰孢菌素A对多种临床上相关的真菌和革兰氏阳性细菌,例如金黄色葡萄球菌(Staphylococcus aureus)(MIC值范围:0.78-3.12μg/mL)已经显示出最有前景的抗微生物活性(ChemMedChem 7,871-882,2012)。已经建立了含有替代天然存在的GHPD的12-胍基-十二烷酸(12-GDA)或12-氨基-十二烷酸(12-ADA)的杀镰孢菌素类似物的合成,但是12-ADA替代GHPD导致完全丧失抗微生物活性,而12-GDA替代GHPD保留了抗微生物活性(Tetrahedron Lett.47,8587-8590,2006;ChemMedChem 7,871-882,2012)。
表1:杀镰孢菌素家族的结构
杀镰孢菌素 | X2 | X3 | X5 |
A(LI-F04a) | D-Val | L-Val | D-Asn |
B(LI-F04b) | D-Val | L-Val | D-Gln |
C(LI-F03a) | D-Val | L-Tyr | D-Asn |
D(LI-F03b) | D-Val | L-Tyr | D-Gln |
LI-F05a | D-Val | L-Ile | D-Asn |
LI-F05b | D-Val | L-Ile | D-Gln |
LI-F06a | D-allo-Ile | L-Val | D-Asn |
LI-F06b | D-allo-Ile | L-Val | D-Gln |
LI-F07a | D-Val | L-Phe | D-Asn |
LI-F07b | D-Val | L-Phe | D-Gln |
LI-F08a | D-Ile | L-allo-Ile | D-Asn |
LI-F08b | D-Ile | L-allo-Ile | D-Gln |
其中箭头定义在GHPD的羰基结构部分和L-Thr(L-苏氨酸)的氨基之间或者在一个氨基酸的羰基和相邻氨基酸的氨基之间的单个(酰胺)键,其中箭头的尖端表示连接到所述氨基酸L-Thr或所述相邻氨基酸的氨基;以及其中不带箭头的单线定义D-Ala(D-丙氨酸)的羰基和L-Thr的羟基之间的单个(酯)键;并且其中GHPD是15-胍基-3-羟基十五烷酸。
也报道了杀镰孢菌素A、B、C和D抑制植物病原性真菌,例如尖镰孢(Fusariumoxysporum)、黑曲霉(Aspergillus niger)、米曲霉(Aspergillus oryzae)和托姆青霉(Penicillus thomii)(J.Antibiotics 49(2),129-135,1996;J.Antibiotics 50(3),220-228,1997)。已经发现杀镰孢菌素如Li-F05、LI-F07和LI-F08对各种植物病原性真菌如串珠镰刀菌(Fusarium moniliforme)、尖镰孢(F.oxysporum)、粉红镰刀菌(F.roseum)、藤仓赤霉(Giberella fujkuroi)、芝麻长蠕孢(Helminthosporium sesamum)和扩展青霉(Penicillium expansum)具有一定抗真菌活性(J.Antibiotics 40(11),1506-1514,1987)。杀镰孢菌素还对包括金黄色葡萄球菌在内的革兰氏阳性细菌具有抗细菌活性(J.Antibiotics 49,129-135,1996;J.Antibiotics 50,220-228,1997)。此外,杀镰孢菌素引起卡罗拉黑色根腐病的对斑点小球腔菌(Leptosphaeria maculans)具有抗真菌活性(Can.J.Microbiol.48,159-169,2002)。此外,发现某些类芽孢杆菌属菌株产生的杀镰孢菌素A和B及其两种相关化合物(其中D-allo-Thr经由其羟基使用酯桥与另外的丙氨酸键合)在培养的欧芹细胞中诱导抗性反应并且抑制尖镰孢的生长(WO 2006/016558;EP 1 788074 A1)。
WO 2007/086645描述了从多粘类芽孢杆菌菌株E681分离的杀镰孢菌素合成酶及其编码基因,该酶参与杀镰孢菌素A、B、C、D、LI-F03、LI-F04、LI-F05、LI-F07和LI-F08的合成。
在上述WO 2016/020371中发现类芽孢杆菌属菌株Lu16774、Lu17007和Lu17015的全培养液、培养基和无细胞提取物由其对链格孢属(Alternaria)数种、灰葡萄孢(Botrytiscinerea)和致病疫霉(Phytophthora infestans)显示出抑制活性。这些菌株的有机提取物的生物活性导向分离导致了杀镰孢菌素型化合物(本文中称作杀镰孢菌素1A和1B)的分离,其结构通过1D-和2D-NMR光谱法以及质谱法阐明:
然而,生物农药在一些条件下也可能具有缺点,如特异性高(要求病害/病原体的准确识别和使用多重产品)、作用速度慢(因此如果作物受到病害爆发的即时威胁,其是不适合的)、由于各种生物和非生物因素的影响而功效不定(因为生物农药通常是活的生物体,其通过在目标昆虫病害/病原体内繁殖来实现病害/病原体防治)和抗性产生。
农业实践经验已经显示,防治有害真菌或昆虫或其他病害时反复和排他性施用单独活性组分在许多情况下导致快速选出那些已经对所述活性组分形成天然或适应性抵抗力的真菌菌株或病害分离株。随后不再可能用所述活性组分有效防治这些真菌或病害。
为了降低选出抗性真菌菌株或昆虫分离株的风险,现在通常将不同活性组分的混合物用于防治有害真菌或昆虫或其他病害。通过组合农药活性化合物和/或具有不同作用机理的生物农药,可以在相对长的时间范围内确保成功防治。
本发明的目的是克服上述缺点并且为了以尽可能低的施用率有效管理抗性和有效防治植物病原性有害真菌、昆虫或其他病害或有效调节植物生长,提供在减少施用活性化合物的总量下对有害真菌或病害具有改善的活性或改善的植物生长调节活性(协同性混合物)和拓宽的活性谱—特别对某些适应症而言—的组合物。
病害防治领域中出现的一个常见问题在于需要减少活性成分的剂量率以减少或避免不利的环境作用或毒理作用,同时仍然允许有效防治病害。就本发明而言,术语病害包括动物病害和有害真菌。
因此,本发明的目的是要提供农药混合物,其解决减少剂量率和/或增强活性谱和/或改善抗性管理的问题。
我们发现该目的由本文所定义的混合物和组合物实现。
发明描述
本发明的一个实施方案是一种混合物,包含如下组分作为活性组分:组分1
杀镰孢菌素A和杀镰孢菌素B的组合,其中杀镰孢菌素A和杀镰孢菌素B具有通式
其中
R选自15-胍基-3-羟基十五烷酸(GHPD)和12-胍基十二烷酸(12-GDA);
X1是苏氨酸;
X2是缬氨酸;
X3是缬氨酸;
X4是苏氨酸;
X5选自谷氨酰胺和天冬酰胺;
X6是丙氨酸;并且
其中箭头定义R的羰基结构部分和氨基酸X1的氨基之间或一个氨基酸的羰基和相邻氨基酸的氨基之间的单个(酰胺)键,其中箭头的尖端表示连接到所述氨基酸X1或所述相邻氨基酸的氨基;并且
其中不带箭头的单线定义X6的羰基和X1的羟基之间的单个(酯)键,以及杀镰孢菌素A具有天冬酰胺作为X5,以及
杀镰孢菌素B具有谷氨酰胺作为X5,
并且包含作为组分2的醚唑、螺茂胺、氟唑菌酰胺、啶酰菌胺、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝,优选包含作为组分2的螺茂胺、啶酰菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝;
以及其中组分1和组分2的混合物提供协同增效杀真菌效果。
术语“协同增效效果“应理解为尤其涉及由Colby公式(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)所定义的效果。
术语“协同增效效果“还应理解为涉及通过应用Tammes方法(Tammes,P.M.L.,”等效线法,农药中协同增效现象的图解表示法“,Netherl.J.Plant Pathol.70,1964)所限定的效果。
作为组分2列出的杀真菌剂在本领域中是已知的。
杀镰孢菌素A和杀镰孢菌素B的组合(组分1)优选具有的杀镰孢菌素A与杀镰孢菌素B之比为10:1-1:10,9:1-1:9,8:1-1:8,7:1-1:7,6:1-1:6,5:1-1:5,4:1-1:4,3:1-1:3,2:1-1:2,9:5-5:9,8:5-5:8,7:5-5:7,6:5-5:6,11:10-10:11或1:1。在一个实施方案中,杀镰孢菌素A与杀镰孢菌素B的比例为1:1,10:9,10:8,10:7,10:6,10:5,10:4,10:3,10:2和10:1。
在另一实施方案中,杀镰孢菌素A与杀镰孢菌素B的比例为1:1,9:10,8:10,7:10,6:10,5:10,4:10,3:10,2:10和1:10。
若无其他说明,本文所定义的比例应理解为重量比,这意味着化合物A与化合物B的比例为1:2转化为1克化合物A对2克化合物B或者1千克化合物A对2千克化合物B。
杀镰孢菌素A和杀镰孢菌素B的组合可以作为已经从该生产性类芽孢杆菌属菌株或其培养液分离的化合物存在。术语“分离的“涉及已经根据本领域已知的任何常规分离或提纯方法提纯的化合物,所述方法包括但不限于用常规树脂(例如阴离子或阳离子交换树脂,非离子性吸附树脂等)处理,用常规吸附剂(例如活性炭、硅酸、硅胶、纤维素、氧化铝等)处理,改变pH,溶剂萃取(例如用常规溶剂如醇、乙酸乙酯、己烷等),蒸馏,渗析,过滤,浓缩,结晶,再结晶,pH调节,冻干等。例如,代谢物可以通过首先除去微生物而由培养基回收。对于分离包括杀镰孢菌素A和B以及类似化合物在内的杀镰孢菌素设计的方法已经描述于现有技术,例如WO 2016/020371和WO 2016/154297中。
但是,还可以涉及包含杀镰孢菌素A和杀镰孢菌素B的无细胞提取物的制备。本文所用“无细胞提取物“是指微生物的营养细胞、孢子和/或全培养液的提取物,其包含可以通过本领域已知的方法如溶剂基方法(例如有机溶剂,如醇,有时与合适的盐组合)获得的相应微生物产生的杀镰孢菌素A和杀镰孢菌素B。适合杀镰孢菌素A和杀镰孢菌素B的提取方法在本领域中是已知的。可以通过常规浓缩技术,如干燥、蒸发、离心等来浓缩所需提取物。优选在使用前,也可以将使用有机溶剂和/或水基介质的一些洗涤步骤应用于粗提物。
替换地,杀镰孢菌素A和杀镰孢菌素B的混合物可以作为全培养液存在,其包含产生杀镰孢菌素A和杀镰孢菌素B和/或具有产生杀镰孢菌素A和杀镰孢菌素B的能力的微生物,优选类芽孢杆菌属数种的细胞或孢子。本文所用“全培养液“是指含有悬浮在培养基中的营养细胞和/或孢子的微生物液体培养物。
在优选实施方案中,杀镰孢菌素A和杀镰孢菌素B的混合物与产生杀镰孢菌素A和杀镰孢菌素B和/或具有产生杀镰孢菌素A和杀镰孢菌素B的能力的微生物,优选类芽孢杆菌属数种的细胞或孢子一起存在,其中细胞或孢子已经与用于使相应微生物生长的液体培养基分离,优选已经洗涤并浓缩。浓缩方法对熟练技术人员而言是众所周知的,该类方法可以是过滤或离心,但不排除其他方法。离心可以在约2-60℃,更优选4-60℃的温度和约5,000-20,000×g(更优选约15,000×g)下进行约10-60分钟,更优选约15-30分钟。分离的细胞或孢子通常并没有分离至纯净,而是仅仅分离至包含伴有用来使相应微生物生长的液体培养基的其他固体组分(发酵固体)的细胞或孢子的级分。
因此,在一个实施方案中,杀镰孢菌素A和杀镰孢菌素B的组合与一种或多种仍在产生或者已经产生该组合的杀镰孢菌素A和杀镰孢菌素B的类芽孢杆菌属菌株的细胞或孢子组合而存在。
这些类芽孢杆菌属菌株可以是具有产生杀镰孢菌素A和杀镰孢菌素B的能力的任何类芽孢杆菌属菌株。该类类芽孢杆菌属菌株可以通过测试杀镰孢菌素A和杀镰孢菌素B的产生而确认。杀镰孢菌素A和/或杀镰孢菌素B的充分指导生产条件和用于测试杀镰孢菌素A和/或杀镰孢菌素B的存在的方法在本领域中是众所周知的,例如在本文中的“发明背景“部分所提到的文献,例如WO2016/020371中。合适菌株的预选可以通过生物信息检索包含与WO2007/086645中所述杀镰孢菌素合酶基因具有相似性的基因的菌株而进行。
产生杀镰孢菌素A和/或杀镰孢菌素B的类芽孢杆菌属菌株可以在许多类芽孢杆菌属数种,例如—但不排除其他—类芽孢杆菌属数种中发现:多粘类芽孢杆菌、附生类芽孢杆菌(Paenibacillus epiphyticus)、皮氏类芽孢杆菌(Paenibacillus peoriae)、土地类芽孢杆菌(Paenibacillus terrae)、杰米拉类芽孢杆菌(Paenibacillus jamilae)和胶冻样类芽孢杆菌(Paenibacillus kribbensis)。
具有产生杀镰孢菌素A和/或杀镰孢菌素B的能力的示例性类芽孢杆菌属菌株为多粘类芽孢杆菌(P.polymyxa)菌株PKB1,多粘类芽孢杆菌菌株JB05-01-1,多粘类芽孢杆菌菌株AC-1,多粘类芽孢杆菌菌株HY96-2,类芽孢杆菌属数种菌株NRRL B-50972,NRRL B-67129,NRRL B-67304,NRRL B-67306和NRRL B-67615,NRRL B-50374,NRRL B-67721,NRRLB-67723,NRRL B-67724,多粘类芽孢杆菌菌株VMC10/96,类芽孢杆菌属数种菌株10.6D和类芽孢杆菌属数种菌株9.4E,类芽孢杆菌属数种菌株Lu16774、Lu17007和Lu17015,多粘类芽孢杆菌菌株M1,多粘类芽孢杆菌菌株SC2和多粘类芽孢杆菌菌株Sb3-1以及多粘类芽孢杆菌菌株E681。
本文所用“菌株”是指显示出属于相同谱系,不同于相同数种的其他分离物或菌株的表型和/或遗传性状的细菌分离物或一组分离物。类芽孢杆菌属菌株通常作为分离培养物存在。“分离的培养物”或“基本上纯化的培养物”是指本发明菌株的培养物,其不包括显著量的通常在菌株在其中生长和/或菌株通常可以由其获得的天然栖息地中发现的其他物质。因此,此类“分离的培养物”或“基本上纯化的培养物”至少60%不含,优选至少75%不含,更优选至少90%不含,甚至更优选至少95%不含,最优选至少99%不含通常在菌株在其中生长和/或菌株通常可以由其获得的天然栖息地中发现的其他物质。此类“分离的培养物”或“基本上纯化的培养物”通常不包括其量足以干扰已经产生或者正在产生杀镰孢菌素A和杀镰孢菌素B的菌株复制的任何其他微生物。
在本发明混合物中使用的类芽孢杆菌属菌株可以连续培养,或在分批工艺中或在进料分批或重复进料分批工艺中不连续培养。已知培养方法的综述可以在Chmiel的教科书(Bioprozesstechnik 1.Einführung in die Bioverfahrenstechnik(Gustav FischerVerlag,Stuttgart,1991))或Storhas的教科书(Bioreaktoren und periphereEinrichtungen(Vieweg Verlag,Braunschweig/Wiesbaden,1994))中找到。
用于类芽孢杆菌属菌株培养的培养基必须以适合的方式满足特定菌株的需求。用于各种微生物的培养基描述在美国细菌学协会(American Society for Bacteriology)的手册“普通细菌学方法手册(Manual ofMethods for General Bacteriology)”(Washington D.C.,USA,1981)中给出。其他合适的培养基公开于现有技术,例如本文所引用的文献中。
优选该类芽孢杆菌属菌株对选自早疫链格孢(Alternaria solani)、灰葡萄孢、致病疫霉和大豆菌核病(Sclerotinia sclerotiorum)的至少两种植物病原体具有抗真菌活性。
优选存在于该混合物中的类芽孢杆菌属菌株产生本领域中描述的其他杀镰孢菌素,如杀镰孢菌素C(LI-F03a)、杀镰孢菌素D(LI-F03b)或者杀镰孢菌素LI-F05a、LI-F05b、LI-F06a、LI-F06b、LI-F07a、LI-F07b、LI-F08a和LI-F08b或其他抗真菌化合物,如抗真菌的酶或肽。在另一实施方案中,杀镰孢菌素A和杀镰孢菌素B已经与其他杀镰孢菌素或其他抗真菌化合物一起从类芽孢杆菌属菌株分离。
WO2016/020371描述了由类芽孢杆菌属数种,例如—但不排除其他—菌株Lu16774、Lu17007和Lu17015以及由其衍生的菌株产生的杀镰孢菌素—具有式1A的杀镰孢菌素1A和具有式1B的杀镰孢菌素1B。
WO2016/020371进一步描述了杀镰孢菌素1A和杀镰孢菌素1B对于植物病原性真菌,如—但不排除其他—早疫链格孢、灰葡萄孢、稻瘟病菌(Pyricularia oryzae)、颖枯球腔菌(Leptosphaeria nodorum)和小麦叶枯菌(Zymoseptoria tritici)具有高活性。
因此,另一优选实施方案包括一种包含在上面的实施方案中所述的组分1和组分2并且另外包含杀镰孢菌素1A或杀镰孢菌素1B或二者的混合物。
WO2016/154297公开了类似杀镰孢菌素的化合物,称为paeniserine和paeniprolixin,它们由类芽孢杆菌属数种,尤其是菌株NRRL B-50972、NRRL B-67129和由其衍生的菌株产生。下列paeniserine和paeniprolixin描述于WO2016/154297中:paeniserine A1,paeniserine A2,paeniserine A3,paeniserine A4,paeniserine B1,paeniserine B2,paeniserine B3,paeniserine B4,paeniserine C1,paeniserine C2和paeniserine C3,paeniprolixin A1,paeniprolixin A2,paeniprolixin B1,paeniprolixin B2,paeniprolixin CI,paeniprolixin Dl,paeniprolixin E1,paeniprolixin E2,paeniprolixin F1,paeniprolixin F2,paeniprolixin G1和paeniprolixin G2。
相同的公开描述了杀镰孢菌素A和paeniserine A1的混合物以及杀镰孢菌素A和paeniprolixin C1的混合物对植物病原性真菌具有,如—但不排除其他—早疫链格孢具有改进的活性。
因此,另一优选实施方案是一种包含在上面的实施方案中所述的组分1和组分2并且另外包含至少一种paeniserine或paeniprolixine,优选包含paeniserine A1或paeniprolixin C1或二者的混合物。
包含组分1和组分2的混合物对植物病原性真菌,尤其是葫芦科刺盘孢(Colletotrichum orbiculare)、大豆菌核病、灰葡萄孢、早疫链格孢、颖枯球腔菌、小麦叶枯菌和稻瘟病菌中的至少一种具有协同增效杀真菌效果。
在一个优选实施方案中,包含组分1和组分2的混合物对葫芦科刺盘孢具有协同增效杀真菌效果并且包含螺茂胺、四唑菌酮、二甲嘧菌胺、苯酰菌胺、苯啶菌酮或二噻农作为组分2。
在一个优选实施方案中,包含组分1和组分2的混合物对大豆菌核病具有协同增效杀真菌效果并且包含肟菌酯、苯酰菌胺、双炔酰菌胺或二噻农作为组分2。
在一个优选实施方案中,包含组分1和组分2的混合物对灰葡萄孢具有协同增效杀真菌效果并且包含肟菌酯、苯酰菌胺、双炔酰菌胺、氟噻唑吡乙酮或苯啶菌酮作为组分2。
在一个优选实施方案中,包含组分1和组分2的混合物对稻瘟病菌具有协同增效杀真菌效果并且包含醚唑、螺茂胺、啶酰菌胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、氟吡菌胺、苯啶菌酮、苯菌酮、代森联、代森锰锌、藻菌磷或乙磷铝作为组分2。
在上面的实施方案中所述的混合物优选包含其他杀真菌剂作为组分3。优选组分3的杀真菌剂也以与杀镰孢菌素A、杀镰孢菌素B和/或杀镰孢菌素1A、杀镰孢菌素1B、一种或多种paeniserine、一种或多种paeniprolixin和/或组分2的杀真菌剂中的至少一种的混合物提供协同增效杀真菌效果的量存在于该混合物中。
优选用作组分3的杀真菌剂选自下组a)-m):
a)醚唑、丙硫菌唑(prothioconazol)、氯氟醚菌唑(mefentrifluconazol)、环戊唑菌(metconazole)、戊叉唑菌(triticonazol)、醚唑、iriadimenol、丙氯灵(prochloraz)、戊唑醇(tebuconazol)、氧唑菌(epoxiconazol)、环戊唑醇(ipconazol)、精甲霜灵(metalaxyl-M)、高效甲霜灵(mefenoxam)、螺茂胺、氟唑菌苯胺(penflufen)、异丙噻菌胺(isofetamid)、联苯吡菌胺(bixafen)、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑(benzovindiflupyr)、氟吡菌酰胺(fluopyram)、吡噻菌胺(penthiopyrad)、氟唑环菌胺(sedaxan)、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、环丙嘧啶(cyprodinil)、二甲嘧菌胺、氟嘧菌酯、腈嘧菌酯(azoxystrobin)、肟菌酯、唑菌胺酯(pyraclostrobin)、四唑菌酮、醚菌胺(dimoxystrobin)、四唑吡氨酯(picarbutrazox)、氟菌(fludioxonil)、托布津(thiophanate)、甲基托布津(thiophanate-methyl)、涕必灵(thiabendazol)、硅噻菌胺(silthiofam)、啶氧菌酯(picoxystrobin)、肟醚菌胺(orysastrobin)、环酰菌胺(fenhexamid)、胺苯吡菌酮(fenpyrazamine)、氰霜唑、吲唑磺菌胺、苯酰菌胺、噻唑菌胺(ethaboxam)、清菌脲、百维灵(propamocarb)、氟啶胺、唑菌嗪(triazoxide)、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、fluoxapiprolin、苯啶菌酮、苯菌酮、硫、代森联、代森锰锌、福美双(thiram)、灭菌丹(folpet)、二噻农、藻菌磷和乙磷铝,优选醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇(triadimenol)、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、高效甲霜灵、螺茂胺、氟菌、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、氰霜唑、吲唑磺菌胺、涕必灵、甲基托布津、苯酰菌胺、噻唑菌胺、清菌脲、四唑吡氨酯、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、硅噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、福美双、二噻农、藻菌磷或乙磷铝,更优选醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、二甲嘧菌胺、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、噻唑菌胺、烯酰吗啉、福美双、四唑吡氨酯、氟菌、托布津、甲基托布津、涕必灵和硅噻菌胺,
b)腈嘧菌酯、甲香菌酯(coumethoxystrobin)、丁香菌酯(coumoxystrobin)、醚菌胺、烯肟菌酯(enestroburin)、烯肟菌胺(fenaminstrobin)、fenoxystrobin/氟菌螨酯(flufenoxystrobin)、氟嘧菌酯、四唑菌酮、亚胺菌(kresoxim-methyl)、甲哌喹(mandestrobin)、叉氨苯酰胺(metominostrobin)、肟醚菌胺、啶氧菌酯、唑菌胺酯、唑胺菌酯(pyrametostrobin)、唑菌酯(pyraoxystrobin)、肟菌酯、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、吡本卡布(pyribencarb)、氯啶菌酯(triclopyricarb)/chlorodincarb、唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、N-[2-[(1,4-二甲基-5-苯基吡唑-3-基)氧甲基]苯基]-N-甲氧基氨基甲酸甲酯、四唑菌酮、(Z,2E)-5-[1-(2,4-二氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、(Z,2E)-5-[1-(4-氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、嘧螨胺(pyriminostrobin)、吡氟菌酯(bifujunzhi)、2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯,优选腈嘧菌酯、醚菌胺、氟嘧菌酯、四唑菌酮、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯和四唑菌酮;
c)氰霜唑、吲唑磺菌胺、2-甲基丙酸(6S,7R,8R)-8-苄基-3-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]-6-甲基-4,9-二氧代-1,5-二氧壬环-7-基]酯、fenpicoxamid、florylpicoxamid,优选氰霜唑、吲唑磺菌胺和fenpicoxamid,更优选氰霜唑和吲唑磺菌胺;
d)麦锈灵(benodanil)、苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、萎锈灵(carboxin)、呋菌胺(fenfuram)、氟吡菌酰胺、氟酰胺(flutolanil)、氟唑菌酰胺、呋吡唑灵(furametpyr)、异丙噻菌胺、吡唑萘菌胺(isopyrazam)、丙氧灭绣胺(mepronil)、氧化萎锈灵(oxycarboxin)、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、联苯吡嗪菌胺(pyraziflumid)、氟唑环菌胺、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、inpyrfluxam、pyrapropoyne、氟茚唑菌胺、N-[2-[2-氯-4-(三氟甲基)苯氧基]苯基]-3-(二氟甲基)-5-氟-1-甲基吡唑-4-甲酰胺、(E)-2-[2-[(5-氰基-2-甲基苯氧基)甲基]苯基]-3-甲氧基丙-2-烯酸甲酯、isoflucypram、2-(二氟甲基)-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1,3-三甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-乙基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-3-乙基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(1,1-二甲基-3-丙基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1-二甲基-3-丙基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺,优选苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、异丙噻菌胺、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、氟唑环菌胺、inpyrfluxam、氟茚唑菌胺、isoflucypram,更优选苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、氟唑菌苯胺、吡噻菌胺、氟唑环菌胺;
e)氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、氟菌、环酰菌胺、甲霜灵(metalaxyl)、精甲霜灵、二噻农,优选氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、氟菌、甲霜灵、精甲霜灵和二噻农;更优选氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、甲霜灵、精甲霜灵和二噻农;
f)戊环唑(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑、烯唑醇(diniconazole)、烯唑醇M(diniconazole-M)、氧唑菌、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、环戊唑菌、腈菌唑(myclobutanil)、咪唑(oxpoconazole)、多效唑(paclobutrazole)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑、硅氟唑(simeconazole)、戊唑醇、氟醚唑(tetraconazole)、三唑酮(triadimefon)、唑菌醇、戊叉唑菌、烯效唑(uniconazole)、2-(2,4-二氟苯基)-1,1-二氟-3-(四唑-1-基)-1-[5-[4-(2,2,2-三氟乙氧基)苯基]-2-吡啶基]丙-2-醇、2-(2,4-二氟苯基)-1,1-二氟-3-(四唑-1-基)-1-[5-[4-(三氟甲氧基)苯基]-2-吡啶基]丙-2-醇、4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苄腈、伊芬三氟康唑(ipfentrifluconazole)、氯氟醚菌唑、(2R)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丙-2-醇、(2S)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丙-2-醇、2-(氯甲基)-2-甲基-5-(对甲苯基甲基)-1-(1,2,4-三唑-1-基甲基)环戊醇;咪唑类:抑霉唑(imazalil)、稻瘟酯(pefurazoate)、丙氯灵、氟菌唑(triflumizol),嘧啶类、吡啶类、哌嗪类:异嘧菌醇(fenarimol)、啶斑肟(pyrifenox)、嗪氨灵(triforine)、[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)异唑-4-基]-(3-吡啶基)甲醇、4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苄腈、2-[6-(4-溴苯氧基)-2-(三氟甲基)-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇、2-[6-(4-氯苯氧基)-2-(三氟甲基)-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇,优选醚唑、氧唑菌、环戊唑醇、环戊唑菌、丙硫菌唑、戊唑醇、唑菌醇、戊叉唑菌和丙氯灵;
g)涕必灵、甲基托布津、乙霉威(diethofencarb)、噻唑菌胺、戊菌隆(pencycuron)、氟吡菌胺、苯酰菌胺、苯菌酮和苯啶菌酮,优选涕必灵、甲基托布津、噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮、苯啶菌酮,更优选噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮、苯啶菌酮;
h)环丙嘧啶、嘧菌胺(mepanipyrim)、二甲嘧菌胺,优选二甲嘧菌胺;
i)烯酰吗啉、氟吗啉(flumorph)、双炔酰菌胺、丁吡吗啉(pyrimorph)、苯噻菌胺、异丙菌胺、霜霉灭,优选烯酰吗啉、双炔酰菌胺、苯噻菌胺、异丙菌胺、霜霉灭;
j)氟噻唑吡乙酮、fluoxapiprolin、4-[1-[2-[3-(二氟甲基)-5-甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3,5-二(二氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3-(二氟甲基)-5-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-环丙基-3-(二氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-甲基-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-(二氟甲基)-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3,5-二(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、(4-[1-[2-[5-环丙基-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺,优选氟噻唑吡乙酮和fluoxapiprolin,更优选氟噻唑吡乙酮;
k)福美铁(ferbam)、代森锰锌、代森锰(maneb)、威百亩(metam)、代森联、甲基代森锌(propineb)、福美双、代森锌(zineb)、福美锌(ziram),优选代森锰锌、代森联和福美双;
l)藻菌磷、乙磷铝、亚磷酸及其盐、膦酸钙、膦酸钾,优选藻菌磷和乙磷铝;
m)清菌脲、胺苯吡菌酮、唑菌嗪、四唑吡氨酯,优选清菌脲,其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
优选组分3为醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、高效甲霜灵、螺茂胺、氟菌、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、氰霜唑、吲唑磺菌胺、涕必灵、甲基托布津、苯酰菌胺、噻唑菌胺、清菌脲、四唑吡氨酯、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、硅噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、福美双、二噻农、藻菌磷或乙磷铝,其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
在其中该混合物还包含杀镰孢菌素1A和/或杀镰孢菌素1B或能够产生杀镰孢菌素1A和/或杀镰孢菌素1B的类芽孢杆菌属菌株的细胞或孢子的情况下,组分3优选为醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、高效甲霜灵、螺茂胺、氟菌、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、氰霜唑、吲唑磺菌胺、涕必灵、甲基托布津、苯酰菌胺、噻唑菌胺、清菌脲、四唑吡氨酯、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、硅噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、福美双、二噻农、藻菌磷或乙磷铝,其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
与杀镰孢菌素1A和/或杀镰孢菌素1B显示协同增效效果的杀真菌剂为醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、二甲嘧菌胺、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、噻唑菌胺、烯酰吗啉、福美双、四唑吡氨酯、氟菌、托布津、甲基托布津、涕必灵和硅噻菌胺,其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
在一个实施方案中,组分2为螺茂胺且组分3为麦锈灵、苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、萎锈灵、呋菌胺、氟吡菌酰胺、氟酰胺、氟唑菌酰胺、呋吡唑灵、异丙噻菌胺、吡唑萘菌胺、丙氧灭绣胺、氧化萎锈灵、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、联苯吡嗪菌胺、氟唑环菌胺、叶枯酞、溴氟唑菌、inpyrfluxam、pyrapropoyne、氟茚唑菌胺、N-[2-[2-氯-4-(三氟甲基)苯氧基]苯基]-3-(二氟甲基)-5-氟-1-甲基吡唑-4-甲酰胺、(E)-2-[2-[(5-氰基-2-甲基苯氧基)甲基]苯基]-3-甲氧基丙-2-烯酸甲酯、isoflucypram、2-(二氟甲基)-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1,3-三甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-乙基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-3-乙基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(1,1-二甲基-3-丙基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1-二甲基-3-丙基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺或2-(二氟甲基)-N-[(3R)-3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺,优选组分3为苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、异丙噻菌胺、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、氟唑环菌胺、inpyrfluxam、氟茚唑菌胺和isoflucypram,更优选组分3为苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、氟唑菌苯胺、吡噻菌胺或氟唑环菌胺,最优选组分3为氟吡菌酰胺。
在一个实施方案中,组分2为啶酰菌胺或氟唑菌酰胺且组分3为腈嘧菌酯、甲香菌酯、丁香菌酯、醚菌胺、烯肟菌酯、烯肟菌胺、fenoxystrobin/氟菌螨酯、氟嘧菌酯、四唑菌酮、亚胺菌、甲哌喹、叉氨苯酰胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、唑胺菌酯、唑菌酯、肟菌酯、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、吡本卡布、氯啶菌酯/chlorodincarb、唑酮菌、咪唑菌酮、N-[2-[(1,4-二甲基-5-苯基吡唑-3-基)氧甲基]苯基]-N-甲氧基氨基甲酸甲酯、四唑菌酮、(Z,2E)-5-[1-(2,4-二氯苯基]吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、(Z,2E)-5-[1-(4-氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、嘧螨胺、吡氟菌酯或2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯,优选组分3为亚胺菌、腈嘧菌酯、醚菌胺、氟嘧菌酯、四唑菌酮、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯或四唑菌酮,更优选组分3为亚胺菌或唑菌胺酯。
在一个实施方案中,组分2为二甲嘧菌胺且组分3为氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、氟菌、环酰菌胺、甲霜灵、精甲霜灵或二噻农,优选组分3为氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、氟菌、甲霜灵、精甲霜灵或二噻农;更优选组分3为氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、甲霜灵、精甲霜灵或二噻农。
在一个实施方案中,组分2为二甲嘧菌胺且组分3为腈嘧菌酯、甲香菌酯、丁香菌酯、醚菌胺、烯肟菌酯、烯肟菌胺、fenoxystrobin/氟菌螨酯、氟嘧菌酯、四唑菌酮、亚胺菌、甲哌喹、叉氨苯酰胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、唑胺菌酯、唑菌酯、肟菌酯、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、吡本卡布、氯啶菌酯/chlorodincarb、唑酮菌、咪唑菌酮、N-[2-[(1,4-二甲基-5-苯基吡唑-3-基)氧甲基]苯基]-N-甲氧基氨基甲酸甲酯、四唑菌酮、(Z,2E)-5-[1-(2,4-二氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、(Z,2E)-5-[1-(4-氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、嘧螨胺、吡氟菌酯或2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯,优选组分3为腈嘧菌酯、醚菌胺、氟嘧菌酯、四唑菌酮、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯或四唑菌酮。
在一个实施方案中,组分2为肟菌酯、氟嘧菌酯或四唑菌酮且组分3为环丙嘧啶、嘧菌胺或二甲嘧菌胺,优选组分3为二甲嘧菌胺。
在一个实施方案中,组分2为肟菌酯、氟嘧菌酯或四唑菌酮且组分3为麦锈灵、苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、萎锈灵、呋菌胺、氟吡菌酰胺、氟酰胺、氟唑菌酰胺、呋吡唑灵、异丙噻菌胺、吡唑萘菌胺、丙氧灭绣胺、氧化萎锈灵、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、联苯吡嗪菌胺、氟唑环菌胺、叶枯酞、溴氟唑菌、inpyrfluxam、pyrapropoyne、氟茚唑菌胺、N-[2-[2-氯-4-(三氟甲基)苯氧基]苯基]-3-(二氟甲基)-5-氟-1-甲基吡唑-4-甲酰胺、(E)-2-[2-[(5-氰基-2-甲基苯氧基)甲基]苯基]-3-甲氧基丙-2-烯酸甲酯、isoflucypram、2-(二氟甲基)-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1,3-三甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-乙基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-3-乙基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(1,1-二甲基-3-丙基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1-二甲基-3-丙基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺或2-(二氟甲基)-N-[(3R)-3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺,优选组分3为苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、异丙噻菌胺、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、氟唑环菌胺、inpyrfluxam或氟茚唑菌胺、isoflucypram,更优选组分3为苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、氟唑菌苯胺、吡噻菌胺或氟唑环菌胺。
在一个实施方案中,组分2为苯酰菌胺或噻唑菌胺且组分3为烯酰吗啉、氟吗啉、双炔酰菌胺、丁吡吗啉、苯噻菌胺、异丙菌胺或霜霉灭,优选组分3为烯酰吗啉、双炔酰菌胺、苯噻菌胺、异丙菌胺或霜霉灭;
在一个实施方案中,组分2为苯酰菌胺或噻唑菌胺且组分3为氟噻唑吡乙酮、fluoxapiprolin、4-[1-[2-[3-(二氟甲基)-5-甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3,5-二(二氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3-(二氟甲基)-5-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-环丙基-3-(二氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-甲基-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-(二氟甲基)-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3,5-二(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺或(4-[1-[2-[5-环丙基-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺,优选组分3为氟噻唑吡乙酮或fluoxapiprolin,更优选组分3为氟噻唑吡乙酮。
在一个实施方案中,组分2为苯酰菌胺或噻唑菌胺且组分3为福美铁、代森锰锌、代森锰、威百亩、代森联、甲基代森锌、福美双、代森锌或福美锌,优选组分3为代森锰锌、代森联和福美双。
在一个实施方案中,组分2为清菌脲且组分3为烯酰吗啉、氟吗啉、双炔酰菌胺、丁吡吗啉、苯噻菌胺、异丙菌胺、霜霉灭,优选组分3为烯酰吗啉、双炔酰菌胺、苯噻菌胺、异丙菌胺或霜霉灭。
在一个实施方案中,组分2为霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺或烯酰吗啉,优选组分2为霜霉灭、苯噻菌胺、异丙菌胺或双炔酰菌胺且组分3为戊环唑、双苯三唑醇、糠菌唑、环唑醇、醚唑、烯唑醇、烯唑醇M、氧唑菌、腈苯唑、喹唑菌酮、氟硅唑、粉唑醇、己唑醇、酰胺唑、环戊唑醇、环戊唑菌、腈菌唑、咪唑、多效唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、氟醚唑、三唑酮、唑菌醇、戊叉唑菌、烯效唑、2-(2,4-二氟苯基)-1,1-二氟-3-(四唑-1-基)-1-[5-[4-(2,2,2-三氟乙氧基)苯基]-2-吡啶基]丙-2-醇、2-(2,4-二氟苯基)-1,1-二氟-3-(四唑-1-基)-1-[5-[4-(三氟甲基)苯基]-2-吡啶基]丙-2-醇、4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苄腈、伊芬三氟康唑、氯氟醚菌唑、(2R)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丙-2-醇、(2S)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丙-2-醇、2-(氯甲基)-2-甲基-5-(对甲苯基甲基)-1-(1,2,4-三唑-1-基甲基)环戊醇;咪唑类:抑霉唑、稻瘟酯、丙氯灵、氟菌唑、嘧啶类、吡啶类、哌嗪类:异嘧菌醇、啶斑肟、嗪氨灵、[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)异唑-4-基]-(3-吡啶基)甲醇、4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苄腈、2-[6-(4-溴苯氧基)-2-(三氟甲基)-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇或2-[6-(4-氯苯氧基)-2-(三氟甲基)-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇,优选组分3为醚唑、氧唑菌、环戊唑醇、环戊唑菌、丙硫菌唑、戊唑醇、唑菌醇、戊叉唑菌和丙氯灵。
在一个实施方案中,组分2为霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺或烯酰吗啉,优选组分2为霜霉灭、苯噻菌胺、异丙菌胺或双炔酰菌胺且组分3为清菌脲、胺苯吡菌酮、唑菌嗪或四唑吡氨酯,优选组分3为清菌脲,
在一个实施方案中,组分2为霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺或烯酰吗啉,优选组分2为霜霉灭、苯噻菌胺、异丙菌胺或双炔酰菌胺且组分3为腈嘧菌酯、甲香菌酯、丁香菌酯、醚菌胺、烯肟菌酯、烯肟菌胺、fenoxystrobin/氟菌螨酯、氟嘧菌酯、四唑菌酮、亚胺菌、甲哌喹、叉氨苯酰胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、唑胺菌酯、唑菌酯、肟菌酯、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、吡本卡布、氯啶菌酯/chlorodincarb、唑酮菌、咪唑菌酮、N-[2-[(1,4-二甲基-5-苯基吡唑-3-基)氧甲基]苯基]-N-甲氧基氨基甲酸甲酯、四唑菌酮、(Z,2E)-5-[1-(2,4-二氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、(Z,2E)-5-[1-(4-氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、嘧螨胺、吡氟菌酯或2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯,优选组分3为腈嘧菌酯、醚菌胺、氟嘧菌酯、四唑菌酮、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯或四唑菌酮。
在一个实施方案中,组分2为霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺或烯酰吗啉,优选组分2为霜霉灭、苯噻菌胺、异丙菌胺或双炔酰菌胺且组分3为涕必灵、甲基托布津、乙霉威、噻唑菌胺、戊菌隆、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮,优选组分3为涕必灵、甲基托布津、噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮,更优选组分3为噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮;
在一个实施方案中,组分2为氟吡菌胺且组分3为藻菌磷、乙磷铝、亚磷酸及其盐、膦酸钙或膦酸钾,优选组分3为藻菌磷或乙磷铝。
在一个实施方案中,组分2为唑嘧菌胺且组分3为烯酰吗啉、氟吗啉、双炔酰菌胺、丁吡吗啉、苯噻菌胺、异丙菌胺或霜霉灭,优选至少一种其他杀真菌剂为烯酰吗啉、双炔酰菌胺、苯噻菌胺、异丙菌胺或霜霉灭。
在一个实施方案中,组分2为氟噻唑吡乙酮或fluoxapiprolin,优选组分2为氟噻唑吡乙酮且组分3为涕必灵、甲基托布津、乙霉威、噻唑菌胺、戊菌隆、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮,优选组分3为涕必灵、甲基托布津、噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮,更优选组分3为噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮;
在一个实施方案中,组分2为代森联、代森锰锌或福美双,优选组分2为代森联或代森锰锌且组分3为涕必灵、甲基托布津、乙霉威、噻唑菌胺、戊菌隆、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮,优选组分3为涕必灵、甲基托布津、噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮,更优选组分3为噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮。
在一个实施方案中,组分2为代森联、代森锰锌或福美双,优选组分2为代森联或代森锰锌且组分3为精苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、kiralaxyl、甲霜灵、精甲霜灵、甲呋酰胺(ofurace)、霜灵(oxadixyl);优选组分3为甲霜灵或精甲霜灵。
在一个实施方案中,组分2为代森联、代森锰锌或福美双,优选组分2为代森联或代森锰锌且组分3为烯酰吗啉、氟吗啉、双炔酰菌胺、丁吡吗啉、苯噻菌胺、异丙菌胺或霜霉灭,优选组分3为烯酰吗啉、双炔酰菌胺、苯噻菌胺、异丙菌胺或霜霉灭。
在一个实施方案中,组分2为二噻农且组分3为环丙嘧啶、嘧菌胺或二甲嘧菌胺,优选组分3为二甲嘧菌胺。
在一个实施方案中,组分2为二噻农且组分3为烯酰吗啉、氟吗啉、双炔酰菌胺、丁吡吗啉、苯噻菌胺、异丙菌胺或霜霉灭,优选组分3为烯酰吗啉、双炔酰菌胺、苯噻菌胺、异丙菌胺或霜霉灭。
在一个实施方案中,组分2为藻菌磷或乙磷铝且组分3为麦锈灵、苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、萎锈灵、呋菌胺、氟吡菌酰胺、氟酰胺、氟唑菌酰胺、呋吡唑灵、异丙噻菌胺、吡唑萘菌胺、丙氧灭绣胺、氧化萎锈灵、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、联苯吡嗪菌胺、氟唑环菌胺、叶枯酞、溴氟唑菌、inpyrfluxam、pyrapropoyne、氟茚唑菌胺、N-[2-[2-氯-4-(三氟甲基)苯氧基]苯基]-3-(二氟甲基)-5-氟-1-甲基吡唑-4-甲酰胺、(E)-2-[2-[(5-氰基-2-甲基苯氧基)甲基]苯基]-3-甲氧基丙-2-烯酸甲酯、isoflucypram、2-(二氟甲基)-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1,3-三甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-乙基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-3-乙基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(1,1-二甲基-3-丙基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1-二甲基-3-丙基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺或2-(二氟甲基)-N-[(3R)-3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺,优选组分3为苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、异丙噻菌胺、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、氟唑环菌胺、inpyrfluxam、氟茚唑菌胺,或者isoflucypram,更优选组分3为苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、氟唑菌苯胺、吡噻菌胺或氟唑环菌胺。
在一个实施方案中,组分2为藻菌磷或乙磷铝且组分3为涕必灵、甲基托布津、乙霉威、噻唑菌胺、戊菌隆、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮,优选组分3为涕必灵、甲基托布津、噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮,更优选组分3为噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮或苯啶菌酮。
优选组分2的杀真菌剂为啶酰菌胺、肟菌酯、苯酰菌胺、清菌脲、双炔酰菌胺、异丙菌胺、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝。
在一个实施方案中,组分2的杀真菌剂为螺茂胺、啶酰菌胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝(乙磷铝)且组分3的杀真菌剂为螺茂胺、啶酰菌胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝(乙磷铝),其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
在一个实施方案中,组分2的杀真菌剂为醚唑、螺茂胺、氟唑菌酰胺、啶酰菌胺、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝,优选螺茂胺、肟菌酯、清菌脲、异丙菌胺、双炔酰菌胺、氟吡菌胺、氟噻唑吡乙酮、代森联、代森锰锌、藻菌磷或乙磷铝并且组分3的杀真菌剂为丙硫菌唑、氟吡菌酰胺、二甲嘧菌胺、fluoxapiprolin或百维灵,优选丙硫菌唑、二甲嘧菌胺、fluoxapiprolin或百维灵,甚至更优选丙硫菌唑。
在一个实施方案中,组分2的杀真菌剂为啶酰菌胺、氟嘧菌酯、四唑菌酮、氰霜唑、吲唑磺菌胺、苯酰菌胺、苯噻菌胺、异丙菌胺、唑嘧菌胺、苯啶菌酮、苯菌酮或二噻农并且组分3的杀真菌剂为醚唑、螺茂胺、氟唑菌酰胺、啶酰菌胺、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝,优选螺茂胺、肟菌酯、清菌脲、异丙菌胺、双炔酰菌胺、氟吡菌胺、氟噻唑吡乙酮、代森联、代森锰锌、藻菌磷或乙磷铝,其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
在一个实施方案中,组分2的杀真菌剂为啶酰菌胺、氟嘧菌酯、四唑菌酮、氰霜唑、吲唑磺菌胺、苯酰菌胺、苯噻菌胺、异丙菌胺、唑嘧菌胺、苯啶菌酮、苯菌酮或二噻农并且组分3的杀真菌剂为螺茂胺、啶酰菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝,其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
类似的优选实施方案是下列混合物,其中:
组分2为螺茂胺且组分3为氟吡菌酰胺,或者
组分2为啶酰菌胺且组分3为唑菌胺酯,或者
组分2为二甲嘧菌胺且组分3为二噻农或肟菌酯,或者
组分2为肟菌酯且组分3为二甲嘧菌胺或氟吡菌酰胺;或者
组分2为苯酰菌胺且组分3为双炔酰菌胺、氟噻唑吡乙酮或代森锰锌;或者
组分2为清菌脲且组分3为双炔酰菌胺;或者
组分2为双炔酰菌胺且组分3为醚唑、清菌脲、腈嘧菌酯和/或苯酰菌胺;或者
组分2为氟吡菌胺且组分3为乙磷铝;或者
组分2为唑嘧菌胺且组分3为烯酰吗啉;或者
组分2为氟噻唑吡乙酮且组分3为苯酰菌胺;或者
组分2为代森锰锌且组分3为苯酰菌胺、甲霜灵、精甲霜灵或烯酰吗啉;或者
组分2为二噻农且组分3为二甲嘧菌胺或烯酰吗啉;或者
组分2为藻菌磷或乙磷铝且组分3为氟吡菌酰胺或氟吡菌胺。
组分1和组分2之间以及适用的话,组分1和组分3之间的重量比为300:1-1:300,250:1-1:250,200:1-1:200,150:1-1:150,100:1-1:100,90:1-1:90,80:1-1:80,70:1-1:70,60:1-1:60,50:1-1:50,40:1-1:40,30:1-1:30,20:1-1:20,10:1-1:10,9:1-1:9,8:1-1:8,7:1-1:7,6:1-1:6,5:1-1:5,4:1-1:4,3:1-1:3,2:1-1:2和1:1。
组分1和组分2之间以及适用的话,组分1和组分3之间的优选重量比为300:1-1:1,250:1-1:1,200:1-1:1,150:1-1:1,100:1-1:1,90:1-1:1,80:1-1:1,70:1-1:1,60:1-1:1,50:1-1:1,40:1-1:1,30:1-1:1,20:1-1:1,10:1-1:1,9:1-1:1,8:1-1:1,7:1-1:1,6:1-1:1,5:1-1:1,4:1-1:1,3:1-1:1,2:1-1:1。
组分1和组分2之间以及适用的话,组分1和组分3之间的优选重量比还为1:1-1:300,1:1-1:250,1:1-1:200,1:1-1:150,1:1-1:100,1:1-1:90,1:1-1:80,1:1-1:70,1:1-1:60,1:1-1:50,1:1-1:40,1:1-1:30,1:1-1:20,1:1-1:10,1:1-1:9,1:1-1:8,1:1-1:7,1:1-1:6,1:1-1:5,1:1-1:4,1:1-1:3,1:1-1:2。
杀镰孢菌素A和杀镰孢菌素B的总量与当用作组分2或者适用的话,组分3时螺茂胺、清菌脲、苯噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、苯酰菌胺、代森联和啶酰菌胺的总量之间的更优选重量比选自1:1-1:30,1:1-1:20,1:1-1:19,1:1-1:18,1:1-1:17,1:1-1:16,1:1-1:15,1:1-1:14,1:1-1:13,1:1-1:12,1:1-1:11,1:1-1:10,1:1-1:9,1:1-1:8,1:1-1:7,1:1-1:6,1:1-1:5,1:1-1:4,1:1-1:3,1:1-1:2,更优选1:1-1:20,1:1-1:19,1:1-1:18,1:1-1:17,1:1-1:16。
杀镰孢菌素A和杀镰孢菌素B的总量与当用作组分2或者适用的话,组分3时霜霉灭、唑嘧菌胺、二噻农、藻菌磷和乙磷铝的总量之间的更优选重量比选自20:1-1:20,10:1-1:10,9:1-1:9,8:1-1:8,7:1-1:7,6:1-1:6,5:1-1:5,4:1-1:4,3:1-1:3,2:1-1:2和1:1,优选5:1-1:5,4:1-1:4,3:1-1:3,2:1-1:2和1:1。
杀镰孢菌素A和杀镰孢菌素B的总量与当用作组分2或者适用的话,组分3时联苯吡菌胺、氟嘧菌酯、肟菌酯、四唑菌酮、氰霜唑、吲唑磺菌胺、氟啶胺、异丙菌胺、氟吡菌胺、苯菌酮和代森锰锌的总量之间的更优选重量比选自300:1-1:1,250:1-1:1,200:1-1:1,150:1-1:1,100:1-1:1,90:1-1:1,80:1-1:1,70:1-1:1,60:1-1:1,50:1-1:1,40:1-1:1,30:1-1:1,20:1-1:1,10:1-1:1,9:1-1:1,8:1-1:1,7:1-1:1,6:1-1:1,5:1-1:1,4:1-1:1,3:1-1:1,2:1-1:1,优选250:1-1:1,70:1-1:1或10:1-1:1。
杀镰孢菌素A和杀镰孢菌素B的总量与当用作组分2或者适用的话,组分3时双炔酰菌胺的总量之间的更优选重量比为1:1-1:100,1:1-1:90,1:1-1:80,1:1-1:70,1:1-1:60,1:1-1:50,1:1-1:40,1:1-1:30,1:1-1:20,1:1-1:10,1:1-1:9,1:1-1:8,1:1-1:7,1:1-1:6,1:1-1:5,1:1-1:4,1:1-1:3,1:1-1:2,优选1:1-1:80,1:1-1:70,1:1-1:60,1:1-1:50,1:1-1:40,1:1-1:30,1:1-1:20,1:1-1:10,1:1-1:9,1:1-1:8,1:1-1:7,1:1-1:6,1:1-1:5,1:1-1:4,1:1-1:3,1:1-1:2。
混合物可以转化成农业化学组合物常用的类型,例如溶液、乳液、悬浮液、粉剂、粉末、糊、颗粒、模压品、胶囊及其混合物。组合物类型(也见“Catalogue of pesticideformulation types and international coding system“,Technical Monograph,第2期,2008年5月第6版,CropLife International)的实例是悬浮液(SC、OD、FS),可乳化浓缩物(EC),乳液(EW、EO、ES、ME),胶囊(例如CS、ZC),糊,锭剂,可湿性粉末或粉剂(WP、SP、WS、DP、DS),模压品(例如BR、TB、DT),颗粒(例如WG、SG、GR、FG、GG、MG),杀虫制品(例如LN)以及处理植物繁殖材料如种子的凝胶配制剂(例如GF)。
组合物如Mollet和Grubemann,Formulation technology,Wiley VCH,Weinheim,2001;或Knowles,New developments in crop protection product formulation,AgrowReports DS243,T&F Informa,London,2005所述以已知方式制备。本发明还涉及包含助剂和任一种上述混合物的农业化学组合物。
合适的助剂是溶剂,液体载体,固体载体或填料,表面活性剂,分散剂,乳化剂,润湿剂,辅助剂,加溶剂,渗透促进剂,保护性胶体,粘附剂,增稠剂,保湿剂,驱除剂,引诱剂,进食刺激剂,相容剂,杀菌剂,防冻剂,消泡剂,着色剂,增粘剂和粘合剂。
合适的溶剂和液体载体是水和有机溶剂,如中到高沸点的矿物油馏分,例如煤油、柴油;植物或动物来源的油;脂族、环状和芳族烃类,例如甲苯、石蜡、四氢萘和烷基化萘;醇类,如乙醇、丙醇、丁醇、苄醇、环己醇;二醇类;DMSO;酮类,例如环己酮;酯类,例如乳酸酯、碳酸酯、脂肪酸酯、γ-丁内酯;脂肪酸;膦酸酯;胺类;酰胺类,例如N-甲基吡咯烷酮,脂肪酸二甲基酰胺;以及它们的混合物。
合适的固体载体或填料是矿土,例如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、粘土、白云石、硅藻土、膨润土、硫酸钙、硫酸镁、氧化镁;多糖,例如纤维素、淀粉;肥料,例如硫酸铵、磷酸铵、硝酸铵、脲类;植物来源的产品,例如谷粉、树皮粉、木粉和坚果壳粉,以及它们的混合物。
合适的表面活性剂是表面活性化合物,如阴离子、阳离子、非离子和两性表面活性剂,嵌段聚合物,聚电解质,以及它们的混合物。该类表面活性剂可以用作乳化剂、分散剂、加溶剂、润湿剂、渗透促进剂、保护性胶体或辅助剂。表面活性剂的实例列于McCutcheon’s,第1卷:Emulsifiers&Detergents,McCutcheon’s Directories,Glen Rock,USA,2008(International Ed.或North American Ed.)中。
合适的阴离子表面活性剂是磺酸、硫酸、磷酸、羧酸的碱金属、碱土金属或铵盐以及它们的混合物。磺酸盐的实例是烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木素磺酸盐、脂肪酸和油的磺酸盐、乙氧基化烷基酚的磺酸盐、烷氧基化芳基酚的磺酸盐、缩合萘的磺酸盐、十二烷基-和十三烷基苯的磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例是脂肪酸和油的硫酸盐、乙氧基化烷基酚的硫酸盐、醇的硫酸盐、乙氧基化醇的硫酸盐或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸盐酯。羧酸盐的实例是烷基羧酸盐以及羧化醇或烷基酚乙氧基化物。
合适的非离子表面活性剂是烷氧基化物,N-取代的脂肪酸酰胺,胺氧化物,酯类,糖基表面活性剂,聚合物表面活性剂及其混合物。烷氧基化物的实例是诸如已经被1-50当量烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可以将氧化乙烯和/或氧化丙烯用于烷氧基化,优选氧化乙烯。N-取代的脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯类的实例是脂肪酸酯,甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨醇、乙氧基化脱水山梨醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。聚合物表面活性剂的实例是乙烯基吡咯烷酮、乙烯醇或乙酸乙烯酯的均聚物或共聚物。
合适的阳离子表面活性剂是季型表面活性剂,例如具有1或2个疏水性基团的季铵化合物,或长链伯胺的盐。合适的两性表面活性剂是烷基甜菜碱和咪唑啉类。合适的嵌段聚合物是包含聚氧乙烯和聚氧丙烯的嵌段的A-B或A-B-A类型嵌段聚合物,或包含链烷醇、聚氧乙烯和聚氧丙烯的嵌段的A-B-C类型嵌段聚合物。合适的聚电解质是聚酸或聚碱。聚酸的实例是聚丙烯酸的碱金属盐或聚酸梳状聚合物。聚碱的实例是聚乙烯基胺或聚乙烯胺。
合适的辅助剂是本身具有可忽略的农药活性或者本身甚至没有农药活性且改善化合物I对目标物的生物学性能的化合物。实例是表面活性剂,矿物油或植物油以及其他助剂。其他实例由Knowles,Adjuvants and additives,Agrow Reports DS256,T&F InformaUK,2006,第5章列出。
合适的增稠剂是多糖(例如黄原胶、羧甲基纤维素)、无机粘土(有机改性或未改性的)、聚羧酸盐和硅酸盐。
合适的杀菌剂是拌棉醇(bronopol)和异噻唑啉酮衍生物如烷基异噻唑啉酮类和苯并异噻唑啉酮类。
合适的防冻剂是乙二醇、丙二醇、尿素和甘油。
合适的消泡剂是聚硅氧烷、长链醇和脂肪酸盐。
合适的着色剂(例如着红色、蓝色或绿色)是低水溶性颜料和水溶性染料。实例是无机着色剂(例如氧化铁、氧化钛、六氰合铁酸铁)和有机着色剂(例如茜素着色剂、偶氮着色剂和酞菁着色剂)。
合适的增粘剂或粘合剂是聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇、聚丙烯酸酯、生物蜡或合成蜡以及纤维素醚。
农业化学组合物通常包含0.01-95重量%,优选0.1-90重量%,更优选1-70%,尤其是10-60重量%混合物。在组分1伴随有产生杀镰孢菌素的类芽孢杆菌属菌株的细胞或孢子或者经由其提供的情况下,这些细胞或孢子的量优选为该农业化学组合物的5-50重量%,10-50重量%,15-50重量%,30-50重量%或40-50重量%或5-40重量%,10-40重量%,15-40重量%,30-40重量%或10-40重量%,15-40重量%,30-40重量%。
产生杀镰孢菌素的类芽孢杆菌属菌株的细胞或孢子通常以平均粒度为1-150μm,或者以优选顺序增加的1-100μm,1-75μm,1-50μm,1-25μm,1-10μm或1-8μm(根据光散射方法在液体分散体中根据CIPAC方法187测定)的固体颗粒形式存在。
每ml的孢子密度数可以通过在约20-35℃的温度下温育几天之后确认在琼脂培养基,例如马铃薯葡萄糖琼脂上菌落形成单位(CFU)数而确定。用来制备本发明农业化学组合物的CFU/g生物质的量通常可以为1×108-1×1011CFU/g,或者1×108-1×1010CFU/g,或者5×108-5×1010CFU/g,优选1×109-1×1010CFU/g。CFU/g生物质将影响用来制备本发明配制剂的生物质的量。具有相对高的CFU/g量的生物质可以用来制备生物质的量相对低的配制剂。通常选择用于制备本发明配制剂的生物质的量以符合应对相应目的应用的每公顷的CFU量。
每克产生杀镰孢菌素的类芽孢杆菌属菌株的细胞或孢子的杀镰孢菌素A和杀镰孢菌素B的总量取决于选择产生细菌或孢子的特定类芽孢杆菌属菌株和生长条件。熟练技术人员能够使用标准方法来确定每克所用特定菌株的细胞或孢子的杀镰孢菌素A和杀镰孢菌素B的总量并且能够调节细胞或孢子的克量,适用的话还有细胞或孢子和其他发酵固体的克量,以确定应在混合物中使用多少的细胞或孢子和发酵固体以与杀真菌剂的用量实现协同增效杀真菌效果。
农业化学组合物通常包含5-99.9重量%,优选10-99.9重量%,更优选30-99重量%,尤其是40-90重量%的至少一种助剂。适用的话,活性物质,尤其是组分2和组分3的杀真菌剂以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,通常使用种子处理用溶液(LS),悬浮乳液(SE),可流动浓缩物(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)。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。施用可以在播种之前或期间进行。混合物或包含混合物的农业化学组合物分别在幼苗和繁殖材料如秧苗、生根/未生根插条、衍生于细胞培养的植物上的施用方法包括拌种、包衣、造粒、撒粉、浸泡以及犁沟内施用方法。优选通过不诱发萌发的方法,例如通过拌种、造粒、包衣和撒粉将混合物及其农业化学组合物分别施用于种子上。
可以向混合物或其农业化学组合物中作为预混物加入或者在紧临使用前加入(桶混合)各种类型的油、润湿剂、辅助剂、肥料或微营养素和其他农药(例如杀真菌剂、生长调节剂、除草剂、杀虫剂、安全剂)。这些试剂可以以1:100-100:1,优选1:10-10:1的重量比与本发明混合物或农业化学组合物混合。
混合物和组合物通常以农药有效量施用。“农药有效量”通常是指对生长获得可观察到的效果所需的混合物或包含该混合物的组合物的量,所述效果包括坏死、死亡、阻滞、预防和去除效果,破坏效果或减少目标生物体的出现和活动的效果。对于在本发明中使用的各种混合物/组合物,农药有效量可以变化。混合物/组合物的农药有效量也会根据主要条件如所需农药效果及持续时间、气候、目标物种、场所、施用方式等而变化。
当使用混合物或农业化学组合物时,作为叶面处理施用或者施用于土壤,优选作为叶面处理施用。在叶面处理中的施用率通常为50-2000g/ha,100-2000g/ha,150-2000g/ha,600-2000g/ha或800-2000g/ha,或者50-1000g/ha,100-1000g/ha,150-1000g/ha,600-1000g/ha或800-1000g/ha,或者50-800g/ha,100-800g/ha,150-800g/ha,600-800g/ha或150-1000g/ha,300-1000g/ha,600-1000g/ha包含杀镰孢菌素的细胞或孢子,体积为1000-100L/ha,600-100L/ha,400-100L/ha,200-100L/ha或者1000-600L/ha,1000-400L/ha或1000-200L/ha,或者600-200L/ha,600-400L/ha水基喷雾液。
将本发明的配制剂用于种子处理中时,相对于植物繁殖材料的施用率通常在约1×101-1×1012(或更高)CFU/种子,优选约1×103-1×1010CFU/种子,甚至更优选约1×103-1×106CFU/种子范围内。替换地,相对于植物繁殖材料的施用率优选在约1×107-1×1016(或更高)CFU/100kg种子,优选1×109-约1×1015CFU/100kg种子,甚至更优选1×1011-约1×1015CFU/100kg种子范围内。
混合物具有抗真菌效果并且可以用于抑制或防止植物真菌感染的方法中。
混合物通过用杀真菌有效量的活性物质处理真菌,植物,幼苗如秧苗、生根/未生根插条、衍生于细胞培养的植物或植物繁殖材料如种子;待保护以防真菌侵袭的土壤、表面、材料或空间而直接或者以农业化学组合物形式使用。施用可以在植物、植物繁殖材料如种子;土壤、表面、材料或空间被真菌感染之前和之后进行。
农业化学组合物包含杀真菌有效量的混合物。“杀真菌有效量”表示足以在植物上防治有害真菌并且不会对被处理植物,幼苗如秧苗、生根/未生根插条、衍生于细胞培养的植物或植物繁殖材料如种子产生显著损害的组合物或混合物的量。该量可以在宽范围内变化并且取决于各种因素,如待防治的真菌品种、被处理植物品种、气候条件和所用具体混合物。
植物繁殖材料可以在种植或移栽时或在种植或移栽之前用混合物本身或者组合物或混合物预防性地处理。
当用于植物保护中时,取决于所需效果的种类,施用混合物的组分1、组分2和任选组分3的总量为0.001-2kg/ha,优选0.005-2kg/ha,更优选0.05-0.9kg/ha,特别是0.1-0.75kg/ha。
在植物繁殖材料如种子例如通过撒粉、包衣或浸润的处理中,通常要求每100kg植物繁殖材料(优选种子)0.1-1000g,优选1-1000g,更优选1-100g,最优选5-100g混合物的活性物质量。
用户通常将该农业化学组合物用于前剂量装置、小背包喷雾器、喷雾罐、喷雾飞机或灌溉系统。这里将该农业化学组合物用水、缓冲剂和/或其他助剂配制至所需施用浓度,从而得到即用喷雾液或本发明农业化学组合物。每公顷农业利用区通常施用20-2000升,优选50-400升即用喷雾液。
混合物及其农业化学组合物分别适合作为有效对抗宽范围的植物病原性真菌的杀真菌剂,所述真菌包括土传真菌,特别是选自如下种类: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(Fungi imperfecti))。它们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。
混合物及其农业化学组合物优选可以用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,例如仁果(苹果、梨等),核果(例如李、桃、杏仁、樱桃)或也称为浆果的无核小果(草莓、悬钩子、黑莓、鹅莓等);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,例如笋瓜、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;甜叶菊(也称甜菊(Stevia));天然橡胶植物;或观赏和森林植物,例如花卉、灌木、阔叶树或常绿树(针叶树、桉树等);植物繁殖材料如种子和这些植物的作物材料上防治植物病原性真菌。
更优选将混合物及其农业化学组合物分别用于在大田作物,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;酿酒葡萄或水果葡萄,或者观赏植物;或蔬菜如黄瓜、西红柿、甜椒、菜豆或笋瓜上防治真菌。
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。
因此,本发明的一个实施方案是包含混合物或者包含含有混合物的农业化学组合物的包衣的植物繁殖材料。优选该植物繁殖材料是幼苗,如秧苗、生根/未生根插条、衍生于细胞培养的植物。甚至更优选该植物繁殖材料来自水果或蔬菜植物品种,包括葡萄。
根据本发明,所有上面的栽培植物应理解为包括所有属于相应栽培植物的和属种、亚种、变种和/或杂种。玉米例如也称为印度玉米或玉蜀黍(夏玉米(Zea mays)),包括所有种类的玉米如大田玉米和甜玉米。根据本发明包括所有玉蜀黍或玉米亚种和/或变种,尤其是粉质玉米(Zea mays var.amylacea),爆米花(Zea mays var.everta),顶陷玉米(Zeamays var.indentata),硬质玉米(Zea mays var.indurata),甜玉米(Zea maysvar.saccharata和Zea mays var.rugosa),糯玉米(Zea mays var.ceratina),淀粉玉米(高直链淀粉玉米变种),荚玉米或野生玉米(Zea mays var.tunicata)和七彩玉米(Zeamays var.japonica)。熟练技术人员知道其他植物品种,如甜椒、确定或未确定大豆以及其他的类似变种。
混合物及其农业化学组合物分别特别适合防治植物病害的下列诱因:观赏植物、蔬菜(例如白锈菌(A.candida))和向日葵(例如婆罗门参白锈菌(A.tragopogonis))上的白锈菌属(Albugo)(白锈病);蔬菜(例如胡萝卜黑斑病(A.dauci)或大葱紫斑病(A.porri))、油菜(例如芸苔生链格孢(A.brassicola)或芸苔链格孢(A.brassicae))、糖用甜菜(例如细链格孢(A.tenuis))、水果(例如巨链格孢(A.grandis))、稻、大豆、土豆和西红柿(例如早疫链格孢(A.solani)、巨链格孢(A.grandis)或链格孢(A.alternata))、西红柿(例如早疫链格孢或链格孢)和小麦(例如小麦链格孢(A.triticina))上的链格孢属(Alternaria)(链格孢叶斑病);糖用甜菜和蔬菜上的丝囊霉属(Aphanomyces);禾谷类和蔬菜上的壳二孢属(Ascochyta),例如小麦上的A.tritici(炭疽病)和大麦上的大麦壳二孢(A.hordei);玉米上的玉米北方炭疽病菌(Aureobasidium zeae)(同义词玉米眼斑病菌(Kapatiellazeae));平脐蠕孢属(Bipolaris)和内脐蠕孢属(Drechslera)(有性型:旋孢腔菌属(Cochliobolus)),例如玉米上的叶斑病(玉蜀黍平脐蠕孢(D.maydis)或玉米生离蠕孢(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)(洋葱科上的葱鳞葡萄孢(B.squamosal)或葱腐葡萄孢(B.allii)、油菜或观赏植物(例如百合灰霉病(B eliptica))、葡萄藤、森林植物和小麦上的灰葡萄孢(Botrytiscinerea)(有性型:灰葡萄孢霉(Botryotinia fuckeliana):灰霉病);莴苣上的莴苣盘梗霉(Bremia lactucae)(霜霉病);阔叶树和常绿树上的长喙壳属(Ceratocystis)(同义词线嘴壳属(Ophiostoma))(腐烂病或枯萎病),例如榆树上的榆枯萎病菌(C.ulmi)(荷兰榆病);玉米(例如灰叶斑病:玉米尾孢菌(C.zeae-maydis))、稻、糖用甜菜(例如甜菜生尾孢(C.beticola))、甘蔗、蔬菜、咖啡、大豆(例如大豆灰斑病菌(C.sojina)或大豆紫斑病菌(C.kikuchii))和稻上的尾孢属(Cercospora)(尾孢叶斑病);蘑菇上的Cladobotryum spp.(同义词指孢霉属(Dactylium))(例如C.mycophilum(旧名:树状指孢霉(Dactyliumdendroides),有性型:Nectria albertinii,Nectria rosella,同义词粉红寄生菌(Hypomyces rosellus));西红柿(例如番茄叶霉菌(C.fulvum):叶霉病)和禾谷类(例如小麦上的草芽枝孢(C.herbarum)(穗腐病))上的枝孢属(Cladosporium);禾谷类上的麦角菌(Claviceps purpurea)(麦角病);玉米(灰色长蠕孢(C.carbonum))、禾谷类(例如禾旋孢腔菌(C.sativus),无性型:麦根腐平脐蠕孢)和稻(例如宫部旋孢腔菌(C.miyabeanus),无性型:水稻长蠕孢(H.oryzae))上的旋孢腔菌属(无性型:长蠕孢属(Helminthosporium)或平脐蠕孢属)(叶斑病);棉花(例如棉炭疽病菌(C.gossypii))、玉米(例如禾生炭疽病菌(C.graminicola):炭疽茎腐病)、浆果、土豆(例如西瓜炭疽病菌(C.coccodes):黑点病)、菜豆(例如菜豆炭疽病菌(C.lindemuthianum))、大豆(例如大豆炭疽病菌(C.truncatum)或毛豆炭疽病菌(C.gloeosporioides))、蔬菜(例如黄瓜炭疽病菌(C.lagenarium)或辣椒炭疽病菌(C.capsici))、水果(例如尖孢炭疽菌(C.acutatum))、咖啡(例如咖啡刺盘孢(C.coffeanum)或卡哈瓦刺盘孢(C.kahawae))和各种作物(胶孢炭疽菌(C.gloeosporioides)上的剌盘孢属(Colletotrichum)(有性型:围小丛壳菌属(Glomerella))(炭疽病);伏革菌属(Corticium),例如稻上的笹木伏革菌(C.sasakii)(纹枯病);大豆、棉花和观赏植物上的黄瓜褐斑病菌(Corynespora cassiicola)(叶斑病);锈斑病菌属(Cycloconium),例如橄榄树上的油橄榄孔雀斑病(C.oleaginum);果树、葡萄藤(例如C.liriodendri,有性型:Neonectria liriodendri:乌脚病)和观赏植物上的人参生柱隔孢属(Cylindrocarpon)(例如果树腐烂病或葡萄藤乌脚病,有性型:丛赤壳属(Nectria)或杓兰菌根菌属(Neonectria));大豆上的白纹羽菌(Dematophora(有性型:Rosellinia)necatrix)(根腐病/茎腐病);北茎溃疡菌属(Diaporthe),例如大豆上的大豆北茎溃疡病菌(D.phaseolorum)(立枯疡);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,有性型:核腔菌属(Pyrenophora));由斑褐孔菌(Formitiporia(同义词Phellinus)punctata)、地中海嗜蓝孢孔菌(F.mediterranea)、Phaeomoniellachlamydospora(旧名:Phaeoacremonium chlamydosporum)、Phaeoacremonium aleophilum和/或葡萄座腔菌(Botryosphaeria obtuse)引起的葡萄藤上的埃斯卡(Esca)(葡萄藤枯萎病,干枯病);仁果(E.pyri)、浆果(覆盆子痂囊腔菌(E.veneta):炭疽病)和葡萄藤(葡萄痂囊腔菌(E.ampelina):炭疽病)上的痂囊腔菌属(Elsinoe);稻上的稻叶黑粉菌(Entylomaoryzae)(叶黑粉病);小麦上的附球菌属(Epicoccum)(黑穗病);糖用甜菜(甜菜白粉菌(E.betae))、蔬菜(例如豌豆白粉菌(E.pisi))如葫芦科植物(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);果树、葡萄藤和观赏树上的侧弯孢菌(Eutypa lata)(Eutypa溃疡病或枯萎病,无性型:Cytosporina lata,同义词Libertella blepharis);玉米(例如玉米大斑病菌(E.turcicum))上的突脐蠕孢属(Exserohilum)(同义词长蠕孢属);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、黑星病或银尖病),西红柿上的尖镰孢(F.oxysporum),大豆上的茄镰孢(F.solani)(甘氨酸镰刀菌(f.sp.glycines),现在的同义词为北美大豆猝死综合症病菌(F.virguliforme)及各自引起猝死综合症的南美大豆猝死综合症病菌(F.tucumaniae)和巴西镰刀菌(F.brasiliense)以及玉米上的轮枝镰孢(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、仁果和其他植物上的苹果炭疽病菌(Glomerella cingulata)以及棉花上的棉炭疽病菌(G.gossypii);稻上的Grainstainingcomplex;葡萄藤上的葡萄黑腐病菌(Guignardia bidwellii)(黑腐病);蔷薇科植物和刺柏上的锈菌属(Gymnosporangium),例如梨上的G.sabinae(锈病);玉米、禾谷类、土豆和稻上的长蠕孢属(同义词内脐蠕孢属,有性型:旋孢腔菌属);驼孢锈菌属(Hemileia),例如咖啡上的咖啡驼孢锈菌(H.vastatrix)(咖啡叶锈病);葡萄藤上的褐斑拟棒束孢(Isariopsisclavispora)(同义词Cladosporium vitis);大豆和棉花上的菜豆壳球孢(Macrophominaphaseolina(同义词phaseoli))(根腐病/茎腐病);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);大豆上的扩散叉丝壳(Microsphaeradiffusa)(白粉病);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(同义词丛梗孢属(Monilia spp.):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:叶枯病菌(Zymoseptoria tritici),旧名: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)(同义词Pseudocercospora fijiensis:Sigatoka黑斑病)和香蕉黄条叶斑病菌(M.musicola),花生上的花生球腔菌(M.arachidicola)(同义词花生褐斑病菌(M.arachidis)或Cercospora arachidis),伯克利球腔菌(M.berkeleyi),豌豆上的M.pisi和芥属植物上的M.brassiciola;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);例如葡萄藤(例如P.tracheiphila和P.tetraspora)和大豆(例如大豆茎褐腐病菌(P.gregata):茎病害)上的瓶霉菌属(Phialophora);油菜和卷心菜上的黑胫茎点霉(Phoma lingam)(同义词黑胫病菌(Leptosphaeria biglobosa)和斑点小球腔菌(L.maculans):根腐病和茎腐病),糖用甜菜上的甜菜茎点霉(P.betae)(根腐病、叶斑病和立枯疡)以及玉米上的P.zeae-maydis(同义词Phyllostica zeae);向日葵、葡萄藤(例如葡萄黑腐病菌(P.viticola):蔓割病和叶斑病)和大豆(例如茎腐病:菜豆拟茎点霉(P.phaseoli),有性型:大豆北茎溃疡病菌(Diaporthe phaseolorum))上的拟茎点霉属(Phomopsis);玉米上的玉米褐斑病菌(Physoderma maydis)(褐斑病);各种植物如柿子椒和葫芦科植物(例如辣椒疫霉(P.capsici))、大豆(例如大豆疫霉(P.megasperma),同义词大豆疫霉菌(P.sojae))、土豆和西红柿(例如致病疫霉(P.infestans):晚疫病)和阔叶树(例如栎树猝死病菌(P.ramorum):橡树急死病)上的疫霉属(Phytophthora)(枯萎病,根腐病,叶腐病,果树腐烂病和茎腐病);卷心菜、油菜、小萝卜和其他植物上的芸苔根肿菌(Plasmodiophorabrassicae)(根肿病);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)和向日葵上的霍尔斯单轴霉(P.halstedii);蔷薇科植物、啤酒花、仁果和浆果(例如苹果上的苹果白粉病菌(P.leucotricha))以及葫芦科植物(甜瓜白粉病(P.xanthii))上的叉丝单囊壳属(Podosphaera)(白粉病);例如禾谷类如大麦和小麦(禾谷多粘菌(P.graminis))以及糖用甜菜(甜菜多粘菌(P.betae))上的多粘菌属(Polymyxa)以及由此传播的病毒病害;禾谷类如小麦或大麦上的小麦基腐病菌(Pseudocercosporellaherpotrichoides)(同义词Oculimacula yallundae,O.acuformis:眼斑病,有性型:Tapesia yallundae);各种植物上的假霜霉属(Pseudoperonospora)(霜霉病),例如葫芦科植物上的古巴假霜霉(P.cubensis)或啤酒花上的葎草假霜(P.humili);葡萄藤上的Pseudopezicula tracheiphila(葡萄角斑叶焦病菌或‘rotbrenner’,无性型:瓶霉属(Phialophora));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)(褐锈病或叶锈病),条形柄锈病(P.striiformis)(条纹病或黄锈病),大麦柄锈病(P.hordei)(大麦黄矮叶锈病),禾柄锈菌(P.graminis)(茎腐病或黑锈病)或小麦叶锈菌(P.recondita)(褐锈病或叶锈病),甘蔗上的屈恩柄锈菌(P.kuehnii)(橙锈病)和芦笋上的天门冬属柄锈病(P.asparagi);油菜上的核盘菌属(Pyrenopeziza spp.),例如P.brassicae;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:Magnaporthegrisea,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))和蘑菇(寡雄腐霉(P.oligandrum))上的腐霉属(Pythium)(立枯病);柱隔孢属(Ramularia),例如大麦上的辛加柱隔孢(R.collo-cygni)(柱隔孢叶斑病,生理叶斑病),棉花上的白斑柱隔孢(R.areola)(有性型:网孢球腔菌(Mycosphaerellaareola))和糖用甜菜上的甜菜叶斑病菌(R.beticola);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/茎腐病),稻上的立枯丝核菌(纹枯病)或小麦或大麦上的禾谷丝核菌(R.cerealis)(小麦纹枯病);草莓、胡萝卜、卷心菜、葡萄藤和西红柿上的葡枝根霉(Rhizopus stolonifer)(黑霉病,软腐病);大麦、黑麦和小黑麦上的黑麦喙孢(Rhynchosporium secalis)和R.commune(叶斑病);稻上的稻帚枝霉(Sarocladiumoryzae)和S.attenuatum(叶鞘腐败病);蔬菜(小核盘菌(S.minor)和核盘菌(S.sclerotiorum))和大田作物如油菜、向日葵(例如核盘菌(S.sclerotiorum))以及大豆、花生、蔬菜、玉米、禾谷类和观赏植物(白绢病(S.rolfsii)(同义词罗耳阿太菌(Atheliarolfsii))上的核盘菌属(Sclerotinia)(茎腐病或白绢病);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)(同义词叶枯病菌(Zymoseptoria tritici),壳针孢叶斑病)和禾谷类上的颖枯壳多孢(S.(同义词Stagonospora)nodorum)(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:葡萄粉孢(Oidium tuckeri));玉米(例如玉米大斑病菌(S.turcicum),同义词大斑凸脐蠕孢(Helminthosporium turcicum))和草坪上的大斑病菌属(Setosphaeria)(叶枯病);玉米(例如丝轴黑粉菌(S.reiliana),同义词Ustilago reiliana:丝黑穗病)、高粱和甘蔗上的轴黑粉菌属(Sphacelotheca)(黑穗病);葫芦科植物上的单丝壳白粉菌(Sphaerotheca fuliginea)(同义词甜瓜白粉病(Podosphaera xanthii):白粉病);土豆上的粉痂菌(Spongospora subterranea)(粉痂病)以及由此传播的病毒病害;禾谷类上的壳多孢属(Stagonospora),例如小麦上的颖枯壳多孢(S.nodorum)(斑枯病,有性型:颖枯球腔菌(Leptosphaeria[同义词Phaeosphaeria]nodorum),同义词颖枯壳多孢(Septoria nodorum));土豆上的马铃薯癌肿病菌(Synchytrium endobioticum)(土豆癌肿病);外囊菌属(Taphrina),例如桃上的畸形外囊菌(T.deformans)(缩叶病)和李上的李外囊菌(T.pruni)(囊果李);烟草、仁果、蔬菜、大豆和棉花上的根串珠霉属(Thielaviopsis)(黑色根腐病),例如黑色根腐病菌(T.basicola)(同义词根黑腐病(Chalara elegans));禾谷类上的腥黑粉菌属(Tilletia)(腥黑穗病或光腥黑穗病),例如小麦上的小麦腥黑粉菌(T.tritici)(同义词小麦网腥黑粉菌(T.caries),小麦腥黑穗病)和小麦矮腥黑穗病(T.controversa)(矮腥黑穗病);蘑菇上的哈茨木霉菌(Trichoderma harzianum);大麦或小麦上的肉孢核瑚菌(Typhula incarnata)(灰雪腐病);黑粉菌属(Urocystis),例如黑麦上的隐条黑粉菌(U.occulta)(条黑粉病);蔬菜如菜豆(例如疣顶单胞锈菌(U.appendiculatus),同义词U.phaseoli)、糖用甜菜(例如甜菜锈病菌(U.betae)或U.beticola))和豆类(例如豇豆锈菌(U.vignae)、豌豆锈菌(U.pisi)、蚕豆单孢锈菌(U.viciae-fabae)和蚕豆锈菌(U.fabae))上的单孢锈属(Uromyces)(锈病);禾谷类(例如大麦散黑粉菌(U.nuda)和燕麦散黑粉菌(U.avaenae))、玉米(例如玉蜀黍黑粉菌(U.maydis):玉米黑穗病)和甘蔗上的黑粉菌属(Ustilago)(黑穗病);苹果(例如苹果黑星病(V.inaequalis))和梨上的黑星菌属(Venturia)(黑星病);以及各种植物如果树和观赏树、葡萄藤、浆果、蔬菜和大田作物上的轮生菌属(Verticillium)(枯萎病),例如油菜上的油菜黄萎菌(V.longisporum),草莓、油菜、土豆和西红柿上的茄黄萎病菌(V.dahliae)及蘑菇上的蘑菇褐腐病(V.fungicola);禾谷类上的叶枯病菌(Zymoseptoria tritici)。
混合物及其农业化学组合物分别特别适合防治下列属的植物病原性真菌:链格孢属(Alternaria),葡萄孢属(Botrytis),黑星菌属(Venturia),小球腔菌属(Leptosphaeria),镰孢霉属(Fusarium),丝核菌属(Rhizoctonia),疫霉属(Phytophthora),腐霉属(Pythium),刺盘孢属(Colletotrichum),梨孢属(Pyricularia),核盘菌属(Sclerotinia),叶枯菌属(Zymoseptoria)。
混合物及其农业化学组合物分别特别适合防治下列植物病原性真菌:番茄交链孢(Alternaria solanum),链格孢(Alternaria alternata),芸苔链格孢(Alternariabrassicae),芸苔生链格孢(Alternaria brassicicola),柠檬交链孢(Alternariacitri),苹果链格孢(Alternaria mali),灰葡萄孢,葱腐葡萄孢(Botrytis allii),蚕豆葡萄孢(Botrytis fabae),葱鳞葡萄孢(Botrytis squamosa),苹果黑星病,碧根黑斑病(Venturia effusa),桃黑星病(Venturia carpophila),梨黑星病(Venturia pyrina),斑点小球腔菌,颖枯球腔菌,尖镰孢,禾本科镰孢,轮枝镰孢,立枯丝核菌,致病疫霉,辣椒疫霉,草莓疫霉(Phytophthora fragariae),烟草疫霉(Phytophthora nicotianae),大豆疫霉,终极腐霉菌,棘腐霉(Pythium acanthicum),德里腐霉(Pythium deliense),禾生腐霉(Pythium graminicola),异宗结合腐霉(Pythium heterothallicum),顶生腐霉(Pythiumhypogynum),奇雄腐霉(Pythium middletonii),葫芦科刺盘孢,辣椒炭疽病菌,西瓜炭疽病菌,草莓炭疽病菌(Colletotrichum fragariae),菜豆炭疽病菌,稻瘟病菌,大豆菌核病,小核盘菌,三叶草核盘菌(Sclerotinia trifoliorum),小麦叶枯菌。
混合物及其农业化学组合物分别特别适合防治下列植物病原性真菌:番茄交链孢、灰葡萄孢、苹果黑星病、斑点小球腔菌、颖枯球腔菌、尖镰孢、禾本科镰孢、立枯丝核菌、致病疫霉、终极腐霉菌、葫芦科刺盘孢、稻瘟病菌、大豆菌核病和小麦叶枯菌。
混合物及其农业化学组合物分别特别适合防治下列植物病原性真菌:番茄交链孢、灰葡萄孢、颖枯球腔菌、致病疫霉、葫芦科刺盘孢、稻瘟病菌、大豆菌核病和小麦叶枯菌。
上面详细描述的混合物特别适合用于抑制或防止植物真菌感染的方法中。
因此,本发明的一个实施方案是一种使用上述混合物中的任一种抑制或防止植物真菌感染的方法,其中用该混合物处理植物、植物部分或靠近植物的土壤。该混合物可以作为混合物施用或者可以通过将组分1和组分2以及适用的话,组分3分开施用于植物、植物部分或靠近植物的土壤以在植物、植物部分或靠近植物的土壤处产生该混合物而产生。
因此,本发明包括一种抑制或防止植物真菌感染的方法,其特征在于将杀镰孢菌素A和杀镰孢菌素B的混合物与至少一种选自如下的杀真菌剂组合施用于植物、植物部分或靠近植物的土壤:醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、高效甲霜灵、螺茂胺、氟菌、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、氟嘧菌酯、四唑菌酮、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、氰霜唑、吲唑磺菌胺、涕必灵、甲基托布津、苯酰菌胺、噻唑菌胺、清菌脲、四唑吡氨酯、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、硅噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、福美双、二噻农、藻菌磷和乙磷铝,优选醚唑、螺茂胺、氟唑菌酰胺、啶酰菌胺、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷和乙磷铝,更优选螺茂胺、啶酰菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷和乙磷铝(乙磷铝),
其中该至少一种杀真菌剂以如下方式施用:
a)以与杀镰孢菌素A和杀镰孢菌素B的混合物,或者
b)在施用杀镰孢菌素A和杀镰孢菌素B的混合物之前不超过10、9、8、7、6、5、4、3、2、1天,或者
c)在施用杀镰孢菌素A和杀镰孢菌素B的混合物之后不超过5、4、3、2、1天,或者
d)在与施用杀镰孢菌素A和杀镰孢菌素B的同一天。
本发明的另一实施方案是一种抑制或防止植物真菌感染的方法,其特征在于将杀镰孢菌素A和杀镰孢菌素B的混合物与至少一种选自如下的杀真菌剂组合施用于植物:醚唑、螺茂胺、氟唑菌酰胺、啶酰菌胺、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷和乙磷铝,优选螺茂胺、啶酰菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、二噻农、藻菌磷和乙磷铝(乙磷铝),其中该至少一种杀真菌剂以如下方式施用:
a)以与杀镰孢菌素A和杀镰孢菌素B的混合物,或者
b)在施用杀镰孢菌素A和杀镰孢菌素B的混合物之前不超过10、9、8、7、6、5、4、3、2、1天,或者
c)在施用杀镰孢菌素A和杀镰孢菌素B的混合物之后不超过5、4、3、2、1天,或者
d)在与施用杀镰孢菌素A和杀镰孢菌素B的同一天。
在一个实施方案中,该至少一种杀真菌剂以与杀镰孢菌素A和杀镰孢菌素B的混合物施用于植物,或者在与施用杀镰孢菌素A和杀镰孢菌素B的同一天施用于植物。
在一个实施方案中,该至少一种杀真菌剂在施用杀镰孢菌素A和杀镰孢菌素B的混合物之前不超过10、9、8、7、6、5、4、3、2、1天施用于植物。
在一个实施方案中,该至少一种杀真菌剂在施用杀镰孢菌素A和杀镰孢菌素B的混合物之后不超过5、4、3、2、1天施用于植物。
在一个实施方案中,组分2为联苯吡菌胺、氟嘧菌酯、肟菌酯、四唑菌酮、氰霜唑、吲唑磺菌胺、氟啶胺、异丙菌胺、氟吡菌胺、苯菌酮或代森锰锌并且以与组分1的混合物或者在与施用组分1的同一天施用或者在施用组分1之前不超过10、9、8、7、6、5、4、3、2、1天施用。
在一个实施方案中,组分2为螺茂胺、清菌脲e、苯噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、苯酰菌胺、代森联、啶酰菌胺、霜霉灭、唑嘧菌胺、二噻农、藻菌磷、乙磷铝或双炔酰菌胺并且以与组分1的混合物或者在与施用组分1的同一天施用或者在施用组分1之前不超过5、4、3、2、1天施用。
在一个实施方案中,杀镰孢菌素A和杀镰孢菌素B的混合物作为分离的化合物施用,在替换实施方案中,将杀镰孢菌素A和杀镰孢菌素B的混合物与一种或多种已经产生杀镰孢菌素A和B或者具有产生杀镰孢菌素A和杀镰孢菌素B的能力的类芽孢杆菌属菌株的孢子或细胞一起施用。优选孢子或细胞属于多粘类芽孢杆菌、附生类芽孢杆菌、皮氏类芽孢杆菌、土地类芽孢杆菌、杰米拉类芽孢杆菌和胶冻样类芽孢杆菌,优选属于如下菌株:多粘类芽孢杆菌菌株PKB1,多粘类芽孢杆菌菌株JB05-01-1,多粘类芽孢杆菌菌株AC-1,多粘类芽孢杆菌菌株HY96-2,类芽孢杆菌属数种菌株NRRL B-50972,NRRL B-67129,NRRL B-67304,NRRL B-67306和NRRL B-67615,NRRL B-50374,NRRL B-67721,NRRL B-67723,NRRL B-67724,多粘类芽孢杆菌菌株VMC10/96,类芽孢杆菌属数种菌株10.6D和类芽孢杆菌属数种菌株9.4E,类芽孢杆菌属数种菌株Lu16774,Lu17007和Lu17015,多粘类芽孢杆菌菌株M1,多粘类芽孢杆菌菌株SC2和多粘类芽孢杆菌菌株Sb3-1以及多粘类芽孢杆菌菌株E681。
在该抑制或防止植物真菌感染的方法的优选实施方案中,其中混合物组分1、组分2以及适用的话,组分3在如下生长阶段之间至少施用一次:
a)对于果树和坚果树,优选樱桃、樱桃、李子、桃、杏、苹果、杏仁和柑橘,生长阶段56-89,或者
b)对于浆果,优选醋栗和草莓,生长阶段56-85,优选生长阶段61-85,或者
c)对于葡萄藤,生长阶段61-89,优选生长阶段68-83,或者
d)对于头形蔬菜,优选卷心菜,生长阶段41-49,优选生长阶段45-49,或者
e)对于瓜类蔬菜,优选黄瓜、甜瓜和南瓜,生长阶段22-81,优选生长阶段61-81,或者
f)对于茄科蔬菜,优选西红柿、茄子、甜椒和青椒,生长阶段51-71,优选生长阶段61-71。
生长阶段数字涉及在扩展BBCH标准中定义的生长阶段的两位数编码。该标准按照源自the Biologische Bundesanstalt Bundessortenamt und Chemical Industry并且已经公布在Meier,Uwe:Growth stages of mono-and dicotyledonous plants.BBCHMonograph.Quedlinburg 2018.Open Agrar Repositorium DOI(10.5073/20180906-074619)中的BBCH命名。
实施例
借助下列实施例更详细地描述本发明。下列实施例是为了举例说明的目的,并不意欲限制本发明的范围。
微试验
在二甲亚砜中将活性化合物分开配制成浓度为10000ppm的储备溶液。
用于实施例中的杀镰孢菌素是比例为0.6:1并且由衍生于BASF的类芽孢杆菌属菌株17007的类芽孢杆菌属菌株的培养物纯化的杀镰孢菌素A和杀镰孢菌素B的混合物。类芽孢杆菌属菌株17007已经公开于WO2016/020371中以及已经从德国的种植地分离并且于2013年2月20日由BASF SE按照the Budapest Treaty with the Deutsche Sammlung vonMikroorganismen und Zellkulturen(DSMZ)以登录号DSM 26969保藏。
产品氟噻唑吡乙酮作为市售成品配制剂使用并且用水稀释至活性化合物的所述浓度。
将测量的参数与不含活性化合物的对照方案的生长(100%)以及不含真菌的空白值相比较,以确定病原体在各活性化合物中的相对生长百分数。将这些百分数转化为效力。
效力为0意味着病原体的生长水平对应于未处理对照的生长水平;效力为100意味着病原体未生长。
活性化合物混合物的预期效力使用Colby等式[R.S.Colby,“计算除草剂组合的协同增效和拮抗响应”,Weeds 15,20-22(1967)]确定并与观察到的效力相比较。
1.在微滴定板试验中对葫芦科刺盘孢的活性(COLLLA)
1.将储备溶液根据比例混合,用移液管移到微滴定板(MTP)中并用水稀释至所述浓度。然后加入葫芦科刺盘孢在生物麦芽或酵母-细菌蛋白胨-乙酸钠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天后使用吸收光度计在405nm下测量MTP。
COLLLA
2.在微滴定板试验中对大豆菌核病的活性(SCLESC)
1.将储备溶液根据比例混合,用移液管移到微滴定板(MTP)中并用水稀释至所述浓度。然后加入大豆菌核病在生物麦芽或酵母-细菌蛋白胨-乙酸钠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天后使用吸收光度计在405nm下测量MTP。
Sclesc
3.在微滴定板试验中灰霉病菌—灰葡萄孢的活性(BOTRCI)
1.将储备溶液根据比例混合,用移液管移到微滴定板(MTP)中并用水稀释至所述浓度。然后加入灰葡萄孢在生物麦芽或酵母-细菌蛋白胨-乙酸钠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天后使用吸收光度计在405nm下测量MTP。
BOTRCI
4.在微滴定板试验中对稻瘟病—稻瘟病菌的活性(PYRIOR)
1.将储备溶液根据比例混合,用移液管移到微滴定板(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或酵母-细菌蛋白胨-甘油或DOB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天后使用吸收光度计在405nm下测量MTP。
PYRIOR
Claims (23)
1.一种混合物,包含如下组分作为活性组分:
作为组分1的杀镰孢菌素A和杀镰孢菌素B的组合,其中杀镰孢菌素A和杀镰孢菌素B具有通式
其中
R选自15-胍基-3-羟基十五烷酸(GHPD)和12-胍基十二烷酸(12-GDA);
X1是苏氨酸;
X2是缬氨酸;
X3是缬氨酸;
X4是苏氨酸;
X5选自谷氨酰胺和天冬酰胺;
X6是丙氨酸;并且
其中箭头定义R的羰基结构部分和氨基酸X1的氨基之间或一个氨基酸的羰基和相邻氨基酸的氨基之间的单个(酰胺)键,其中箭头的尖端表示连接到所述氨基酸X1或所述相邻氨基酸的氨基;并且
其中不带箭头的单线定义X6的羰基和X1的羟基之间的单个(酯)键,以及杀镰孢菌素A具有天冬酰胺作为X5,以及
杀镰孢菌素B具有谷氨酰胺作为X5,
作为组分2的选自如下的杀真菌剂:醚唑、螺茂胺、氟唑菌酰胺、啶酰菌胺、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、肟菌酯、氰霜唑、吲唑磺菌胺、苯酰菌胺、清菌脲、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、
烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、
代森联、代森锰锌、二噻农、藻菌磷或乙磷铝;
以及其中组分1和组分2的混合物提供协同增效杀真菌效果。
2.如权利要求1所要求保护的混合物,其中杀镰孢菌素A和杀镰孢菌素B的组合具有的杀镰孢菌素A与杀镰孢菌素B之比为10:1-1:10,9:1-1:9,8:1-1:8,7:1-1:7,6:1-1:6,5:1-1:5,4:1-1:4,3:1-1:3,2:1-1:2,1.8:1-1:1.8,1.7:1-1:1.7,1.6:1-1:1.6,1.5:1-1:1.5,1.4:1-1:1.4,1.3:1-1:1.3,1.2:1-1:1.2,1.1:1-1:1.1或1:1。
3.如权利要求1或2所要求保护的混合物,包含一种或多种仍在产生或者已经产生杀镰孢菌素A和杀镰孢菌素B的类芽孢杆菌属菌株的细胞或孢子。
4.如权利要求3所要求保护的混合物,其中所述至少一种类芽孢杆菌属菌株对至少一种选自如下属的植物病原性真菌具有抗真菌活性:链格孢属(Alternaria),葡萄孢属(Botrytis),黑星菌属(Venturia),小球腔菌属(Leptosphaeria),镰孢霉属(Fusarium),丝核菌属(Rhizoctonia),疫霉属(Phytophthora),腐霉属(Pythium),刺盘孢属(Colletotrichum),梨孢属(Pyricularia),核盘菌属(Sclerotinia)或叶枯菌属(Zymoseptoria)。
5.如权利要求1-4中任一项所要求保护的混合物,进一步包含下列化合物中的至少一种:
6.如权利要求1-7中任一项所要求保护的混合物,进一步包含paeniprolixin、paeniserin。
7.如权利要求1-6中任一项所要求保护的混合物,包含其他杀真菌剂作为组分3,其中组分2的杀真菌剂和组分3的杀真菌剂不同。
8.如权利要求1-7中任一项所要求保护的混合物,包含至少一种选自下组a)-m)的其他杀真菌剂作为组分3:
a)醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、iriadimenol、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、高效甲霜灵、螺茂胺、氟唑菌苯胺、异丙噻菌胺、联苯吡菌胺、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、氟茚唑菌胺、isoflucypram、inpyrfluxam、氟唑菌酰羟胺、环丙嘧啶、二甲嘧菌胺、氟嘧菌酯、腈嘧菌酯、肟菌酯、唑菌胺酯、四唑菌酮、醚菌胺、四唑吡氨酯、氟菌、托布津、甲基托布津、涕必灵、硅噻菌胺、啶氧菌酯、肟醚菌胺、环酰菌胺、胺苯吡菌酮、氰霜唑、吲唑磺菌胺、苯酰菌胺、噻唑菌胺、清菌脲、百维灵、氟啶胺、唑菌嗪、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、fluoxapiprolin、苯啶菌酮、苯菌酮、硫、代森联、代森锰锌、福美双、灭菌丹、二噻农、藻菌磷和乙磷铝,优选醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、高效甲霜灵、螺茂胺、氟菌、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、氰霜唑、吲唑磺菌胺、涕必灵、甲基托布津、苯酰菌胺、噻唑菌胺、清菌脲、四唑吡氨酯、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、硅噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、福美双、二噻农、藻菌磷或乙磷铝,更优选醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、二甲嘧菌胺、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、噻唑菌胺、烯酰吗啉、福美双、四唑吡氨酯、氟菌、托布津、甲基托布津、涕必灵和硅噻菌胺,
b)腈嘧菌酯、甲香菌酯、丁香菌酯、醚菌胺、烯肟菌酯、烯肟菌胺、fenoxystrobin/氟菌螨酯、氟嘧菌酯、四唑菌酮、亚胺菌、甲哌喹、叉氨苯酰胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、唑胺菌酯、唑菌酯、肟菌酯、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、吡本卡布、氯啶菌酯/chlorodincarb、唑酮菌、咪唑菌酮、N-[2-[(1,4-二甲基-5-苯基吡唑-3-基)氧甲基]苯基]-N-甲氧基氨基甲酸甲酯、四唑菌酮、(Z,2E)-5-[1-(2,4-二氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、(Z,2E)-5-[1-(4-氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺、嘧螨胺、吡氟菌酯、2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯,优选腈嘧菌酯、醚菌胺、氟嘧菌酯、四唑菌酮、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯和四唑菌酮;
c)氰霜唑、吲唑磺菌胺、2-甲基丙酸(6S,7R,8R)-8-苄基-3-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]-6-甲基-4,9-二氧代-1,5-二氧壬环-7-基]酯、fenpicoxamid、florylpicoxamid,优选氰霜唑、吲唑磺菌胺和fenpicoxamid,更优选氰霜唑和吲唑磺菌胺;
d)麦锈灵、苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、萎锈灵、呋菌胺、氟吡菌酰胺、氟酰胺、氟唑菌酰胺、呋吡唑灵、异丙噻菌胺、吡唑萘菌胺、丙氧灭绣胺、氧化萎锈灵、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、联苯吡嗪菌胺、氟唑环菌胺、叶枯酞、溴氟唑菌、inpyrfluxam、pyrapropoyne、氟茚唑菌胺、N-[2-[2-氯-4-(三氟甲基)苯氧基]苯基]-3-(二氟甲基)-5-氟-1-甲基吡唑-4-甲酰胺、(E)-2-[2-[(5-氰基-2-甲基苯氧基)甲基]苯基]-3-甲氧基丙-2-烯酸甲酯、isoflucypram、2-(二氟甲基)-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1,3-三甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-乙基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-3-乙基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(1,1-二甲基-3-丙基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-1,1-二甲基-3-丙基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺、2-(二氟甲基)-N-(3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺、2-(二氟甲基)-N-[(3R)-3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺,优选苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟
唑菌酰胺、异丙噻菌胺、氟唑菌苯胺、吡噻菌胺、氟唑菌酰羟胺、氟唑环菌胺、inpyrfluxam、氟茚唑菌胺、isoflucypram,更优选苯并烯氟菌唑、联苯吡菌胺、啶酰菌胺、氟吡菌酰胺、氟唑菌酰胺、氟唑菌苯胺、吡噻菌胺、氟唑环菌胺;
e)氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、氟菌、环酰菌胺、甲霜灵、精甲霜灵、二噻农,优选氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、氟菌、甲霜灵、精甲霜灵和二噻农,更优选氟啶胺、唑嘧菌胺、硅噻菌胺、螺茂胺、甲霜灵、精甲霜灵和二噻农;
f)戊环唑、双苯三唑醇、糠菌唑、环唑醇、醚唑、烯唑醇、烯唑醇M、氧唑菌、腈苯唑、喹唑菌酮、氟硅唑、粉唑醇、己唑醇、酰胺唑、环戊唑醇、环戊唑菌、腈菌唑、咪唑、多效唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、氟醚唑、三唑酮、唑菌醇、戊叉唑菌、烯效唑、2-(2,4-二氟苯基)-1,1-二氟-3-(四唑-1-基)-1-[5-[4-(2,2,2-三氟乙氧基)苯基]-2-吡啶基]丙-2-醇、2-(2,4-二氟苯基)-1,1-二氟-3-(四唑-1-基)-1-[5-[4-(三氟甲氧基)苯基]-2-吡啶基]丙-2-醇、4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苄腈、伊芬三氟康唑、氯氟醚菌唑、(2R)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丙-2-醇、(2S)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1,2,4-三唑-1-基)丙-2-醇、2-(氯甲基)-2-甲基-5-(对甲苯基甲基)-1-(1,2,4-三唑-1-基甲基)环戊醇;咪唑类:抑霉唑、稻瘟酯、丙氯灵、氟菌唑,嘧啶类、吡啶类、哌嗪类:异嘧菌醇、啶斑肟、嗪氨灵、[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)异唑-4-基]-(3-吡啶基)甲醇、4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苄腈、2-[6-(4-溴苯氧基)-2-(三氟甲基)-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇、2-[6-(4-氯苯氧基)-2-(三氟甲基)-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇,优选醚唑、氧唑菌、环戊唑醇、环戊唑菌、丙硫菌唑、戊唑醇、唑菌醇、戊叉唑菌和丙氯灵;
g)涕必灵、甲基托布津、乙霉威、噻唑菌胺、戊菌隆、氟吡菌胺、苯酰菌胺、苯菌酮和苯啶菌酮,优选涕必灵、甲基托布津、噻唑菌胺、氟吡菌
胺、苯酰菌胺、苯菌酮、苯啶菌酮,更优选噻唑菌胺、氟吡菌胺、苯酰菌胺、苯菌酮、苯啶菌酮;
h)环丙嘧啶、嘧菌胺、二甲嘧菌胺,优选二甲嘧菌胺;
i)烯酰吗啉、氟吗啉、双炔酰菌胺、丁吡吗啉、苯噻菌胺、异丙菌胺、霜霉灭,优选烯酰吗啉、双炔酰菌胺、苯噻菌胺、异丙菌胺、霜霉灭;
j)氟噻唑吡乙酮、fluoxapiprolin、4-[1-[2-[3-(二氟甲基)-5-甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3,5-二(二氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3-(二氟甲基)-5-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-环丙基-3-(二氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-甲基-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[5-(二氟甲基)-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、4-[1-[2-[3,5-二(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺、(4-[1-[2-[5-环丙基-3-(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺,优选氟噻唑吡乙酮和fluoxapiprolin,更优选氟噻唑吡乙酮;
k)福美铁、代森锰锌、代森锰、威百亩、代森联、甲基代森锌、福美双、代森锌、福美锌,优选代森锰锌、代森联和福美双;
l)藻菌磷、乙磷铝、亚磷酸及其盐、膦酸钙、膦酸钾,优选藻菌磷和乙磷铝;
m)清菌脲、胺苯吡菌酮、唑菌嗪、四唑吡氨酯优选清菌脲,
其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
9.如权利要求1-8中任一项所要求保护的混合物,其中组分3为醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、高效甲霜灵、螺茂胺、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、二甲嘧菌胺、氟嘧菌酯、四唑菌酮、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、氰霜唑、吲唑磺菌胺、涕必灵、甲基托布津、苯酰菌胺、噻唑菌胺、清菌脲、四唑吡氨酯、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、硅噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、福美双、二噻农、藻菌磷或乙磷铝,其中组分2的杀真菌剂和组分3的杀真菌剂不相同。
10.如权利要求1-9中任一项所要求保护的混合物,其中组分2为啶酰菌胺、肟菌酯、苯酰菌胺、清菌脲、双炔酰菌胺、异丙菌胺、氟吡菌胺、唑嘧菌胺、氟噻唑吡乙酮、代森联、代森锰锌、二噻农、藻菌磷或乙磷铝。
11.如权利要求7-10中任一项所要求保护的混合物,其中组分2为螺茂胺且组分3为氟吡菌酰胺,或者
组分2为啶酰菌胺且组分3为唑菌胺酯,或者
组分2为二甲嘧菌胺且组分3为二噻农或肟菌酯,或者
组分2为肟菌酯且组分3为二甲嘧菌胺或氟吡菌酰胺;或者
组分2为苯酰菌胺且组分3为双炔酰菌胺、氟噻唑吡乙酮或代森锰锌;或者
组分2为清菌脲且组分3为双炔酰菌胺;或者
组分2为双炔酰菌胺且组分3为醚唑、清菌脲、腈嘧菌酯或苯酰菌胺;或者
组分2为氟吡菌胺且组分3为乙磷铝;或者
组分2为唑嘧菌胺且组分3为烯酰吗啉;或者
组分2为氟噻唑吡乙酮且组分3为苯酰菌胺;或者
组分2为代森锰锌且组分3为苯酰菌胺、甲霜灵(metalayl)、精甲霜灵或烯酰吗啉;或者
组分2为二噻农且组分3为二甲嘧菌胺或烯酰吗啉;或者
组分2为藻菌磷或乙磷铝且组分3为氟吡菌酰胺或氟吡菌胺。
12.一种农业化学组合物,包含如权利要求1-10中任一项所定义的混合物和助剂。
13.一种植物繁殖材料,具有包含如权利要求1-11中任一项所定义的混合物或如权利要求12所定义的农业化学组合物的包衣。
14.如权利要求1-11中任一项所定义的混合物或如权利要求12所定义的农业化学组合物在防治或抑制植物病原体或防止植物病原体感染或保护材料以防有害微生物的侵染破坏中的用途。
15.一种抑制或防止真菌感染的方法,其中用有效量的如权利要求1-11中任一项所定义的混合物或有效量的如权利要求12所定义的组合物处理真菌、其栖息地或待保护以防真菌侵袭的材料或植物或者土壤或植物繁殖材料。
16.一种抑制或防止植物真菌感染的方法,其特征在于用如权利要求1-11中任一项所要求保护的混合物处理植物、植物部分或靠近植物的土壤并且将所述混合物以其中组分2以如下方式施用于植物的形式施用于植物、植物部分或靠近植物的土壤:
a)以如权利要求1-11中任一项所要求保护的混合物或者作为如权利要求12所要求保护的农业化学组合物,或者
b)在施用组分1之前不超过10天,或者
c)在施用组分1之后不超过5天,或者
d)在与施用组分1的同一天。
17.如权利要求16所要求保护的抑制或防止植物真菌感染的方法,其中组分2为醚唑、丙硫菌唑、氯氟醚菌唑、环戊唑菌、戊叉唑菌、醚唑、唑菌醇、丙氯灵、戊唑醇、氧唑菌、环戊唑醇、精甲霜灵、高效甲霜灵、螺茂胺、氟菌、氟唑菌苯胺、联苯吡菌胺、氟唑菌酰胺、啶酰菌胺、苯并烯氟菌唑、氟吡菌酰胺、吡噻菌胺、氟唑环菌胺、氟嘧菌酯、四唑菌酮、腈嘧菌酯、肟菌酯、唑菌胺酯、醚菌胺、啶氧菌酯、肟醚菌胺、氰霜唑、吲唑磺菌胺、涕必灵、甲基托布津、苯酰菌胺、噻唑菌胺、清菌脲、四唑吡氨酯、氟啶胺、霜霉灭、苯噻菌胺、异丙菌胺、双炔酰菌胺、烯酰吗啉、氟吡菌胺、唑嘧菌胺、硅噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、代森联、代森锰锌、福美双、二噻农、藻菌磷或乙磷铝。
18.如权利要求16或17所要求保护的抑制或防止植物真菌感染的方法,其中所述混合物包含杀真菌剂作为组分3并且组分2的杀真菌剂和组分3不相同。
19.如权利要求18所要求保护的抑制或防止真菌感染的方法,其中a.组分2为螺茂胺且组分3为氟吡菌酰胺,或者
b.组分2为啶酰菌胺且组分3为唑菌胺酯,或者
c.组分2为二甲嘧菌胺且组分3为二噻农和/或肟菌酯;或者
d.组分2为苯酰菌胺且组分3为双炔酰菌胺、氟噻唑吡乙酮或代森锰锌;或者
e.组分2为清菌脲且组分3为双炔酰菌胺;或者
f.双炔酰菌胺且组分3为醚唑、清菌脲、腈嘧菌酯和/或苯酰菌胺;或
者
g.组分2为氟吡菌胺且组分3为乙磷铝;或者
h.组分2为唑嘧菌胺且组分3为烯酰吗啉;或者
i.组分2为氟噻唑吡乙酮且组分3为苯酰菌胺;或者
j.组分2为代森锰锌且组分3为苯酰菌胺、甲霜灵、精甲霜灵或烯酰吗啉;或者
k.组分2为二噻农且组分3为二甲嘧菌胺或烯酰吗啉;或者l.组分2为藻菌磷或乙磷铝且组分3为氟吡菌酰胺或氟吡菌胺。
20.如权利要求15-19中任一项所要求保护的抑制或防止真菌感染的方法,其中杀镰孢菌素A和杀镰孢菌素B的混合物通过类芽孢杆菌属菌株,优选类芽孢杆菌属数种多粘类芽孢杆菌、附生类芽孢杆菌、皮氏类芽孢杆菌、土地类芽孢杆菌、杰米拉类芽孢杆菌或胶冻样类芽孢杆菌的菌株提供。
21.如权利要求15-20中任一项所要求保护的抑制或防止真菌感染的方法,其中组分2为联苯吡菌胺、氟嘧菌酯、肟菌酯、四唑菌酮、氰霜唑、吲唑磺菌胺、氟啶胺、异丙菌胺、氟吡菌胺、苯菌酮或代森锰锌并且组分2以与组分1的混合物或者在与施用组分1的同一天施用或者在施用组分1之前不超过10、9、8、7、6、5、4、3、2、1天施用。
22.如权利要求15-20中任一项所要求保护的抑制或防止真菌感染的方法,其中组分2为螺茂胺、清菌脲、苯噻菌胺、氟噻唑吡乙酮、苯啶菌酮、苯菌酮、苯酰菌胺、代森联、啶酰菌胺、霜霉灭、唑嘧菌胺、二噻农、藻菌磷、乙磷铝或双炔酰菌胺并且以与组分1的混合物或者在与施用组分1的同一天施用或者在施用组分1之前不超过5、4、3、2、1天施用。
23.如权利要求15-23中任一项所要求保护的抑制或防止植物真菌感染的方法,其中混合物组分1、组分2以及适用的话,组分3在如下生长阶段之间至少施用一次:
a)对于果树和坚果树,优选樱桃、樱桃、李子、桃、杏、苹果、杏仁和柑橘,生长阶段56-89,或者
b)对于浆果,优选醋栗和草莓,生长阶段56-85,优选生长阶段61-85,或
者
c)对于葡萄藤,生长阶段61-89,优选生长阶段68-83,或者
d)对于头形蔬菜,优选卷心菜,生长阶段41-49,优选生长阶段45-49,或
者
e)对于瓜类蔬菜,优选黄瓜、甜瓜和南瓜,生长阶段22-81,优选生长阶段61-81,或者
f)对于茄科蔬菜,优选西红柿、茄子、甜椒和青椒,生长阶段51-71,优选生长阶段61-71。
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